Note: Descriptions are shown in the official language in which they were submitted.
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BLACK CERAMIC ADDITIVES, PIGMENTS AND FORMULATIONS
[0001] This application: (i) claims under 35 U.S.C. 119(e)(1) the
benefit of the filing date of February 28, 2014 of US provisional application
serial
nurnber 61/946,598; (ii) claims under 35 U.S.C. 119(e)(1) the benefit of the
filing
date of January 21, 2015 of US provisional application serial number
62/106,094;
(iii) is a continuation-in-part of US patent application serial nurnber
14/268,150
filed May 2, 2014; and (iv) is a continuation-in-part of US patent application
serial
number 14/212,896 filed March 14, 2014, the entire disclosures of each of
which
are incorporated herein by reference.
BACKGROUND OF THE INVENTION
Field of the Invention
[0002] The present inventions relate to black rnaterials and
formulations utilizing these materials. Generally, the present inventions
relate to:
ceramic materials having blackness, black color, and which are black; starting
compositions for these ceramic materials, and methods of making these ceramic
materials; and formulations, compositions, materials and devices that utilize
or
have these ceramic materials. In particular, embodiments of the present
inventions include: black ceramics having silicon, oxygen and carbon, and
methods of making these ceramics; and devices, structures and apparatus that
have or utilize these formulations, plastics, paints, inks, coatings and
adhesives
containing these black ceramics.
[0003] As used herein, unless stated otherwise, the terms "color,"
"colors" "coloring" and sirnilar such terms are be given their broadest
possible
meaning and would include, among other things, the appearance of the object or
material, the color imparted to an object or material by an additive, methods
of
changing, modifying or affecting color, the reflected refracted and
transmitted
wavelength(s) of light detected or observed from an object or material, the
reflected refracted and transmitted spectrum(s) of light detected or observed
from
an object or material, all colors, e.g. white, grey, black, red, violet,
amber,
almond, orange, aquamarine, tan, forest green, etc., primary colors, secondary
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colors, and all variations between, and the characteristic of light by which
any two
structure free fields of view of the same size and shape can be distinguish
between.
[00041 As used herein, unless stated otherwise, the terms "black",
"blackness", and similar such terms, are to be given there broadest possible
meanings, and would include among other things, the appearance of an object,
color, or material: that is substantially the darkest color owing to the
absence, or
essential absence of, or absorption, or essential abortion of light; where the
reflected refracted and transmitted spectrum(s) of light detected or observed
from
an object or material has no, substantially no, and essentially no light in
the
visible wavelengths; the colors that are considered generally black in any
color
space characterization scheme, including the colors that are considered
generally black in L a b color space, the colors that are considered generally
black in the Hunter color space, the colors that are considered generally
black in
the CIE color space, and the colors that are considered generally black in the
CIELAB color space; any color, or object or material, that matches or
substantially matches any Pantone color that is referred to as black,
including
PMS 433, Black 3, Black 4, Black 5, Black 6, Black 7, Black 2 2x, Black 3 2x,
Black 4 2x, Black 5 2x, Black 6 2x, Black 7 2x, 412, 419, 426, and 423; values
on
a Tri-stimulus Colorimeter of X= from about 0.05 to about 3.0; Y = from about
0.05 to about 3.0, and Z = from about 0.05 to about 3.0; in non glossy
formulations; a CIE L.. a b of L = less than about 40, less than about 20,
less than
about 10, less than about 1, and about zero, of "a" = of any value; of "b" =
of any
value; and a CIE L a b of L = less than 50 and b = less than 1.0; an L value
less
than 30, a "b" value less than 0.5 (including negative values) and an "a"
value
less than 2 (including negative values); having a jetness value of about 200
My
and greater, about 250 My and greater, 300 My and greater, and greater; having
an L = 40 or less and a My of greater than about 250; having an L. = 40 or
less
and a My of greater than about 300; having a dM value of 10; having a dM value
of -15; and combinations and variations of these.
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[0005] As used herein, unless stated otherwise, the term "gloss" is to
be given its broadest possible meaning, and would include the appearance from
specular reflection. Generally the reflection at the specular angle is the
greatest
amount of light reflected for any specific angle. In general, glossy surfaces
appear darker and more chromatic, while matte surfaces appear lighter and less
chromatic.
[0006] As used herein, unless stated otherwise, the term "Jetness" is
to
be given its broadest possible meaning, and would include among other things,
a
Color independent blackness value as measured by My (which may also be
called the "blackness value"), or Mc, the color dependant blackness value, and
My and Mc values obtained from following DIN 55979 (the entire disclosure of
which is incorporated herein by reference).
[0007] As used herein, unless stated otherwise, the term "undertone,"
"hue" and similar such terms are to be given their broadest possible meaning,
and would include among other things.
[0008] As used herein, unless stated otherwise, the terms "visual
light,"
"visual light source," "visual spectrum" and similar such terms refers to
light
having a wavelength that is visible, e.g., perceptible, to the human eye, and
includes light generally in the wave length of about 390 nm to about 770 rim.
[0009] As used herein, unless stated otherwise, the term "paint" is to
be given its broadest possible meaning, and would include among other things,
a
liquid composition that after application as a thin layer to a substrate upon
drying
forms a thin film on that substrate, and includes all types of paints such as
oil,
acrylic, latex, enamels, varnish, water reducible, alkyds, epoxy, polyester-
epoxy,
acrylic-epoxy, polyamide-epoxy, urethane-modified alkyds, and acrylic-
urethane.
[0010] As used herein, unless stated otherwise, the term "plastic" is
to
be given its broadest possible meaning, and would include among other things,
synthetic or semi-synthetic organic polymeric materials that are capable of
being
molded or shaped, thermosetting, thermoforming, thermoplastic, orientable,
biaxially orientable, polyolefins, polyamide, engineering plastics, textile
adhesives
coatings (TAC), plastic foams, styrenic alloys, acrylonitrile butadiene
styrene
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(ABS), polyurethanes, polystyrenes, acrylics, polycarbonates (PC), epoxies,
polyesters, nylon, polyethylene, high density polyethylene (HDPE), very low
density polyethylene (VLDPE), low density polyethylene (LDPE), polypropylene
(PP), polyvinyl chloride (PVC), polyethylene terephthalate (PET), polybutylene
terephthalate (PBT), poly ether ethyl ketone (PEEK), polyether sulfone (PES),
bis
maleimide, and viscose (cellulose acetate).
[0011] As used herein, unless stated otherwise, the term "ink" is to
be
given its broadest possible meaning, and would include among other things, a
colored liquid for marking or writing, toner (solid, powder, liquid, etc.) for
printers
and copiers, and colored solids that are used for marking materials, pigment
ink,
dye ink, tattoo ink, pastes, water-based, oil-based, rubber-based, and acrylic-
based.
[00121 As used herein, unless stated otherwise, the term "nail polish"
and similar such terms, are to be given its broadest term, and would include
all
types of materials, coatings and paints that can be applied to, or form a
film, e.g.,
a thin film, on the surface of a nail, including natural human nails,
synthetic "fake"
nails, and animal nails.
[00131 As used herein, unless stated otherwise, the term "adhesive" is
to be given its broadest possible meaning, and would include among other
things, substances (e.g., liquids, solids, plastics, etc.) that are applied to
the
surface of materials to hold them together, a substance that when applied to a
surface of a material imparts tack or stickiness to that surface, and includes
all
types of adhesives, such as naturally occurring, synthetic, glues, cements,
paste,
mucilage, rigid, semi-rigid, flexible, epoxy, urethane, methacrylate, instant
adhesives, super glue, permanent, removable, and expanding.
[00141 As used herein, unless stated otherwise, the term "coating" is
to
be given its broadest possible meaning, and would include among other things,
the act of applying a thin layer to a substrate, any material that is applied
as a
layer, film, or thin covering (partial or total) to a surface of a substrate,
and
includes inks, paints, and adhesives, powder coatings, foam coatings, liquid
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coatings, and includes the thin layer that is formed on the substrate, e.g. a
coating.
[0015] As used herein, unless stated otherwise, the term "sparkle" is
to
be given its broadest possible meaning, and would include among other things,
multi angle reflections simultaneously imparted from the surface facets.
[0016] As used herein, unless stated otherwise, room temperature is
25 C. And, standard temperature and pressure is 25 C and 1 atmosphere.
[0017] Generally, the term "about" as used herein unless specified
otherwise is meant to encompass a variance or range of 1O%, the experimental
or instrument error associated with obtaining the stated value, and preferably
the
larger of these.
SUMMARY
[0018] There has been a long-standing and unfulfilled need for,
improved pigments and additives for plastics, paints, inks, coatings and
adhesives, as well as a continued need for improved formulations for these
coatings and materials. The present inventions, among other things, solve
these
needs by providing the compositions of matter, materials, articles of
manufacture,
devices and processes taught, disclosed and claimed herein.
[0019] There is provided a coating formulation having: a first
material
and a second material; wherein the first material defines a first weight
percent of
the coating formulation and the second material defines a second weight
percent
of the coating formulation; wherein the second material is a black polymer
derived ceramic material; and wherein the first weight percent is larger than
the
second weight percent.
[0020] Further there is provided the present coatings, materials and
coating formulations having one or more of the following features: wherein the
polymer derived ceramic material is a polysilocarb; wherein the formulation is
a
paint; wherein the formulation is a powder coat; wherein the formulation is an
adhesive; wherein the black polymer derived ceramic material has a particle
size
of less than about 1.5 pm; wherein the black polymer derived ceramic material
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has a particle size of less than about 1.5 pm; wherein the black polymer
derived
ceramic material has a particle size D50 of from about 1 pm to about 0.1 pm;
wherein the black polymer derived ceramic material has a particle size D50 of
from about 1 pm to about 0.1 pm; wherein the coating defines a blackness
selected from the group consisting of: PMS 433, Black 3, Black 3, Black 4,
Black
5, Black 6, Black 7, Black 2 2x, Black 3 2x, Black 4 2x, Black 5 2x, Black 6
2x,
and Black 7 2x; wherein the coating defines a blackness selected from the
group
consisting of: Tri-stimulus Colorimeter of X from about 0.05 to about 3.0, Y
from
about 0.05 to about 3.0, and Z from about 0.05 to about 3.0: a CIE L a b of L
of
less than about 40; a CIE L a b of L of less about 20; a CIE I_ a b of L of
less than
50, b of less than 1.0 and a of less than 2; and a jetness value of at least
about
200 M. wherein the polymer derived ceramic material is a polysilocarb, and the
paint is a paint selected from the group consisting of oil, acrylic, latex,
enamel,
varnish, water reducible, alkyd, epoxy, polyester-epoxy, acrylic-epoxy,
polyamide-epoxy, urethane-modified alkyd, and acrylic-urethane; wherein the
formulation is essentially free of metals; wherein the formulation has less
than
about 100 ppm heavy metals; wherein the formulation has less than 10 ppm
heavy metals; wherein the formulation has less than 1 ppm heavy metals;
wherein the formulation has less than 0.01 ppm of heavy rnetals; wherein the
formulation has less than about 0.001 ppm of heavy metals.
[0021] Still further there is provided a paint formulation having: a
resin,
a solvent, and a polymer derived ceramic pigment.
[0022] Moreover there is provided the present coatings, materials and
coating formulations having one or more of the following features: wherein the
polymer derived ceramic pigment is a polysilocarb derived ceramic pigment;
wherein the polymer derived ceramic pigment has a primary particle D50 size of
from about 0.1 pm to about 2.0 pm; wherein the polymer derived ceramic
pigment has a primary particle D50 size of from about 0.3 pm to about 1.0 pm;
wherein the polymer derived ceramic pigment is loaded at from about 1.5
pounds/gallon to about 10 pounds/gallon; wherein the resin is selected from
the
group of resins consisting of thermoplastic acrylic polyols, Bisphenol A
diglycidal
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ether, silicone, oil based, and water-reducible acrylic; wherein the
formulation
has less than about 0.1 ppm of heavy metals, and the paint formulation is a
very
high temperature coating, wherein the paint formulation is thermally stable to
greater than 700 0C; wherein the formulation has less than about 0.1 ppm of
heavy metals, and the paint formulation is a very high temperature coating,
wherein the paint formulation is thermally stable to greater than 800 0C;
wherein
the formulation has less than about 0.1 ppm of heavy metals, and the paint
formulation is a very high temperature coating, wherein the paint formulation
is
thermally stable to greater than 500 0C; wherein the formulation has less than
about 0.1 ppm of heavy metals, and the paint formulation is a very high
temperature coating, wherein the paint formulation is thermally stable to
greater
than 900 0C; wherein the paint formulation is a very high temperature coating,
and wherein the paint formulation is thermally stable to greater than 1000 0C.
[00231 Yet further there is provided a coating formulation having: a
first
material and a second material; wherein the first material is a majority of
the
coating formulation; and wherein the second material is a black polymer
derived
ceramic material selected from the group consisting of polysilocarb,
carbosilane,
polycarbosilane, silane, polysilane, silazane, polysilazane, silicon carbide,
carbosilazane, polycarbosilazane, siloxane, and polysiloxanes.
[00241 Additionally there is provided the present coatings, materials
and coating formulations having one or more of the following features: wherein
the polymer derived ceramic material has a primary particle D50 size of from
about 0.1 pm to about 2.0 pm; wherein the first material is a system selected
from the group of systems consisting of acrylics, lacquers, alkyds, latex,
polyurethane, phenolics, epoxies and waterborne; wherein the first material is
a
material selected from the group consisting of HDPE, LDPE, PP, Acrylic, Epoxy,
Linseed Oil, PU, PUR, EPDM, SBR, PVC, water based acrylic emulsions, ABS,
SAN, SEBS, SBS, PVDF, PVDC, PMMA, PES, PET, NBR, PTFE, siloxanes,
polyisoprene and natural rubbers; wherein the coating formulation is a paint
formulation selected from the group consisting of oil, acrylic, latex, enamel,
varnish, water reducible, alkyd, epoxy, polyester-epoxy, acrylic-epoxy,
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polyamide-epoxy, urethane-modified alkyd, and acrylic-urethane; wherein the
coating is a coating selected from the group consisting of ink, powder coat,
nail
polish, and paint: wherein the coating is a coating selected from the group
consisting of industrial coatings, residential coatings, furnace coatings,
engine
component coatings, pipe coatings, and oil field coatings; wherein the coating
is
a coating selected from the group consisting of industrial coatings,
residential
coatings, furnace coatings, engine component coatings, pipe coatings, and oil
field coatings.
[0025] Still further there is provided an ink formulation having: a
first
material and a black polymer derived ceramic pigment.
[0026] Further there is provided an ink formulation having 10-30
weight
A) polysilocarb black ceramic pigment, 10-60 weight % submicron glass frit, 10-
20 weight % sucrose acetate isobutyrate, 4-15 weight % hydrocarbon resin, and
5-15 weight % ethyleneglycol.
[0027] Still further there is provided a packaging ink having 2-30
weight
% polysilocarb black ceramic pigment, 5-15 weight % nitrocellulose resin, 25-
35
weight % ethanol solvent, 10-20 weight % ethyl acetate solvent, 1-2 weight %
citrate plasticizer, 1 weight % polyethylene wax solution, and 5-10 weight %
additives.
[0028] Yet additionally there is provided an ink formulation having 10-
30 weight % polysilocarb black ceramic pigment, 10-60 weight % submicron
glass frit, and 4-15 weight % hydrocarbon resin.
[0029] Further there is provided a packaging ink having 2-30 weight %
polysilocarb black ceramic pigment, 5-15 weight % resin, and 25-35 weight %
solvent.
[0030] Moreover, there is provided a nail polish formulation, having a
carrier material and a black polymer derived ceramic pigment.
[0031] Additionally, there is provided a plastic material, having a
first
material and a second material, wherein the first material is a plastic and
makes
up at least 50% of the total weight of the plastic material, and the second
material
is a black polymer derived ceramic material.
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(0032] Still further there is provided the present coatings, materials
and
coating formulations having one or more of the following features; wherein the
plastic is selected from the group consisting of HDPE, LDPE, PP, Acrylic,
Epoxy,
Linseed Oil, PU, PUR, EPDM, SBR, PVC, water based acrylic emulsions, ABS,
SAN, SEBS, SBS, PVDF, PVDC, PMMA, PES, PET, NBR, PTFE, siloxanes,
polyisoprene and natural rubbers; wherein the plastic is selected from the
group
consisting of thermosetting, thermoforming, thermoplastic, orientable,
biaxially
orientable, polyolefins, polyamide, engineering plastics, textile adhesives
coatings (TAC) and plastic foams; wherein the plastic is selected from the
group
consisting of styrenic alloys, acrylonitrile butadiene styrene (ABS),
polyurethanes, polystyrenes, acrylics, polycarbonates (PC), epoxies,
polyesters,
nylon, polyethylene, high density polyethylene (HOPE), very low density
polyethylene (VLDPE); wherein the plastic is selected from the group
consisting
of low density polyethylene (LDPE), polypropylene (PP), polyvinyl chloride
(PVC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT),
poly
ether ethyl ketone (PEEK), polyether sulfone (PES), bis maleimide, and viscose
(cellulose acetate); wherein the black polymer derived ceramic material is a
polysilocarb derived ceramic pigment.
[0033] Yet additionally, there is proved a paint having: a resin and a
polymer derived ceramic pigment.
[0034] Further there is provided an ink having: a carrier material and
a
black polymer derived ceramic pigment.
[0035] In addition there is provided a nail polish formulation having:
a
carrier material and a black polymer derived ceramic pigment.
[0036] Yet additionally, there is provided an adhesive having: a
carrier
material and a black polymer derived ceramic pigment.
[0037] Still further there is provided a coating having: a first
material
and a second material; wherein the first material defines a first weight
percent of
the coating formulation and the second material is a second weight percent of
the
total coating formulation; and wherein the second material is a black polymer
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derived ceramic material having a polysilocarb, and the first weight percent
is
larger than the second weight percent.
[0038] Moreover over there is provided a paint having a resin and a
polymer derived pigment.
[0039] Yet further there is provided a coating having: a first
material
and a second material; wherein the first material is a majority of the
coating; and
wherein the second material is a black polymer derived ceramic material
selected
from the group consisting of polysilocarb, carbosilane, polycarbosilane,
silane,
polysilane, silazane, polysilazane, silicon carbide, carbosilazane,
polycarbosilazane, siloxane, and polysiloxanes.
[0040] There is provided a coating formulation having: a first
material
and a second material; wherein the first material defines a first material
weight
percent of the coating formulation and the second material defines a second
material weight percent of the coating formulation; wherein the second
material is
a black polymer derived ceramic material having from about 30 weight % to
about 60 weight % silicon, from about 5 weight % to about 40 weight 'Ye
oxygen,
and from about 3 weight 9/0 to about 35 weight % carbon; and wherein the first
material weight percent is larger than the second material weight percent.
[0041] There is further provided the pigments, coatings, coating
formulations and materials that have one or more of the following features:
wherein 20 weight % to 80 weight % of the carbon is free carbon; wherein 20
weight % to 80 weight % of the carbon is silicon-bound-carbon; wherein the
formulation is selected from the group consisting of paint, powder coat,
adhesive,
nail polish, and ink; wherein the black polymer derived ceramic material has a
particle size of less than about 1.5 pm; wherein the black polymer derived
ceramic material has a particle size D50 of from about 1 pm to about 0.1 pm;
wherein the coating defines a blackness selected from the group consisting of:
PMS 433, Black 3, Black 3, Black 4, Black 5, Black 6, Black 7, Black 2 2x,
Black
3 2x, Black 4 2x, Black 5 2x, Black 6 2x, and Black 7 2x; wherein the coating
defines a blackness selected from the group consisting of: Tri-stimulus
Colorimeter of X from about 0.05 to about 3.0, Y from about 0.05 to about 3.0,
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and Z from about 0.05 to about 3.0; a CIE L a b of L of less than about 40; a
CIE
I_ a b of L of less about 20; a CIE L a b of L of less than 50, 1) of less
than 1.0 and
a of less than 2; and a jetness value of at least about 200 My; wherein the
formulation is essentially free of heavy metals; wherein the formulation has
less
than about 100 ppm of heavy metals; wherein the formulation has less than
about 10 ppm heavy metals; wherein the formulation has less than about 1 ppm
heavy metals; wherein the formulation has less than about 0.1 ppm heavy
metals; wherein the coating is essentially free of heavy metals; wherein the
coating has less than about 100 ppm of heavy metals; wherein the coating has
less than about 10 ppm heavy metals; wherein the coating has less than about 1
ppm heavy metals; wherein the coating has less than about 0.1 ppm heavy
rnetals; wherein the pigment has less than about 10 ppm heavy metals, less
than
about 1 ppm heavy metals, and less than about 0.1 ppm heavy metals; and
wherein the heavy metals are Cr and Mn.
[0042] Yet further there is provided a paint formulation having: a
resin,
a solvent, and a polymer derived ceramic pigment having from about 30 weight
% to about 60 weight % silicon, from about 5 weight % to about 40 weight %
oxygen, and from about 3 weight % to about 35 weight % carbon, and wherein
20 weight A) to 80 weight % of the carbon is silicon-bound-carbon.
[0043] There is further provided the pigments, coatings, coating
formulations and rnaterials that have one or rnore of the following features:
wherein the polymer derived ceramic pigment has a primary particle D5 size of
from about 0.1 pm to about 2.0 pm; wherein the polymer derived ceramic
pigment is loaded at from about 1.5 pounds/gallon to about 10 pounds/gallon,
wherein the resin is selected from the group of resins consisting of
thermoplastic
acrylic polyols, Bisphenol A diglycidal ether, silicone, oil based, and water-
reducible acrylic; wherein the formulation has less than about 0.01 ppm of
heavy
metals; wherein the formulation has less than about 0.1 ppm of heavy metals;
wherein the formulation has less than about 1 ppm of heavy metals, and the
paint formulation is a very high temperature coating, wherein the paint
formulation is thermally stable to greater than 700 0C; wherein the
formulation
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has less than about 10 ppm of heavy metals, and the paint formulation is a
very
high temperature coating; wherein the paint formulation is a very high
temperature coating, and wherein the paint formulation is thermally stable to
greater than 1000 C; wherein the first material has a system selected from
the
group of systems consisting of acrylics, lacquers, alkyds, latex,
polyurethane,
phenolics, epoxies and waterborne; wherein the first material has a material
selected from the group consisting of HOPE, LOPE, PP, Acrylic, Epoxy, Linseed
Oil, PU, PUR, EPDM, SBR, PVC, water based acrylic emulsions, ABS, SAN,
SEBS, SBS, PVDF, PVDC, PMMA, PES, PET, NBR, PTFE, siloxanes,
polyisoprene and natural rubbers; wherein the coating formulation is a paint
formulation selected from the group consisting of oil, acrylic, latex, enamel,
varnish, water reducible, alkyd, epoxy, polyester-epoxy, acrylic-epoxy,
polyamide-epoxy, urethane-modified alkyd, and acrylic-urethane; and wherein
the coating has a coating selected from the group consisting of industrial
coatings, residential coatings, furnace coatings, engine component coatings,
pipe
coatings, and oil field coatings.
[00441 Yet moreover there is provided an ink formulation having: a
first
material and a black polymer derived ceramic pigment having from about 30
weight % to about 60 weight % silicon, from about 5 weight % to about 40
weight
% oxygen, and from about 3 weight % to about 35 weight % carbon, and wherein
20 weight % to 80 weight % of the carbon is silicon-bound-carbon.
[00451 Furthermore there is provided a nail polish formulation, having
a
carrier material and a black polymer derived ceramic pigment having from about
30 weight % to about 60 weight % silicon, from about 5 weight % to about 40
weight % oxygen, and from about 3 weight % to about 35 weight % carbon, and
wherein 20 weight % to 80 weight % of the carbon is silicon-bound-carbon..
[00461 Additionally there is provided a plastic material, having a
first
material and a second material, wherein the first material is a plastic and
makes
up at least 50% of the total weight of the plastic material, and the second
material
is a black polymer derived ceramic material having from about 30 weight % to
about 60 weight % silicon, from about 5 weight % to about 40 weight % oxygen,
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and from about 3 weight % to about 35 weight % carbon, and wherein 20 weight
% to 80 weight % of the carbon is silicon-bound-carbon.
[0047] There is further provided the pigments, coatings, coating
formulations and materials that have one or more of the following features:
wherein the plastic is selected from the group consisting of HDPE, LDPE, PP,
Acrylic, Epoxy, Linseed Oil, PU, PUR, EPDM, SBR, PVC, water based acrylic
emulsions, ABS, SAN, SEBS, SBS, PVDF, PVDC, PMMA, PES, PET, NBR,
PTFE, siloxanes, polyisoprene and natural rubbers; wherein the plastic is
selected from the group consisting of thermosetting, thermoforming,
thermoplastic, orientable, biaxially orientable, polyolefins, polyamide,
engineering
plastics, textile adhesives coatings (TAC) and plastic foams; wherein the
plastic
is selected from the group consisting of styrenic alloys, acrylonitrile
butadiene
styrene (ABS), polyurethanes, polystyrenes, acrylics, polycarbonates (PC),
epoxies, polyesters, nylon, polyethylene, high density polyethylene (HDPE),
very
low density polyethylene (VLDPE); and wherein the plastic is selected from the
group consisting of low density polyethylene (LDPE), polypropylene (PP),
polyvinyl chloride (PVC), polyethylene terephthalate (PET), polybutylene
terephthalate (PBT), poly ether ethyl ketone (PEEK), polyether sulfone (PES),
bis
maleinlide, and viscose (cellulose acetate).
[0048] Still additionally there is provided a paint having: a resin
and a
polymer derived ceramic pigment having from about 30 weight % to about 60
weight % silicon, from about 5 weight % to about 40 weight % oxygen, and from
about 3 weight % to about 35 weight % carbon, and wherein 20 weight % to 80
weight % of the carbon is silicon-bound-carbon.
[0049] Yet further there is provided an ink having: a carrier material
and a black polymer derived ceramic pigment having from about 30 weight A to
about 60 weight % silicon, from about 5 weight % to about 40 weight % oxygen,
and from about 3 weight % to about 35 weight % carbon, and wherein 20 weight
% to 80 weight % of the carbon is silicon-bound-carbon.
[0050] Moreover there is provided a nail polish formulation having: a
carrier material and a black polymer derived ceramic pigment having from about
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30 weight % to about 60 weight % silicon, from about 5 weight % to about 40
weight % oxygen, and from about 3 weight % to about 35 weight % carbon, and
wherein 20 weight % to 80 weight % of the carbon is silicon-bound-carbon.
[0051] Yet additionally there is provided an adhesive having: a
carrier
material and a black polymer derived ceramic pigment having from about 30
weight % to about 60 weight % silicon, from about 5 weight % to about 40
weight
% oxygen, and from about 3 weight % to about 35 weight % carbon, and wherein
20 weight % to 80 weight % of the carbon is silicon-bound-carbon.
[0052] Further there is provided a coating having: a first material
and a
second material; wherein the first rnaterial defines a first material weight
percent
of the coating formulation and the second material has a second material
weight
percent of the total coating formulation; and wherein the second material is a
black polymer derived ceramic material having from about 30 weight % to about
60 weight % silicon, from about 5 weight % to about 40 weight % oxygen, and
from about 3 weight % to about 35 weight % carbon, and wherein 20 weight % to
80 weight % of the carbon is silicon-bound-carbon, and the first material
weight
percent is larger than the second material weight percent.
[0053] There is further provided the pigments, coatings, coating
formulations and materials that have one or more of the following features:
wherein the coating is a paint; wherein the coating is a powder coat; wherein
the
black polymer derived ceramic material has a particle size of less than about
1.5
pm; wherein the coating defines a blackness selected from the group consisting
of: PS 433, Black 3, Black 3, Black 4, Black 5, Black 6, Black 7, Black 2 2x,
Black 3 2x, Black 4 2x, Black 5 2x, Black 6 2x, and Black 7 2x; wherein the
coating defines a blackness selected from the group consisting of: Tri-
stimulus
Colorimeter of X from about 0.05 to about 3.0, Y from about 0.05 to about 3.0,
and Z from about 0.05 to about 3.0; a CIE L a b of L of less than about 40; a
CIE
L a b of L of less about 20; a CIE I_ a b of L of less than 50, b of less than
1.0 and
a of less than 2; and a jetness value of at least about 200 My; and wherein
the
paint is a paint selected from the group consisting of oil, acrylic, latex,
enamel,
varnish, water reducible, alkyd, epoxy, polyester-epoxy, acrylic-epoxy,
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polyamide-epoxy, urethane-modified alkyd, and acrylic-urethane; wherein the
coating is essentially free of heavy metals; wherein the coating has less than
about 10 ppm of heavy metals.
[0054] Additionally there is provided a paint having a resin and a
polymer derived pigment having from about 30 weight % to about 60 weight %
silicon, from about 5 weight % to about 40 weight % oxygen, and from about 3
weight % to about 35 weight % carbon, and wherein 20 weight % to 80 weight %
of the carbon is silicon-bound-carbon.
[0055] There is further provided the pigments, coatings, coating
=formulations and materials that have one or more of the following features:
wherein the first material has a material selected from the group of materials
consisting of acrylics, lacquers, alkyds, latex, polyurethane, phenolics,
epoxies
and waterborne; wherein the coating is a paint selected from the group
consisting
of oil, acrylic, latex, enamel, varnish, water reducible, alkyd, epoxy,
polyester-
epoxy, acrylic-epoxy, polyamide-epoxy, urethane-modified alkyd, and acrylic-
urethane; wherein the black polymer derived ceramic material has about 40
weight % to about 50 weight % silicon, and wherein about 25 weight % to about
40 weight % of the carbon is silicon-bound-carbon; wherein the black polymer
derived ceramic material has about 40 weight % to about 50 weight % silicon,
and wherein about 55 weight % to about 75 weight % of the carbon is free
carbon; wherein the black polymer derived ceramic material has about 20 weight
% to about 30 weight % oxygen, and wherein about 25 weight % to about 40
weight % of the carbon is silicon-bound-carbon; wherein the black polymer
derived ceramic material has about about 20 weight % to about 30 weight ./0
oxygen, and wherein about 55 weight % to about 75 weight % of the carbon is
free carbon; wherein the black polymer derived ceramic material has about 20
weight % to about 30 weight % carbon, and wherein about 25 weight % to about
40 weight A) of the carbon is silicon-bound-carbon; wherein the black polymer
derived ceramic material has about about 20 weight % to about 30 weight %
carbon, and wherein about 55 weight % to about 75 weight % of the carbon is
free carbon; wherein the black polymer derived ceramic material has about 40
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weight % to about 50 weight % silicon, and wherein about 25 weight % to about
40 weight % of the carbon is silicon-bound-carbon; wherein the black polymer
derived ceramic material has about 40 weight ./0 to about 50 weight %
silicon,
and wherein about 55 weight `)//0 to about 75 weight % of the carbon is free
carbon; wherein the black polymer derived ceramic material has about 20 weight
% to about 30 weight % oxygen, and wherein about 25 weight % to about 40
weight % of the carbon is silicon-bound-carbon; wherein the black polymer
derived ceramic material has about about 20 weight 9/0 to about 30 weight %
oxygen, and wherein about 55 weight 'Ye to about 75 weight % of the carbon is
free carbon; wherein the black polymer derived ceramic material has about 20
weight % to about 30 weight % carbon, and wherein about 25 weight % to about
40 weight ./0 of the carbon is silicon-bound-carbon; and wherein the black
polymer derived ceramic material has about about 20 weight % to about 30
weight % carbon, and wherein about 55 weight % to about 75 weight % of the
carbon is free carbon.
[0056] Furthermore there is provided a black polysilocarb derived
ceramic pigment having from about 30 weight % to about 60 weight % silicon,
from about 5 weight `)//0 to about 40 weight % oxygen, and from about 3 weight
%
to about 35 weight % carbon, and wherein 20 weight ./0 to 80 weight ,10 of
the
carbon is silicon-bound-carbon and 80 weight % to about 20 weight % of the
carbon is free carbon.
[0057] There is further provided the pigments, coatings, coating
formulations and materials that have one or more of the following features:
wherein the pigment is a UV absorber; wherein the pigment has an absorption
coefficient of greater than 500 dB/cm/(g/100g); wherein the pigment has an
absorption coefficient of greater than 500 dB/cm/(g/100g); wherein the pigment
has an absorption coefficient of greater than 1,000 dB/cm/(g/100g); wherein
the
pigment has an absorption coefficient of greater than 5,000 dB/cm/(g/100g);
wherein the pigment has an absorption coefficient of greater than 10,000
dB/cm/(g/100g); wherein the pigment has an agglornerate of primary pigment
particles; wherein the agglomerate has a size D50 of at least about 10 pm;
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wherein the primary pigment particles have a size 1:1:0 of less than about 1
pm;
wherein the agglomerate has a strength A, and the primary particle has a
strength PP, and PP, is at least 100 times greater than As; wherein the
agglomerate has a strength As and the primary particle has a strength Pips and
PP, is at least 500 times greater than As; wherein the agglomerate has a
strength
A, and the primary particle has a strength PP, and PP, is at least 1,000 times
greater than As; wherein the pigment has an oil absorption of less than about
50
g1100 g; wherein the pigment has an oil absorption of less than about 20 g/100
g;
wherein the polymer derived ceramic pigment has a primary particle D50 size of
from about 0.1 pm to about 1.5 ium; wherein the polymer derived ceramic
pigment has a primary particle D50 size of greater than about about 0.1 pm;
wherein the polymer derived ceramic pigment has a primary particle D50 size of
less than about about 10.0 pm; wherein the polymer derived ceramic pigment
has a primary particle D50 size of from about 0.1 pm to about 3.0 pm; wherein
the
polymer derived ceramic pigment has a primary particle D5osize of from about 1
pm to about 5.0 pm; wherein the pigment is microwave safe; wherein the pigment
is non-conductive; wherein the pigment is hydrophilic; and wherein the pigment
is
hydrophobic.
[0058] There is provided a method for making a black ceramic pigment
aggregate, the method including: pyrolizing a polymer derived ceramic to form
black polymer derived ceramic bulk material, reducing the size of the polymer
derived ceramic bulk material to form primary pigment particles having a
particle
size D50 of from about 1 pm to about 0.1 pm, the primary pigment particles
including from about 30 weight % to about 60 weight % silicon, from about 5
weight % to about 40 weight % oxygen, and from about 3 weight % to about 35
weight % carbon.
[0059] There is further provided the methods that have one or more of
the following features: wherein the primary pigment particles are formed into
agglomerate particles; wherein the agglomerate particles have a particle size
D50
of at least about 10 pm; wherein the act of reducing the size of the particles
includes using equipment selected from the group consisting of a ball mill, an
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attrition mill, a rotor stator mill, a hammer mill, a jet-mill, a roller mill,
a bead mill,
a media mill, a grinder, a homogenizer, and a two-plate mill; wherein reducing
includes using equipment selected from the group consisting of a ball mill, a
rotor
stator mill, a hammer mill, a jet-mill, a roller mill, a bead mill, a
homogenizer, and
a two-plate mill; wherein spray drying forms the agglomerate; wherein a binder
is
used to, in part, form the agglomerate; wherein the binder is selected from
the
group consisting of dispersants, surfactants, soaps, copolymers, starches,
natural and synthetic polymers and saccharides, lipids, fatty acids, petroleum-
derived polymers and oligomers; wherein the binder is selected from the group
consisting of sodium alginate, corn starch, starch, fructoses, saccharides
carrageenan and water-soluble polymers; wherein about 0.01% to about 5% by
weight binder is used; and wherein about 0.1% to about 2% by weight binder is
used.
[0060] Still further there is provided a method of making a coating
including: combining an agglomerated black polysilocarb derived pigment with a
primary formation material, mixing the combination whereby the agglomerated
pigment is broken down into primary pigment particles; and wherein the
prirnary
pigment particles are dispersed throughout the primary formation material.
[0061] There is further provided the methods that have one or more of
the following features: wherein the prirnary pigrnent particles comprise frorn
about 30 weight % to about 60 weight % silicon, from about 5 weight % to about
40 weight ./0 oxygen, and from about 3 weight ,10 to about 35 weight %
carbon;
wherein the primary formation material is a resin; wherein the resin is
selected
from the group consistent of oil, acrylic, latex, enamel, varnish, water
reducible,
alkyd, epoxy, polyester-epoxy, acrylic-epoxy, polyamide-epoxy, urethane-
modified alkyd, and acrylic-urethane; wherein the resin is selected from the
group
consistent of acrylics, lacquers, alkyds, latex, polyurethane, phenolics,
epoxies
and waterborne; wherein the pigment dispersed resin has a reading of about 7
or
greater on the Hagman guage; wherein the pigment dispersed resin has reading
of about 7 or greater on the Hagman guage after 15 minutes of mixing; wherein
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the pigment dispersed resin has a reading of about 7 or greater on the Hagman
guage.
[0062] The method of claim 13, wherein the pigment dispersed resin
has reading of about 7 or greater on the Hagman guage after 15 minutes of
mixing; wherein the pigment dispersed in the primary formation material has
reading of about 7 or greater on the Hagman guage after 15 minutes of mixing;
wherein the coating is selected from the group consisting of an ink, an
adhesive,
and a paint; and wherein the coating is selected from the group consisting of
an
ink, an adhesive, and a paint.
[0063] Still additionally there is provided a method for making a
black
ceramic pigment, the method including: placing a polymer derived ceramic
precursor on a forming surface, curing the polymer derived ceramic precursor
on
the forming surface, removing the cured polymer derived ceramic precursor from
the forming surface, pyrolizing the cured polymer derived ceramic precursor,
and
thereby forming a black polymer derived ceramic pigment including from about
30 weight % to about 60 weight % silicon, from about 5 weight % to about 40
weight % oxygen, and from about 3 weight % to about 35 weight % carbon.
[0064] There is further provided the methods that have one or more of
the following features: wherein 20 weight % to 80 weight % of the carbon is
free
carbon; wherein 20 weight % to 80 weight % of the carbon is silicon-bound-
carbon; wherein the forming surface is moving; wherein the cured polymer
derived ceramic is reduced in size by action of removal from the forming
surface;
wherein the pyrolized polymer derived ceramic is reduced in size to form a
primary pigment particle; wherein the primary pigment particle has a particle
size
D50 of less than about 4 pm; wherein the primary pigment particle has a a
particle
size D50 of from about 3 pm to about 0.1 pm; wherein the primary pigment
particle has a a particle size D50 of from about 2 pm to about 0.5 pm; wherein
the
formulation is selected from the group consisting of paint, powder coat,
adhesive,
nail polish, and ink; wherein the pigment defines a blackness selected from
the
group consisting of: FMS 433, Black 3, Black 3, Black 4, Black 5, Black 6,
Black
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7, Black 2 2x, Black 3 2x, Black 4 2x, Black 5 2x, Black 6 2x, and Black 7 2x;
wherein the pigment defines a blackness selected from the group consisting of:
Tri-stimulus Colorimeter of X from about 0.05 to about 3.0, Y from about 0.05
to
about 3.0, and Z from about 0.05 to about 3.0; a CIE L a 1) of L of less than
about
40; a CIE L a b of L of less about 20; a CIE L a b of L of less than 50, b of
less
than 1.0 and a of less than 2; and a jetness value of at least about 200 My;
wherein the coating defines a blackness selected from the group consisting of:
PMS 433, Black 3, Black 3, Black 4, Black 5, Black 6, Black 7, Black 2 2x,
Black
3 2x, Black 4 2x, Black 5 2x, Black 6 2x, and Black 7 2x; wherein the coating
defines a blackness selected from the group consisting of: Tri-stimulus
Colorimeter of X from about 0.05 to about 3.0, Y from about 0.05 to about 3.0,
and Z frorn about 0.05 to about 3.0; a CIE L a b of L of less than about 40; a
CIE
L a b of L of less about 20; a CIE L. a b of L of less than 50, b of less than
1.0 and
a of less than 2; and a jetness value of at least about 200 My
[0065] Still further there is provided a method of making a paint
formulation including: combining a resin, a solvent, and a polymer derived
ceramic pigrnent including from about 30 weight % to about 60 weight ,10
silicon,
from about 5 weight ./0 to about 40 weight A oxygen, and from about 3 weight
%
to about 35 weight % carbon, and wherein 20 weight % to 80 weight % of the
carbon is silicon-bound-carbon.
[0066] There is further provided the methods that have one or more of
the following features: wherein the polyrner derived cerarnic pigment has a
primary particle D50 size of from about 0.1 pm to about 2.0 pm; wherein the
polymer derived ceramic pigment is loaded at from about 1.5 pounds/gallon to
about 10 pounds/gallon: wherein the resin is selected from the group of resins
consisting of thermoplastic acrylic polyols, Bisphenol A diglycidal ether,
silicone,
oil based, and water-reducible acrylic; wherein the formulation has less than
about 10 ppm of heavy metals; wherein the formulation has less than about 1
ppm of heavy metals; wherein the forrnulation has less than about 0.1 ppm of
heavy metals; and wherein the coating includes a coating selected from the
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group consisting of industrial coatings, residential coatings, furnace
coatings,
engine component coatings, pipe coatings, and oil field coatings.
[0067] There is further provided the methods that have one or more of
the following features: wherein the black polymer derived ceramic pigment
includes about 40 weight % to about 50 weight % silicon, and wherein about 25
weight ,10 to about 40 weight ./0 of the carbon is silicon-bound-carbon;
wherein
the black polymer derived ceramic pigment includes about 40 weight % to about
50 weight ./0 silicon, and wherein about 55 weight % to about 75 weight ./0
of the
carbon is free carbon; wherein the black polymer derived ceramic pigment
includes about 20 weight % to about 30 weight % oxygen, and wherein about 25
weight % to about 40 weight % of the carbon is silicon-bound-carbon; wherein
the black polymer derived ceramic pigment includes about about 20 weight % to
about 30 weight % oxygen, and wherein about 55 weight % to about 75 weight
./0
of the carbon is free carbon; wherein the black polymer derived ceramic
pigment
includes about 20 weight % to about 30 weight ,10 carbon, and wherein about
25
weight % to about 40 weight % of the carbon is silicon-bound-carbon; and
wherein the black polymer derived ceramic pigment includes about about 20
weight % to about 30 weight % carbon, and wherein about 55 weight % to about
75 weight % of the carbon is free carbon.
[0068] There is further provided the methods that have one or more of
the following features: wherein the black polysilocarb derived ceramic pigment
is
hydrophilic and the primary material is aqueous; wherein the black
polysilocarb
derived ceramic pigment is hydrophilic and the primary material is aqueous;
wherein the black polysilocarb derived ceramic pigment is rendered hydrophobic
and the resin is non- aqueous.
[0069] nn
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BRIEF DESCRiPTION OF THE DRAWINGS
[0070] FIG. 1 is a schematic flow diagram of an embodiment of a
system in accordance with the present inventions.
[0071] FIG. 2A is a scanning electron photomicrograph 'SEPM) of an
embodiment of a polysilocarb derived ceramic pigment. SEPM legend bar ¨ HV
5.00 kV, WD 10.6 mm, magnification 5,000x, dwell 5 ps, spot 5.0, HFW 41.4 pm.
[0072] FIG. 2B is a SEPM of an embodiment of a polysilocarb derived
ceramic pigment. SEPM legend bar ¨ HV 5.00 kV, WD 10.6 mm, magnification
10,000x, dwell 5 ps, spot 5Ø HFW 20.7 pm.
[0073] FIG. 3A is a SEPM of an embodiment of a polysilocarb derived
ceramic pigrnent. SEPM legend bar ¨ HV 5.00 kV, WD 10.5 mm, rnagnification
5,000x, dwell 5 ps, spot 5.0, HFW 41.4 pm.
[0074] FIG. 3B is a SEPM of an embodiment of a polysilocarb derived
ceramic pigment. SEPM legend bar ¨ HV 5.00 kV, WD 10.5 mm, magnification
10,000x, dwell 5 ps, spot 5.0, HFW 20.7 pm.
[0075] FIG. 4A is a SEPM of an embodiment of a polysilocarb derived
ceramic pigment. SEPM legend bar¨ HV 5.00 kV, WD 10.8 mm, magnification
6,500x, dwell 5 ps, spot 5.0, HFW 31.9 pm.
[0076] FIG. 4B is a SEPM of an embodiment of a polysilocarb derived
ceramic pigrnent. SEPM legend bar ¨ HV 5.00 kV, WD 10.8 mm, rnagnification
8,000x, dwell 2 ps, spot 5.0, HFW 25.9 pm.
[0077] FIG. 4C is a SEPM of an embodiment of a polysilocarb derived
ceramic pigment. SEPM legend bar ¨ HV 5.00 kV, WD 10.8 mm, magnification
65,000x, dwell 5 ps, spot 5.0, HFW 31.9 pm.
[0078] FIG. 5A is a SEPM of an embodiment of a polysilocarb derived
ceramic pigment. SEPM legend bar¨ HV 5.00 kV, WD 10.1 mm, magnification
6,500x, dwell 5 ps, spot 5.0, HFW 31.9 pm.
[0079] FIG. 5B is a SEPM of an embodiment of a polysilocarb derived
ceramic pigrnent. SEPM legend bar ¨ HV 5.00 kV, WD 10.6 mm, rnagnification
10,000x, dwell 5 ps, spot 5.0, HFW 20.7 pm.
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DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0080] In general the present inventions relate to ceramic black
materials for use as, or in, colorants, inks, pigments, dyes, additives and
formulations utilizing these black materials. Embodiments of the present
inventions, among other things, relate to ceramic materials having blackness,
black color, and which are black; starting compositions for these ceramic
materials, and methods of making these ceramic materials; and formulations,
compositions, materials that utilize or have these ceramic materials. These
various embodiments of the present inventions, in particular, relate to, or
utilize,
such ceramic black materials that are polymer derived ceramics. Embodiments
of the present inventions also relate to black ceramics having silicon, oxygen
and
carbon, and methods of making these ceramics; formulations utilizing these
black
ceramics; and devices, structures and apparatus that have or utilize these
formulations. Embodiments of the present invention in general include
plastics,
paints, inks, coatings, formulations, liquids and adhesives containing ceramic
black materials, preferably polymer derived black ceramic materials, and more
preferably polysilocarb polymer derived ceramic materials.
[00811 Polymer derived ceramics (PDC) are ceramic materials that are
derived from, e.g., obtained by, the pyrolysis of polymeric materials. These
materials are typically in a solid or semi-solid state that is obtained by
curing an
initial liquid polymeric precursor, e.g., PDC precursor, PDC precursor
formulation, precursor batch, and precursor. The cured, but unpyrolized,
polymer
derived material can be referred to as a preform, a PDC preform, the cured
material, and similar such terms. Polymer derived ceramics may be derived from
many different kinds of precursor formulations, e.g., starting materials,
starting
formulations. PDCs may be made of, or derived from, carbosilane or
polycarbosilane (Si-C), silane or polysilane (Si-Si), silazane or polysilazane
(Si-
N-Si), silicon carbide (SiC), carbosilazane or polycarbosilazane (Si-N-Si-C-
Si),
siloxane or polysiloxanes (Si-0), to name a few.
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[00821 A preferred PDC is "polysilocarb", e.g., material containing
silicon (Si), oxygen (0) and carbon (C). Polysilocarb materials may also
contain
other elements. Polysilocarb materials can be made from one or more
polysilocarb precursor formulation or precursor formulation. The polysilocarb
precursor formulations can contain, for example, one or more functionalized
silicon polymers, other polymers, non-silicon based cross linking agents,
monomers, as well as, potentially other ingredients, such as for example,
inhibitors, catalysts, initiators, modifiers, dopants, fillers, reinforcers
and
combinations and variations of these and other materials and additives.
Silicon
oxycarbide materials, SiOC compositions, and similar such terms, unless
specifically stated otherwise, refer to polysilocarb materials, and would
include
liquid materials, solid uncured materials, cured materials, and ceramic
materials.
[0083] Examples of PDCs, PDC formulations and starting materials,
are found in US Patent Application Serial Nos. 14/212,986, 14/268,150,
14/324,056, 14/514,257, 61/946,598, and 62/055,397, US Patent Publication No
2008/0095942, 2008/0093185, 2007/0292690, 2006/0230476, 2006/0069176,
2006/0004169, and 2005/0276961, and US Patent Nos. 5,153,295, 4,657,991,
7,714,092, 7,087,656 and 8,742,008, and 8,119,057, the entire disclosures of
each of which are incorporated herein by reference.
[0084] Turning to FIG. 1 there is provided a process flow chart 100
for
an embodiment having several embodiments of the present processes and
systems. Thus, there is a precursor make-up segment 101, where the PDC
precursor formulations are prepared. There is a forming segment 102 where the
PDC precursor is formed into a shape, e.g., bead, slab, and particle. There is
a
curing segment 103, where the PDC precursor is cured to a cured material,
which is substantially solid, and preferably a solid. There is a pyrolysis
segment
104 where the cured material is converted to a ceramic, e.g., a PDC, which
preferably is a SiOC. There is a post-processing segment 105, where the
ceramic is further processed, e.g., washing, grinding, agglomeration, milling,
cycloning, sieving, etc. There is a formulation segment 106 where the PDC is
processed into a material formulation (e.g., paint, plastic, ink, coating and
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adhesive), containing the PDC, i.e., a PDC containing material formulation.
PDC
containing material formulations include, among other things, PDC paints, PDC
plastics, PDC inks, PDC adhesives, and PDC coatings. There is an application
segment 107, where a PDC containing material formulation is applied to a
substrate, e.g., a refrigerator, vehicle, appliance or other items, and
components
of such items.
[0085] The precursor make-up segment can be any of the systems,
processes and materials disclosed and taught in this specification, as well
as,
those disclosed and taught in US Patent Applications Serial Numbers
14/212,986, 14/268,150, 14/324,056, 14/514,257, 61/946,598 and 62/055,397
and 62/106,094, the entire disclosure of each of which are incorporated herein
by
reference.
[0086] The forming segment can be any of the systems, processes and
materials disclosed and taught in this specification, as well as, those
disclosed
and taught in US Patent Application Serial Numbers 14/212,986, 14/268,150,
14/324,056, 14/514,257, 61/946,598 and 62/055,397 and 62/106,094, the entire
disclosure of each of which are incorporated herein by reference.
[0087] The curing segment can be any of the systems, processes and
materials disclosed and taught in this specification, as well as, those
disclosed
and taught in US Patent Application Serial Numbers 14/212,986, 14/268,150,
14/324,056, 14/514,257, 61/946,598 and 62/055,397 and 62/106,094, the entire
disclosure of each of which are incorporated herein by reference.
[0088] The pyrolizing segment can be any of the systems, processes
and materials disclosed and taught in this specification, as well as, those
disclosed and taught in US Patent Application Serial Numbers 14/212,986,
14/268,150, 14/324,056, 14/514,257, 61/946,598 and 62/055,397 and
62/106,094, the entire disclosure of each of which are incorporated herein by
reference. By way of exarnple, furnaces can that can be used for the
pyrolizing
segment include, among others: RF furnaces, Microwave furnaces, pressure
furnaces, fluid bed furnaces, box furnaces, tube furnaces, crystal-growth
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furnaces, arc melt furnaces, induction furnaces, kilns, MoSi2 heating element
furnaces, gas-fired furnaces, carbon furnaces, and vacuum furnaces.
[0089] The post-processing segment can involve any type of further
processing activities to enhance, effect, or modify the performance,
handleability,
processability, features, size, surface properties, and combinations and
variations of these. Thus, for example, the post-processing step can involve a
grinding step in which the PDC is reduced in size to diameters of less than
about
pm, less than about 5 pm, less than about 1 pm, less than about 0.5 pm, and
less than about 0.1 pm. The PDC can be ground, for example, by the use of a
ball mill, an attrition mill, a rotor stator mill, a hammer mill, a jet-mill,
a roller mill, a
bead mill, a media mill, a grinder, a homogenizer, a two-plate mill, a dough
mixer,
and other types of grinding, milling and processing apparatus. The post-
processing segment can involve, for example, an agglomeration, where smaller
PDC particles are combined to form larger particles, preferably agglomerated
particles having diameters of at least about 2 pm, at least about 2.5 prfl,
greater
than 2.5 pm, at least about 3 pm, at least about 5 pm, at least about 10 pm,
greater than 10 pm, and greater than 12 pm. Preferably, the agglomerated
particles are sufficiently bound, or held together, to prevent the particles
from
falling off, e.g., separating from, the agglomeration during handling,
shipping,
storage, and processing, e.g., "handling strength." More preferably, the
strength
of the agglomerations is only slightly greater than the handling strength, and
in
this manner can readily be broken apart into the smaller particles for use in
a
PDC material formulation. For example, the agglomeration can have a strength,
e.g., crush strength, that is less than about 1/2000 of the strength of the
smaller
particles, e.g., primary particles, that form the agglomeration, less than
about
1/500 of the strength of the smaller particles, less than about 1/75 of the
strength
of the smaller particles, and less than 1/2 of the strength of the smaller
particles.
The agglomeration can, for example, be formed by using spray drying
techniques. Suitable binders, including for example sizing agents, for use in
spray drying techniques include for example: dispersants, surfactants, soaps,
copolymers, starches, natural and synthetic polymers and saccharides, lipids,
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fatty acids, petroleum-derived polymers and oligomers. Sodium alginate, corn
starch, potato starch, and other naturally derived starches, fructoses,
sucroses,
dextroses and other naturally or synthetically derived saccharides and sugars,
polylactic acid and other naturally derived polymers, cellulosic byproducts,
carrageenan and other natural products, poly vinyl acetate and other water-
soluble polymers, wetting and dispersing agents such as polyacrylates,
polyethylene oxides, polypropylene oxides, and copolymers containing them.
Parrafins and other waxes, other petrochemical derivatives and petroleum based
polymers. Surfactants such as Tween, Span, Brij, and other types of
surfactants;
Stearates, oleates, and other modified oils; linear copolymers, branched
copolymers, star polymers and copolymers, hyperbranched polymers and
copolyrners, cornb-like polymers, and combinations and variations of these.
[0090] The
amount of binder used to PDC can range from about 0.01%
to 5%, about 0.1% to about 2%, and preferably less than about 1% and less than
about 0.5%. Agglomerates can also be formed by batch evaporation and
casting, thin film evaporation, wiped-film evaporation, tray drying, oven
drying,
freeze drying, and other suitable evaporation methods, aggregation techniques
such as sedimentation, solvent exchange and coagulation, pin mixing,
filtration,
and others, preferably combined with a drying technique, and cornbinations and
variations of these. Further, processing may involve the application of a
surface
treatment, wash, or coating to the surface of the PDC particles to provide
predetermined features to the PDCs, such as for example, enhanced antistatic,
wettability, material formulation compatibility, mixability, etc. It should be
noted
that while surface treatments are contemplated by the present inventions to
further enhance, e.g., specialize the PDC particles for a particular purpose;
an
advantage of the present inventions is the feature that they are more readily
mixed, added, or compiled into material formations, e.g., paints, plastics,
inks,
coating and adhesives, than the prior art black pigments, e.g., carbon black
((ASTM Color Index) Cl Black 1,6,7) or graphite (Cl Black 10) or metal oxides
and mixed metal oxides, including but riot limited to iron oxides (Cl Black
11) and
Manganese Iron oxide (Cl Black 26) or Iron Manganese oxide (Cl Black 33),
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Manganese oxide (Cl Black 14), Copper oxide (Cl Black 13), Copper Manganese
Iron oxide (Cl Black 26) or Copper Chrome oxide (Cl Black 28), and pigment
rnade by ashing organic matter (Cl Black 8, 9) which typically for many
applications require surface treatments. Thus, an advantage of the present
inventions, among other things, is the ability to use untreated PDC particles,
e.g.,
no surface treatments, in materials formulation.
[0091] In the formulation segment, the making of the PDC material
formulation takes place. Thus, for example, the PDC ceramic is mixed into,
added to, or otherwise combined with the materials used to make up the
material
formulation. Generally, an agglomerate easily breaks down into its primary
particles, e.g., the primary party state; and the primary particles are
uniformly and
smoothly distributed or suspended in the primary formulation material, which
can
be obtained in less than 60 minutes of mixing, less than 30 minutes of mixing
and
quicker. Typically, the PDC ceramic is much more easily mixed into the
material
formulation than carbon black to a fully dispersed state. For example, and by
way
of illustration, PDC ceramic can be easily and quickly mixed within 10 minutes
into a vessel in which a simple 3 blade stirrer is mixing at 1,000 rpm tip
speed.
The resin, PDC Ceramic mixture will be fully dispersed which is illustrated by
a
reading of greater than 7 on the Hegman gauge. The Hegman gauge is a
calibrated device to quickly show how fine a dispersion is made. A carbon
black
or oxide black pigment mixed into the resin in the same mariner would produce
a
Hegman reading of less than 1 which indicates very large particles still in
the
resin, because these pigments require high energy milling to break up the
aggregates in the as supplied' pigment. Generally, the PDC ceramic can be
mixed into, added to, or otherwise combined with the material formulation in
the
same manner, using the same or existing equipment, that are present for use
with other black pigments or colorants. Preferably, for many applications less
expensive, quicker, more efficient equipment and much less expensive
processes than are needed for carbon black can be used with the PDC particles.
[0092] In the application segment the PDC containing material
formulation is applied to an end product, or a component that may be used in
an
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end product. The PDC containing material formulation can typically, and
preferably, be applied using the same types of techniques that are used for
carbon black based formulations, e.g., brush, spray, dip, etc. Moreover, the
PDC
containing material formulations have applications, and the ability to be
applied,
in manners that could not be accomplished with a similar carbon black based
formulation.
[0093] It should be understood that the various segments of the
embodiment of Fig. 1 can be combined (e.g., a single piece of equipment could
perform one of more of the operations of different segments, such as curing
and
pyrolizing), conducted serially, conducted in parallel, conducted multiple
times,
omitted (e.g., post-processing many not be necessary or required), conducted
in
a step wise or batch process (included where the segments are at different
locations, separated by time, e.g., a few hours, a few days, months or longer,
and both), conducted continuously, and in different orders and combinations
and
variations of these. Thus, for example the post-processing segment of grinding
can be performed on the cured material prior to pyrolysis, and can also be
performed on both the cured and pyrolized materials.
[0094] FIGS. 2A and 2B, are SEPMs of an embodiment of a
polysilocarb derived ceramic pigment having a primary particle size of 3 yin
D50,
that was made by curing and pyrolizing the polysilocarb precursor formulation
into a monolithic block, and then breaking down that block into primary
particles.
FIGS. 3A and 3B are SEPMs of agglomerates formed by spray drying 0.5 pm D50
primary particles, which were obtained by further milling of the 3,0 pm
primary
particles shown in FIGS. 2A and 2B.
[0095] FIGS. 4A, 4B and 4C, are SEPMs of 1 .5 pm D50 primary
particles of an embodiment of a polysilocarb derived ceramic pigment, that
were
formed by a liquid-liquid system. (Liquid-liquid systems are described and set
=forth in detail in US Patent Application Serial No. 62/106,094, the entire
disclosure of which is incorporated herein by reference) and generally involve
the
formation of a drop of precursor material in another liquid, and would include
for
example solution polymerization type systems, emulsion polymerization type
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systems, nano-emulsion formation type systems, and the like.) FIGS. 5A and 5B
are SEPMs of the primary particles of FIGS. 4A and 4B that have been further
milled down to 0.9 pm D50.
[0096] An embodiment of a polysilocarb ceramic pigment is a colorant
suitable and advantageous in multiple fields such as industrial,
architectural,
marine and automotive systems. The polysilocarb ceramic pigment can
preferably easily disperses into acrylics, lacquers, alkyds, latex,
Polyurethane,
phenolics, epoxies and waterborne systems providing a durable, uniform coating
and pleasant aesthetics in all types of finishes, e.g., matte and gloss.
[0097] The polysilocarb ceramic pigment can preferably be low dusting.
The polysilocarb ceramic pigment does not typically accumulate charge, it is
easy to clean up, and does not cling to surfaces. The polysilocarb ceramic
pigment is considerably easier to clean up, and control dusting than typical
carbon black. It is theorized that the typical carbon black's strong
hydrophobicity,
light particle weight, and very small particle size (e.g., 50 nm to 200 nm),
among
other things, makes carbon black much more difficult to clean up and control
than
the polysilocarb ceramic pigment. As such, it is preferably a non-sticking,
non-
clinging black pigment. These, among other features, are a significant
improvement over carbon black, which is typically difficult to clean up,
dusts, and
clings to surfaces.
[0098] The polysilocarb ceramic pigment can have low oil absorption,
leading to lower viscosities, which among other things, permits formulations
to
move to higher solids loading with lower VOC content. This pigment can have a
diameter, for example, from about 0.1 pm to 300 pm, from about 1 pm to about
150 pm, less than 10 pm, less than 1 pm, less than 0.3 pm, and less than or
equal to 0.1 pm.
[0099] An embodiment of a batch of the polysilocarb pigment, can have
narrow or tight particle size (e.g., diameter) distribution. Thus, embodiments
of
these black ceramic pigments are particles that are within at least 90% of the
targeted size, at least 95% of the targeted size, and at least 99% of the
targeted
size. For example, the patch of particles, can have size distributions such as
at
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least about 90% of their size within a 10 pm range, at least about 95% of
their
size within a 10 pm range, at least about 98% of their size within a 10 prIl
range,
and at least about 99% of their size within a 10 pm range. Further, and for
example, the process can produce particles each of which can have at least
about 90% of their size within a 5 pm range, at least about 95% of their size
within a 5 pm range, at least about 98% of their size within a 5 pm range, and
at
least about 99% of their size within a 5 pm range. Further, and in submicron
particle sized, for example, the process can produce particles each of which
can
have at least about 90% of their size within a 0.2 pm range, at least about
95% of
their size within a 0.2 pm range, at least about 98% of their size within a
0.2 pm
range, and at least about 99% of their size within a 0.2 pm range. More
preferably, in sub micron sizes, embodiments these percentage tolerances can
be for the 0.1 pm range, and the 0.05 pm range. Preferably, these levels of
uniformity in the production of the particles are obtained without the need
for
filtering, sorting or screening the particles.
[001001 It should further be noted that preferably these size distributions
are for particles, as used in the formulation. Thus, these particle size
distributions can be agglomerated, and then upon de-agglomeration and
preferably will have the same, substantially the same particle size
distribution. In
this manner, preferably the particle size, and size distribution after de-
agglomeration are predictable and predetermined.
(001011 In a preferred embodiment the polysilocarb pigments is a black
non-conductive, acid and alkali resistant, and thermally stable up to about
300
C, up to about 400 C and up to about 500 C, or greater. In other embodiments
the conductive properties of the pigment can be modified with additives and
fillers, during the making of the pigment, and in this way providing a pigment
that
is conductive, and has a predetermined conductivity. The color and jetness of
these black polysilocarb pigrnents is typically a function of the particle
size. In a
preferred embodiment of the polysilocarb pigment, mass-tone and tint strength
can be comparable to, and in a further preferred embodiment can be superior
to,
current black pigments, e.g., carbon, carbonaceous, and oxide based black
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pigments. In preferred embodiments the polysilocarb pigments are non-
hazardous, having no toxicological effects.
[00102] Ernbodirnents of the black polysilocarb pigments can be used in;
among other things, spray, brush-on and power coatings for applications on
essentially all metal, ceramic and plastic surfaces in the industrial, marine,
architectural, graphic arts & inks, and automotive fields. Embodiments of
these
pigments further can find applications in cosmetics, nail polish, food
packaging,
and pharmaceutical applications and fields, to name a few.
[00103] Embodiments of the black polymer derived ceramic pigments
are easily dispersed in most media. The black polysilocarb pigments are easily
and readily dispersed in most types of media, basis, resins and carriers. For
example, HDPE, LDPE, PP, Acrylic; Epoxy, Linseed Oil, PU, PUR, EPDM, SBR,
PVC. water based acrylic emulsions, ABS, SAN, SEBS, SBS, PVDF, PVDC,
PMMA, PES, PET, NBR, PTFE, siloxanes, polyisoprene and natural rubbers, and
combinations of these and others.
[00104] Embodiments of the black polymer derived ceramic pigments
have very low oil absorption. The oil absorption for polysilocarb ceramic
pigments can be less than about 50 (grams linseed oil per 100 grams of
pigment,
i.e. g/100 g), less than about 30 g/100 g, and less than about 15 g/100 g. On
the other hand, typical specialty carbon black pigments have oil absorptions
ranging from about 150 g/100 g to more than 200 g/100 g. Thus, embodiments
of the present black polysilocarb ceramic pigments can have oil absorptions
that
are at least 13x, 5x or 3x lower than carbon black pigments having the same or
similar blackness.
[00105] Embodiments of the black polymer derived ceramic pigments
can find use in many applications and industries. For example, the
polysilocarb
derived ceramic pigments provide high temperature resistance capabilities,
they
are indoor/outdoor color fast, UV resistant, and are resistant to most
chemicals;
finding applications in harsh environments, such as marine and oil field
environments. They are non-corrosive and non-conductive, which enables uses
beyond that which most black pigments could be utilized. These uses would
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include Industrial and residential furnace coatings; engine components as high
heat resistant plastic parts or coatings on metal parts; pipe coatings;
chemical
plant equipment coatings; oil field coatings; residential barbeques;
aftermarket
coatings; ceramic and glass inkjet inks; electronic coatings; battery anodes;
gun
barrel coatings; PVC siding, metal roof coatings; coloration of ceramic parts
for
many end uses; space craft coatings; sand coatings; microwave curable
elastomers, plastics, inks and coatings; cookware; hotplates; satellite
components; high heat absorbing coatings; proprietary military coatings; high
heat resistant potting compound; electrical insulation; Fluoropolymer
elastomers
for use as seals and gaskets in extremely harsh environments; high emissivity
coatings, thermal protection systems, thermal barrier coatings, thermal
imaging
coatings, injection-molded parts, thermoformed parts, transfer molded parts,
compression molded parts, rotational molded parts, blow-molded parts, cast
parts, vacuum formed parts, hot-isostatic pressed parts, sinterable parts,
vacuum
impregnated parts, impregnated fiber forms, woven fabrics, textiles,
engineering
textiles, woven fiber fabrics, fiber mats, wear resistant metal matrix
composites,
wear resistant ceramic matrix composites, wear resistant polymer matrix
composites, mixed oxide ceramics, refractory applications, and combinations
and
variations of these and others.
[00106] Embodiments of the black polymer derived ceramic pigments
are microwave safe, e.g., they do not absorb and are not effect by microwaves.
Typical carbon black pigments, are effected by microwaves, and cannot be used
in microwave environments or applications.
[00107] In an embodiment of a process to make polymer derived
ceramic pigment, and preferably to make a black polymer derived ceramic
pigment, in the make-up segment a precursor formulation is metered into a one
cubic meter tank having an in-line mix at rate of about 0.22 cubic meters per
hour
along with a stream of the catalyst at a ratio of 1 part catalyst to 100 parts
precursor. The in-line mix tank is equipped with a high speed mixer. Residence
time in the mix tank is about twenty-five minutes. The polymerization reaction
starts in the mix tank.
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[00108] In this embodiment of the process, the forming and curing
segments are combined. Thus, the catalyzed precursor formulation, after
mixing,
is continuously feed to a drum, or a moving belt, e.g., a flaker belt, and
preferably
a stainless steel flaker belt or other similar device. Nozzles, a drip trough,
an
elongated opening, or slice, or other metering and distribution apparatus can
be
used to preferably obtain a uniform distribution, including thickness, of the
liquid
precursor on the moving belt. When the precursor is laid down onto the belt,
the
precursor can be moving at the same speed as the belt, at a faster speed than
the belt (e.g., rushed), or at a slower speed than the belt (e.g., dragged).
As the
liquid precursor is moved with the belt it is heated to a sufficient
temperature to
cure the precursor formulation to form a cured material. For example, radiant
heaters may be use above the belt, tunnel dryers may be used, the belt itself
may be heated, e.g., with steam or electric heaters, and combinations and
variations of these and other apparatus and methods to heat and maintain the
temperature of the precursor material being carried on the belt. For example,
in
a preferred embodiment the belt is heated to about 100-200 C by a steam coil
along the underside of the belt. The cross linking reaction, which first began
in
the mixing tank, continues as the precursor travels along the belt to the
point that
it solidifies, preferably the precursor has reached a predetermined and
predicted
cure amount, e.g., green cure, hard cure, final cure, by the time it reaches
the
end of the belt. Depending upon the precursor formulation, the amount of
catalyst, the temperature and other factors, the residence time on the belt
can be
about 5 to about 60 minutes, more than about 10 minutes, more than about 20
minutes, about 20 minutes, and more than about 40 minutes, and greater and
lesser durations.
[00109] In this embodiment, at the end of the belt, the cured precursor,
e.g., green material, falls from the belt and into a chopper, which reduces
the
size of the green material to about pm, about s100 pm, about s200 pm, and
about s500 pm, as well as other sizes. The chopped cured material can be
stored, in for example a storage hopper.
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[001 101 In this embodiment of the process, in the pyrolizing segment the
polymer from the storage hopper is transferred to cars and fed to a furnace,
e.g.,
a kiln, periodic (e.g., box) kiln, and preferably an oxygen deficient, natural
gas
fired tunnel kiln. The kiln is operated in an oxygen deficient regime to
maintain a
non-oxidizing atmosphere in the polymer. The cars move through the kiln,
preferably at a constant rate, which results in a three phase, 24-hour
pyrolysis
process, e.g., a reforming process. In the first phase, the temperature of the
polymer is raised to 1000 C over a period of '16 hours. At the end of the 16-
hour
ramp period, it remains at this temperature, 1000 C, for two hours. In the
final
phase the material is air cooled to ambient temperature over the next six
hours.
Through this pyrolizing segment of the process the cured material, e.g., green
material, is converted to a ceramic material. The ceramic material is removed,
e.g., dumped from the kiln cars into an intermediate storage hopper awaiting
further processing.
[001111 In this embodiment of the processes, throughout the pyrolizing
segment, the exhaust gases from the kiln are preferably ducted away to a
cleaning or waste handling system, for example to a Vapor Destruction Unit
(VDU) to destroy residual combustibles. The VDU can than be followed by other
cleaning systems, such as for example, a wet scrubber to remove any
particulates (predominately silica). The silica can then be removed from the
water
effluent and recovered for reuse, sale or proper disposal. After removal of
the
silica, the effluent from the scrubber can be reused for example in a grey
water
loop, further cleaned and reused, or transferred to a waste water treatment
facility for eventual discard.
[001121 In this embodiment of the process, in the post-processing
segment three post processing techniques are used jet milling, bead milling
and spray drying. In many embodiments of applications for polymer derived
ceramic pigments, and in particular for black polymer derived ceramic
pigments,
a particular particle size can be a factor, an application requirement, and in
some
instances a very important parameter for the pigment. In this embodiment, jet
milling is the first stage of the size reduction process. Ceramic material
having a
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particle size of about 300-500 pm, is taken from the intermediate storage; and
is
fed into the jet milling receiver. At the jet milling receiver the ceramic
material is
directed to several, e.g., two, three, four or more, parallel mills. The jet
mills
reduce the particle size from 300-500 pm, to about 1-20 pm, about 3 pm, and
about 2 pm. The use of stearn jet milling can reduce the particle size to
about 1
pm, less than about 1 pm and about 0.5 pm and potentially smaller, these
reductions in size can preferably be achieved un-surface treated, i.e., with
out the
need to provide a surface treatment to the larger particles prior to milling.
The
milled ceramic can then be classified and those sizes not meeting the
requirernents for further processing can be removed and preferably repurposed.
For example, about 10% of the product can be classified and sold at an
intermediate size.
[001131 The remaining 90% of the jet mill product is transferred to the
bead mill receiver for further size reduction. The 1-20 pm jet milled product
is fed
to a slurry tank where it is mixed with a liquid phase or solvent, such as
demineralized water, and a dispersant at a ratio of approximately 60 parts
solids,
39 parts solvent and 1 part dispersant. The dispersant can be a soap,
detergent,
surfactant, fatty acid, natural oil, synthetic oil, wetting agent, dispersing
agent,
natural and synthetic oils, natural and synthetic glycols and polyglycols,
modified
waxes and hydrocarbons. Dispersants function to stabilize the particle via
either
steric, electrosteric, or electrostatic rneans and can be non-ionic, anionic,
cationic, or zwitterionic. Structures can be linear polymers and copolymers,
head-tail type modified polymers and copolymers, AB-block copolymers, ABA
block copolymers, branched block copolymers, gradient copolymers, branched
gradient copolymers, hyperbranched polymers and copolymers, star polymers
and copolymers. BASF, Lubrizol, RT Vanderbilt, and BYK are all common
manufacturers of dispersants. Trade names include: Lubrizol Solsperse series,
Vanderbilt Darvan series, BASF Dispex series BYK DisperByk series, BYK LP-C
2XXXX series. Grades can include BYK DisperByk 162, 181, 182, 190, 193,
2200, and 2152; LP-C 22091, 22092, 22116, 22118, 22120, 22121, 22124,
22125, 22126, 22131, 22134, 22136, 22141, 22146, 22147, 22435; LP-N 22269;
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Solsperse 3000, Darvan C-N. A proper dispersant will provide good reduction in
viscosity from a high-solids content paste with <5% additive, causing it to
become a flowable liquid instead of a non-flowable paste. The ratio of
dispersant to ceramic solids can range from about 0.01wt% to 8wt%, to 0.5wt%
to 4wr/o, lwt% to 3wt%, and greater and lesser ratios. This slurry is fed,
e.g.,
batch wise, semi-continuous or continuously, to single, to several parallel,
two-
stage bead milling systems, e.g., two, three, four, five or more. These mills
may
also have other mills serially connected to their outputs. Bead milling
further
reduces the particle size to less than 1 pm, and preferably for submicron
applications to a particle size of about 0.1 pm.
[00114] In this embodiment the wet product from the bead is fed to a
spray dryer, which can be steam heated, gas heated, air, inert gas, or
electrically
heated, where the water content is reduced to <1 percent. In the spray dryer,
the
0.1 pm particles agglomerate to a 10-80 pm particle size, e.g., agglomerate
size,
agglomerated particle size. Preferably, a batch, lot, or shipment of the
agglomerate particles has a median particle size distribution, e.g., D50, of
greater
than about 10 pm, greater than about 20 pm, and greater than about 50 pm.
Preferably these agglomerates are stable through the handling and shipping
process and the unpacking and initial use for an application. In addition to
the
preferred median particle size distribution of greater than 10 pm, the mean
agglomerate particle size may be from 10 pm or less, from about 10 pm to about
80 pm, and may be larger than 80 pm.
[00115] In this embodiment the exhaust from the spray dryer goes
through a cyclone, followed by a bag filter to remove any particulates prior
to
release to the atmosphere. The collected dust is recycled to the bead mill or
spray dryer feed. The water or solvent evaporated from the powder in the spray
dryer is condensed, recovered and recycled to the bead mill feed slurry. The
dry
product from the spray dryer can be stored, packaged, shipped to users, or
further processed or treated.
[00116] The product, e.g., the stored, packaged, shipped etc. pigment,
can be in: a dry powered form; a dry agglomerate form; a sheet form, a block
or
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other larger volumetric shape; a suspension having from about 20% solids (or
less solids) to about 50% solids (or more), a paste, an aqueous paste, an
aqueous suspension, and combinations and variations of these and other forms.
For an embodiment of the product that is a dry powder, or dry agglomerate, the
moisture content can be from about 0% to about 10% moisture, about less than
5%, about less than 3%, and about less than 1%.
[00117] In the foregoing embodiment of a process to make polymer
derived ceramic pigment, a preferable embodiment of the polymer derived
ceramic pigment is a black polysilocarb derived ceramic pigment. The black
polysilocarb derived pigment can be used in many applications.
[00118] Polymer derived black ceramic pigments, and preferably black
polysilocarb derived ceramic pigments have applications in, for example,
coatings used on, or in, walls, appliances, automobiles, engines, pipes,
grills,
microwaves, cook wear, wires, printed circuit boards, human and animal nails,
cosmetics, pipes, interior of components such as automobile components, food
packaging and other devices, structures components and articles. They have
applications in coatings that provide end use features, such as for example,
corrosion protection, abrasion protection, skid resistance, decorative and
astatic
effects, photosensitive properties, UV protection, heat resistance and
protection,
and combinations and variations of these and other features. They have
applications in coating that are organic, inorganic and cornbinations of
these.
They have applications in coatings that are porcelain, enamels, electroplated,
to
name a few others. They have applications in architectural coating, product
coatings used by original equipment manufacturers ("OEM coatings"), special
purpose coatings and other types of coatings. Architectural coatings would
include for example paints and varnishes. Product coatings would include OEM
coatings, industrial coatings, industrial finishes, boats, water craft, ships,
after
market coatings, and repair/refurbishing coatings, the products to which
product
coatings are applied is essentially endless, and would include for example
automobiles, aircraft, appliances, wire, pipes, furniture, metal cans, chewing
gum
wrappers, packaging, equipment, etc. Specialty coatings would include for
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example, specialty coatings for cars, specialty marine coatings, stripping for
highways, and others.
[00119] Polyrner derived black ceramic pigments; and preferably black
polysilocarb derived ceramic pigments have applications in coatings
ernbodirnents that contain a binder, volatile components, a pigment (which may
be solely one or more polymer derived black ceramic pigments or combinations
of the polymer derived black pigment and other pigments), and additives
(noting
that the polymer derived pigment, which may be other colors than black and
preferably embodiments of polysilocarb pigments, which may be other colors
than black, can function as, or are, additives). These pigments are used with
all
types of resin, including acrylics, alkyds, amino, cellulosics, epoxies,
polyesters,
urethanes, poly(vinyl acetates), poly(vinyl chlorides), and others.
[001201 The polymer derived black ceramic pigments, and preferably
black polysilocarb derived ceramic pigments can have surface properties and
sizes such that they do not change the rheology of existing formulations that
use
other types of black pigments. In this manner they can be directly substituted
for
some, or all of the other type of pigment in a particular formulation without
changing the rheology of that formulation and providing for example improved
blackness and opacity. The nature of these pigments also provides the ability
to
have an embodiment of these pigments that provides functionality to control,
rnodify, and regulate the rheology of a formulation. In this manner these
pigments would have a dual role in the formulation as a pigment and as a
rheology control additive.
[00121] Embodiments of coatings containing black polysilocarb derived
ceramic pigments provided enhanced abrasion resistance, e.g., the wearing
away of a surface, and enhanced mar resistance, e.g., disturbances in the
surface that alters its appearance. Abrasion and mar resistance would include
resistance to scratching, gouging, wearing, and generally the resistance to
the
detrimental effects that occur when two surfaces are in sliding contact.
Coatings
using the black polysilocarb derived ceramic pigments have abrasion resistance
as measured by Taber Abrasion Tester (reported as number of mg of coating
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worn off after 1,000 cycles) of at most 30 mg, at most 150 mg, from about 10
mg
to about 200 mg, and greater than 200 mg.
[00122] Ernbodirnent of coatings containing black polysilocarb derived
ceramic pigments provided enhanced hardness. Hardness for coatings typically
is measured by way of indentations, scratch, and pendulum tests. Hardness
tests for coatings typically include an indentation test, the falling ball
indentation
Test (ASTM D-2394, which is well known to and available to the art, and the
entire disclosure of which is incorporated herein by reference), a scratch
test, the
pencil hardness test (ASTM-D-3363-00, which is well known to and available to
the art, and the entire disclosure of which is incorporated herein by
reference),
and a pendulum test, the Sward rocker (ASTM-2134-93), which is well known to
and available to the art, and the entire disclosure of which is incorporated
herein
by reference).
[00123] Embodiment of Coatings using the black polysilocarb derived
ceramic pigments have indentation test results of at least 100 inch pounds at
least 160 inch pounds, from about 50 to about 150 inch pounds, and greater
than
160 inch pounds. Coatings using the black polysilocarb derived ceramic
pigments can have the same or better blackness, while having increases in
indentation test results of at least about 50 inch pounds, at least about 160
inch
pounds, and greater, when compared to a similar formulation using carbon black
or metal oxides as the pigment.
[00124] Embodiments of coatings using the black polysilocarb derived
ceramic pigments have scratch test results of at least 7B pencil, at least F
pencil,
from about 8B pencil to about 6H pencil, and greater than 6H pencil. Coatings
using the black polysilocarb derived ceramic pigments can have the same or
better blackness, while having increases in scratch test results of at least
about
7B pencil, at least about F pencil, and greater, when compared to a similar
=formulation using carbon black or metal oxides as the pigment.
[00125] Embodiments of coatings using the black polysilocarb derived
ceramic pigrnents have pendulum test results of at least 20 oscillations at
least
25 oscillations, from about 15 to about 55 oscillations, and greater than 56
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oscillations. Coatings using the black polysilocarb derived ceramic pigments
can have the same or better blackness, while having increases in pendulum test
results of at least about 20 oscillations, at least about 50 oscillations, and
greater, when compared to a similar formulation using carbon black or metal
oxides as the pigment.
[00126] The polymer derived black ceramic pigments, and preferably
black polysilocarb derived ceramic pigments can be used in formulations having
UV stabilizers. These pigments do not diminish or adversely affect the UV
stabilizing ability performance of the UV stabilizers. It is theorized that
the
polysilocarb derived ceramic pigments may provide added UV stabilization to
these UV stabilized formulations. The UV stabilizers can be UV absorbers, UV
quenchers, and combinations of these. Typical UV stabilizes include, for
example, 2-hydroxybenzophenones, 2-(2-hydroxyphenyl)-2H-benztriazoles, 2-(2-
hydroxyphenyl)-4,6-phenyl-1,3,5-triazines, benzylidenemalonates, oxalanilides
and others.
[00127] Typically, embodiments of the polymer derived black ceramic
pigments, and preferably black polysilocarb derived ceramic pigments can
function as a UV absorber, and can be added to coatings to provide these
function, thus function as both a additive and a pigment. Embodiments of a 3.0
pm D50 black polysilocarb derived ceramic pigment exhibit UV absorption (e.g.,
absorption coefficient, e.g., absorptivity) based upon the UV-vis data taken
in
diluted Dl water solutions, set out in Table 1. The concentration of material
is
given in grams per 100 g of water (equivalently, g/100 rriL). These
concentrations gave a translucent solution.
[00128] Table 1
absorption coefficient
concentration dB/cm/concentration dB/cm/concentration dB/cm/concentration
(g/100g) @ 300nm @ 450nm @ 800nm
0.00952 3538.894732 3526.83657 3451.4463
0.02590 979.6193238 961.519095 946.46022
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[00129] Generally, embodiments of the polysilocarb derived ceramic
pigment can have absorption coefficients of greater than 500 dBicm/(g/100g),
greater than 5,000 dB/cm/(g/100g), greater than 10,000 dB/cm/(g/100g), from
about 500 dB/cmi(g/100g) to about 1,000 dBicm/(g/100g), from about 1,000 to
about 5,000 dB/cm/(g/100g), and from about 500 dB/cm/1(000g) to about 10,000
dBicmi(g1100g). In general, the smaller the pigments size, for the same
pigment
the higher will be the absorption coefficients.
[00130] The polymer derived black ceramic pigments, and preferably
black polysilocarb derived ceramic pigments can be used in formulations having
antioxidants. These pigments do not diminish or adversely affect the anti-
oxidizing performance of the antioxidants. It is theorized that the
polysilocarb
derived ceramic pigments may provide added anti-oxidation protection to these
antioxidant containing formulations. Typical antioxidants include for example
preventive antioxidants, peroxide decomposers, sulfides, phosphites, metal
complex agents, and others.
[00131] The polymer derived black ceramic pigments, and preferably
black polysilocarb derived ceramic pigments can be used in formulations having
hinder amine light stabilizers ("HALS"), which function to prevent the photo
oxidative degradation of coatings. These pigments do not diminish or adversely
affect the photo-oxidizing performance of the HALS. It is theorized that the
polysilocarb derived ceramic pigments may provide added photo-oxidation
protection to these HALS containing formulations. Further, the black
polysilocarb
derived ceramic pigments in some embodiments can be used to replace some,
most, and all, of the HALS in the coating.
[00132] The polymer derived black ceramic pigments, and preferably
black polysilocarb derived ceramic pigments can be used in many types of
coating or formulations, such as for example thermoplastic acrylic resins,
thermosetting acrylic resins, hydroxy-functional acrylic resins, water
reducible
thermosetting acrylic resins, waterborne coatings (i.e., any coating with an
aqueous media, e.g., latex coatings), water reducible coatings (i.e., a
waterborne
coating based on a resin having hydrophilic groups in most or all of its
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molecules), water soluble coatings (i.e., are soluble in water), latexes,
acrylic
latexes, vinyl ester latexes, thermosetting latexes, polyester resins, hydroxy-
terminated polyester resins, amino resins, aminoplast resins, baked
thermosetting coatings, melamine-formaldehyde resins (e.g., class 1 and class
11),
urea-formaldehyde resins, benzoguanamine-formaldehyde resins, glycoluril-
formaldehyde resins, poly(meth)acrylamide-formaldehyde resins, polyurethane
resins, two package solvent borne urethane coatings, epoxy resins, waterborne
epoxy-amine systems, drying oil based resins, varnishes, alkyd resins,
silicones,
silicone rubber resins, and tetraethylorthosilicate (TEOS) based resins, among
others.
[00133] The polymer derived black ceramic pigments, and preferably
black polysilocarb derived ceramic pigments can be used in many types of
coating or formulations that utilize different types of solvents, such as for
example, weak hydrogen-bonding solvents (e.g., aliphatic and aromatic
hydrocarbons), hydrogen-bond acceptor solvents (e.g., esters and ketones) and
hydrogen-bond donor-acceptor solvents (e.g., alcohols and propylene glycol).
[00134] In general, the smaller the particle size, the greater the fraction
of light that will be absorbed by the same quantity, i.e., weight of
particles. For
pigments, and generally for embodiments of the polymer derived black ceramic
pigments, and preferably black polysilocarb derived ceramic pigments, the
smaller the particle size of the pigment the greater the absorption of light.
[00135] The ability of a coating to hiding the substrate, i.e., hiding, is a
property that can be affected by many factors. Generally, hiding increases as
film or coating thickness increases at the same pigment loading. Lower hiding
coatings require thicker films. Also, hiding increases as pigment particle
size
decreases until a maximum hiding is reached and then hiding begins to
decrease. Two coatings will hide the substrate the same, one with a lower
pigment loading (of smaller particle size) and one with a higher pigment
loading
of a larger particle size. In general, embodiments of the polymer derived
black
ceramic pigments, and preferably black polysilocarb derived ceramic pigments,
provide higher hiding coatings, or hiding ability, for the same loading (e.g.,
weight
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of pigment to volume of coating) of black mixed metal oxide pigments and more
quickly approach the hiding power of furnace carbon black.
[00136] Table 2
Pigment Particle Pigment
Type size (micron) loading to hiding
PolySiloCarb 2.5 to 3.5 1 lb/gallon to 1.5 lbs/gallon
PolySiloCarb 1.5 to 2.5 0.8 lbs/gallon to 1 lb/gallon
PolySiloCarb 1.0 to 1.5 0.7 to 0.8 lbs/gallon
PolySiloCarb 0.8 to 1.0 0.6 to 0.7 lbs/gallon
0.55 to 0.60
PolySiloCarb 0.6 to 0.8 lbs/gallon
0A5 to 0.55
PolySiloCarb 0.4 to 0.6 lbs/gallon
0.35 to 0.45
PolySiloCarb 0.2 to 0.4 lbs/gallon
0.25 to 0.35
PolySiloCarb 0.1. to 0.2 lbs/gallon
PolySiloCarb less than 0.1 less than 0.25 lbs/gallon
Cl Black 28 about 0.5 about 0.5 lbs/gallon
Cl Black 26 about 0.3 about 0.3 lbs/gallon
Thermal
Carbon Black 0.25 to 0.35 about 0.4 lbs/gallon
FurnaceCarbon
Black 0.03-0.05 0.1 to 0.2 lbs/gallon
[00137] Pigment loading to hiding is the required weight of pigment in a
50 micron dry film coating to cover a black and white substrate such that the
eye
cannot differentiate a difference in color over either colored background.
[00138] In general, in using the polymer derived black ceramic
pigments, and preferably the black polysilocarb derived ceramic pigments, they
can be formulated, mixed or made into a concentrated composition that can
typically, although not necessarily, have other ingredients. These
concentrated
compositions are typically liquids, although not necessarily, they typically
are call
mill bases, dispersions, colorants, master-batches, and similar terms, which
terms for the purposes of this specification, unless specifically stated
otherwise,
will be used to interchangeably. The present black ceramic pigments have
excellent wettability, separation properties, and stability properties in both
organic
and aqueous media.
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[00139] Polymer derived ceramic mill bases can contain one
embodiment of the present ceramic pigments, several different embodiments of
the present ceramic pigments, other types of pigments, such as carbon black,
and combinations and variations of these. When more than one pigment is
present the mill base can be referred to as a composite grind, or cornposite
grind
mill base. Thus, for example, an embodiment of a polymer derived ceramic a
composite grind mill base has a black polysilocarb ceramic pigment and one or
more of the following pigments: organic pigments, such as arylamide yellow (PY
73), diarylide yellow, barium red 2B toner (PR 48.1); polycyclic pigments,
such as
copper phthalocyanine, dioxanzine violet (PV 23), tetrachloro thiondigo (PR
88);
inorganic pigments, such as carbon black, titanium dioxide, iron oxides,
azurite,
cadmium sulphides.
[001401 Although in embodiments of the present black ceramic
pigments, dispersants are not needed or required, they may be added to either
the mill base, or with the mill base at the time it is added to the coating
formulation. Dispersants such as polymeric dispersants, A-B copolymer
dispersants, hyperdispersants, superdispersants, and others may be used. In
general dispersants function to stabilize the particle via either steric,
electrosteric,
or electrostatic means and can be non-ionic, anionic, cationic, or
zwitterionic.
Embodiments of dispersant structures can be linear polymers and copolymers,
head-tail type modified polyrners and copolymers, AB-block copolymers, ABA
block copolymers, branched block copolymers, gradient copolymers, branched
gradient copolymers, hyperbranched polymers and copolymers, star polymers
and copolymers, and combinations and various of these and others.
[00141] It being understood that the mill base can be prepared and
stored for later use, shipped, or used immediately. Further the step of making
a
mill base may be combined with, a part of, or otherwise incorporated into the
process of formulation and making the coating. Generally in making a polymer
derived ceramic pigmented coating three steps typically may be used ¨
prernixing, e.g., stirring the dry pigment into a liquid vehicle and
eliminating any
lumps; imparting shear stress to separate the pigment aggregates, which may be
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done in the presence of a dispersion stabilizer: and, letting down, which
entails
combining the pigment dispersion, e.g., mill base, with the remainder of the
ingredients for the coating formulation. It being understood that some
equipment is capable of performing only one or two of the steps, while other
are
capable of performing all three steps.
[00142] Equipment that may be used for forming the mill base can
include, for example, high-speed disk dispersers, rotor¨stator mixers, ball
mills,
basket mills, shot mills, hammer mills, media mills (e.g., sand mills, shot
mills,
bead mills), three roll mills, two roll mills, extruders, kneaders, internal
batch
mixers, such as banbury machines, extruders, ultrasound dispersers, and
others.
[00143] The polymer derived black ceramic pigments, and preferably the
black polysilocarb derived ceramic pigments can be used to make tinting pastes
in this manner providing an embodiment of a polymer derived tinting paste. In
general tinting paste will have a high loading of pigment to a small amount of
resin so that a small amount of paste will give the maximum color. The polymer
derived black ceramic pigments, and preferably the black polysilocarb derived
ceramic pigments improve the tint strength as the particle size decreases. In
general, tinting embodiments of the polymer derived black ceramic pigments,
and
preferably black polysilocarb derived ceramic pigments, provide higher tinting
strength in coatings, (less black pigment required to reach the same grey
color
with a lightness value between 72 and 75 on the CIELAB Lab scale, the
lightness
coming from a larger amount of TiO2 white pigment which is tinted to a grey
color
by small additions of the black pigment). The smaller particle size polymer
derived black ceramic pigment has higher tinting strength than black mixed
metal
oxide pigments and more quickly approaches the tinting strength of furnace
carbon black. Tinting pastes can use multiple black additives, including
polysilocarb materials.
[00144] Table 3
Pigment Particle Pigment
Type size (micron) loading to light grey
PolySiloCarb 2.5 to 3.5 12 to 15 parts
PolySiloCarb 1.5 to 2.5 11 to 12 parts
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PolySiloCarb 1.0 to 1.5 10 to 11 parts
PolySiloCarb 0.8 to 1.0 9 to 10 parts
PolySiloCarb 0.6 to 0.8 7.5 to 9 parts
6.5 to 7.5
PolySiloCarb 0.4 to 0.6 parts
4.5 to 6.5
PolySiloCarb 0.2 to 0.4 parts
2.5 to 4.5
PolySiloCarb 0.1 to 0.2 parts
PolySiloCarb less than 0.1 less than 2.5 parts
Cl Black 28 about 0.5 7 to 8 parts
3.5 to 4.5
CI Black 26 about 0.3 parts
FurnaceCarbon
Black 0.03-0.05 1 part
[00145] lt should be understood that the use of headings in this
specification is for the purpose of clarity, reference, and is not limiting in
any way.
Thus, the processes compositions, and disclosures described under a heading
should be read in context with the entirely of this specification, including
the
various examples. The use of headings in this specification should not limit
the
scope of protection afford the present inventions.
General Processes for Obtaining a Polysilocarb Precursor
[00146] Typically polymer derived ceramic precursor formulations, and
in particular polysilocarb precursor formulations can generally be made by
three
types of processes, although other processes, and variations and combinations
of these processes may be utilized. These processes generally involve
combining precursors to form a precursor formulation. One type of process
generally involves the mixing together of precursor materials in preferably a
solvent free process with essentially no chemical reactions taking place,
e.g.,
"the mixing process." The other type of process generally involves chemical
reactions, e.g., "the reaction type process," to form specific, e.g., custom,
precursor formulations, which could be monomers, dimers, trimers and polymers.
A third type of process has a chemical reaction of two or more components in a
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solvent free environment, e.g., "the reaction blending type process."
Generally,
in the mixing process essentially all, and preferably all, of the chemical
reactions
take place during subsequent processing, such as during curing, pyrolysis and
both.
[00147] It should be understood that these terms - reaction type
process, reaction blending type process, and the mixing type process - are
used
for convenience and as a short hand reference. These terms are not, and should
not be viewed as, limiting. For example, the reaction process can be used to
create a precursor material that is then used in the mixing process with
another
precursor material.
[00148] These process types are described in this specification, among
other places, under their respective headings. It should be understood that
the
teachings for one process, under one heading, and the teachings for the other
processes, under the other headings, can be applicable to each other, as well
as,
being applicable to other sections, embodiments and teachings in this
specification, and vice versa. The starting or precursor materials for one
type of
process may be used in the other type of processes. Further, it should be
understood that the processes described under these headings should be read in
context with the entirely of this specification, including the various
examples and
embodiments.
[00149] It should be understood that combinations and variations of
these processes may be used in reaching a precursor formulation, and in
reaching intermediate, end and final products. Depending upon the specific
process and desired features of the product the precursors and starting
materials
for one process type can be used in the other. A formulation from the mixing
type process may be used as a precursor, or component in the reaction type
process, or the reaction blending type process. Similarly, a formulation from
the
reaction type process may be used in the mixing type process and the reaction
blending process. Similarly, a formulation from the reaction blending type
process may be used in the mixing type process and the reaction type process.
Thus, and preferably, the optimum performance and features from the other
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processes can be combined and utilized to provide a cost effective and
efficient
process and end product. These processes provide great flexibility to create
custom features for intermediate, end, and final products, and thus, any of
these
processes, and combinations of them, can provide a specific predetermined
product. In selecting which type of process is preferable, factors such as
cost,
controllability, shelf life, scale up, manufacturing ease, etc., can be
considered.
[00150] In addition to being commercially available the precursors may
be made by way of an alkoxylation type process, e.g., an ethoxylation process.
In this process chlorosilanes are reacted with ethanol in the presences of a
catalysis, e.g., FICI, to provide the precursor materials, which materials
rnay
further be reacted to provide longer chain precursors. Other alcohols, e.g.,
methanol may also be used. Thus, for example SiCI4, SiCI3H, SiC12(CH3)2,
SiC12(CH3)H, Si(CH3)3CI, Si(CH3)CIH, are reacted with ethanol CH3CH2OH to
form precursors. In some of these reactions phenols may be the source of the
phenoxy group, which is substituted for a hydride group that has been placed
on
the silicon. One, two or more step reactions may need to take place.
[00151] Precursor materials may also be obtained by way of an
acetylene reaction route. In general there are several known paths for adding
acetylene to Si-H. Thus, for example, tetrarnethylcyclotetrasiloxane can be
reacted with acetylene in the presence of a catalyst to produce
tetramethyltetravinylcyclotetrasiloxane. This product can then be ring opened
and polymerized in order to form linear vinyl,methylsiloxanes. Alternatively,
typical vinyl silanes can be produced by reacting methyl,dichlorosilane
(obtained
from the direct process or Rochow process) with acetylene. These monomers
can then be purified (because there may be some scrambling) to form vinyl,
methyl, dichlorosilane. Then the vinyl monomer can be polymerized via
hydrolysis to form many cyclic, and linear siloxanes, having various chain
lengths, including for example various cyclotetrasiloxanes (e.g., D4') and
various
cyclopentasiloxanes (e.g., D5'). These paths, however, are costly, and there
has
been a long standing and increasing need for a lower cost raw material source
to
produce vinyl silanes. Prior to the present inventions, it was not believed
that
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MHF could be used in an acetylene addition process to obtain vinyl silanes.
MHF is less expensive than vinyl,methyl (either linear or cyclic), and adding
acetylene to MHF to make vinyl meets, among other things, the long standing
need to provide a more cost effective material and at relatively inexpensive
costs.
In making this addition the following variables, among others, should be
considered and controlled: feed (D4', linear methyl, hydrogen siloxane
fluids);
temperature; ratio of acetylene to Si-H; homogeneous catalysts (Karstedt's,
DBT
Laureate, no catalyst, Karstedt's with inhibitor); supported catalysts (Pt on
carbon, Pt on alumina, Pd on alumina); flow rates (liquid feed, acetylene
feed);
pressure; and, catalyst concentration. Examples of embodiments of reactions
providing for the addition of acetylene to MHF (cyclic and linear) are
provided in
Tables A and B. Table A are batch acetylene reactions. Table B are continuous
acetylene reactions. It should be understood that batch, continuous, counter
current flow of MHF and acetylene feeds, continuous recycle of single pass
material to achieve higher conversions, and combinations and variations of
these
and other processes can be utilized.
[00152] TABLE A: Batch Acetylene Reactions
ci
ty c4 et"
".?.? "4' ID * ¨ e, "ri lr= "1 e.
I3. IS te `1, IP 474
a
r .5 a et mer.¨^
;a
===-=' ==== ,===
-
Z e 0
PD 9.5
MH 400 0.48% 0.00% -- 80 - 0.20
100
2 MH 1000 0.27% 0.00% -- 65 - 276 - 0.75 3A%
75 328
3 MIT 1000 0.00% 0.00 10 ¨ 80 378 - 6.33
49.4%
100 729
120
4 MH 117 0.20% 0.00 ,10 Hexan 1000 60 - 155 - 4.50
188.0%
F e 66 242
MH 1000 0.40% 0.40% -- 55 - 102 7.5 15.7%
6 MH 360 1.00% 0.00 10 He Kan 392 65 102 6.4
40.3%
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7a MH 360 0.40% 0.00% Hexan 400 65 2.0
23.4%
7b MH 280 0.40% 0.00% Hexan 454 68 =137.0
23.4%
8 D4 1000 0.27% 0.00% -- 79 327 - 6.5
61.3%
745
9 MH 370 0.40% 0.00% Hexan 402 65 155 - 8.0 140.3%
412
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[00153] TABLE B: Continuous Acetylene Reactions
rzi
z n)
rs'g et, '41
a.
76,0 74
2 et,
a
cL:
er.
,o
ti=
D4' 5% Pt on 0.00% 100.0% -- 60 - 100 50 40.0%
Carbon
11 D4 5% Pt on 0.00% 100.0% ¨ 50 - 90 100 20.0%
Carbon
12 D4' 1% Pt on 0.00% 100.0% -- 40 - 50 50 23.8%
Alumina
13 Miff' 5% Pt on 0.00% 100.0% -- 55 -60 55 - 60
13.6%
Carbon
14 MHF 0.01% Pt on 0.00% 20.0% Hexan 20 - 25 50
108.5%
Alumina
MHF 0.01% Pt on 0.00% 20.0% Hexan 60 50. 55 117.1%
Alumina
16 MHF 0.01% Pt on 0.00% 20.0% Hexan 70 50
125.1%
Alumina
17 MHF 0.12% Pt on 0.00% 20.0% Hexan 60 50
133.8%
Alumina
18 MHF 0.12% Pt on 0.00% 4.0% Hexan 60 = 50
456.0%
Alumina
(D4' is tetramethyl tetrahydride cyclotetrasiloxane)
[00154] Continuous High Pressure Reactor ("CHPR") embodiments
may be advantageous for, among other reasons: reaction conversion saving
more acetylene needed in liquid phase; tube reactors providing pressures which
in turn increases solubility of acetylene; reaction with hexyne saving
concentration and time (e.g., 100 hours,); can eliminate homogeneous catalyst
and thus eliminate hydrosilylation reaction with resultant vinyls once
complete;
and, using a heterogeneous (Solid) catalyst to maintain product integrity,
increased shelf-life, increase pot-life and combinations and variations of
these.
[00155] In addressing the various conditions in the acetylene
addition reactions, some factors may be: crosslinking retardation by dilution,
acetylene and lower catalyst concentration; and conversion (using
heterogeneous catalyst) may be lower for larger linear molecules compared to
smaller molecules.
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[001561 The presence and quality of vinyl and vinyl conversions can
be determined by, among other things,: FT-IR for presence of vinyl
absorptions,
decrease in SiH absorption; 1H NMR for presence of vinyls and decrease in
SiH; '3C NMR for presence of vinyls.
[00157] As used herein, unless specified otherwise the terms %, weight
% and mass % are used interchangeably and refer to the weight of a first
component as a percentage of the weight of the total, e.g., formulation,
mixture,
material or product. As used herein, unless specified otherwise "volume %" and
"% volume" and similar such terms refer to the volume of a first component as
a
percentage of the volume of the total, e.g., formulation, material or product.
The Mixing Type Process
[00158] Precursor materials may be methyl hydrogen, and substituted
and modified methyl hydrogens, siloxane backbone additives, reactive
monomers, reaction products of a siloxane backbone additive with a silane
modifier or an organic modifier, and other similar types of materials, such as
silane based materials, silazane based materials, carbosilane based materials,
phenol/formaldehyde based materials, and combinations and variations of these.
The precursors are preferably liquids at room temperature, although they may
be
solids that are melted, or that are soluble in one of the other precursors.
(In this
situation, however, it should be understood that when one precursor dissolves
another, it is nevertheless not considered to be a "solvent" as that term is
used
with respect to the prior art processes that employ non-constituent solvents,
e.g.,
solvents that do not form a part or component of the end product, are treated
as
waste products, and both.)
[00159] The precursors are mixed together in a vessel, preferably at
room temperature. Preferably, little, and more preferably no solvents, e.g.,
water, organic solvents, polar solvents, non-polar solvents, hexane, THF,
toluene, are added to this mixture of precursor materials. Preferably, each
precursor material is miscible with the others, e.g., they can be mixed at any
relative amounts, or in any proportions, and will not separate or precipitate.
At
this point the "precursor mixture" or "polysilocarb precursor formulation" is
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compete (noting that if only a single precursor is used the material would
simply
be a "polysilocarb precursor" or a "polysilocarb precursor formulation" or a
"formulation"). Although complete, fillers and reinforcers may be added to the
formulation. In preferred embodiments of the formulation, essentially no, and
more preferably no chemical reactions, e.g., crosslinking or polymerization,
takes
place within the formulation, when the formulation is mixed, or when the
formulation is being held in a vessel, on a prepreg, or over a time period,
prior to
being cured.
[00160] The precursors can be mixed under numerous types of
atmospheres and conditions, e.g., air, inert, N2, Argon, flowing gas, static
gas,
reduced pressure, elevated pressure, ambient pressure, and combinations and
variations of these.
[00161] Additionally, inhibitors such as cyclohexane, 1-Ethyny1-1-
cyclohexanol (which may be obtained from ALDRICH),
Octamethylcyclotetrasiloxane, and tetramethyltetravinylcyclotetrasiloxane, may
be added to the polysilocarb precursor formulation, e.g., an inhibited
polysilocarb
precursor formulation. It should be noted that
tetramethyltetravinylcyclotetrasiloxane may act as both a reactant and a
reaction
retardant (e.g., an inhibitor), depending upon the amount present and
temperature, e.g., at room temperature it is a retardant and at elevated
temperatures it is a reactant. Other materials, as well, may be added to the
polysilocarb precursor formulation, e.g., a filled polysilocarb precursor
formulation, at this point in processing, including fillers such as SiC
powder,
carbon black, sand, polymer derived ceramic particles, pigments, particles,
nano-
tubes, whiskers, or other materials, discussed in this specification or
otherwise
known to the arts. Further, a formulation with both inhibitors and fillers
would be
considered an inhibited, filled polysilocarb precursor formulation.
[00162] Depending upon the particular precursors and their relative
amounts in the polysilocarb precursor formulation, polysilocarb precursor
formulations may have shelf lives at room temperature of greater than 12
hours,
greater than 1 day, greater than 1 week, greater than 1 month, and for years
or
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more. These precursor formulations may have shelf lives at high temperatures,
for example, at about 90 F, of greater than 12 hours, greater than 1 day,
greater
than 1 week, greater than 1 month, and for years or more. The use of
inhibitors
may further extend the shelf life in time, for higher temperatures, and
combinations and variations of these. The use of inhibitors, may also have
benefits in the development of manufacturing and commercial processes, by
controlling the rate of reaction, so that it takes place in the desired and
intended
parts of the process or manufacturing system.
[00163] As used herein the term "shelf life" should be given its broadest
possible meaning, unless specified otherwise, and would include, for example,
the formulation being capable of being used for its intended purpose, or
performing, e.g., functioning, for its intended use, at 100% percent as well
as a
freshly made formulation, at least about 90% as well as a freshly made
formulation, at least about 80% as well as a freshly made formulation, and at
at
least about 70% as well as a freshly made formulation.
[00164] Precursors and precursor formulations are preferably non-
hazardous materials. They have flash points that are preferably above about 70
C, above about 80 C, above about 100 C and above about 300 C, and above.
Preferably, they may be noncorrosive. Preferably, they may have a low vapor
pressure, may have low or no odor, and may be non- or mildly irritating to the
skin.
[00165] A catalyst or initiator may be used, and can be added at the
time of, prior to, shortly before, or at an earlier time before the precursor
formulation is formed or made into a structure, prior to curing. The catalysis
assists in, advances, and promotes the curing of the precursor formulation to
form a preform.
[00166] The time period where the precursor formulation remains useful
for curing after the catalysis is added is referred to as "pot life", e.g.,
how long
can the catalyzed formulation remain in its holding vessel before it should be
used. Depending upon the particular formulation, whether an inhibitor is being
used, and if so the amount being used, storage conditions, e.g., temperature,
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02 atmosphere, and potentially other factors, precursor formulations can have
pot lives, for example, of from about 5 minutes to about 10 days, about 1 day
to
about 6 days, about 4 to 5 days, about 30 minutes, about 15 minutes, about 1
hour to about 24 hours, and about 12 hours to about 2.4 hours.
[00167] The catalyst can be any platinurn (Pt) based catalyst, which can,
for example, be diluted to a ranges of: about 0.01 parts per million (ppm) Pt
to
about 250 ppm Pt, about 0.03 ppm Pt, about 0.1 ppm Pt, about 0.2 ppm Pt,
about 0.5 ppm Pt, about 0.02 to 0.5 ppm Pt, about 1 ppm to 200 ppm Pt and
preferably, for some applications and embodiments, about 5 ppm to 50 ppm Pt.
The catalyst can be a peroxide based catalyst with, for example, a 10 hour
half
life above 90 C at a concentration of between 0.1% to 3% peroxide, and about
0.5% and 2% peroxide. It can be an organic based peroxide. It can be any
organometallic catalyst capable of reacting with Si-H bonds, Si-OH bonds, or
unsaturated carbon bonds, these catalysts may include: dibutyltin dilaurate,
zinc
octoate, peroxides, organometallic compounds of for example titanium,
zirconium, rhodium, iridium, palladium, cobalt or nickel. Catalysts may also
be
any other rhodium, rhenium, iridium, palladium, nickel, and ruthenium type or
based catalysts. Combinations and variations of these and other catalysts may
be used. Catalysts may be obtained from ARKEMA under the trade name
LUPEROX, e.g., LUPEROX 231; and from Johnson Matthey under the trade
narnes: Karstedt's catalyst, Ashby's catalyst, Speier's catalyst.
[00168] Further, custom and specific combinations of these and other
catalysts may be used, such that they are matched to specific formulations,
and
in this way selectively and specifically catalyze the reaction of specific
constituents. Moreover, the use of these types of matched
catalyst¨formulations
systems may be used to provide predetermined product features, such as for
example, pore structures, porosity, densities, density profiles, high purity,
ultra
high purity, and other morphologies or features of cured structures and
ceramics.
[00169] In this mixing type process for making a precursor formulation,
preferably chemical reactions or molecular rearrangements only take place
during the making of the starting materials, the curing process, and in the
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pyrolizing process. Chemical reactions, e.g., polymerizations, reductions,
condensations, substitutions, take place or are utilized in the making of a
starting
material or precursor. In making a polysilocarb precursor formulation by the
mixing type process, preferably no and essentially no, chemical reactions and
molecular rearrangements take place. These embodiments of the present mixing
type process, which avoid the need to, and do not, utilize a polymerization or
other reaction during the making of a precursor formulation, provides
significant
advantages over prior methods of making polymer derived ceramics. Preferably,
in the embodiments of these mixing type of formulations and processes,
polymerization, crosslinking or other chemical reactions take place primarily,
preferably essentially, and more preferably solely during the curing process.
[00170] The precursor may be a siloxane backbone additive, such as,
methyl hydrogen (MH), which formula is shown below.
CH3 CH3 CH3 CH3
CH3- Si -Si -- 0- Si-O- Si -CH3
CH3 H CH3 CH3
X
[00171] The MH may have a molecular weight ("mw" which can be
measured as weight averaged molecular weight in amu or as g/mol) from about
400 mw to about 10,000 mw, from about 600 mw to about 3,000 mw, and may
have a viscosity preferably from about 20 cps to about 60 cps. The percentage
of methylsiloxane units "X" may be from 1% to 100%. The percentage of the
dimethylsiloxane units "Y" may be from 0% to 99%. This precursor may be used
to provide the backbone of the cross-linked structures, as well as, other
features
and characteristics to the cured preform and ceramic material. This precursor
may also, among other things, be modified by reacting with unsaturated carbon
compounds to produce new, or additional, precursors. Typically, methyl
hydrogen fluid (MHF) has minimal amounts of "r, and more preferably "Y" is for
all practical purposes zero.
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[00172] The precursor may be a siloxane backbone additive, such as
vinyl substituted polydimethyl siloxane, which formula is shown below.
CH3 CH3 CH3 CH3
I
CH3- Si -
CH3 C CH3 CH3
C x -av
[00173] This precursor may have a molecular weight (mw) from about
400 mw to about 10,000 mw, and may have a viscosity preferably from about 50
cps to about 2,000 cps. The percentage of methylvinylsiloxane units "X" may be
from 1% to 100%. The percentage of the dimethylsiloxane units "Y" may be from
0% to 99%. Preferably, X is about 100%. This precursor may be used to
decrease cross-link density and improve toughness, as well as, other features
and characteristics to the cured prefomi and ceramic material.
[00174] The precursor may be a siloxane backbone additive, such as
vinyl substituted and vinyl terminated polydime.thyl siloxane, which formula
is
shown below.
CH3 CH3 CH3 CH3
C
C- Si - 0 --Si- 0 _______ ' Si -0 = Si -C
I 1
CH3 C CH3 CH3
_
C x-
[00175] This precursor may have a molecular weight (mw) from about
500 mw to about 15,000 mw, and may preferably have a molecular weight from
about 500 mw to 1,000 mw, and may have a viscosity preferably from about 10
cps to about 200 cps. The percentage of methylvinylsiloxane units "X" may be
from 1% to 100%. The percentage of the. dimethylsiloxane units "Y" may be from
0% to 99%. This precursor may be used to provide branching and decrease the
cure temperature, as well as, other features and characteristics to the cured
prefomi and ceramic material.
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[00176] The precursor may be a siloxane backbone additive, such as
vinyl substituted and hydrogen terminated polydimethyl siloxane, which formula
is shown below.
CH3 CH CH3 CH3
CH3 C l CH3 CH3
C X
[00'177] This precursor may have a molecular weight (mw) from about
300 mw to about 10,000 mw, and may preferably have a molecular weight from
about 400 mw to 800 mw, and may have a viscosity preferably from about 20 cps
to about 300 cps. The percentage of methylvinylsiloxane units "X" may be from
1% to 100%. The percentage of the dime.thylsiloxane units "Y" may be from 0%
to 99%. This precursor may be used to provide branching and decrease the
cure temperature, as well as, other features and characteristics to the cured
preform and ceramic material.
[00178] The precursor may be a siloxane backbone additive, such as
allyl terminated polydimethyl siloxane, which formula is shown below.
CH CH3 CH3 CH3
C = C
C- Si - 0 -Si 0 Si -0-- Si C
C= C CH3 CH3 J
CH3 CH3
X
[00179] This precursor may have a molecular weight (mw) from about
400 mw to about 10,000 mw, and may have a viscosity preferably from about 40
cps to about 400 cps. The repeating units are the same. This precursor may be
used to provide UV curability and to extend the polymeric chain, as well as,
other
features and characteristics to the cured preform and ceramic material.
[00180] The precursor may be a siloxane backbone additive, such as
vinyl terminated polydimethyl siloxane, which formula is shown below.
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CH3 CH3 CH3 CH3
1l l lC
C- Si - 0 -Si- 0 Si 0 ¨ Si C
1 1 1 1
C C1-13 CH3 CH3 CH3
X
[00181] This precursor may have a molecular weight (mw) from about
200 mw to about 5,000 mw, and may preferably have a molecular weight from
about 400 mw to 1,500 mw, and may have a viscosity preferably from about 10
cps to about 400 cps. The repeating units are the same. This precursor may be
used to provide a polymeric chain extender, improve toughness and to lower
cure temperature down to for example room temperature curing, as well as,
other
features and characteristics to the cured preform and ceramic material.
[00182] The precursor may be a siloxane backbone additive, such as
silanol (hydroxy) terminated polydimethyl siloxane, which formula is shown
below.
CH3 CH3 CH CH3
HO- S1- 0 -S1 0 ___________ Si -0 ¨ Si -OH
1 1 1 1
CH3 CH3 CH3 CH3
X Thf
_
[00183] This precursor may have a molecular weight (mw) from about
400 mw to about 10,000 mw, and may preferably have a molecular weight from
about 600 mw to 1,000 mw, and may have a viscosity preferably from about 30
cps to about 400 cps. The repeating units are the same. This precursor may be
used to provide a polymeric chain extender, a toughening mechanism, can
generate nano- and micro- scale porosity, and allows curing at room
temperature, as well as other features and characteristics to the cured
preform
and ceramic material.
[00184] The precursor may be a siloxane backbone additive, such as
silanol (hydroxy) terminated vinyl substituted dimethyl siloxane, which
formula is
shown below.
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CH3 CH3 CH3 CH3
HO- Si - 0¨Si 0 _____________ Si-O--Si-OH
CH CH3 CH3
X
[001851 This precursor may have a molecular weight (mw) from about
400 mw to about 10,000 mw, and may preferably have a molecular weight from
about 600 mw to 1,000 mw, and may have a viscosity preferably from about 30
cps to about 400 cps. The percentage of methylvinylsiloxane units "X" may be
from 1% to 100%. The percentage of the dimethylsiloxane units "Y" may be from
0% to 99%. This precursor may be used, among other things, in a dual-cure
system; in this manner the dual-cure can allow the use of multiple cure
mechanisms in a single formulation. For example, both condensation type cure
and addition type cure can be utilized. This, in turn, provides the ability to
have
complex cure profiles, which for example may provide for an initial cure via
one
type of curing and a final cure via a separate type of curing.
[00186] The precursor may be a siloxane backbone additive, such as
hydrogen (hydride) terminated polydimethyl siloxane, which formula is shown
below.
CH3 CH3 CH CH3
1 1 I
H- Si -0 -Si- 0 __________ Si -0 ¨ Si - H
I
CH3 CH3 CH3 CH3
X
[001871 This precursor may have a molecular weight (mw) from about
200 mw to about 10,000 mw, and may preferably have a molecular weight from
about 500 mw to 1,500 mw, and may have a viscosity preferably from about 20
cps to about 400 cps. The repeating units are the same. This precursor may be
used to provide a polymeric chain extender, as a toughening agent, and it
allows
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lower temperature curing, e.g., room temperature, as well as, other features
and
characteristics to the cured preform and ceramic material.
[00188] The precursor may be a siloxane backbone additive, such as di-
phenyl terminated siloxane, which formula is shown below.
CH3 CH3 CH3 CH3
0 - Si - 0 - Si 0 ____________________ Si - 0 - Si
CH3 R CH3 CH3
-X- --Y
[00189] Where here R is a reactive group, such as vinyl, hydroxy, or
hydride. This precursor may have a molecular weight (am) from about 500 mw
to about 2,000 mw, and may have a viscosity preferably from about 80 cps to
about 300 cps. The percentage of methyl - R siloxane units "X" may be from
1% to 100%. The percentage of the dimethylsiloxane units "Y" may be from 0%
to 99%. This precursor may be used to provide a toughening agent, and to
adjust the refractive index of the polymer to match the refractive index of
various
types of glass, to provide for example transparent fiberglass, as well as,
other
features and characteristics to the cured preform and ceramic material.
[00190] The precursor may be a siloxane backbone additive, such as a
mono-phenyl terminated siloxane, which formulas are shown below.
CH3 CH3 CH3 CH3
I
CH3- Si SI ______________ Si -0 ¨ Si -
CH3 R CH3 CH3
--Y
[00191] Where R is a reactive group, such as vinyl, hydroxy, or hydride.
This precursor may have a molecular weight (mw) from about 500 mw to about
2,000 mw, and may have a viscosity preferably from about 80 cps to about 300
cps. The percentage of methyl - R siloxane units "X" may be from 1% to 100%.
The percentage of the dimethylsiloxane units "Y" may be from 0% to 99%. This
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precursor may be used to provide a toughening agent and to adjust the
refractive
index of the polymer to match the refractive index of various types of glass,
to
provide for example transparent fiberglass, as well as, other features and
characteristics to the cured preform and ceramic material,
[00'192] The precursor may be a siloxane backbone additive, such as
diphenyl dimethyi polysiloxane, which formula is shown below.
CH3 CH3
0CH3
I I
CH3- Si - 0 -Si 0 Si 0 -- Si CH3
1
CH3 CH3cH3
X --Y
[00'193] This precursor may have a molecular weight (mw) from about
500 mw to about 20,000 mw, and may have a molecular weight from about 800
to about 4,000, and may have a viscosity preferably from about 100 cps to
about
800 cps. The percentage of dimethylsiloxane units "X" may be from 25% to 95%.
The percentage of the diphenyl siloxane units "Y" may be from 5% to 75%. This
precursor may be used to provide similar characteristics to the mono-phenyl
terminated siloxane, as well as, other features and characteristics to the
cured
preform and ceramic material.
[00194] The precursor may be a siloxane backbone additive, such as
vinyl terminated diphenyl dimethyl polysiloxane, which formula is shown below.
CH3 FCH CH
I I 3
C- Si 0 Si 0 ___ Si 0 Si C
eY I
C CH3 CH3
0 CH3
X
[00195] This precursor may have a molecular weight (mw) from about
400 mw to about 20,000 mw, and may have a molecular weight from about 800
to about 2,000, and may have a viscosity preferably from about 80 cps to about
600 cps. The percentage of dimethylsiloxane units "X" may be from 25% to 95%.
The percentage of the diphenyl siloxane units "Y" may be from 5% to 75%. This
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precursor may be used to provide chain extension, toughening agent, changed or
altered refractive index, and improvements to high temperature thermal
stability
of the cured material, as well as, other features and characteristics to the
cured
preform and ceramic material.
[00196] The precursor may be a siloxane backbone additive, such as
hydroxy terminated diphenyl dimethyl polysiloxane, which formula is shown
below.
CH3 CH3 - -1? ¨ CH3
HO- Si - 0 -Si 0 ___________ Si 0 ¨Si - OH
CH3 CH3 _C) CH3
X
[00197] This precursor may have a molecular weight (mw) from about
400 mw to about 20,000 mw, and may have a molecular weight from about 800
to about 2,000, and may have a viscosity preferably from about 80 cps to about
400 cps. The percentage of dimethylsiloxane units "X" may be from 25% to 95%.
The percentage of the diphenyl siloxane units "Y" may be from 5% to 75%. This
precursor may be used to provide chain extension, toughening agent, changed or
altered refractive index, and improvements to high temperature thermal
stability
of the cured material, can generate nano- and micro- scale porosity, as well
as
other features and characteristics to the cured preform and ceramic material.
[00198] A variety of cyclosiloxanes can be used as reactive molecules in
the formulation. They can be described by the following nomenclature system or
formula: DxD*y, where "D" represents a dimethyl siloxy unit and "D*"
represents a
substituted methyl siloxy unit, where the "*" group could be vinyl, allyl,
hydride,
hydroxy, phenyl, styryl, alkyl, cyclopentadienyl, or other organic group, x is
from
0-8, y is >=1, and x+y is from 3-8.
[00199] The precursor batch may also contain non-silicon based cross-
linking agents, be the reaction product of a non-silicon based cross linking
agent
and a siloxane backbone additive, and combinations and variation of these. The
non-silicon based cross-linking agents are intended to, and provide, the
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capability to cross-link during curing. For example, non-silicon based cross-
linking agents that can be used include: cyclopentadiene (CP),
methylcyclopentadiene (MeCP), dicyclopentadiene ("DCPD-),
methyldicyclopentadiene (MeDCPD), tricyclopentadiene (TCPD), piperylene,
divnylbenzene, isoprene, norbornadiene, vinylnorbornene, propenylnorbornene,
isopropenylnorbomene, methylvinylnorbornene, bicyclononadiene,
methylbicyclononadiene, propadiene, 4-vinylcyclohexene, 1,3-heptadiene,
cycloheptadiene, 1,3-butadiene, cyclooctadiene and isomers thereof. Generally,
any hydrocarbon that contains two (or more) unsaturated, C=C, bonds that can
react with a Si-H, Si-OH, or other Si bond in a precursor, can be used as a
cross-
linking agent. Some organic materials containing oxygen, nitrogen, and sulphur
may also function as cross-linking moieties.
[002001 The precursor may be a reactive monomer. These would
include molecules, such as tetramethyltetravinylcyclotetrasiloxane ("TV"),
which
formula is shown below.
ro
0 0 ,
s, s(
õ0..õ
[002011 This precursor may be used to provide a branching agent, a
three-dimensional cross-linking agent, as well as, other features and
characteristics to the cured preform and ceramic material. (It is also noted
that in
certain formulations, e.g., above 2%, and certain temperatures, e.g., about
from
about room temperature to about 60 C, this precursor may act as an inhibitor
to
cross-linking, e.g., in may inhibit the cross-linking of hydride and vinyl
groups.)
[00202] The precursor may be a reactive monomer, for example, such
as trivinyl cyclotetrasiloxane,
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e 1
. 0
Siõ S
0
0
[00203] divinyi cyclotetrasiloxane,
SV' í-
0 /
0
[00204] trivinyi monohydride cyclotetrasiloxane,
0 0
\\\
Si Si
[00205]
[00206] divinyi dihydride cyclotetrasiloxane,
(7- ,
,0,
0 0
[00207] and a hexamethyl cyclotetrasiloxane, such as,
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,
-- Si - Si Si ' 'Si ¨H
0 0 0 0
Si., Si " ..¨
/ 0 t H
[00208] The precursor may be a silane modifier, such as vinyl phenyl
methyl snarl% diphenyl silane, diphenyl methyl silane, and phenyl methyl
silane
(some of which may be used as an end capper or end termination group). These
silane modifiers can provide chain extenders and branching agents. They also
improve toughness, alter refractive index, and improve high temperature cure
stability of the cured material; as well as improving the strength of the
cured
material, among other things. A precursor; such as diphenyl methyl silane, may
function as an end capping agent, that may also improve toughness, alter
refractive index, and improve high temperature cure stability of the cured
material, as well as, improving the strength of the cured material, among
other
things.
[00209] The precursor may be a reaction product of a silane modifier
with a vinyl terminated siloxane backbone additive. The precursor may be a
reaction product of a silane modifier with a hydroxy terminated siloxane
backbone additive. The precursor may be a reaction product of a silane
modifier
with a hydride terminated siloxane backbone additive. The precursor may be a
reaction product of a silane modifier with W. The precursor may be a reaction
product of a silane. The precursor may be a reaction product of a silane
modifier
with a cyclosiloxane, taking into consideration steric hindrances. The
precursor
may be a partially hydrolyzed tetraethyl orthosilicate, such as TES 40 or
Silbond
40. The precursor may also be a i-nethylsesquisiloxane such as SR-350
available from General Electric Company, Wilton, Conn. The precursor may
also be a phenyl methyl siloxane such as 604 from Wacker Chemie AG. The
precursor may also be a rriethylphenylvirlyisiloxano, such as HS2 C from
Wacker
Chemie AG.
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[00210] The precursors may also be selected from the following:
SiSiB FIF2020, TRIMETHYLSILYL TERMINATED METHYL HYDROGEN
SILICONE FLUID 63148-57-2; SiSiB HF2050 TRIMETHYLSILYL
TERMINATED METHYLHYDROSILOXANE DIMETHYLSILOXANE
COPOLYMER 68037-59-2; SiSiB HF2060 HYDRIDE TERMINATED
METHYLHYDROSILOXANE DIMETHYLSILOXANE COPOLYMER 69013-23-6;
SiSiB HF2038 HYDROGEN TERMINATED POLYDIPHENYL SILOXANE;
SiSIM) HF2068 HYDRIDE TERMINATED METHYLHYDROSILOXANE
DIMETHYLSILOXANE COPOLYMER 115487-49-5; SiSiB HF2078 HYDRIDE
TERMINATED POLY(PHENYLDIMETHYLSILOXY) SILOXANE PHENYL
SILSESQUIOXANE, HYDROGEN-TERMINATED 68952-30-7; SiSiB VF6060
VINYLDIMETHYL TERMINATED VINYLMETHYL DIMETHYL POLYSILOXANE
COPOLYMERS 68083-18-1; SiSiB V1"6862 VINYLDIMETHYL TERmINATED
DIMETHYL DIPHENYL POLYSILOXANE COPOLYMER 68951-96-2; SiSiB
VF6872 VINYLDIrvIETHYL TERMINATED DIMETHYL-METHYLVINYL-
DIPHENYL POLYSILOXANE COPOLYMER; SiSiB PC9401 1,1,3,3-
TETRAMETHYL-1,3-DIVINYLDISILOXANE 2627-95-4; SiSiB PF1070
SILANOL TERMINATED POLYDIMETHYLSILO.XANE (0E1070) 70131-67-8;
SiSiB 0E1070 SILANOL TERMINATED POLYDIMETHYSILOXANE 70131-67-
8; OH-ENDCAPPED POLYDIMETHYLSILO.XANE HYDROXY TERMINATED
OLYDIMETHYLSILOXANE 73138-87-1; SiSiB VF6030 VINYL TERMINATED
POL\y`DIMETHYL SILOXANE 68083-19-2; and, SiSiB HF2030 HYDROGEN
TERMINATED POLYDIMETHYLSILOXANE FLUID 70900-21-9.
[00211] Thus, in additional to the forgoing type of precursors, it is
contemplated that a precursor may be a compound of the following general
formula.
-{ _... _
Ri R3
I 1
E1-0 S 0 _________________ Si-0 __ E2
1 1
R2 R4
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[00212] Wherein end cappers E. and E2 are chosen from groups such
as trimethyl silicon (-Si(CH3)3), dimethyl silicon hydroxy (-Si(CH3)90H),
dimethyl
silicon hydride (-Si(0H3)2H), dimethyl vinyl silicon (-Si(0H3)2(CH=CH2)),
(-Si(CH3)2(C6H5)) and dimethyl alkoxy silicon (-Si(CH3)2(0R). The R groups R1,
R2, R3, and R4 may all be different, or one or more may be the same. Thus, for
example, R2 is the same as R3, R3 is the same as R4, Ri and R2 are different
with
R3 and R4 being the same, etc. The R groups are chosen from groups such as
hydride (-H), methyl (Me)(-C), ethyl (-C-C), vinyl (-C=C), alkyl (-
R)(CnH2n+1), ally!
(-C-C=C), aryl CR), phenyl (Ph)(-C6H5), methoxy (-0-C), ethoxy (-0-C-C),
siloxy
(-0-Si-R3), alkoxy (-0-R), hydroxy (-0-H), phenylethyl (-C-C-C6H5) and
methyl,phenyl-ethyl (-C-C(-C)(-C6H5).
[00213] In general, embodiments of formulations for polysilocarb
formulations may for example have from about 0% to 50% MH, about 20% to
about 99% MH, about 0% to about 30% siloxane backbone additives, about 1%
to about 60% reactive monomers, about 30% to about 100% TV, and, about 0%
to about 90% reaction products of a siloxane backbone additives with a silane
modifier or an organic modifier reaction products.
[00214] In mixing the formulations sufficient time should be used to
permit the precursors to become effectively mixed and dispersed. Generally,
mixing of about 15 minutes to an hour is sufficient. Typically, the precursor
formulations are relatively, and essentially, shear insensitive, and thus the
type of
pumps or mixing are not critical. It is further noted that in higher viscosity
formulations additional mixing time may be required. The temperature of the
formulations, during mixing should preferably be kept below about 45 C, and
preferably about 10 C. (it is noted that these mixing conditions are for the
pre-
catalyzed formulations.)
The Reaction Type Process
[00215] In the reaction type process, in general, a chemical reaction is
used to combine one, two or more precursors, typically in the presence of a
solvent, to form a precursor formulation that is essentially made up of a
single
polymer that can then be, catalyzed, cured and pyrolized. This process
provides
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the ability to build custom precursor formulations that when cured can provide
plastics having unique and desirable features such as high temperature, flame
resistance and retardation, strength and other features. The cured materials
can
also be pyrolized to form ceramics having unique features. The reaction type
process allows for the predetermined balancing of different types of
functionality
in the end product by selecting functional groups for incorporation into the
polymer that makes up the precursor formulation, e.g., phenyls which typically
are not used for ceramics but have benefits for providing high temperature
capabilities for plastics, and styrene which typically does not provide high
temperature features for plastics but provides benefits for ceramics.
[00216] In general a custom polymer for use as a precursor formulation
is made by reacting precursors in a condensation reaction to form the polymer
precursor formulation. This precursor formulation is then cured into a preform
through a hydrolysis reaction. The condensation reaction forms a polymer of
the
type shown below.
Ri RI
Si _____ 0¨Sí ---------- 0¨Si ----- ¨ Si -- ¨ Si
End 1 i i End 2
R2_ R2
A2 A,
[00217] Where R1 and R2 in the polymeric units can be a hydride (-H), a
methyl (Me)(-C), an ethyl (-C-C), a vinyl (-C=C), an alkyl (-R)(CnH2n 1), an
unsaturated alkyl (-CnH2n..1), a cyclic alkyl (-CnN2n..1), an ally! (-C-C=C),
a butenyl
(-C4H7), a pentenyl (-05H9), a cyclopentenyl (-05H7), a methyl cyclopentenyl (-
05H6(CH3)), a norbornenyl (-CxHy, where X = 7-15 and Y = 9 -18), an aryl ('R),
a
phenyl (Ph)(-C6H5), a cycloheptenyl (-C7Hi 1), a cyclooctenyl (-C81113), an
ethoxy
(-O-C-C), a siloxy (-0-Si-R3), a methoxy (-0-C), an alkoxy, (-0-R), a hydroxy,
(-
0-H), a phenylethyl (¨C-C-C6H5) a methyl,phenyl-ethyl (-C-C(-C)(-C6H5)) and a
vinylphenyl-ethyl (-C-C(C6H4(-C=C))). R1 and R2 may be the same or different.
The custom precursor polymers can have several different polymeric units,
e.g.,
, A2, An, and may include as many as 10, 20 or more units, or it may contain
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only a single unit, for example, MHF made by the reaction process may have
only a single unit.
[00218] Embodiments may include precursors, which include among
others, a triethoxy methyl silane, a diethoxy methyl phenyl silane, a diethoxy
methyl hydride silane, a diethoxy methyl vinyl silane, a dimethyl ethoxy vinyl
silane, a diethoxy dimethyl silane. an ethoxy dimethyl phenyl silane, a
diethoxy
dihydride silane, a triethoxy phenyl silane, a diethoxy hydride trimethyl
siloxane,
a diethoxy methyl trimethyl siloxane, a trimethyl ethoxy silane, a diphenyl
diethoxy silane, a dimethyl ethoxy hydride siloxane, and combinations and
variations of these and other precursors, including other precursors set forth
in
this specification.
[00219] The end units, Si End 1 and Si End 2, can come from the
precursors of dimethyl ethoxy vinyl silane, ethoxy dimethyl phenyl silane, and
trimethyl ethoxy silane. Additionally, if the polymerization process is
properly
controlled a hydroxy end cap can be obtained from the precursors used to
provide the repeating units of the polymer.
[00220] In general, the precursors are added to a vessel with ethanol (or
other material to absorb heat, e.g., to provide thermal mass), an excess of
water,
and hydrochloric acid (or other proton source). This mixture is heated until
it
reaches its activation energy, after which the reaction typically is
exothermic.
Generally, in this reaction the water reacts with an ethoxy group of the
silicon of
the precursor monomer, forming a hydroxy (with ethanol as the byproduct).
Once formed this hydroxy becomes subject to reaction with an ethoxy group on
the silicon of another precursor monomer, resulting in a polymerization
reaction.
This polymerization reaction is continued until the desired chain length(s) is
built.
[00221] Control factors for determining chain length, among others, are:
the monomers chosen (generally, the smaller the monomers the more that can
be added before they begin to coil around and bond to themselves); the amount
and point in the reaction where end cappers are introduced; and the amount of
water and the rate of addition, among others. Thus, the chain lengths can be
from about 180 mw (viscosity about 5 cps) to about 65,000 mw (viscosity of
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about 10,000 cps), greater than about 1000 mw, greater than about 10,000 mw,
greater than about 50,000 mw and greater. Further, the polymerized precursor
formulation may, and typically does, have polymers of different molecular
weights, which can be predetermined to provide formulation, cured, and ceramic
product performance features.
[00222] Upon completion of the polymerization reaction the material is
transferred into a separation apparatus, e.g., a separation funnel, which has
an
amount of deionized water that, for example, is from about 1.2x to about 1.5x
the
mass of the material. This mixture is vigorously stirred for about less than 1
minute and preferably frorn about 5 to 30 seconds. Once stirred the material
is
allowed to settle and separate, which may take from about 1 to 2 hours. The
polymer is the higher density material and is removed frorn the vessel. This
removed polymer is then dried by either warming in a shallow tray at 90 C for
about two hours; or, preferably, is passed through a wiped film distillation
apparatus, to remove any residual water and ethanol. Alternatively, sodium
bicarbonate sufficient to buffer the aqueous layer to a pH of about 4 to about
7 is
added. It is further understood that other, and commercial, manners of mixing,
reacting and separating the polymer from the material may be employed.
[00223] Preferably a catalyst is used in the curing process of the
polymer precursor formulations from the reaction type process. The same
polymers, as used for curing the precursor formulations from the mixing type
process can be used. It is noted that, generally unlike the mixing type
formulations, a catalyst is not necessarily required to cure a reaction type
polymer. Inhibitors may also be used. However, if a catalyst is not used,
reaction time and rates will be slower. The curing and the pyrolysis of the
cured
material from the reaction process is essentially the same as the curing and
pyrolysis of the cured material from the mixing process and the reaction
blending
process.
[00224] The reaction type process can be conducted under numerous
types of atmospheres and conditions, e.g., air, inert, N2, Argon, flowing gas,
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static gas, reduced pressure, ambient pressure, elevated pressure, and
combinations and variations of these.
The Reaction Blending Type Process
[00225] In the reaction blending type process precursor are reacted to
=from a precursor formulation, in the absence of a solvent.
For example, an embodiment of a reaction blending type process has a
precursor formulation that is prepared from MHF and Dicyclopentadiene
("DCPD"). Using the reactive blending process a MI-IF/DCPD polymer is created
and this polymer is used as a precursor formulation. (It can be used alone to
form
a cured or pyrolized product, or as a precursor in the mixing or reaction
processes.) MHF of known molecular weight and hydride equivalent mass; "P01"
(P01 is a 2% Pt(0) tetravinylcyclotetrasiloxane complex (e.g.,
tetramethyltetravinylcyclotetrasiloxane) in tetravinylcyclotetrasiloxane,
diluted 20x
with tetravinylcyclotetrasiloxane to 0.1% of Pt(0) complex. In this manner 10
ppm Pt is provided for every 1% loading of bulk cat.) catalyst 0.20 wt% of MHF
starting material (with known active equivalent weight), from 40 to 90%; and
Dicyclopentadiene with 83% purity, from 10 to 60% are utilized. In an
embodiment of the process, a sealable reaction vessel, with a mixer, can be
used for the reaction. The reaction is conducted in the sealed vessel, in air;
although other types of atmosphere can be utilized. Preferably, the reaction
is
conducted at atmospheric pressure, but higher and lower pressures can be
utilized. Additionally, the reaction blending type process can be conducted
under numerous types of atmospheres and conditions, e.g., air, inert, N2,
Argon,
flowing gas, static gas, reduced pressure, ambient pressure, elevated
pressure,
and combinations and variations of these.
[00226] In an embodiment, 850 grams of MHF (85% of total polymer
mixture) is added to reaction vessel and heated to about 503 C. Once this
temperature is reached the heater is turned off, and 0.20% by weight P01
Platinum catalyst is added to the MHF in the reaction vessel. Typically, upon
addition of the catalyst bubbles will form and temp will initially rise
approximately
2-20 C.
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[00227] When the temperature begins to fall, about 150 g of DCPD (15
wt% of total polymer mixture) is added to the reaction vessel. The temperature
may drop an additional amount, e.g., around 5-7 C.
[00228] At this point in the reaction process the temperature of the
reaction vessel is controlled to, maintain a predetermined temperature profile
over time, and to manage the temperature increase that may be accompanied by
an exotherm. Preferably, the temperature of the reaction vessel is regulated,
monitored and controlled throughout the process.
[00229] In an embodiment of the MHF/DCPD embodiment of the
reaction process, the temperature profile can be as follows; let temperature
reach
about 80 C (may take ¨15-40 min, depending upon the amount of materials
present); temperature will then increase and peak at ¨104 C, as soon as
temperature begins to drop, the heater set temperature is increased to 100 C
and the temperature of the reaction mixture is monitored to ensure the polymer
temp stays above 80 C for a minimum total of about 2 hours and a maximum
total of about 4 hours. After 2-4 hours above 80 C, the heater is turned off,
and
the polymer is cooled to ambient. It being understood that in larger and
smaller
batches, continuous, semi-continuous, and other type processes the temperature
and time profile may be different.
[002301 In larger scale, and commercial operations, batch, continuous,
and combinations of these, may be used. Industrial factory automation and
control systems can be utilized to control the reaction, temperature profiles
and
other processes during the reaction.
[002311 Table C sets forth various embodiments of reaction blending
processes.
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[00232] Table C
=4. .0
To
... 0
0 CI rfl CI CI 5 ttl 1'1 -I
..0 l: .... SI 10
B
t'; µ.< SI. r.r, ..0 .., SI c. .... c.c. at c.
t":? c. F.
-:. z.
-.
ri. i a Uri ..e il i',.:
'4. r a F. 2 ¨ a ¨ a vs r . 2
1 ,... _ ,,
e
tf, Cr, Gs: eT a a r
*
-%
tetramethylcyclotet
rasiloxane (04) 4 4 4 4 0 4 4 240.53.
MHF 33_ 35 34 33 0 39 39 _
2145.345 _
VMF 5 7 6 0 5 11 21 592.959 118.59
TV i 4 4 4 0 4 4 1.2 344.52
86.13
VT 0200 125 127 126 0 2 . 254 258
9451.206 4725.60
VT 0020 24 26 25 0 2 52 56 1965.187
982.59
VT 0080 , 79 81 80 0 2 1.62 166
6041.732 3020.87
Styrene 2 104.15 52.08
t
Dicyclopentodiene 2 132.2 66.10
1,4-diyinylbenzene , 2 1.30.19 65.10
isoprene 2 62.12 31.06
1,3 Butadiene 2 54.09 27.05
Catalyst 10 ppm Pt
Catalyst LP 231
[00233] In the above table, the "degree of polymerization" is the number
of monomer units, or repeat units, that are attached together to form the
polymer.
"Equivalents /mol" refers to the molar equivalents. "Grams/mole of vinyl"
refers to the amount of a given polymer needed to provide 'I molar equivalent
of
vinyl functionality. "VMH" refers to methyl vinyl fluid, a linear vinyl
material from
the ethoxy process, which can be a substitute for TV. The numbers "0200" etc.
for VT are the viscosity in centipoise for that particular VT.
Curing and Pyrolysis
[00234] Precursor formulations, including the polysilocarb precursor
formulations from the above types of processes, as well as others, can be
cured
to form a solid, semi-sold, or plastic like material. Typically, the precursor
formulations are spread, shaped, or otherwise formed into a preform, which
would include any volumetric structure, or shape, including thin and thick
films.
In curing, the polysilocarb precursor formulation may be processed through an
initial cure, to provide a partially cured material, which may also be
referred to,
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for example, as a preform, green material, or green cure (not implying
anything
about the material's color). The green material may then be further cured.
Thus,
one or more curing steps may be used. The material may be "end cured," i.e.,
being cured to that point at which the material has the necessary physical
strength and other properties for its intended purpose. The amount of curing
may be to a final cure (or "hard cure"), i.e., that point at which all, or
essentially
all, of the chemical reaction has stopped (as measured, for example, by the
absence of reactive groups in the material, or the leveling off of the
decrease in
reactive groups over time). Thus, the material may be cured to varying
degrees,
depending upon its intended use and purpose. For example, in some situations
the end cure and the hard cure may be the same. Curing conditions such as
atmosphere and temperature may affect the composition of the cured material.
[002351 In making the precursor formulation into a structure, or preform,
the precursor formulation, e.g., polysilocarb formulation, can be, for
example,
formed using the following techniques: spraying, spray drying, atomization,
nebulization, phase change separation, flowing, thermal spraying, drawing,
dripping, forming droplets in liquid and liquid-surfactant systems, painting,
molding, forming, extruding, spinning, ultrasound, vibrating, solution
polymerization, emulsion polymerization, micro-emulsion polymerization,
injecting, injection molding, or otherwise manipulated into essentially any
volumetric shape. These volumetric shapes may include for example, the
following: spheres, pellets, rings, lenses, disks, panels, cones,
frustoconical
shapes, squares, rectangles, trusses, angles, channels, hollow sealed
chambers,
hollow spheres, blocks, sheets, coatings, films, skins, particulates, beams,
rods,
angles, slabs, columns, fibers, staple fibers, tubes, cups, pipes, and
combinations and various of these and other more complex shapes, both
engineering and architectural.
[00236] The forming step, the curing steps, and the pyrolysis steps may
be conducted in batch processes, serially, continuously, with time delays
(e.g.,
material is stored or held between steps), and combinations and variations of
these and other types of processing sequences. Further, the precursors can be
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partially cured, or the cure process can be initiated and on going, prior to
the
precursor being formed into a volumetric shape. These steps, and their various
combinations may be, and in some embodiments preferably are, conducted
under controlled and predetermined conditions (e.g., the material is exposed
to a
predetermined atmosphere, and temperature profile during the entirely of its
processing, e.g., reduced oxygen, temperature of cured preform held at about
140 C prior to pyrolysis). It should be further understood that the system,
equipment, or processing steps, for forming, curing and pyrolizing may be the
same equipment, continuous equipment, batch and linked equipment, and
combinations and variations of these and other types of industrial processes.
Thus, for example, a spray drying technique could form cured particles that
are
feed directly into a fluidized bed reactor for pyrolysis.
[00237] The polysilocarb precursor formulations can be made into neat,
non-reinforced, non-filled, composite, reinforced, and filled structures,
intermediates, end products, and combinations and variations of these and
other
compositional types of materials. Further, these structures, intermediates and
end products can be cured (e.g., green cured, end cured, or hard cured),
uncured, pyrolized to a ceramic, and combinations and variations of these
(e.g.,
a cured material may be filled with pyrolized material derived from the same
polysilocarb as the cured material).
[00238] The precursor formulations may be used to form a "neat"
material, (by "neat" material it is meant that all, and essentially all of the
structure
is made from the precursor material or unfilled form(Jlation; and thus, there
are no
fillers or reinforcements).
[00239] The polysilocarb precursor formulations may be used to coat or
impregnate a woven or non-woven fabric, made from for example carbon fiber,
glass fibers or fibers made from a polysilocarb precursor formulation (the
same
or different formulation), to from a prepreg material. Thus, the polysilocarb
precursor formulations may be used to form composite materials, e.g.,
reinforced
products. For example, the formulation may be flowed into, impregnated into,
absorbed by or otherwise combined with a reinforcing material, such as carbon
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fibers, glass fiber, woven fabric, grapheme, carbon nanotubes, thin films,
precipitates, sand, non-woven fabric, copped fibers, fibers, rope, braided
structures, ceramic powders, glass powders, carbon powders, graphite powders,
ceramic fibers, metal powders, carbide pellets or components, staple fibers,
tow,
nanostructures of the above, polymer derived ceramics, any other material that
meets the temperature requirements of the process and end product, and
combinations and variations of these. The reinforcing material may also be
made from, or derived from the same material as the formulation that has been
formed into a fiber and pyrolized into a ceramic, or it may be made from a
different precursor formulation material, which has been formed into a fiber
and
pyrolized into a ceramic.
[00240] The polysilocarb precursor formulation may be used to form a
filled material. A filled material would be any material having other solid,
or semi-
solid, materials added to the polysilocarb precursor formulation. The filler
material may be selected to provide certain features to the cured product, the
ceramic product and both. These features may relate to, or be, for example,
aesthetic, tactile, thermal, density, radiation, chemical, cost, magnetic,
electric,
and combinations and variations of these and other features. These features
may be in addition to strength. Thus, the filler material may not affect the
strength
of the cured or ceramic material, it may add strength, or could even reduce
strength in some situations. The filler material could impart color, magnetic
capabilities, fire resistances, flame retardance, heat resistance, electrical
conductivity, anti-static, optical properties (e.g., reflectivity,
refractivity and
iridescence), aesthetic properties (such as stone like appearance in building
products), chemical resistivity, corrosion resistance, wear resistance,
reduced
cost, abrasions resistance, thermal insulation, UV stability, UV protective,
and
other features that may be desirable, necessary, and both, in the end product
or
material. Thus, filler materials could include carbon black, copper lead
wires,
thermal conductive fillers, electrically conductive fillers, lead, optical
fibers,
ceramic colorants, pigments, oxides, sand, dyes, powders, ceramic fines,
polymer derived ceramic particles, pore-formers, carbosilanes, silanes,
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silazanes, silicon carbide, carbosilazanes, siloxane, powders, ceramic
powders,
metals, metal complexes, carbon, tow, fibers, staple fibers, boron containing
materials, milled fibers, glass, glass fiber, fiber glass, and nanostructures
(including nanostructures of the forgoing) to name a few.
[00241] The polysilocarb formulation and products derived or made from
that formulation may have metals and metal complexes. Filled materials would
include reinforced materials. In many cases, cured, as well as pyrolized
polysilocarb filled materials can be viewed as composite materials. Generally,
under this view, the polysilocarb would constitute the bulk or matrix phase,
(e.g.,
a continuous, or substantially continuous phase), and the filler would
constitute
the dispersed (e.g., non-continuous), phase. Depending upon the particular
application, product or end use, the filler can be evenly distributed in the
precursor formulation, unevenly distributed, distributed over a predetermined
and
controlled distribution gradient (such as from a predetermined rate of
settling),
and can have different amounts in different formulations, which can then be
formed into a product having a predetermined amounts of filler in
predetermined
areas (e.g., striated layers having different filler concentration). It should
be
noted, however, that by referring to a material as "filled" or "reinforced" it
does not
imply that the majority (either by weight, volume, or both) of that material
is the
polysilcocarb. Thus, generally, the ratio (either weight or volume) of
polysilocarb
to filler material could be from about 0.1:99.9 to 99.9:0.1.
[002421 The polysilocarb precursor formulations may be used to form
non-reinforced materials, which are materials that are made of primarily,
essentially, and preferably only from the precursor materials; but may also
include formulations having fillers or additives that do not impart strength.
[002431 The curing may be done at standard ambient temperature and
pressure ("SATP", 1 atmosphere, 25 C), at temperatures above or below that
temperature, at pressures above or below that pressure, and over varying time
periods. The curing can be conducted over various heatings, rate of heating,
and
temperature profiles (e.g., hold times and temperatures, continuous
temperature
change, cycled temperature change, e.g., heating followed by maintaining,
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cooling, reheating, etc.). The time for the curing can be from a few seconds
(e.g., less than about 1 second, less than 5 seconds), to less than a minute,
to
minutes, to hours, to days (or potentially longer). The curing may also be
conducted in any type of surrounding environment, including for example, gas,
liquid, air, water, surfactant containing liquid, inert atmospheres, N2,
Argon,
flowing gas (e.g., sweep gas), static gas, reduced 02, reduced pressure,
elevated
pressure, ambient pressure, controlled partial pressure and combinations and
variations of these and other processing conditions. For high purity
materials,
the furnace, containers, handling equipment, atmosphere, and other components
of the curing apparatus and process are clean, essentially free from, and do
not
contribute any elements or materials, that would be considered impurities or
contaminants, to the cured material. In an embodiment, the curing environment,
e.g., the furnace, the atmosphere, the container and combinations and
variations
of these can have materials that contribute to or effect, for example, the
composition, catalysis, stoichiometry, features, performance and combinations
and variations of these in the preform, the ceramic and the final applications
or
products.
[002441 Preferably, in embodiments of the curing process, the curing
takes place at temperatures in the range of from about 5 C or more, from about
20 C to about 250 C, from about 20 C to about 150 C, from about 75 C to about
125 C, and from about 80 C to 90 C. Although higher and lower temperatures
and various heating profiles, (e.g., rate of temperature change over time
("ramp
rate", e.g., A degrees/time), hold times, and temperatures) can be utilized.
[002451 The cure conditions, e.g., temperature, time, ramp rate, may be
dependent upon, and in some embodiments can be predetermined, in whole or in
part, by the formulation to match, for example the size of the preform, the
shape
of the preform, or the mold holding the preform to prevent stress cracking,
off
gassing, or other phenomena associated with the curing process. Further, the
curing conditions may be such as to take advantage of, preferably in a
controlled
manner, what may have previously been perceived as problems associated with
the curing process. Thus, for example, off gassing may be used to create a
foam
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material having either open or closed structure. Similarly, curing conditions
can
be used to create or control the microstructure and the nanostructure of the
rnaterial. In general, the curing conditions can be used to affect, control or
modify the kinetics and thermodynamics of the process, which can affect
morphology, performance, features and functions, among other things.
[00246] Upon curing the polysilocarb precursor formulation a cross
linking reaction takes place that provides in some embodiments a cross-linked
structure having, among other things, an -R1-Si-C-C-Si-O-Si-C-C-Si-R2- where
R1
and R2 vary depending upon, and are based upon, the precursors used in the
=formulation. In an embodiment of the cured materials they may have a cross-
linked structure having 3-coordinated silicon centers to another silicon atom,
being separated by fewer than 5 atoms between silicons.
[00247] During the curing process some formulations may exhibit an
exotherm, i.e., a self heating reaction, that can produce a small amount of
heat to
assist or drive the curing reaction, or that may produce a large amount of
heat
that may need to be managed and removed in order to avoid problems, such as
stress fractures. During the cure off gassing typically occurs and results in
a loss
of material, which loss is defined generally by the amount of material
remaining,
e.g., cure yield. Embodiments of the formulations, cure conditions, and
polysilocarb precursor formulations of embodiments of the present inventions
can
have cure yields of at least about 90%, about 92%, about 100%. In fact, with
air
cures the materials may have cure yields above 100%, e.g., about 101-105%, as
a result of oxygen being absorbed from the air. Additionally, during curing
the
material typically shrinks, this shrinkage may be, depending upon the
formulation, cure conditions, and the nature of the preform shape, and whether
the preform is reinforced, filled, neat or unreinforced, from about 20%, less
than
20%, less than about 15%, less than about 5%, less than about 1%, less than
about 0.5%, less than about 0.25% and smaller.
[00248] Curing of the preform may be accomplished by any type of
heating apparatus, or mechanisms, techniques, or morphologies that has the
requisite level of temperature and environmental control, for example, heated
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water baths, electric furnaces, microwaves, gas furnaces, furnaces, forced
heated air, towers, spray drying, falling film reactors, fluidized bed
reactors,
lasers, indirect heating elements, direct heating, infrared heating. UV
irradiation,
RF furnace, in-situ during emulsification via high shear mixing, in-situ
during
ernulsification via ultrasonication.
[00249] The cured preforms, either unreinforced, neat, filled or
reinforced, may be used as a stand alone product, an end product, a final
product, or a preliminary product for which later machining or processing may
be
performed on. The preforms may also be subject to pyrolysis, which converts
the
preform material into a ceramic.
[00250] In pyrolizing the preform, or cured structure, or cured material, it
is heated to about 600 C to about 2,300 C; from about 650 C to about 1,200
C, from about 800GC to about 1300 C, from about 900 C to about 1200 C and
from about 950 C to 1150 C. At these temperatures typically all organic
structures are either removed or combined with the inorganic constituents to
form
a ceramic. Typically at temperatures in the about 650 C to 1,200 C range the
resulting material is an amorphous glassy ceramic. When heated above about
1,200' C the material typically may from nano crystalline structures, or micro
crystalline structures, such as SiC, Si3N4, SiCN, 1.3 SiC, and above 1,900' C
an a
SiC structure may form, and at and above 2,200 C a SC is typically formed.
The pyrolized, e.g., ceramic materials can be single crystal, polycrystalline,
amorphous, and combinations, variations and subgroups of these and other
types of morphologies.
[00251] The pyrolysis may be conducted under many different heating
and environmental conditions, which preferably include therm control, kinetic
control and combinations and variations of these, among other things. For
example, the pyrolysis may have various heating ramp rates, heating cycles and
environmental conditions. In some embodiments, the temperature may be
raised, and held a predetermined temperature, to assist with known transitions
(e.g., gassing, volatilization, molecular rearrangements, etc.) and then
elevated
to the next hold temperature corresponding to the next known transition. The
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pyrolysis may take place in reducing atmospheres, oxidative atmospheres, low
0.7, gas rich (e.g., within or directly adjacent to a flame), inert, N2,
Argon, air,
reduced pressure, ambient pressure, elevated pressure, flowing gas (e.g.,
sweep
gas, having a flow rate for example of from about from about 15.0 GHSV to
about
0.1 GHSV, from about 6.3 GHSV to about 3.1 GHSV, and at about 3.9 GHSV),
static gas, and combinations and variations of these.
[00252] The pyrolysis is conducted over a time period that preferably
results in the complete pyrolysis of the preform. For high purity materials,
the
furnace, containers, handling equipment, and other components of the pyrolysis
apparatus are clean, essentially free from, free from and do not contribute
any
elements or materials, that would be considered impurities or contaminants, to
the pyrolized material. A constant flow rate of "sweeping" gas can help purge
the furnace during volatile generation. In an embodiment, the pyrolysis
environment, e.g., the furnace, the atmosphere, the container and combinations
and variations of these, can have materials that contribute to or effect, for
example, the composition, stoichiometry, features, performance and
combinations and variations of these in the ceramic and the final applications
or
products.
[00253] During pyrolysis material may be lost through off gassing. The
amount of material remaining at the end of a pyrolysis step, or cycle, is
referred
to as char yield (or pyrolysis yield). The formulations and polysilocarb
precursor
formulations of embodiments of the present formulations can have char yields
for
SiOC formation of at least about 60%, about 70%, about 80%, and at least about
90%, at least about 91% and greater. In fact, with air pyrolysis the materials
may
have char yields well above 91%, which can approach 100%. In order to avoid
the degradation of the material in an air pyrolysis (noting that typically
pyrolysis is
conducted in inert atmospheres, reduced oxygen atmosphere, essentially inert
atmosphere, minimal oxygen atmospheres, and combinations and variations of
these) specifically tailored formulations can be used. For example,
formulations
high in phenyl content (at least about 11%, and preferably at least about 20%
by
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weight phenyls), formulations high in ally! content (at least about 15% to
about
60%) can be used for air pyrolysis to mitigate the degradation of the
material.
[00254] The initial or first pyrolysis step for SiOC formation, in some
embodiments and for some uses, generally yields a structure that is not very
dense, and for example, may not reached the density required for its intended
use. However, in some examples, such as the use of lightweight spheres,
proppants, pigments, and others, the first pyrolysis may be, and is typically
sufficient. Thus, generally a reinfiltration process may be performed on the
pyrolized material, to add in additional polysilocarb precursor formulation
material, to fill in, or fill, the voids and spaces in the structure. This
reinfiltrated
material may then be cured and repyrolized. (In some embodiments, the
reinfiltrated materials is cured, but not pyrolized.) This process of
pyrolization,
reinfiltration may be repeated, through one, two, three, and up to 10 or more
times to obtain the desired density of the final product.
[00255] In some embodiments, upon pyrolization, graphenic, graphitic,
amorphous carbon structures and combinations and variations of these are
present in the Si-O-C ceramic. A distribution of silicon species, consisting
of
SiOxCy structures, which result in SiO4, SiO3C, SiO2C2, Si0C3, and SiC4 are
formed in varying ratios, arising from the precursor choice and their
processing
history. Carbon is generally bound between neighboring carbons and/or to a
Silicon atom. In general, in the ceramic state, carbon is largely not
coordinated
to an oxygen atom, thus oxygen is largely coordinated to silicon
[00256] The pyrolysis may be conducted in any heating apparatus that
maintains the request temperature and environmental controls. Thus, for
example pyrolysis may be done with gas fired furnaces, electric furnaces,
direct
heating, indirect heating, fluidized beds, kilns, tunnel kilns, box kilns,
shuttle kilns,
coking type apparatus, lasers, microwaves, and combinations and variations of
these and other heating apparatus and systems that can obtain the request
temperatures for pyrolysis.
[00257] Custom and predetermined control of when chemical reactions,
arrangements and rearrangements, occur in the various stages of the process
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from raw material to final end product can provide for reduced costs,
increased
process control, increased reliability, increased efficiency, enhanced product
features, increased purity, and combinations and variation of these and other
benefits. The sequencing of when these transformations take place can be
based upon the processing or making of precursors, and the processing or
making of precursor formulations; and may also be based upon cure and
pyrolysis conditions. Further, the custom and predetermined selection of these
steps, formulations and conditions, can provide enhanced product and
processing features through the various transformations, e.g., chemical
reactions; molecular arrangements and rearrangements; and microstructure
arrangements and rearrangements.
[00258] At various points during the manufacturing process, the polyrner
derived ceramic structures, e.g., polysilocarb structures, intermediates and
end
products, and combinations and variations of these, may be machined, milled,
molded, shaped, drilled, etched, or otherwise mechanically processed and
shaped.
[00259] Starting materials, precursor formulations, polysilocarb
precursor formulations, as well as, methods of formulating, making, forming,
curing and pyrolizing, precursor materials to form polymer derived rnaterials,
structures and ceramics, are set forth in Published US Patent Applications,
Publication Nos. 2014/0343220, 2014/0274658, and 2014/0326453, and US
Patent Applications, Serial Nos. 61/946,598, 62/055,397 and 62/106,094, the
entire disclosures of each of which are incorporated herein by reference.
[00260] In preferred embodiments of the polysilocarb derived ceramic
pigments the amounts of Si, 0, C for the total amount of pigment are set forth
in
the Table 4.
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[00261] Table 4
Si 0 C
Lo Hi lo Hi Lo Hi
Wt% 35.00% 50.00% 10.00% 35.00% 5.00% 30.00%
Mole Ratio 1.000 1.429 0.502 1.755 0.334 2.004
Mole % 15.358% 63.095% 8.821% 56.819% 6.339% 57.170%
[00262] In general, embodiments of the pyrolized ceramic polysilocarb
pigments can have about 30% to about 60% Si, can have about 5% to about
40% Co, and can have about 3% to about 35% carbon. Greater and lesser
amounts are also contemplated.
[00263] The type of carbon present in preferred embodiments of the
polysilocarb derived ceramic pigments can be free carbon, (e.g., turbostratic,
amorphous, graphenic, graphitic forms of carbon) and Carbon that is bound to
Silicon. Embodiments having preferred amounts of free carbon and Silicon-
bound-Carbon (Si-C) are set forth in Table 5.
[00264] Table 5
Embodiment % Free Carbon % Si-C type
1 64.86 35.14
2 63.16 36.85
3 67.02 32.98
4 58.59 41.41
65.70 31.66
6 62.72 30.82
7 61.68 34.44
8 69.25 27.26
9 60.00 27.54
[00265] Generally, embodiments of polysilocarb derived ceramic
pigments can have from about 20% free carbon to about 80% free carbon, and
from about 20% Si-C bonded carbon to about 80% Si-C bonded carbon. Greater
and lesser amounts are also contemplated.
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[00266] Typically, embodiments of the pyrolized ceramic polysilocarb
pigments can have other elements present, such as Nitrogen and Hydrogen.
Embodiments can have the amounts of these other materials as set out in Table
6. (Note that these are typical for embodiments of net materials. If fillers,
additives, or other materials are combined with or into the precursor
formulation;
then such materials can generally be present to a greater or lesser extent in
the
pyrolized ceramic material)
[00267] Table 6
Lo Hi Lo Hi
Wt% 0.00% 2.20% 0% 2%
Mole Ratio 0.000 1.751 0 0.1
Mole % 0.000% 48.827% 0% 3%
[00268] The polysilocarb derived ceramic pigments can exhibit sparkle,
and impart sparkle to a coating. The degree and effect of sparkle can be
predetermined by such factors as for example the surface exposure during
pyrolysis, heat profile, and the type of gas (nitrogen, argon etc.) used
during
pyrolysis.
[00269] Examples
[00270] The following examples are provided to illustrate various
embodiments of, among other things, precursor formulations, processes,
methods, apparatus, articles, compositions, and applications of the present
inventions. These examples are for illustrative purposes, and should not be
viewed as, and do not otherwise limit the scope of the present inventions. The
percentages used, unless specified otherwise, are weight percent of the total
batch, pigment, formulation or structure.
[00271] EXAMPLE 1
[00272] A polymer derived ceramic black pigment having 41% Si, 31 %
0, and 27 % C (with 27.5% of the carbon being the Si-C bonded type, and the
remaining carbon being the graphitic type) has the following properties.
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[00273] Physical and Chemical Properties
Particle Size (D50) capabilities 1 - 150pm
Specific Gravity 2.10
Bulk Density, lbs/ft3 78
g/cc 1.25
Morphology Angular -
Fragmented
Solubility in 12/3 HCUHF Acid (% weight loss) 0.4
[00274] Masstone (typical) 800 series
DFT (mii/p) 0.8/20
Gloss 200 74.6
Gloss 600 974
Color
Development*
L* 4.64
a* 0.25
0.95
* commercial automotive binder system.
[00275] Weather test 500 hr.
Chalking none
Blistering none
Whitening none
Color
Development*
L (init./final) 4.64/4.51
a (init./final) 0.25/0.17
b (init./final) 0.95/0.97
Gloss 98.4 %
Retention
*QUV per ASTM G154.
[00276] Environmental properties
Salt Spray (500 hrs.) Pass
Conductivity (6) <1O
Scratch resistance (ISO 1518 stylus)
To 5 Kg weight No cut
(pass)
Pencil Hardness HB
[00277] EXAMPLE 2
[00278] A polymer derived ceramic black pigment having 45 % Si, 22 %
0, and 33% C (with 34.4% of the carbon being the Si-C bonded type, and the
remaining carbon being the graphitic type) and an agglomerate size of 10 pm
and a particle size of 0.1 pm.
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[00279] EXAMPLE 3
[00280] A polymer derived ceramic black pigment having 44 % Si, 31 %
0, and 25% C (with 27.3% of the carbon being the Si-C bonded type, and the
remaining carbon being the graphitic type) and an agglomerate size of 15 pm
and a particle size of 1 pm.
[00281] EXAMPLE 4
[00282] A polymer derived ceramic black pigment having 50 'Ye Si, 20 'Ye
0, and 30% C (with 25% of the carbon being the Si-C bonded type, and the
remaining carbon being the graphitic type) and an agglomerate size of 10 pm
and a particle size of 0.5 pm.
[00283] EXAMPLE 5
[00284] A polysilocarb batch having 75% MH, 15% TV, 10% VT and 1%
catalyst (10 ppm platinum and 0.5% Luperox 231 peroxide) is cured and
pyrolized to form black ceramic pigment.
[00285] EXAMPLE 6
[00286] A polysilocarb batch having 70% MH, 20% TV, 10% VT and 1%
catalyst (10 ppm platinum and 0.5% Luperox 231 peroxide) is cured and
pyrolized to form black ceramic pigment.
[00287] EXAMPLE 7
[00288] A polysilocarb batch having 50% by volume carbon black is
added to a polysilocarb batch having 70% MH, 20% TV, 10% VT and 1% catalyst
(10 ppm platinum and 0.5% Luperox 231 peroxide) is cured and pyrolized to form
black ceramic filled pigment.
[00289] EXAMPLE 8
[00290] A polysilocarb batch having 70% of the MH precursor
(molecular weight of about 800) and 30% of the TV precursor is cured and
pyrolized to form black ceramic pigment.
[00291] EXAMPLE 9
[00292] A polysilocarb batch having 10% of the MH precursor
(molecular weight of about 800), 73% of the methyl terrninated phenylethyl
polysiloxane precursor (molecular weight of about 1,000), and 16% of the TV
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precursor, and 1% of the OH terminated is cured and pyrolized to form black
ceramic pigment.
[00293] EXAMPLE 10
[00294] A polysilocarb reaction blend batch having 85/15 MHF/DCPD is
cured and pyrolized in a single heating step in a gas rich furnace at 1,100 C
to
form black ceramic pigment.
[00295] EXAMPLE 11
[00296] A polysilocarb reaction blend batch having 85/15 MHF/DCPD
with 1% P01 catalyst and 1% peroxide catalyst is cured at 100 C in a reduced
oxygen atmosphere and the cure material is then pyrolized in a reduced
pressure
argon flowing environment at 1,200 C to form black ceramic pigment.
[00297] EXAMPLE 12
[00298] A polysilocarb reaction blend batch having 85/15 MHF/DCPD
with 1% P01 catalyst and 3% TV (which functions as a curie rate accelerator)
is
cured and pyrolized to form a black ceramic pigment.
[00299] EXAMPLE 13
[00300] A polysilocarb reaction blend batch having 65/35 MHF/DCPD is
cured and pyrolized to form a black ceramic pigment.
[00301] EXAMPLE 14
[00302] A polysilocarb reaction blend batch having 70/30 MHF/DCPD is
cured and pyrolized to form a black ceramic pigment.
[00303] EXAMPLE 15
[00304] A polysilocarb reaction blend batch having 60/40 MHF/DCPD is
cured and pyrolized to form a black ceramic pigment.
[00305] EXAMPLE 16
[00306] A polysilocarb batch having 50 - 65% MHF; 5 - 10% Tetravinyl;
and 25 ¨ 40% Diene (Diene = Dicyclopentadiene or Isoprene or Butadiene),
preferably catalyzed with P01 or other Platinum catalyst is cured and
pyrolized to
form a black ceramic pigment.
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[00307] EXAMPLE 17
[00308] A polysilocarb batch having 60 - 80% (AM" and 20 - 40%
Isoprene, preferably catalyzed with P01 or other Platinum catalyst is cured
and
pyrolized to form a black ceramic pigment.
[00309] EXAMPLE 18
[00310] A polysilocarb batch having 50 - 65% MHF and 35 ¨ 50%
Tetravinyl, preferably catalyzed with P01 or other Platinum catalyst is cured
and
pyrolized to form a black ceramic pigment.
[00311] EXAMPLE 19
[00312] A polysilocarb reaction blend batch having 85/15 MHFIDCPD,
and preferably using P01 and Luperox 231 catalysts is cured and pyrolized to
form a black ceramic pigment.
[00313] EXAMPLE 20
[00314] A polysilocarb reaction blend batch having 65/35 MHFIDCPD,
and preferably using P01 and Luperox 231 catalysts is cured and pyrolized to
form a black ceramic pigment.
[00315] EXAMPLE 21
[00316] A polysilocarb batch having 46% MHF and 34% TV and 20 VT,
with P01 catalyst is cured and pyrolized to form a black ceramic pigment.
[00317] EXAMPLE 22
[00318] A polysilocarb reaction blend batch having 50/50 MHF/DCPD
with 4% TV and 5 ppm Pt catalyst is cured and pyrolized to form a black
ceramic
pigment.
[00319] EXAMPLE 23
[00320] Using the reaction type process a precursor formulation was
made using the following formulation. The temperature of the reaction was
maintained at 61 C for 21 hours.
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[00321]
Moles of % of Total
% of Reactant/ Moles of Moles
Moles
Reactant or Solvent Mass Total MW solvent Silane of Si
of Et0H
Methyltriethoxysilane (FIG.
37)
120.00 193% 178.30 0.67 47.43% 0.67 2.02
Phenylmethyldiethoxysilane
(FIG. 38) 0.00 0.0% 210.35 0.00%
Dimethyldiethoxysilane (FIG.
42)
70.00 11.4% 148.28 0.47 33.27% 0.47 0.94
Methyldiethoxysilane (FIG. 39) 20.00 3.3% 134.25 0.15
10.50% 0.15 0.30
Vinylmethyldiethoxysilane
(FIG. 40) 20.00 3.3% 160.29 0.12 8.79%
0.12 0.25
Trimethyethoxysilane (FIG. 48) 0.00 0.0% 118.25 0.00%
Hexane in hydrolyzer 0.00 0.0% 86.18
Acetone in hydrolyzer 320.00 52.0% 58.08 5.51
Ethanol in hydrolyzer 0.00 0.0% 46.07
Water in hydrolyzer 64.00 10.4% 18.00 3.56
HCI 0.36 0.1% 36.00 0.01
Sodium bicarbonate 0.84 0.1% 84.00 0.01
[00322] Is cured and pyrolized to form a black ceramic pigment.
[003231 EXAMPLE 24
[00324] Using the reaction type process a precursor formulation was
made using the following formulation. The temperature of the reaction was
maintained at 72 C for 21 hours.
Moles of % of Total
% of Reactant/ Moles of Moles
Moles
Reactant or Solvent Mass Total MW solvent Silane
of Si of Et0H
Phenyltriethoxysilane (FIG. 45) 234.00 32.0% 240.37 0.97
54.34% 0.97 2.92
Phenylrnethyldiethoxysilane
(FIG. 38) 90.00 12.3% 210.35 0.43 23.88%
0.43 0.86
Dimethyldiethoxysilane (FIG.
42) 0.00 0.0% 148.28 0.00%
Methyldiethoxysilane (FIG. 39) 28.50 3.9% 134.25 0.21
11.85% 0.21 0.42
Vinylrnethyldiethoxysilane (FIG.
40)
28.50 3.9% 160.29 0.18 9.93% 0.18 0.36
Trimethyethoxysilane (FIG. 48) 0.00 0.0% 118.25 =0.00%
Acetone in hydrolyzer 0.00 0.0% 58.08
Ethanol in hydrolyzer 265.00 36.3% 46.07 5.75
Water in hydrolyzer 83.00 11.4% 18.00 4.61
HCI 0.36 0.0% 36.00 0.01
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Sodium bicarbonate 0.84 0.1% 84.00 0.01
[00325] Is cured and pyrolized to form a black ceramic pigment.
[00326] EXAMPLE 25
[003271 Using the reaction type process a precursor formulation was
made using the following formulation. The temperature of the reaction was
maintained at 61 C for 21 hours.
Moles of % of Total
% of Reactant/ Moles of Moles
Moles
Reactant or Solvent Mass Total MW solvent Silane of Si
of Et0F1
Phenyltriethoxysilane (FIG. 45) 142.00 21.1% 240.37 0.59
37.84% 0.59 1.77
Phenylmethyldiethoxysilane
(FIG. 38) 135.00 20.1% 210.35 0.64 41.11%
0.64 1.28
Dimethyldiethoxysilane (FIG.
42) 0.00 0.0% 148.28 0.00%
Methyldiethoxysilane (FIG. 39) 24.00 3.6% 134.25 0.18
11.45% 0.18 0.36
Vinylmethyldiethoxysilane
(FIG. 40) 24.00 3.6% 1.60.29 0.15 9.59%
0.15 0.30
Trimethyethoxysilane (FIG. 48) 0.00 0.0% 118.25 = 0.00%
Acetone in hydrolyzer 278.00 41.3% 58.08 4.79
Ethanol in hydrolyzer 0.00 0.0% 46.07
Water in hydrolyzer 69.00 10.2% 18.00 3.83
HCI = 0.36 0.1% 36.00 0.01
Sodium bicarbonate 0.84 0.1% 84.00 0.01
[00328] Is cured and pyrolized to form a black ceramic pigment.
[00329] EXAMPLE 26
[00330] Using the reaction type process a precursor formulation was
made using the following formulation. The temperature of the reaction was
maintained at 72 C for 21 hours.
Moles of % of Total
% of Reactant/ Moles of Moles
Moles
Reactant or Solvent Mass Total MW solvent Silane of Si
of Et0H
Methyltriethoxysilane (FIG.
37) 0.00 0.0% 178.30 0.00%
Phenylmethyldiethoxysilane
(FIG. 38) 0.00 0.0% 210.35 0.00%
Dimethyldiethoxysilane (FIG.
42) 56
7.2% 148.28 0.38 17.71% 0.38 0.76
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Methyldiethoxysilane (FIG. 39) 182 23.2% 134.25 3..36 63.57%
1.36 2.71
Vinylmethyldiethoxysilane
(FIG. 40) 64 8.2% 160.29 0.40 18.72% 0.40
0.80
Triethoxysilane (FIG. 44) 0.00 0.0% 164.27 0.00%
Hexane in hydrolyzer 0.00 0.0% 86.18
Acetone in hydrolyzer 0.00 0.0% 58.08
Ethanol in hydrolyzer 400.00 51.1% 46.07 8.68
Water in hydrolyzer 80.00 10.2% 18.00 4.44
Ha 0.36 0.0% 36.00 0.01
Sodium bicarbonate 0.84 0.1% 84.00 0.01
[00331] Is cured and pyrolized to form a black ceramic pigment.
[00332] EXAMPLE 27
[00333] Using the reaction type process a precursor formulation was
made using the following formulation. The temperature of the reaction was
maintained at 61 C for 21 hours.
Moles of % of Total
% of Reactant/ Moles of Moles
Moles
Reactant or Solvent Mass Total MW solvent Silane of
Si of Et0H
Phenyltriethoxysilane (FIG. 45) 198.00 26.6% 240.37
0.82 52.84% 0.82 2.47
Phenylmethyldiethoxysilane
(FIG. 38) = 0.00 0.0% 210.35 0.00%
Dimethyldiethoxysilane (FIG.
42) = 109.00 14.6% 3.48.28 0.74
47.16% 0.74 1.47
Methyldiethoxysilane (FIG. 39) 0.00 0.0% 134.25 = 0.00%
Vinylmethyldiethoxysilane
(FIG. 40) = 0.00 0.0% 160.29 = 0.00%
Trimethyethoxysilane (FIG. 48) 0.00 0.0% 118.25 0.00%
Acetone in hydrolyzer 365.00 49.0% 58.08 6.28
Ethanol in hydrolyzer 0.00 0.0% 46.07
Water in hydrolyzer 72.00 9.7% 18.00 4.00
HCI 0.36 0.0% 36.00 0.01
Sodium bicarbonate 0.84 0.1% 84.00 0.01
[00334] Is cured and pyrolized to form a black ceramic pigment.
[00335] EXAMPLE 28
[00336] Using the reaction type process a precursor formulation was
made using the following formulation. The temperature of the reaction was
maintained at 72 C for 21 hours.
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Moles of % of Total
91., of Reactant/ Moles of Moles
Moles
Reactant or Solvent Mass Total MW solvent Silane of Si
of Et0H
Phenyltriethoxysilane (FIG. 45) 180.00 22.7% 240.37 0.75 =
44.10% 0.75 2.25
Phenylmethyldiethoxysilane
(FIG. 38) 50.00 6.3% 210.35 0.24 14.00%
0.24 0.48
Dimethyldiethoxysilane (FIG.
42)
40.00 5.0% 148.28 0.27 15.89% 0.27 0.54
Methyldiethoxysilane (FIG. 39) 30.00 3.8% 134.25 0.22 = 13.16%
0.22 0.45
Vinylmethyldiethoxysilane
(FIG. 40) 35.00 4.4% 160.29 0.22 = 12.86%
0.22 0.44
Trimethyethoxysilane (FIG. 48) = 0.00 0.0% 118.25
0.00%
Hexane in hydrolyzer 0.00 0.0% 86.18
Acetone in hydrolyzer 0.00 0.0% 58.08
Ethanol in hydrolyzer 380.00 48.0% 46.07 8.25
Water in hydrolyzer 76.00 9.6% 18.00 4.22
HCI 0.36 0.0% 36.00 0.01
Sodium bicarbonate 0.84 0.1% 84.00 0.01.
[00337] Is cured and pyrolized to form a black ceramic pigment.
[00338] EXAMPLE 29
A polysilocarb formulation has 95% MHF and 5% TV is cured and
pyrolized to form a black ceramic pigment.
[00339] EXAMPLE 30
A polysilocarb formulation has 90% MHF, 5% TV, and 5% VT is cured and
pyrolized to form a black ceramic pigment.
[00340] EXAMPLE 31
A polysilocarb formulation has 0-20% MHF, 0-30% TV, 50-100 AI-162 C
and 0-5% a hydroxy terminated dimethyl polysiloxane is cured and pyrolized to
form a black ceramic pigment.
[00341] EXAMPLE 32
[00342] Mill bases using the pigment of Examples 1, 2, 8, 10 and 12 are
made. The mill bases have a thermoplastic acrylic polyol resin, a solvent
Methyl
amyl ketone and has a pigment loading of 1.5 to 6.0 pounds per gallon. The
mill
bases exhibits Newtonian flow characteristics.
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[00343] EXAMPLE 33
[00344] Mill bases using the pigment of Examples 2-4, 5, 6, 11, and 13
are made. The mill bases have a thermoplastic acrylic polyol resin, a solvent
Methyl Amyl ketone and has a pigment loading of 1.5 to 6.0 pounds/gallon. The
mill bases exhibits Newtonian flow characteristics.
[00345] EXAMPLE 34
[00346] Mill bases using the pigment of Examples 1, 13, 14, 16 and 23
are made. The mill bases have a thermoplastic acrylic polyol resin, a solvent
methyl amyl ketone and has a pigment loading of 1.5 to 6.0 pounds per gallon.
The rnill bases exhibits Newtonian flow characteristics.
[00347] EXAMPLE 35
[00348] A mill base using any of the pigments of Examples 1 to 31 is
made. The mill base has a thermoplastic acrylic polyol resin, a solvent methyl
amyl ketone and has a pigment loading of 1.5 to 6.0 pounds/gallon.
[00349] EXAMPLE 36
[00350] Mill bases using the pigment of Examples 1, 2, 8, 10 and 12 are
made. The mill bases have a thermoplastic acrylic emulsion, a solvent water
and has a pigment loading of 1.5 to 6 pounds/gallon
[00351] EXAMPLE 37
[00352] Mill bases using the pigment of Examples 1, 2, 8, 10 and 12 are
rnade. The mill bases have a low molecular weight Bisphenol A diglycidal ether
resin, a solvent xylene, and has a pigment loading of 1.5 to 6.0 pounds/gallon
[00353] EXAMPLE 38
[00354] Mill bases using the pigment of Examples 1, 2, 8, 10 and 12 are
made. The mill bases have a modified hydroxyl ethyl cellulose, surfactant, and
water and has a pigment loading of 1.5 to 8.0 pounds/gallon
[00355] EXAMPLE 39
[00356] Mill bases using the pigment of Examples 1, 2, 8, 10 and 12 are
made. The mill bases have a silicone resin, a solvent xylene and has a pigment
loading of 1.5 to 5.0 pounds/gallon
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[00357] EXAMPLE 40
[00358] Mill bases using the pigment of Examples 1, 2, 8, 10 and 12 are
made. The mill bases have a mineral oil based resin, a solvent mineral spirits
and has a pigment loading of 1.5 to 8 pounds/gallon.
[00359] EXAMPLE 41
[00360] Mill bases using the pigment of Examples 1, 2, 8, 10 and 12 are
made. The mill bases have a mineral oil based resin, a solvent mineral spirits
and has a pigment loading of 2 pounds/gallon.
[00361] EXAMPLE 42
[00362] Black polysilocarb derived ceramic pigment is loaded at 1g/Kg
of a thermoplastic acrylic resin having the composition of S/MMNBA/HEA (where
S is styrene, MMA is methyl methacrylate, BA is n-butyl acrylate, and HEA is 2-
hydroxyethyl acrylate). The resin has a weight ratio for S:MMA:BA:HEA of
15:14:40:30.
[00363] EXAMPLE 43
[00364] Black polysilocarb derived ceramic pigment is loaded at 30g/Kg
of a thermoplastic acrylic resin having the composition of S/MMAIBNHEA (where
S is styrene, MMA is methyl methacrylate, BA is n-butyl acrylate, and HEA is 2-
hydroxyethyl acrylate). The resin has a weight ratio for S:MMA:BA:HEA of
15:14:40:30.
[00365] EXAMPLE 44
[00366] Black polysilocarb derived ceramic pigment is loaded at 100
g/Kg of a thermoplastic acrylic resin having the composition of S/MMA/BAIHEA
(where S is styrene, MMA is methyl methacrylate, BA is n-butyl acrylate, and
HEA is 2-hydroxyethyl acrylate). The resin has a weight ratio for
S:MMA:BA:HEA of 15: 14 : 40 : 30.
[00367] EXAMPLE 45
[00368] Black polysilocarb derived ceramic pigments of Example 1-6, 8
10, and 12 are loaded at 6 pounds/gallon of a water-reducible acrylic resin
having the composition of MMA/BA/HEMA/AA (where HEMA is 2-hydroxyethyl
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methacrylate, and AA is acrylic acid). The resin has a weight ratio for
MMA:BA:HEMA:AA of 60 : 22.2: 10 : 7.8.
[00369] EXAMPLE 46
[00370] Black polysilocarb derived ceramic pigment is loaded at 5
pounds/gallon of a water-reducible acrylic resin having the composition of
MMA/BAIFIEMNAA (where HEMA is 2-hydroxyethyl methacrylate, and AA is
acrylic acid). The resin has a weight ratio for MMA:BA:HEMA:AA of 60 : 22.2:
: 7.8.
[00371] EXAMPLE 47
[00372] Black polysilocarb derived ceramic pigments of Example 1-31
are loaded at 1.5 to 8 pounds/gallon of a water-reducible acrylic resin having
the
composition of MMA/BA/HEMNAA (where HEMA is 2-hydroxyethyl
methacrylate, and AA is acrylic acid). The resin has a weight ratio for
MMA:BA:HEMA:AA of 60 : 22.2: 10 : 7.8.
[00373] EXAMPLE 48
[00374] A very high temperature coating (VHTC) having a silicon based
resin and having polysilocarb ceramic pigment, size 0.25 pm, and a loading of
0.3 lbs/gal (23.97 g/L) has the following characteristics Good hiding power,
excellent heat stability, jet black masstone, excellent UV stability and
outdoor
weather resistance, excellent humidity resistance, excellent corrosion
resistance
and hardness.
[00375] EXAMPLE 49
[00376] A very high temperature coating having a silicon based resin
and having polysilocarb ceramic pigment, size 0.5 pm, and a loading of 0.5
lbsigal (59.91 g/L) has the following characteristics Good hiding power,
excellent
heat stability, jet black masstone: excellent UV stability and outdoor weather
resistance, excellent humidity resistance, excellent corrosion resistance and
hardness.
[00377] EXAMPLE 50
[00378] A very high temperature coating having a silicon based resin
and having polysilocarb ceramic pigment, size 0.1 pm, and a loading of 0.2
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lbsigal (11.83 giL) has the following characteristics Good hiding power,
excellent
heat stability, jet black masstone, excellent UV stability and outdoor weather
resistance, excellent humidity resistance; excellent corrosion resistance and
hardness.
[00379] EXAMPLE 51
[00380] The VHTCs of Examlpes 48 ¨ 50 are essentially free of heavy
metals, having less than about 1 ppm 11.1n, Cr, or other heavy metals, having
less
than about 0.1 ppm Mn, Cr, or other heavy metals, having less than about 0.01
ppm Mn, Cr, or other heavy metals, less than about 0.001 ppm heavy metals,
and having less than 0.0001 ppm heavy metals, and still more preferably being
free from any detectable heavy metals, using standard and established testing
rnethods know to the industry.
[00381] EXAMPLE 52
[00382] A high-solids acrylic enamel mill base having 25% solvent (butyl
acetate), 20 % 13.2 pm polysilocarb ceramic pigment, and 55% resin. The mill
base is then added to an acrylic isocyanate base at a ratio of 1:3. The
acrylic
enamel is sprayed onto a metal substrate and exhibits the following features
Gloss 20 degrees 95%, Gloss 60 degrees 99%, Color Development L 25, a 0, b -
0.5
[00383] EXAMPLE 53
[00384] A polysilocarb ceramic pigment of Examples 1-31 is a colorant
suitable and advantageous in multiple industrial, architectural, marine and
automotive systems. The pigment is low dusting and easily disperses into
acrylics, lacquers, alkyds, latex, polyurethane, phenolics, epoxies and
waterborne systems providing a durable, uniform coating and pleasant aesthetic
in both matte and gloss finishes. The polysilocarb ceramic pigment has low oil
absorption, which among other things, permits formulations to move to higher
solids loading with lower VOC content. The pigment is substantially free, and
preferably entirely free from heavy metals.
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[00385] EXAMPLE 54
[00386] An embodiment of the polysilocarb ceramic pigment of
Examples 1-31 is a colorant suitable and advantageous in rnultiple industrial
settings and is non-conductive, acid, alkali resistant, and thermally stable
up to
700 0C, and 800 0C and 900 0C and 1000 C.
[00387] EXAMPLE 55
[00388] An embodiment of the polysilocarb ceramic pigment of
Examples 1-31, has added to the precursors a filler that provides conductivity
to
the pyrolized pigment, is a colorant suitable and advantageous in multiple
industrial settings and is conductive, acid, alkali resistant, and thermally
stable up
to the melting temperature of the conductive filler.
[00389] EXAMPLE 56
[00390] =The polysilocarb ceramic pigment of Examples 1-6, 8, and 10-
16 added at sufficient levels to obtain the required coverage by the appliance
manufacturer and applied to the interior of a microwave oven. The interior
polysilocarb pigment coating has good gloss, hiding and is non-arching during
microwave use.
[00391] EXAMPLE 57
[00392] A polysilocarb ceramic pigrnent has added to the precursor
formulations carbon black. The pyrolized filled polysilocarb pigment has the
superior wettability and dispersion performance of the net polysilocarb
pigments,
while having the cheaper carbon black material. The carbon black filler is a
cheaper extender for the polysilocarb material.
[00393] EXAMPLE 57a
[00394] The pigments of Example 57 have 20% carbon black filler.
[00395] EXArv1PLE 57b
[00396] =The pigments of Example 57 have 30% carbon black filler.
[003971 EXAMPLE 57c
[00398] The pigments of Example 57 have 40% carbon black filler.
[00399] EXAMPLE 57d
[00400] The pigments of Example 57 have 50% carbon black filler.
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[00401] EXAMPLE 57e
[00402] The pigments of Example 57 have 60% carbon black filler.
[00403] EXAMPLE 58
[00404] A polysilocarb formulation is cured to into the volumetric shape
of a bead. The end cured polysilocarb derived beads are, for example, added to
paints, glues, plastics, and building materials, such as dry wall, sheet rock,
gypsum board, MDF board, plywood, plastics and particleboard. The end cured
polysilocarb derived beads, as additives, can provide, among other things,
binding (e.g., serve as a binder), water resistivity, fire resistance, fire
retardation,
=fire protection and strength; as well as, abrasion resistance, wear
resistance,
corrosion resistance and UV resistance, if located at or near the surface of
the
shape.
[00405] EXAMPLE 58a
[00406] In addition to a beads of Example 58, the polysilocarb additives
can be in the form of a fine powder, fines, a power or other dispersible
forms.
The dispersible form can be obtained by grinding or crushing larger cured
structures. They also may be obtained through the curing process if done under
conditions that cause the structure to fracture, crack or break during curing.
These dispersible forms may also be obtained by other processing techniques,
for example, spray curing or drying.
[00407] EXAMPLE 59
[004081 A polysilocarb formulation is cured to into the volumetric shape
of a bead. The beads are then pyrolized to for a polysilocarb derived ceramic
bead. The polysilocarb derived ceramic beads are added, for example, to
paints,
glues, plastics, and building materials, such as dry wall, sheet rock, gypsum
board. MDF board, plywood, plastics and particleboard. The ceramic
polysilocarb beads, as additives, can provide, among other things, fire
resistance, =fire retardation, fire protection and strength.
[00409] In addition to a bead the polysilocarb additives can be in the
form of a fine power, fines, a power or other dispersible forms. The
dispersible
form can be obtained by grinding or crushing larger cured or pyrolized
structures.
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They also may be obtained through the curing or pyrolysis process if done
under
conditions that cause the structure to fracture, crack or break during curing
or
pyrolysis.
[00410] EXAMPLE 60
[00411] A polysilocarb formulation is pyrolized in the form of a
volumetric structure. The ceramic polysilocarb derived volumetric structure
exhibits reflective and refractive optical properties, such as opalescence,
shine,
twinkle, and sparkle. These optical properties are present when the structure
is
black in color, (e.g., no colorant has been added to the formulation); or if
the
structure is colored (e.g., any color other than black, e.g., white, yellow,
red, etc.).
[00412] EXAMPLE 61
[00413] The volumetric structure of Example 60 is a work surface, such
as a table top, a bench top, an insert, or a kitchen counter top, to name a
few.
[00414] EXAMPLE 62
[00415] The volumetric structure of Example 61 has other colorings or
additive to provide simulated granite like appearance.
[00416] EXAMPLE 63
[00417] The volumetric structures of Example 60 are small beads that
are black and exhibit a twinkle, opalescence or shin. These beads are
incorporated into a paint formulation. The patent formulation is for example
applied to automobiles or appliances. It provides a flat or matte finish,
which is
for example popular on newer BMWs and Mercedes, but adds to that matte finish
an inner sparkle or luster. Thus, the polysiloxane based paint formulation
provides a sparkle matte finish to an automobile, appliance or other article.
[00418] EXAMPLE 64
[00419] Pyrolized polysilocarb beads having a size of from about 100 to
about 1,000 microns are added to a paint formulation at a loading of from
about
1% to about 40%.
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[00420] EXAMPLE 65
[0042'1] The paint of Example 64 in which the paint formulation, is an
automotive paint, and is colored blue and the beads are the same blue color as
the paint, and have size of 350 microns (+I- 5%) and a loading of about 25%.
[00422] EXAMPLE 66
[00423] The paint of Example 64 in which the beads are not colored,
i.e., they are black, and have a size ranging from about 300-500 microns, and
the
paint is a black, although not necessarily the same black as the beads.
[00424] EXAMPLE 67
[00425] A latex paint formulation having pyrolized polysilocarb power
added into the formulation, the power has a size range of about 0.5 ¨ 100
microns, and the powder has a loading of about 15%.
[00426] E XAMP LE 68
[00427] The paint formulation of Example 66 is an enamel.
[00428] EXAMPLE 69
[00429] The polysilocarb ceramic pigments can be made from the
pyrolysis of any polysilocarb batches that are capable of being pyrolized. The
polysilocarb pigment material can be provided, for example, as beads, powder,
=flakes, fines, or other forms that are capable of being dispersed or
suspended in
the paint formulation (e.g., platelets, spheres, crescents, angular, blocky,
irregular or amorphous shapes). Beads can have a size of from about 100 to
about 1,000 microns in diameter. Powders can have a particle size range of
from
about 0.5 to about 100 microns in diameter. Any subset range within these
ranges can create the desired effect or color. Larger and smaller sizes may
also
provide the desired effects in other formulations. For example: 300 ¨ 500
micron range beads; 350 (41- 5%) micron beads; 5 ¨ 15 micron range powder.
Particle size ranges for a particular polysilocarb ceramic pigment preferably
range as tight as +I- 10% and more preferably +I- 5%. The range may also be
broader in certain applications, e.g., 100 ¨ 1000 for beads, and e.g., 0.5 ¨
100 for
powders. The density and hardness of the polysilocarb ceramic pigment can be
varied, controlled and predetermined by the precursor formulations used, as
well
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as the curing and pyrolizing conditions. The polysilocarb ceramic pigments can
provided enhanced corrosion resistance, scratch resistance and color (UV)
stability to paint formulations. Optical properties or effects of the
polysilocarb
ceramic pigment can, among other ways, be controlled by the use of different
gases and gas mixtures, as well as other curing and pyrolysis conditions. The
polysilocarb ceramic pigment loading can be used anywhere from a 1TO to a 40%
in order to achieve the desired effect. Further, the use of the polysilocarb
ceramic pigments can provide enhanced flame retardant benefits. The
polysilocarb ceramic pigments have a further advantage of being low dusting,
and easily mixed into any type of paint formulations, e.g., latex, enamel,
polyurethanes, automotive OEM and refinish, alkyd, waterborne, acrylic and
polyol coatings formulations. The polysilocarb cerarnic pigments can also be
used as a fine colorant in inks and graphic arts formulations.
[00430] EXAMPLE 70a
[00431] A ceramic ink comprising 10-30% polysilocarb black ceramic
pigment, 10-60% zinc or bismuth submicron glass frit, 10-20% Sucrose acetate
isobutyrate, 4-15% hydrocarbon resin, 5-15% ethylene glycol.
[00432] EXAMPLE 70b
[00433] A packaging ink comprising 2-30% polysilocarb black ceramic
pigment, 5-15% nitrocellulose resin, 25-35% ethanol solvent, 10-20% ethyl
acetate solvent, 1-2% citrate plasticizer, 1% polyethylene wax solution, 5-10%
additives.
[00434] EXAMPLE 71a
[00435] A plastic comprising of 75-80% Polypropylene copolymer, 1-6%
polysilocarb black ceramic pigment, 15-20% talc
[00436] EXAMPLE 71b
[00437] A plastic comprising of 94-98% HDPE plastic and 2-6%
polysilocarb black ceramic pigment
[00438] EXAMPLE 71c
[00439] A plastic comprising 94-98% polycarbonate and 2-6%
polysilocarb black ceramic pigment
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[00440] EXAMPLE 71d
[00441] A plastic comprising 94-99% polyamide and 1-6% polysilocarb
black pigment
[00442] EXAMPLE 71e
[00443] A rubber comprising of 55-65% EPDM elastomer, 10-40%
polysilocarb black ceramic pigment, 5-10% paraffinic extender oil, 3% zinc
oxide, 0.5% stearic acid, 0.9% sulfur, 0.9% tetramethyl thiuram monosulphide,
0.5% antioxidant, 0.3% mercaptobenzothiazole.
[00444] EXAMPLE 71f
[00445] A rubber based on 60-70% Fluoroelastomer, 10-20%
polysilocarb black ceramic pigment, 1-2% dimethyl-di (t-butyl peroxy)hexane, 1-
1.5% triallyl iscocyanurate, 1-1.5% Zinc oxide.
[00446] EXAMPLE 71g
[00447] A plastic comprising 75-80% ABS plastic, 2-6% polysilocarb
black ceramic pigment, 15-20% talc.
[00448] EXAMPLE 71h
[00449] A phenolic molding compound comprising 50% phenolic resin,
35-45% talc, 5-15% polysilocarb black ceramic pigment.
[00450] EXAMPLE 711
[00451] A Thermoplastic olefin compound comprising 60%
polypropylene copolymer, 10-15% polyolefin elastomer, 2-6% polysilocarb black
ceramic pigment, 10% talc, 0.2% antioxidant.
[00452] EXAMPLE 71j
[00453] A siloxane compound comprising 75-95% siloxane, 1-18%
fumed silica, and 1-5% polysilocarb black ceramic pigment.
[00454] EXAMPLE 71k
[00455] A siloxane compound comprising 50-80% siloxane, 1-20%
fumed silica, 1-20% talc or other white filler, and 0.5-5% polysilocarb black
pigment.
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[00456] EXAMPLE 72
[00457] A lawnmower piston assembly made from A phenolic molding
compound comprising 50% phenolic resin, 35-45% talc, 5-15% polysilocarb black
ceramic pigment.
[00458] EXAMPLE 73
[00459] A car dashboard made from a plastic comprising of 75-80%
Polypropylene copolymer, 1-6% polysilocarb black ceramic pigment, 15-20%
talc.
[00460] EXAMPLE 74
[00461] A car bumper made from a thermoplastic olefin compound
having 60% polypropylene copolymer, 10-15% polyolefin elastomer, 2-6%
polysilocarb black ceramic pigment, 10% talc, 0.2% antioxidant
[00462] EXAMPLE 75
[00463] A high temperature stable pump housing coating having 30-35%
silicone resin, 8-30% micronized mica filler, 1-15% polysilocarb black ceramic
pigment, 35-50% xylene solvent.
[00464] EXAMPLE 76
[00465] An adhesive comprising 7-10% chlorinated rubber, 5-7%
polysilocarb ceramic black pigment, 4-5% phenol formaldehyde resin, 1-2%
fumed silica, 1-2% zinc oxide, 50-6-% methyl ethyl ketone solvent, 5-10%
xylene
solvent.
[00466] The primary focus of the specification is on black pigment and
additives. lt should be understood, however, that other colors of polymer
derived
ceramic pigments and preferably polysilocarb derived ceramic pigments can be
utilized. These embodiments can have colorants, or fillers that impart
different
colors to the ceramic pigment. Such colorants can be for example glazes or
other fillers or additives that maintain their color properties under
pyrolysis
conditions.
[00467] it is noted that there is no requirement to provide or address the
theory underlying the novel and groundbreaking processes, materials,
performance or other beneficial features and properties that are the subject
of, or
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associated with, embodiments of the present inventions. Nevertheless, various
theories are provided in this specification to further advance the art in this
area.
These theories put forth in this specification, and unless expressly stated
otherwise, in no way limit, restrict or narrow the scope of protection to be
afforded the claimed inventions. These theories many not be required or
practiced to utilize the present inventions. It is further understood that the
present inventions may lead to new, and heretofore unknown theories to explain
the function-features of embodiments of the methods, articles, materials,
devices
and system of the present inventions; and such later developed theories shall
not
limit the scope of protection afforded the present inventions.
[00468] The various embodiments of formulations, batches, materials,
compositions, devices, systems, apparatus, operations activities and methods
set forth in this specification may be used in the various fields where
pigments
and additives find applicability, as well as, in other fields, where pigments,
additives and both, have been unable to perform in a viable manner (either
cost,
performance or both). Additionally, these various embodiments set forth in
this
specification may be used with each other in different and various
combinations.
Thus, for example, the configurations provided in the various embodiments of
this specification may be used with each other; and the scope of protection
afforded the present inventions should not be limited to a particular
embodiment,
configuration or arrangement that is set forth in a particular embodiment,
example, or in an embodiment in a particular Figure.
[00469] The invention may be embodied in other forms than those
specifically disclosed herein without departing from its spirit or essential
characteristics. The described embodiments are to be considered in all
respects
only as illustrative and not restrictive.
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