Note: Descriptions are shown in the official language in which they were submitted.
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FABRICATION FLUIDS
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit under 35 U.S.C. 119(e) of U.S.
Provisional
Patent Application No. 62/570,617 filed October 10, 2017, which application is
incorporated
herein by reference in its entirety.
FIELD OF THE INVENTION
[0002] The present invention relates generally to compositions for
fabricating
materials where heat is generated (e.g., the cutting of metal or stone),
concentrates
thereof, and methods of making and using the compositions.
BACKGROUND
[0003] During the process of fabricating (e.g., cutting) solid materials
such as stone
or metal (e.g., drilling a hole in metal or cutting a piece of metal into
smaller pieces), fluids
are typically utilized to lubricate the cutting or shaping device in order to
lessen wear and
tear on the device involved in fabrication. The fluid, e.g., metal cutting
fluid, is applied at
the location where the material, e.g., metal, is being cut by the cutting
device, e.g., a blade.
The fluid provides various functions, including helping to dissipate the heat
that is generated
during the fabricating process, e.g., the cutting action. Absent dissipation,
the heat can
cause warpage and/or other damage to one or both of the cutting device and the
material,
e.g., metal, that is being cut. Other advantage of fabrication fluids include
enhancing tool
life, improving surface finish, and flushing away chips from the cutting zone.
Practically all
cutting fluids presently in use fall into one of four categories: 1) straight
oils, 2) soluble oils,
3) sennisynthetic fluids, and 4) synthetic fluids.
[0004] Straight oils are non-emulsifiable and are used in machining
operations in an
undiluted form. They are composed of a base mineral or petroleum oil and often
contains
polar lubricants such as fats, vegetable oils and esters as well as extreme
pressure additives
such as chlorine, sulphur and phosphorus. Straight oils provide the best
lubrication and the
poorest cooling characteristics among cutting fluids.
[0005] Soluble oil fluids form an emulsion when mixed with water. The
concentrate
consists of a base mineral oil and emulsifiers to help produce a stable
emulsion. They are
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used in a diluted form (usual concentration = 3 to 10%) and provide good
lubrication and
heat transfer performance. They are widely used in industry and are the least
expensive
among all cutting fluids.
[0006] Semi-synthetic fluids are essentially combination of synthetic and
soluble oil
fluids and have characteristics common to both types. The cost and heat
transfer
performance of semi-synthetic fluids lie between those of synthetic and
soluble oil fluids.
[0007] Synthetic fluids contain no petroleum or mineral oil base and
instead are
formulated from alkaline inorganic and organic compounds along with additives
for
corrosion inhibition. They are generally used in a diluted form (usual
concentration is 3 to
10%). Synthetic fluids often provide the best cooling performance among all
cutting fluids
and the poorest lubricating characteristics among cutting fluids.
[0008] There is a need for improved fabrication fluids, e.g., improved
metal cutting
fluids. The present disclosure is directed to fulfilling this need.
SUMMARY
[0009] Briefly stated, the present disclosure provides fabricating fluid
concentrates,
e.g., metal cutting, fabricating fluid compositions, e.g., metal cutting
fluids, which are
diluted forms of the concentrates, methods of making the concentrates and the
compositions, and methods of using the concentrates and the compositions in
material
fabrication processes, e.g., in order to cut metal, stone, plastic, etc.
[0010] In one embodiment, the present disclosure provides a composition
comprising water and non-volatile components (also referred to herein as
solids, even
though some of the non-volatile components may be, in a pure state, liquids).
The solids
include one or more surfactants, where exemplary surfactants are anionic
surfactants and
annphoteric surfactants. For example, the solids may include a first
surfactant selected from
annphoteric surfactants, a second surfactant selected from anionic
surfactants, and a third
surfactant selected from an annphoteric and an anionic surfactant, the third
surfactant being
different from the first and second surfactants. The solids also include one
or more agents
selected from anti-rust and anti-corrosion agents, which will be referred to
herein
collectively as anti-rust agents.
[0011] Optional non-volatile components present in the composition include
one or
more of a thickener, also referred to as a thickening agent, which is suitable
for increasing
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the viscosity or body of the composition; an inorganic salt which is water
soluble at the
concentration utilized in the composition; an organic solvent which is
miscible with water at
the concentration utilized in the composition; a de-foaming agent, which term
includes anti-
foaming agents, which is used in an amount effective to mitigate foaming of
the
composition during use; and a coloring agent, also referred to herein as a
colorant, that
imparts coloration to the composition.
[0012] As mentioned previously, the compositions of the present disclosure
include
water in addition to the non-aqueous ingredients which are non-volatile. In
one
embodiment, the composition contains relatively little water, so that the
composition has a
high concentration of non-volatile components. Such a composition may be
referred to
herein as a concentrate (or concentrated) composition, or a metal cutting
concentrate. The
concentrate may be provided to facilities that cut metal or otherwise
fabricate materials,
where the operators in those facilities may dilute the concentrate with an
amount of water
that provides a fluid having suitable properties for the particular
fabrication situation, e.g.,
cutting metal or other material. For example, cutting bronze may benefit from
a different
dilution of the concentrate than is utilized for cutting a different metal,
such as stainless
steel. In one embodiment, the concentrate is 5-50% by weight of water. In
another
embodiment, the concentrated composition is 40-50% by weight water, and 50-60%
by
weight of non-aqueous components, including a surfactant, an anti-rust agent,
and at least
one of a thickening agent suitable for an aqueous composition, and an
inorganic salt. In
another embodiment, the present disclosure provides metal cutting fluids that
are ready-to-
use in a metal cutting operation. In such ready-to-use compositions, the water
content will
typically be in the range of 75-99% by weight, or 75.0-99.9% by weight, or 90-
99% by weight
water, or 90.0-99.9% by weight water, or 97.0-99.9 wt% water, or 98.0-99.9 wt%
water, or
99.0-99.9 wt% water.
[0013] In one embodiment, the composition comprises water, a first
surfactant
selected from annphoteric surfactants, a second surfactant selected from
anionic
surfactants, a third surfactant selected from an annphoteric and an anionic
surfactant, the
third surfactant being different from the first and second surfactants, an
inorganic salt, an
organic solvent, a thickening agent, an anti-rust agent, and a de-foaming
agent.
[0014] The following numbered embodiments are additional exemplary
embodiments of the compositions of the present disclosure:
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1) A fabricating fluid composition comprising water, a first surfactant, a
thickening
agent, and an anti-rust agent.
2) A fabricating fluid composition comprising water, a first surfactant, an
inorganic salt,
and an anti-rust agent.
3) A composition of embodiments 1 or 2 wherein the first surfactant is an
anionic
surfactant.
4) A composition of embodiment 3 wherein the first surfactant is an anionic
surfactant
comprising a sulfonate group or comprising a sulfate group.
5) A composition embodiment 3 wherein the first surfactant is sodium
dodecylbenzene
sulfonate.
6) A composition of embodiment 3 wherein the first surfactant is sodium
laureth
sulfate.
7) A composition of embodiments 1 or 2 wherein the first surfactant is an
annphoteric
surfactant.
8) A composition of embodiment 7 wherein the annphoteric surfactant comprises
a
betaine group.
9) A composition embodiment 7 wherein the first surfactant is cocannidopropyl
betaine.
10) A composition of embodiments 1 or 2 comprising two surfactants, each of
the two
surfactants being an anionic surfactant.
11)A composition of embodiment 10 wherein the two surfactants are a sulfate-
containing surfactant and a sulfonate-containing surfactant.
12) A composition of embodiment 10 wherein the two surfactants are sodium
laureth
sulfate and sodium dodecylbenzene sulfonate.
13)A composition of embodiments 1 or 2 comprising two surfactants, one being
an
anionic surfactant and the other being an annphoteric surfactant.
14) A composition of embodiment 13 wherein the two surfactants are a sulfate-
containing anionic surfactant and a betaine-containing annphoteric surfactant.
15) A composition of embodiment 14 wherein the sulfate-containing anionic
surfactant
is sodium laureth sulfate and the betaine-containing annphoteric surfactant is
cocannidopropyl betaine.
16) A composition of embodiment 13 wherein the two surfactants are a sulfonate-
containing anionic surfactant and a betaine-containing annphoteric surfactant.
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17) A composition of embodiment 16 wherein the sulfonate-containing anionic
surfactant is sodium dodecylbenzene sulfonate and the betaine-containing
annphoteric surfactant is cocannidopropyl betaine.
18) A composition of embodiments 1 or 2 comprising three surfactants, two of
the three
surfactants being non-identical anionic surfactants and one of the three
surfactants
being an annphoteric surfactant.
19)A composition of embodiment 18 wherein the three surfactants are a sulfate-
containing surfactant, a sulfonate-containing surfactant, and a betaine-
containing
surfactant.
20) A composition of embodiment 19 wherein the three surfactants are sodium
dodecylbenzene sulfonate, sodium laureth sulfate, and cocannidopropyl betaine.
21) A composition of embodiments 1 or 2 wherein the anti-rust agent is sodium
nitrite.
22) A composition of embodiment 20 wherein the anti-rust agent is sodium
nitrite.
23) A composition of embodiments 1 or 2 comprising a thickening agent which is
a
cellulosic thickening agent.
24) A composition of embodiment 23 wherein the cellulosic thickening agent is
hydroxyl
ethyl cellulose.
25)A composition of embodiment 20 comprising a thickening agent which is a
cellulosic
thickening agent.
26) A composition of embodiment 25 wherein the cellulosic thickening agent is
hydroxyl
ethyl cellulose.
27) A composition of embodiments 1 or 2 comprising an inorganic salt which is
calcium
chloride.
28)A composition of embodiment 20 comprising an inorganic salt.
29)A composition of embodiment 28 wherein the inorganic salt is calcium
chloride
30) A composition of embodiments 1 or 2 comprising a defoanning agent.
31) A composition of embodiment 30 wherein the defoanning agent is a silicone
polymer.
32)A composition of embodiment 20 comprising a defoanning agent.
33)A composition of embodiment 32 wherein the defoanning agent is a silicone
polymer.
34) A composition of embodiment 20 comprising one or more of a cellulosic
thickening
agent, an inorganic salt, and a defoanning agent.
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35) A composition of embodiment 20 comprising a cellulosic thickening agent,
an
inorganic salt, and a defoanning agent.
36)A composition of embodiment 1 comprising water, sodium dodecylbenzene
sulfonate, sodium laureth sulfate, cocannidopropyl betaine, a thickening agent
such
as a cellulosic thickening agent, and an anti-rust agent.
37) A composition of embodiment 2 comprising water, sodium dodecylbenzene
sulfonate, sodium laureth sulfate, cocannidopropyl betaine, an inorganic salt
such as
calcium chloride, and an anti-rust agent.
The composition may be used for metal fabrication, and may be referred to
alternatively as
a metal fabrication composition, or a metal working composition, or a metal
cooling
composition, or a metal cutting composition. The composition may also be used
for
fabricating parts made from stone, plastic or glass, or other solid material
that may be
fabricated by tooling in a heat-generating process.
[0015] In one embodiment, the present disclosure provides a method of
making a
concentrated composition, e.g., a metal cutting fluid concentrate, by
combining the
ingredients as discussed herein. Optionally, the ingredients may be combined
in a batch
method. In this embodiment, a composition, e.g., a metal cutting fluid
concentrated
composition is prepared by a method comprising adding to a container, hot
water, one or
more surfactants such as an anionic surfactant, an annphoteric surfactant, and
optionally a
third surfactant selected from an anionic surfactant and an annphoteric
surfactant, where
the third surfactant is different from the already added anionic and
annphoteric surfactants.
Additional optional ingredients include an inorganic salt, an organic solvent,
a thickening
agent, an anti-rust or anti-corrosion agent, a coloring agent, and a de-
foaming agent;
wherein after an addition of a component to the container, a resulting mixture
is stirred
until it reaches a completely or nearly homogeneous state, for example, for
about 30
minutes with minimal foam generation before addition of a next component. In
one
embodiment, an inorganic salt, an organic solvent, a thickening agent, an anti-
rust or anti-
corrosion agent, and a de-foaming agent are added to the container.
[0016] For example, the present invention provides a process for making a
fabricating fluid composition, such as a composition suitable for metal
cutting, comprising:
a) heating water to about 70-80 C to provide hot water;
b) adding an anionic surfactant to the hot water;
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c) adding an annphoteric surfactant to the mixture of step b);
d) adding hot water to the mixture of step c);
e) optionally adding a third surfactant to the mixture of step d), the third
surfactant selected from an anionic surfactant and an annphoteric surfactant,
the third surfactant being different from the anionic surfactant and the
annphoteric surfactant already present in the mixture;
f) adding inorganic salt to the mixture of step e);
g) cooling the mixture of step f) to ambient temperature; and
h) adding thickening agent to the mixture of step f);
wherein after an addition of a component, a resulting mixture is stirred for a
time effective
to achieve a homogeneous or nearly homogeneous mixture, typically about 30
minutes,
with minimal foam generation before addition of a next component. Exemplary
optional
ingredients that may be used in the process include an inorganic salt, an
organic solvent, a
thickening agent, an anti-rust or anti-corrosion agent, a coloring agent, and
a de-foaming
agent. In one embodiment, an inorganic salt, an organic solvent, a thickening
agent, an anti-
rust or anti-corrosion agent, and a de-foaming agent are added to the mixture.
[0017] In one embodiment, the present disclosure provides a method of
making a
composition, e.g., a metal cutting fluid concentrate, by a continuous method.
In this
embodiment, a composition, e.g., a metal cutting fluid concentrate is prepared
by providing
a continuous reactor, charging water to the continuous reactor, adding to the
water in the
continuous reactor a) an anionic surfactant, b) an annphoteric surfactant, and
optionally c) a
third surfactant selected from an anionic surfactant and a cationic
surfactant, the third
surfactant being different from the anionic and annphoteric surfactant already
charged to
the reactor; and mixing components a), b) and optionally c) to provide a
homogeneous
mixture. Optionally, the water in the continuous reactor is maintained at a
temperature in
excess of 50 C. Optionally, additional ingredients are added to the
formulation, such as
organic solvent, inorganic salt, a thickening agent, an anti-rust or anti-
corrosion agent, a
coloring agent, and a de-foaming agent. In one embodiment, each of an organic
solvent,
inorganic salt, a thickening agent, an anti-rust or anti-corrosion agent, and
a de-foaming
agent are added to the mixture. Optionally, a mixer selected from an inline
mixer and a
static mixer is present in the continuous reactor.
[0018] In one embodiment, the present disclosure provides a method for
forming a
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fabrication fluid from a precursor concentrate, e.g., a metal cutting fluid
composition from
the metal cutting fluid concentrate. According to this embodiment, water and
concentrate
are combined in a suitable water:concentrate ratio, and the two components are
mixed
together to form the metal cutting fluid composition. In various optional
embodiments, the
concentrate is diluted by a factor of 5x, or 10x, or 15x. To be clear, a
dilution of 5x refers to
combining 100 parts of concentrate with 500 parts of water, where parts may be
in either
liquid or solid measurement forms, e.g., grams, kilograms, liters.
[0019] In one embodiment, the present disclosure provides a method for
cutting
metal, where the method comprises applying an effective amount of the metal
cutting fluid
composition of the present disclosure onto metal being cut. The metal cutting
fluids of the
present disclosure may be applied to metal during the process in which the
metal is being
cut. One exemplary process for applying the compositions of the present
disclosure is flood
application, wherein a flood of cutting fluid is applied onto the workpiece
being cut.
Another exemplary process for applying the compositions of the present
disclosure is jet
application, wherein a jet of cutting fluid is applied onto the workpiece
directed at the
cutting zone. Another exemplary process for applying the composition of the
present
disclosure is mist application, wherein cutting fluid is atomized by a jet of
air and the mist is
directed at the cutting zone of the workpiece.
[0020] The following numbered embodiments are additional exemplary
embodiments of the methods of machining meal of the present disclosure, with
reference
to the foregoing composition embodiments:
38) A method of machining a material selected from metal, stone, glass and
plastic,
comprising applying a composition comprising a composition of any of
embodiment
1-37 to a piece of material being machined, in an amount and time that are
effective
to dissipate heat from the material being machined.
39) The method of embodiment 38 wherein the material being machined is metal
selected from aluminum alloy, brass, casting iron, bronze, low-carbon steel,
stainless
steel, alloy steel, and titanium alloy.
40) The method of embodiment 38 whrein the material being machined is stone.
41) The method of embodiment 38 wherein the material being machined is glass.
42) The method of embodiment 38 wherein the material being machined is
plastic.
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43) The method of embodiment 38 wherein the piece of material being machined
is
being subjected to a process selected from broaching, tapping, hobbing,
cutting,
drilling, milling, turning, sawing, honing, and grinding.
[0021] The details of one or more embodiments are set forth in the
description
below. The features illustrated or described in connection with one exemplary
embodiment
may be combined with the features of other embodiments. Other features,
objects and
advantages will be apparent from the description and the claims. In addition,
the
disclosures of all patents and patent applications referenced herein are
incorporated by
reference in their entirety.
DETAILED DESCRIPTION OF THE INVENTION
[0022] In one aspect, the present disclosure provides a materials
fabrication
composition, such as a metal cutting fluid composition, in both concentrated
and diluted
(ready to use) form. In another aspect, the present disclosure provides a
method of forming
a fabrication fluid in a concentrated form and then diluting that concentrated
composition
to a dilute form. In another aspect, the present disclosure provides a method
of using the
compositions in a method wherein a material is fabricated, such as a metal
cutting
operation. Thus, in another aspect, the present disclosure provides a method
of forming
fabricating fluid compositions, e.g., a metal cutting fluid composition, in a
concentrated
form and then diluting that concentrated composition to a dilute form. In
another aspect,
the present disclosure provides a method of using the compositions in a
material cutting or
shaping process, e.g., a metal cutting operation. When the present disclosure
refers to a
metal cutting fluid or a metal cooling fluid, it should be understood that
these fluid
composition may be used generally in material fabrication, e.g., glass
fabrication, stone
fabrication, and plastic fabrication, and are not limited in use to metal
fabrication. Thus, the
metal cutting or metal cooling compositions may be used for metal cutting or
fabrication,
but may also be used for the fabrication of other materials such as stone or
plastic or glass
where fabrication generates heat that is desirably dissipated during the
fabrication process.
[0023] In one embodiment, the present disclosure provides a composition
comprising water and non-volatile components (also referred to herein as
solids, even
though some of the non-volatile components may be, in a pure state, liquids).
The solids
include one or more surfactants, where exemplary surfactants are anionic
surfactants and
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annphoteric surfactants. For example, the solids may include a first
surfactant selected from
annphoteric surfactants, a second surfactant selected from anionic
surfactants, and a third
surfactant selected from an annphoteric and an anionic surfactant, the third
surfactant being
different from the first and second surfactants. The solids also include one
or more agents
selected from anti-rust and anti-corrosion agents, which will be referred to
herein
collectively as anti-rust agents.
[0024] Optional non-volatile components present in the composition include
one or
more of a thickener, also referred to as a thickening agent, which is suitable
for increasing
the viscosity or body of the composition; an inorganic salt which is water
soluble at the
concentration utilized in the composition; an organic solvent which is
miscible with water at
the concentration utilized in the composition and has a boiling point above
the boiling point
of water, e.g., a boiling point of at least 125 C, or at least 150 C, or at
least 170 C; a de-
foaming agent, which term includes anti-foaming agents, which is used in an
amount
effective to mitigate foaming of the composition during use; and a coloring
agent, also
referred to herein as a colorant, that imparts coloration to the composition.
[0025] In one aspect, the fluid composition contains no carbon-halogen
bonds, and
thus is more environmentally friendly than alternative fluid compositions that
contain one
or more components having such bonds.
[0026] The fluid of the present disclosure provides the following effects
during
materials fabrication, and particularly during metal machining. Primary
effects include
lubricating the cutting process primarily at low cutting speeds, cooling the
workpiece
primarily at high cutting speeds, and flushing chips away from the cutting
zone. Secondary
effects include corrosion protection of the machined surface, and enabling
part handling by
cooling the hot surface. Process effects of using cutting fluids of the
present disclosure in
machining include: longer tool life, reduced thermal deformation of workpiece,
better
surface finish, and ease of chip and swarf handling.
[0027] The compositions of the present disclosure provide good heat
transfer
performance, good lubrication performance, good chip flushing performance,
good
generation of fluid mist, good fluid carry off in chips, and good corrosion
inhibition. The
compositions in emulsion form exhibit good fluid stability.
[0028] It is noted that, as used in this specification and the intended
claims, the
singular form "a," "an," and "the" include plural referents unless the context
clearly dictates
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otherwise. Thus, for example, reference to "an annphoteric surfactant"
includes a single
annphoteric surfactant as well as one or more of the same or different
annphoteric
surfactants.
Components
[0029] The compositions of the present disclosure include at least one
surfactant. In
one embodiment, the compositions contain an annphoteric surfactant. In another
embodiment, the compositions contain an anionic surfactant. In one embodiment
the
compositions contain two different annphoteric surfactants, optionally in
combination with
an anionic surfactant. In one embodiment the compositions contain two
different anionic
surfactants, optionally in combination with an annphoteric surfactant.
Annphoteric Surfactant
[0030] In one embodiment, the compositions of the present disclosure
include at
least one, and optionally include more than one, annphoteric surfactant. As
used herein, an
annphoteric surfactant is a molecule that contains both a positively charged
atom and a
negatively charged atom. Surfactant molecules may include polymeric
components, and
may also include a counterion(s) such as sodium and ammonium, however the
counterion is
not considered to be one of the positively or negatively charged atoms that
qualifies the
molecule as being an annphoteric surfactant.
[0031] The positively charged atom may be, for example, a nitrogen atom
which
provides, e.g., an ammonium group, or may be a sulfur atom which provides,
e.g., a
sulfoniunn group. The presence of a positive charge on a particular atom may
be a function
of the pH to which the molecule is exposed. In other words, the annphoteric
surfactant of
the present disclosure need not have a positively charged atom and a
negatively charged
atom at every pH of the surrounding solution, but may have these charged atoms
only
within a pH range. For example, when the molecule has a nitrogen atom that
bears a
positive charge, that charge may only be present when the pH of the
surrounding solution
(an aqueous solution) is sufficiently low that the nitrogen atom becomes
protonated. This
occurs, for example, when the nitrogen atom is part of a primary, secondary or
tertiary
amine. Alternatively, the nitrogen atom may be part of a quaternary ammonium
ion which
maintains its positive charge regardless of the pH of the surrounding
solution.
[0032] The negatively charged atom may be, for example, an oxygen atom
which
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may be part of a recognized functional group such as a carboxylate, sulfate,
sulfonate, or
phosphate group. As with the positive charge, the presence of a negative
charge on a
particular atom may be a function of the pH to which the molecule is exposed.
In other
words, the annphoteric surfactant of the present disclosure need not have a
negatively
charged atom and a positively charged atom at every pH of the surrounding
solution, but
may have these charged atoms only within a pH range. For example, when the
molecule
has an oxygen atom that bears a negative charge, that charge may only be
present when the
pH of the surrounding solution (an aqueous solution) is sufficiently high that
the oxygen
atom becomes deprotonated. This may occur, for example, when the oxygen atom
is part
of, e.g., a carboxylic acid group, where only the carboxylate form of the
carboxylic acid
group has a negatively charged oxygen atom while the corresponding carboxylic
acid form
has a neutral oxygen atom.
[0033] In summary, the annphoteric surfactant need not have both a
positively
charged atom and a negatively charged atom throughout the entire possible pH
range of the
surrounding solution, but will have these two charged atoms at some pH range,
which is
sometimes referred to in the art as the isoelectric pH range. When the
annphoteric
surfactant has both a positively and negatively charged atom, the surfactant
may be said to
be in its zwitterionic form. When a chemical structure of an annphoteric
surfactant is
provided herein, the term X may be used to refer to the counterion which may
be
associated with the positively or negatively charged atom within the
isoelectric pH range.
Exemplary cationic counterions are sodium and ammonium. Exemplary anionic
counterions
are chloride and phosphate. Noteworthy is that either the positive or negative
charge may
be delocalized over a plurality of atoms. For example, when the negative
charge is on an
oxygen atom, and that oxygen atom is part of a carboxylate group, the negative
charge is
delocalized over both of the oxygen atoms of the carboxylate group.
[0034] In addition, and as with all surfactants, the annphoteric
surfactant will have
both a lipophilic (a.k.a., hydrophobic) region and lipophobic (a.k.a.,
hydrophilic) region. The
lipophilic region may be referred to as the fatty region. The fatty region may
be composed
of the hydrocarbon portion which is present in a naturally occurring fatty
acid, fatty alcohol,
fatty amine or the like, however it may alternatively be formed synthetically,
i.e., it may be a
synthetically produced fragment such as polyethylene, polypropylene,
poly(propylene
oxide), etc. As used herein, and when describing a class of annphoteric
surfactant, the term
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"R" will be used to refer to a fatty region of the molecule. In various
embodiments, R
designates a medium or long chain fatty group, such as: a C6-C24 fragment,
i.e., a molecular
fragment having at least 6 and up to 24 carbon atoms, and optionally any other
atoms, e.g.,
hydrogen, halogen (e.g., F, Cl, Br), nitrogen, and oxygen; C6-C24 hydrocarbon,
i.e., a
molecular fragment having 6-24 carbon atoms and sufficient hydrogen atoms to
complete
the valencies of the carbon atoms; C8-C22 fragment; C8-C22 hydrocarbon; Cio-
C20 fragment;
Cio-C20 hydrocarbon; Cu-C18 fragment; and Cu-C18 hydrocarbon. In various
embodiments, R
has at least 6, or at least 8, or at least 10, or at least 12, or at least 14,
or at least 16 carbon
atoms. In various embodiments, R has no more than 30, or no more than 26, or
no more
than 24, or not more than 22, or no more than 20, or no more than 18 carbon
atoms. The
term R may represent an alkyl group, where the term alkyl refers to linear,
branched or
cyclic saturated hydrocarbon groups, generally having any of the number of
carbon atom
ranges specified above (e.g., C6-C24 refers to an alkyl group having 6 to 24
carbon atoms).
Examples of alkyl groups include 3-nnethylhexyl, 2,2-dinnethylpentyl, 2,3-
dinnethylpentyl,
caprylic, capric, lauric, nnyristic, palnnitic, stearic, oleic, linoleic,
linolenic, and behenic.
[0035] The following several paragraphs provide exemplary specific
surfactant
categories and examples of specific annphoteric surfactants that may be
incorporated into
the fluid compositions of the present disclosure. It should be noted that the
categories are
not mutually exclusive in that a specific annphoteric surfactant may fall into
more than one
category, i.e., two categories may overlap in terms of the surfactants that
are encompassed
within a category. There is a diverse nomenclature used in the surfactant art
to categorize
and recognize classes of annphoteric surfactants specifically, and surfactants
in general,
where that nomenclature often does not provide for mutually exclusive
categories of
surfactants. Nevertheless, the following provides for annphoteric surfactants
useful in the
present disclosure. For convenience, the surfactant may be identified by
reference only to
its charged portion. For instance, the annphoteric surfactant may be referred
to as a
betaine, or a betaine surfactant in order to indicate that the annphoteric
surfactant contains
a betaine group. As another example, when the annphoteric surfactant comprises
a
hydroxysultaine group, such a surfactant may be referred to either as a
hydroxysultaine
surfactant, or when the context permits, even more simply as a
hydroxysultaine.
Alternatively, it may be said that the annphoteric surfactant comprises a
specifically
identified charged group such as a betaine or betaine group, a hydroxysultaine
group, an
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amine oxide group, etc.
[0036] In some of the following chemical structures the term "L" is used
to refer to a
linking group. A linking group is a short chain of atoms that links together
two noted
functional groups present in the annphoteric surfactant. In one embodiment, L
is
methylene, i.e., -CH2-. In one embodiment, L is ethylene, i.e., -CH2CH2-. In
one
embodiment, L is propylene, i.e., -CH2CH2CH2-. The linking group may include a
substituent
on an alkylene chain, where the substituent may be, e.g., halogen, hydroxyl or
short-chain
(about C1-C4) alkyl. In one embodiment, L is hydroxyl substituted propylene,
e.g., -CH2CH(OH)CH2-. In another embodiment, L is methyl substituted
methylene, e.g., -
CH(CH3)-. In one embodiment, L is methylene, ethylene or propylene, each
optionally
substituted with hydroxyl. In one embodiment, L is dinnethylether, i.e., -CH2-
0-CH2-. In one
embodiment, L is a chain of 1-5 atoms selected from carbon and oxygen, where
the chain is
optionally substituted with hydroxyl or halide.
[0037] Any of the following terms may be used to specifically recite an
"annphoteric
surfactant" to thereby provide a selection of annphoteric surfactants that are
useful in an
embodiment of the present disclosure: alkyl annidopropyl betaine, alkyl amine
oxide, alkyl
annphoacetates, alkyl betaine, alkyl carboxyglycinate, alkyl glycinate, alkyl
sulphobetaine,
sultaine, alkyl annphopropionates, alkylannphoglycinates, alkyl annidopropyl
hydroxysultaines, acyl taurate and acyl glutamate. Each of these terms is
known in the art,
and many of these terms are described below.
[0038] In one embodiment, the annphoteric surfactant is a betaine
surfactant, which
means that the surfactant includes a betaine group. The betaine surfactant may
be an alkyl
annido propyl betaine which may be represented by the chemical structure CH3-
(CH2)n-
CONH-CH2CH2CH2-N(CH3)2-CH2-COOX when the alkyl group is a linear alkyl group.
More
generally, an annido propyl betaine may be represented by the chemical
structure R-CONH-
CH2CH2CH2-N(CH3)2-CH2-COOX. These are both examples of alkyl annido betaines.
[0039] In one embodiment, the annphoteric surfactant is an alkyl annido
sulfobetaine
which may be represented by the chemical structure R-CONH-L-N(CH3)2-(CH2),,-
S020X
wherein L is propylene. A subset of this class is the alkylbenzene dinnethyl
ammonium
propanesulfonates obtained by quaternization of the alkylbenzene dinnethyl
amine with
propanesulfone. Again, the propylene linking group L may be substituted, e.g.,
with a
hydroxyl group (which provides for 2-hydroxy-1-propanesulfonate derivatives)
to provide
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another annphoteric surfactant suitable for use in the present compositions.
[0040] In one embodiment, the annphoteric surfactant is an alkyl amino
acid
annphoteric surfactant which may be represented by the chemical structure R-NH-
L-COOX,
where R and L are defined above. For example, R may be derived from coconut
oil, L may
be ethylene and X may be sodium ion.
[0041] In one embodiment, the annphoteric surfactant is an alkyl betaine
annphoteric
surfactant which may be represented by the chemical structure R-N(CH3)2-L-COOX
where R
is an alkyl group and L is a linking group. As with other annphoteric
surfactants disclosed
herein, the R group may be a fatty group rather than being limited to an alkyl
group,
however in one embodiment the R represents an alkyl group. As mentioned
previously, the
linking group may be, and in one embodiment is a methylene group. However
alkyl
betaines also include the a-(N,N,N-trialkyl ammonium) alkanoates, having the
structure RI--
N(R2)(R3)-C(R4)H-COOX where L is an alkyl substituted methylene group. Various
alternative
and sometimes more specific names are used to name alkyl betaines, for
example, N-alkyl-
N,N-dinnethylglycine; N-alkyl-N,N-dinnethyl-N-carboxynnethyl ammonium betaine;
alkyl-
dinnethyl ammonium acetate or alkyl-dinnethyl ammonium ethanoate. The
Cosmetic,
Toiletry and Fragrance Association, Inc. (CTFA) uses the name alkyl-betaine
for these
products.
[0042] In one embodiment, the annphoteric surfactant is an alkyl
innidazoline derived
annphoteric surfactant which may be represented by the chemical structure R-
CONH-L-
N(CH2CH2OH)CH2COONa. In another embodiment, the alkyl innidazoline derived
annphoteric
surfactant is a diacid which may be represented by the chemical structure R-
CON(CH2CH2OH)-L-N(CH2COONa)2. In either of these embodiments, the linker L is
optionally ethylene.
[0043] In one embodiment, the annphoteric surfactant is an alkyl innino
diacid
annphoteric surfactant which may be represented by the chemical structure R-
N(CH2CH2COONa)2. In alternative embodiments, the alkyl innino diacid
annphoteric
surfactant is represented by the chemical structure R-N(CH2CH2CH2COONa)2 or R-
N(CH2COONa)2.
[0044] In one embodiment, the annphoteric surfactant is an alkyl
sulfobetaine
annphoteric surfactant. The chemical structure of an alkyl sulfobetaine may be
represented
as R-N(CH3)2-L-S020X (also sometimes represented as ¨L-S03X) where R is alkyl
and L is
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methylene. The following are exemplary of specific alkylsulfobetaines that may
be used in
the practice of the present invention: caprylyl sulfobetaine, hexadecyl
sulfobetaine, lauryl
sulfobetaine, nnyristyl sulfobetaine, n-octyl sulfobetaine, palnnityl
sulfobetaine, tetradecyl
sulfobetaine,
[0045] In one embodiment, the annphoteric surfactant is an alkyl sultaine,
which is a
term favored by CTFA. Alkyl sultaine are sulfobetaine annphoteric surfactants
that include
the propanesulfonate group, i.e., L-S03X wherein L is propylene. An alkyl
sultaines has the
chemical structure R-N(CH3)2-CH2CH2CH2-S020X.
[0046] In one embodiment, the annphoteric surfactants is an annido propyl
betaine
which may be represented by the chemical structure R(C=0)-NH-(CH2)3-N(CH3)2-
CH2COOX.
This class of annidopropyl betaine may also be referred to as an alkyl annido
propyl betaine
since R may be alkyl group. An alkylannidopropyl betaine surfactant is
typically synthesized
by reaction of a fatty acid, for example the fatty acid from natural oils such
as coconut oil,
and 3,3-dinnethylanninopropylannine to provide an annidopropyl dinnethylannine
intermediate, which in turn is reacted with sodium nnonochloroacetic acid to
provide the
corresponding betaine. A betaine surfactant is commonly named after the source
of the
fatty acid used in its preparation, e.g., coconut oil provides for
cocannidopropyl betaine, and
isostearic acid provides for isostearnnidopropylbetaine. Many
alkylannidopropyl betaine
surfactants suitable for use in the present invention are commercially
available in solid and
solution form, and may be purchased from various suppliers.
[0047] The following are specific exemplary annidopropyl betaines that may
be used
in the practice of the present invention: alnnondannidopropyl betaine,
apricotannidopropyl
betaine, avocadannidopropyl betaine, babassuannidopropyl betaine,
behenannidopropyl
betaine, canolannidopropyl betaine, capryl/caprannidopropyl betaine (formed
from a
mixture of caprylic acid and capric acid), coco/oleannidopropyl betaine,
coco/sunflowerannidopropyl betaine (formed from a blend of coconut and
sunflower seed
oils), cupuassuannidopropyl betaine (formed from the pulp of the cupuassu
tree),
isostearannidopropyl betaine, laurannidopropyl betaine,
nneadowfoannannidopropyl betaine
(formed from nneadowfoann seed oil), nnilkannidopropyl betaine,
nninkannidopropyl betaine
(formed from mink oil), nnyristannidopropyl betaine, oatannidopropyl betaine
(formed from
Avena Sativa (oal) kernel oil), oleannidopropyl betaine, olivannidopropyl
betaine,
palnnannidopropyl betaine (formed from palm oil), palnnitannidopropyl betaine,
palm
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kernelannidopropyl betaine (formed from palm kernel oil), ricinoleannidopropyl
betaine,
sesannidopropyl betaine, shea butterannidopropyl betaine (formed from
Butyrospernnunn
Parkii (shea butter)), soyannidopropyl betaine, stearannidopropyl betaine,
tallowannidopropyl
betaine, undecylenannidopropyl betaine, and wheat gernnannidopropyl betaine
(formed from
the oil in wheat germ).
[0048] In one embodiment, the annphoteric surfactant is an amine oxide
annphoteric
surfactant which may be represented by the chemical structure R-N(CH3)2-0-
where R is a
lipophilic group. An exemplary R group is a lipophilic alkyl group, where
amine oxide
surfactants having an alkyl group for R are commonly known as alkyl amino
oxides.
Exemplary alkyl groups are caprylic, capric, lauric, nnyristic, palnnitic,
stearic, oleic, linoleic,
linolenic, and behenic. Exemplary amine oxide annphoteric surfactants include
cocannidopropylannine oxide and lauryldinnethylannine oxide (also known as
dodecyldinnethylannine oxide, N,N-Dinnethyldodecylannine N-oxide, and DDAO),
soyannidopropylannine oxide and nnyristannine oxide. The nitrogen atom of the
amine group
may be bonded to two methyl groups as shown above, however as an alternative,
the
nitrogen atom may be bonded to two hydroxyethyl group to provide the structure
R-
N(CH2CH2OH)2-0-.
[0049] In one embodiment, the annphoteric surfactant is an amino acid
annphoteric
surfactant. This type of annphoteric surfactant displays a zwitterionic
structure within a
certain pH range, which depends on the structure of the surfactant. A common
example of
this type of annphoteric surfactant is the amino acids of the structure R-NH-
CH2CH2-COOH
where R is a fatty group. These are sometimes referred to as fatty amino
acids, or more
precisely as fatty anninopropionates when in the corresponding carboxylate
form. A
variation on this structure has two carboxylic acid groups, i.e., has the
structure R-
N(CH2CH2COOH)2, which are named as fatty inninodipropionates when in the
corresponding
carboxylate form. Any of these classes of annphoteric surfactants may be used
in the
compositions of the present disclosure.
[0050] In one embodiment, the annphoteric surfactant is an annphoacetate
annphoteric surfactant which includes the chemical structure ¨CH2-0O2X in
addition to a
fatty group and a chemical group that will become positive charged under
suitable pH.
These surfactants are sometimes referred to as annphoglycinates. In one
embodiment, the
annphoacetate annphoteric surfactant may be represented by the chemical
structure
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R(CO)NH-CH2CH2-N(CH2CH2OH)(CH2CO2X) wherein R may be an alkyl group or R(CO)
may be
a fatty acyl group derived from a fatty acid such as found in coconut oil to
provide, e.g.,
cocoannphoacetate. Such annphoacetate surfactants may be prepared by reacting
a
compound of formula R(CO)NH-CH2CH2-NHCH2CH2OH with formaldehyde and a cyanide
as
disclosed in US Patent 6232496. Under appropriate conditions, this
annphoacetate may
interconvert to the corresponding annphoacetate annphoteric surfactant
comprising an
innidazoliunn group which provides a positively charged chemical group, such
as
lauroannphoacetate (sodium salt).
[0051] The annphoacetate annphoteric surfactant may comprise two, rather
than
one, acetate group, to provide an annphoteric surfactant having the chemical
structure
R(CO)NH-CH2CH2-N(CH2CH2OCH2CO2X)(CH2CO2X). Exemplary annphoacetate annphoteric
surfactants include disodiunn cocoannphodiacetate, sodium cocoannphoacetate,
disodiunn
lauroannphoacetate, and sodium lauroannphoacetate.
[0052] In one embodiment, the annphoteric surfactant is an annphopropionate
annphoteric surfactant which includes the chemical structure ¨CH2CH2-0O2X in
addition to a
fatty group and a chemical group that will become positive charged under
suitable pH. Such
annphoteric surfactants may be prepared from acrylic acid as described in US
Patent
6030938. Exemplary annphopropionate annphoteric surfactants are the sodium
salts of
capryloannphopropionate, laurinninodipropionate, isostearyl annphopropionate
and
cocoannphopropionate. The annphopropionate annphoteric surfactant may comprise
two,
rather than one, propionate group, to provide an annphoteric surfactant having
the chemical
structure R(CO)NH-CH2CH2-N(CH2CH2OCH2CH2CO2X) (CH2CH2CO2X). This subclass of
annphopropionate annphoteric surfactants is known as annphodipropionate
annphoteric
surfactants, where exemplary annphodipropionate annphoteric surfactants are
the disodiunn
salt of cocoannphodipropionate (also known as N-(2-coconut oil annidoethyl)-N-
(2-(2-
carboxyethyl)oxyethyl)-beta-anninopropionic acid, disodiunn salt) and
capryloannphodipropionate.
[0053] In one embodiment, the annphoteric surfactant is a betaine
surfactant.
Betaine refers to surfactant molecules incorporating both a positively charged
(cationic)
functional group such as a phosphoniunn or quaternary ammonium group which
bears no
hydrogen atom, and a negatively charged (anionic) functional group such as a
carboxylate
group or an oxyanion. In a betaine, the cationic and anionic groups are not
adjacent to one
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another. The betaine surfactants as referred to herein will meet the foregoing
definition,
and will in addition have a lipophilic moiety. In one embodiment, the cation
is a quaternary
amine. In one embodiment, the anion is carboxylate. In another embodiment the
anion is
oxyanion. In another embodiment the anion is sulfate. In another embodiment,
the anion
is sulfonate. In another embodiment, the anion is phosphate. Many commercially
available
betaines have a dialkyl substituted dinnethylannnnoniunn group. Despite the
prevalence of
this group in commercial annphoteric surfactants, the annphoteric surfactants
useful in the
present disclosure do not necessarily (although they may) have a
dinnethylannnnoniunn
group. More generally, they have a dialkylannnnoniunn group, so as to provide,
e.g., a
trialkylannnnoniunn alkanoate of the chemical structure RI--N(R2)(R3)-CH2COOX.
In other
words, R2 and R3 are not necessarily methyl. Some exemplary betaines are alkyl
dinnethylbetaines of the chemical structure R-N(CH3)2-CH2-COOH, and alkyl
annidopropyldinnethylbetaines of the structure R-CONH-CH2CH2CH2-N(CH3)2-CH2-
COOH.
[0054] In one embodiment, the annphoteric surfactant is a hydroxysultaine
having
the chemical structure R-N(CH3)2-CH2CH(OH)-503X where R is a fatty group,
e.g., a long
chain alkyl group. A hydroxysultaine is often named after the source of the R
group, so that,
for example, a hydroxysultaine derived from coconut oil may be named
cocannidopropyl
hydroxysultaine (however it is also known as coco hydroxysulfaine, and CAHS).
Other
exemplary hydroxysultaine annphoteric surfactants include laurannidopropyl
hydroxysultaine, oleannidopropyl hydroxysultaine, tallowannidopropyl
hydroxysultaine,
erucannidopropyl hydroxysultaine, and lauryl hydroxysultaine.
[0055] In one embodiment, the annphoteric surfactant is an innidazoline
derivative
annphoteric surfactant, sometimes referred to as an innidazoliniunn
derivative. Representing
the chemical structure of an innidazoline derivative annphoteric surfactant is
complicated by
the fact that innidazolines characteristically hydrolyze when exposed to
water. Fatty
innidazolines hydrolyze slowly on exposure to moist air, giving an alkyl
annidoannine.
Accordingly, the alkyl annidoannine annphoteric surfactants already described
elsewhere
herein, are examples of innidazoliniunn derivative annphoteric surfactants. In
general,
innidazoliniunn derivative annphoteric surfactants, sometimes referred to as
innidazoline
annphoterics, are well known in the art as a class of surfactant. In one
embodiment, the
annphoteric surfactant is an innidazoline derivative, optionally a fatty alkyl
innidazoline. This
type of annphoteric surfactant form cations in acidic solutions, anions in
alkaline solutions,
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and 'zwitterions' in mid-pH range solutions. The mid-pH range, also referred
to as the
isoelectric range, within which the innidazoline surfactant has a neutral
charge, is compound
specific and depends on the precise structure of the compound, which will
affect the
alkalinity of the nitrogen atom and the acidity of the carboxylic group.
Exemplary suitable
innidazoline type annphoteric surfactants include, without limitation, 2-
cocoy1-2-
innidazoliniunn hydroxide-1-carboxyethyloxy disodiunn.
[0056] The innidazoliniunn derivative annphoteric surfactant may be
prepared by
reaction of sodium chloroacetate and the corresponding 2-alky1-1-(2-
hydroxyethyol+2-
innidazoline. This reaction product is commonly assigned to have the following
chemical
structure:
0
HO'
N+"-NA
0
wherein R is a hydrophobic group. The reactions that produce these cyclic
innidazoliniunn
derivatives can be readily extended to provide the corresponding open chain
molecules
having the following structures: RCO-NH-CH2CH2-N(CH2CH2OH)CH2C00- (with one
equivalent of sodium chloroacetate) and RCO-NH-CH2CH2-N(CH2CH2OH)(CH2C00-)2
(with
two equivalents of sodium chloroacetate). Such open chain structures are often
called
innidazoline derivatives, or alkyl (when R is an alkyl group) annido amino
acids (when a single
equivalent of sodium chloroacetate has been employed in its preparation).
[0057] Commercially available annphoteric innidazoliniunn may be one or
more of the
foregoing structures, which are suitable for use in the present disclosure. A
little care
should be taken in selecting the innidazoliniunn derivative because the same
term is
somewhat confusingly used to refer to cationic (as opposed to annphoteric)
surfactants that
incorporate or are prepared from innidazolines, e.g., the cationic surfactants
having the
following structure:
HONN
Accordingly, those skilled in the art will sometimes refer specifically to
annphoteric
innidazoliniunn surfactants to distinguish from so-called innidazoliniunn
surfactants that are
cationic.
[0058] Examples of suitable annphoteric innidazoliniunn derivatives having
R groups
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selected from C6-C22 alkyl, e.g., caprylic, capric, lauric, nnyristic,
palnnitic, stearic, oleic,
linoleic, linolenic, and behenic.
[0059] In one embodiment, the annphoteric surfactant is a
phosphinatebetaine
annphoteric surfactant. Phosphinatebetaines are similar to alkybetaines and
sulfobetaines
where the carboxy or sulfonic group has been replaced by a phosphine group. A
phosphinatebetaine may be represented by the chemical structure R-N(CH3)2-L-
P(=0)(R)0X.
L may be, for example, propylene.
[0060] In one embodiment, the annphoteric surfactant is a
phosphonatebetaine
annphoteric surfactant. Phosphonatebetaines are similar to alkybetaines and
sulfobetaines
where the carboxy or sulfonic group has been replaced by a phosphonate group.
A
phosphonatebeaine may be represented by the chemical structure R-N(CH3)2-L-
P(=0)(0R)0X. L may be, for example, propylene.
[0061] In one embodiment, the annphoteric surfactant is a pyridiniunn
alkanoate
0
RI
OH
annphoteric surfactant, which may be represented by the chemical structure
where R is a fatty group, e.g., a medium or long chain alkyl. The pyridiniunn
alkanoate
illustrated in the carboxylic acid form, however at suitable pH the carboxylic
acid (-COOH)
group will convert to the carboxylate (COOX) group.
[0062] In one embodiment, the annphoteric surfactant is a sulfate ion-
containing
annphoteric surfactant. The sulfate ion group may be readily added to fatty
unsaturated
amines, such as oleylannine (1-amino-9,10-octadecene) to provide the
corresponding sulfate
ion-containing annphoteric surfactant with the name 9-(10)-
hydroxyoctadecylannine.
[0063] In one embodiment, the annphoteric surfactant is a sulfatobetaine,
also
known as an alkyldinnethylannnnoniunn alkyl sulfate, which may be represented
by the
chemical structure R-N(CH3)2-L-0S03X. Sulfatobetaines are examples of sulfate
ion-
containing annphoteric surfactants that also contain the betaine group.
[0064] In one embodiment, the annphoteric surfactant is a sulfobetaine
annphoteric
surfactant. The chemical structure of the basic compound may be represented as
R-
N(CH3)2-L-S020X (also sometimes represented as ¨L-S03X). As commercially
available, many
sulfobetaines have L as propylene, and such annphoteric surfactants may be
used in an
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embodiment of the present disclosure. Sulfobetaines are an example of sulfonic
acid-
containing annphoteric surfactants which also include a betaine group. This
class of betaine
annphoteric surfactant includes ammonium alkane sulfonates and 2-(N-alkyl-N,N-
dinnethylannnnoniunn) ethane sulfonates. Sulfobetaines also include trialkyl
ammonium
compounds similar to alkylbetaines but having the carboxyl group replaced by
an
alkylsulfonate group. When R is a lipophilic alkyl group, this class of
sulfobetaine may be
referred to as an alkylsulfobetaine. The alkylsulfobetaine surfactants are
commonly named
after the long chain alkyl group present in their structure. For example, when
R has 12
carbons atoms in a straight chain, i.e., is lauryl, the corresponding
sulfobetaine is known as
lauryl sulfobetaine.
[0065] There are a great many sulfobetaine surfactants which are a
variation on the
classic structure shown above. For example, the propylene ((CH2)3) group
designated by "L"
may be substituted with various functional groups, e.g., halogen, hydroxyl,
and nnethoxy.
The R group need not be a straight chain alkyl group, but may be a branched or
even
alicyclic or aromatic hydrocarbon. Indeed, the R group need not even be a
hydrocarbon.
Primarily, the R group needs to be lipophilic, and a great many chemical
structures provide
that property. Examples of sulfobetaine surfactants suitable for use in the
present invention
but which do not fall within the scope of the classic structure shown above
are N-(3-
cocoannidopropy1)-N,N-dinnethyl-N-(2-hydroxy-3-sulfopropyl)annnnoniunn
betaine, and 3-[(3-
chloroannidopropyl) dinnethylannnnoniunn]-1-propanesulfonate.
[0066] In one embodiment, the annphoteric surfactant is a sulfonic acid-
containing
annphoteric surfactant. For example, the annphoteric surfactant may be an N-
alkyl taurine of
the chemical formula RNH-CH2CH2-503H where R is an alkyl group. In a related
embodiment, R is a fatty group. Another sulfonic acid-containing annphoteric
surfactant
may be prepared by sulfonation of the linear annidoannine precursor to 1-
hydroxyethyl 2-
alkyl innidazoline, so as to provide R-CONH-CH2CH2-N(CH2CH2OH)CH2CH2S03H where
R may
be a fatty group, e.g., an alkyl group.
[0067] Specific examples of annphoteric surfactants and classes thereof
that may be
used in the present compositions include, without limitation,
cocoannidopropylannine oxide,
cocannidopropyl betaine, cocannidopropyl hydroxysultaine, cocodinnethyl
sulphopropyl
betaine, disodiunn cocoannphodipropionate, lauryl amine oxide, lauryl annido
propyl betaine;
lauryl betaine, lauryl hydroxyl sulfobetaine, nnyristannine oxide, sodium
cocoannphoacetate,
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and stearyl betaine. As mentioned previously, these terms do not necessarily
define
mutually exclusive groups of surfactants, i.e., a specific annphoteric
surfactant may fall
within the scope of two or more sets of annphoteric surfactants each defined
one of the
selected terms.
Anionic Surfactant
[0068] In one embodiment, the fluid compositions of the present disclosure
include
at least one, and optionally include more than one, anionic surfactant.
Suitable exemplary
anionic surfactants include, without limitation, alkyl sulfates, alkylether
sulfates,
alkylsulfonates, alkylaryl sulfonates, alkyl succinates, alkyl
sulfosuccinates, N-
alkoylsarcosinates, acyl taurates, acyl isethionates, alkyl phosphates, alkyl
ether phosphates,
alkyl ether carboxylates, .alpha.-olefinsulfonates, and the alkali metal and
alkaline earth
metal salts and ammonium and triethanolannine salts thereof. Such alkyl ether
sulfates,
alkyl ether phosphates and alkyl ether carboxylates can have between 1 and 10
ethylene
oxide or propylene oxide units, and in some embodiments, 1 to 3 ethylene oxide
units, per
molecule. For convenience, an anionic surfactant may be referred to by
reference to the
anionic group that forms the charged portion of the surfactant. For example,
an anionic
surfactant that comprises a sulfonate group may be referred to as a sulfonate
surfactant, or
even more simply when the context permits, as a sulfonate. As a further
example, an
anionic surfactant that comprises a sulfate group may be referred to as a
sulfate surfactant,
or when the context permits, even more simply as a sulfate.
[0069] In one embodiment, the anionic surfactant is a carboxylic acid or
carboxylate,
having the anionic group ¨C(0)-0- in addition to a fatty group. The fatty
group, designated
R herein, may be an alkyl group, in which case the carboxylate may be referred
to as an alkyl
carboxylate. Exemplary alkyl carboxylates are the sodium or potassium or
ammonium salts
of fatty acids such as stearic acid and oleic acid. Potassium oleate is an
exemplary alkyl
carboxylate. The fatty group may alternatively be a polyalkylene oxide group
which is not
water soluble. Some carboxylate anionic surfactants are prepared from an alkyl
alcohol,
such as octanol, which is then reacted with ethylene oxide to provide the
polyoxyethyelene
extended octanol known as polyoxyethylene (8) octyl ether carboxylic acid,
when the
average number of ethylene oxide units per molecule is 8.
[0070] In one embodiment, the anionic surfactant is a diphenyl oxide. A
diphenyloxide may also be viewed as a subclass of sulfonate anionic
surfactants, since the
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aromatic rings of the diphenyl precursor is sulfonated in order to provide the
diphenyl oxide
anionic surfactant. The diphenol precursor is typically a diphenylether, i.e.,
Ar-O-Ar, where
one or both of the aromatic rings (Ar) may be substituted with an alkyl group.
The diphenyl
oxide anionic surfactant may be represented by the chemical formula XS03-Ar(R)-
0-Ar(R)-
S03X where R is hydrogen or alkyl at each position of the aromatic ring that
is not sulfonated
or bonded to the ether oxygen. Exemplary diphenyl oxide anionic surfactants
include
disulfonated diphenyl oxide with alkyl substitution such as disulfonated
diphenyl oxide with
linear decyl substitution, disulfonated diphenyl oxide with linear dodecyl
substitution,
disulfonated diphenyl oxide with branched decyl substitution, any of which may
be
neutralized with sodium, potassium or ammonium.
[0071] In one embodiment, the anionic surfactant is a phosphate ester,
which may
be a nnonophosphate ester of the chemical structure R-O-P(0)(OH)2, i.e., or a
phosphate
diester of the chemical structure R-O-P(0)(OH)-0-R where the two Rs in the
diester may be
the same or different. The R group is a fatty group, i.e., a non water soluble
group. The R
group may be an alkyl group, and phosphate esters having R=alkyl are typically
made from
the corresponding alkyl alcohol. In one embodiment, the R group is a
polyalkylene oxide
group so as to provide a polyether phosphate ester of the formula R-(OCH2CH2)n-
O-
P(0)(OH)2. A common naming convention for polyether phosphate esters provides
the
number of polyoxyethylene groups in the surfactant, e.g., polyoxyethylene
(10). The R
group in the polyether phosphate may be an alkyl group (when the polyether
phosphate is
derived from an alkyl alcohol), an aryl group (when the polyether phosphate is
derived from
an aromatic alcohol, e.g., phenol), or an alkyl aryl group, e.g., alkyl-
substituted phenol such
as nonyl-phenol. Exemplary phosphate esters include polyoxyethylene (10)
nonylphenol
phosphate, polyoxyethylene (4) phenol phosphate, and C8I-117 phosphate.
Commercial
preparations of phosphate esters often provide a mixture of phosphate
nnonoester and
phosphate diester, which may be used in the compositions of the present
disclosure.
[0072] In one embodiment, the anionic surfactant is a sarcosinate, i.e., a
compound
having the chemical structure R-C(0)-N(CH3)-CH2-0O2X where R is a fatty group.
The
sarcosinate surfactants include an N-acyl group, where the fatty acid from
which the acyl is
derived is typically used to name the sarcosinate. Exemplary sarcosinates
include sodium
lauroyl sarcosinate, sodium cocoyl sarcosinate, sodium nnyristoyl sarcosinate,
and the
ammonium ion equivalents.
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[0073] In one embodiment, the anionic surfactant is a sulfate, i.e., a
compound
having the anionic -0-S03X group in addition to a fatty group. The fatty group
may be a long
chain alkyl group, where an alkyl group in a surfactant may be branched or
straight chain.
The fatty group need not be an alkyl group, however alkyl groups are commonly
available
from many plant and animal oils, and so are a ready source of fatty groups for
surfactants.
Exemplary sulfate anionic surfactants include sodium laureth sulfate, sodium
dodecyl
sulfate, sodium decyl sulfate, sodium octyl sulfate, ammonium lauryl sulfate,
sodium lauryl
sulfate, sodium rrideceth sulfate, C12-14-tert-alkyl-ethoxylated sodium
sulfate, and poly(oxy-
1,2-ethanediy1), a-sulfo-w-(nonylphenoxy) ammonium salt.
[0074] In one embodiment, the anionic surfactant is a sulfoacetate, i.e.,
a compound
having the anionic ¨CH2-S03X group in addition to a fatty group. A common
fatty group has
the structure R-O-C(0)-, where R is an alkyl group, e.g., Cs-Cm straight chain
alkyl.
Exemplary sulfoacetate anionic surfactants are sodium lauryl sulfoacetate and
the
ammonium salt of cetyl sulfoacetate. Sulfoacetates may be prepared as
described in, e.g.,
US Pat. No. 5616782.
[0075] In one embodiment, the anionic surfactant is a sulfonate, i.e., a
compound
having the anionic -S03X group in addition to a fatty group. The fatty group
may be, for
example, a long chain alkyl group. The sulfonate may be regarded as having the
chemical
structure R-S03X. In one embodiment, the R group is derived from a fatty acid,
and is a
straight long chain alky group such as stearyl and oleyl. Long chain olefins
are often used as
precursors to sulfonates, since the double bond may be treated to convert it
to a sulfonate
group. Such sulfontes are often named by the precursor which is used to form
the
sulfonate, such as C14-C16 olefin sulfonate, where C14-C16 denotes that a
mixture of olefins
having 14 and 16 carbons was sulfonates to provide the anionic surfactant. In
one
embodiment, the R group is an alkylbenzene group, for example, a
dodecylbenzene group.
The alkyl group, e.g., the dodecyl group, may be a linear alkyl group or a
branched alkyl
group. Exemplary sulfonate anionic surfactants are linear dodecylbenzene
sulonate and
branched dodecylbenzene sulfonate. As always, the anionic group may be
neutralized with
any suitable cation, e.g., sodium, potassium, ammonium, etc.
[0076] In one embodiment, the anionic surfactant is a sulfosuccinate,
i.e., a
compound having the chemical structure based on sulfonated succinic acid,
i.e., Fatty
Group-O-C(0)-CH2-CH(sulfate)-C(0)-0-R (which may be a fatty group or
hydrogen).
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Sulfosuccinates are generally sodium salts of alkyl esters of sulfosuccinic
acid that are a
result of condensation of nnaleic anhydride with a fatty alcohol, followed by
sulfonation with
sodium bisulfite (NaHS03). As shown by the foregoing chemical structure, a
sulfosuccinate
will have at least one fatty group, and may have two fatty groups. However,
when the
sulfosuccinate has one fatty group, it may also have an anionic carboxylate
group rather
than a second fatty group. Exemplary sulfosuccinate anionic surfactants
include sodium
dioctyl sulfosuccinate (having two fatty groups) and disodiunn laureth
sulfosuccinate (which
has one fatty group, one sulfate group and one carboxylate group, and is also
known as
DLS).
[0077] Additional specific examples of anionic surfactants include, without
limitation, ammonium lauryl sulfosuccinate, sodium lauryl sulfate, sodium
lauryl ether
sulfate, ammonium lauryl ether sulfate, triethanolannine
dodecylbenzenesulfonate, sodium
lauryl sarcosinate, ammonium lauryl sulfate, sodium oleyl succinate, sodium
dodecyl sulfate,
and sodium dodecylbenzene sulfonate.
[0078] In one embodiment, the fluid concentrations and compositions of the
present disclosure contain a third surfactant selected from annphoteric and
anionic
surfactants. The third surfactant is non-identical to, i.e., is not the same
as, either of the
first (the annphoteric) or the second (the anionic) surfactants. Any of the
annphoteric and
anionic surfactants disclosed previously are optionally used as the third
surfactant in the
present formulations, so long as it (the third surfactant) is not the same as
the first or
second surfactant. In one embodiment, the third surfactant is of a different
class from the
first or second surfactant, i.e., the third surfactant has a different
functional group from the
functional groups that provide the charged functionality present in the first
and second
annphoteric or anionic surfactant. For example, if the second surfactant is a
sulfate anionic
surfactant, then the third surfactant is not a sulfate, but is instead, e.g.,
a sulfonate anionic
surfactant.
[0079] Annphoteric and/or anionic surfactants suitable for use in the
present
invention may be obtained from one or more of the following exemplary
manufacturers
and/or suppliers: Aceto Corp. (Allendale, Ni); Air Products (Allentown, PA);
Akzo Nobel
Chemicals Co. (Chicago, IL); Alzo International (Sayreville, Ni); BASF Corp.
(Florham Park, Ni);
Clariant Corp. (Frankfurt, Germany); Croda, Inc. (Edison, Ni); Dow Chemical
(Midland MI); E.
I. du Pont de Nemours & Co., Inc. (Wilmington, DE); Harcros Chemicals, Inc.
(Kansas City,
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KS); Huntsman Corp. (St. Lake City, UT); Kaiser Industries Ltd. (Bahadurgarh,
Haryana, India),
Kao Chemicals. (Tokyo, Japan); Lonza, Inc. (Basel, Switzerland); NOF
Corporation (Tokyo,
Japan); Pilot Chemicals (Cincinnati, OH); Procter & Gamble (Cincinnati, OH);
Solvay-Rhodia
(Courbevoie, France); Stepan Co. (Northfield, IL); and Unilever PLC (London,
England).
Optional Components
[0080] The following ingredients are optionally present in the compositions
of the
present disclosure, however the present disclosure also provides that each of
the following
ingredients may be specifically excluded from being present in the composition
of the
present disclosure.
[0081] The compositions of the present disclosure may include an anti-rust
agent,
which may also be referred to herein as an anti-corrosion agent. An exemplary
anti-rust
agent is sodium nitrite. Other exemplary anti-rust agents are sodium benzoate,
organic
boron compounds, amines, anninophosphate compounds, zinc
dialkyldithiophosphate, and
tall oil fatty acids. The anti-rust agent may be present in the composition at
an amount of
less than 10 w% of the composition directly used as a material fabrication
fluid, e.g., as a
metal cutting fluid. In optional embodiments, that amount is less than 9 wt%,
or less than 8
wt%, or less than 7 wt%, or less than 6 wt%, or less than 5 wt %, or less than
4 wt%, or less
than 3 wt%, or less than 2 wt%, or less than 1 wt%, or less than 0.5 wt%, or
less than 0.1
wt%. The amount may also be expressed in terms of a minimum amount, such as at
least
500 ppnn, or at least 1000 ppnn, or at least 1500 ppnn, or at least 2000 ppnn,
or at least 2500
ppnn, 0.5 wt%, or at least 1 wt%, or at least 1.5 wt%, or at least 2 wt%, or
at least 2.5 wt%, or
at least 3 wt%, or at least 3.5 wt%, or at least 4 wt%, or at least 4.5 wt%,
or at least 5 wt%.
Anti-rust agents are well known commercial materials.
[0082] The compositions of the present disclosure may include a colorant,
such as a
dye or pigment. The coloring agent should be used in a small amount, just
enough to impart
color visible to the eye, when the composition is being applied to material,
e.g., metal, to be
cut or otherwise shaped. Colorants are well known commercial materials.
[0083] The compositions of the present disclosure may include a de-foaming
agent
which may also be referred to as an anti-form agent. A suitable de-foaming
agent is a
silicone polymer. Silicone defoanning agents are well known commercial
materials. Dow
Corning (Michigan, USA) sells such de-foaming agents. Another suitable de-
foaming agent is
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tributyl phosphate.
[0084] The compositions of the present disclosure may include a thickening
agent.
As used herein, upon addition to, or inclusion in, an aqueous fluid
composition or
concentrate thereof, the thickening agent increases the viscosity of the
composition. The
inclusion of a thickening agent provides for, among other things, an improved
adhesion of
the composition to a surface. This is particularly advantageous when the
surface is not
horizontal and so the material fabrication composition will tend to fall down
the surface
under the force of gravity absent the present of a thickening agent. The
thickening agent
may be water soluble. Thickening agents for aqueous compositions are well
known in the
art, may be referred to as an aqueous thickening agent, and any of such
thickening agents
may be used in the present compositions.
[0085] The amount of thickening agent to be included in the composition
will
depend on the precise identity of the thickening agent and the desired
viscosity of a
concentrated form of the material fabrication fluid composition. For a
thickening agent
selected from a cellulosic or polyannide thickening agent, and to achieve a
viscosity similar
to that of whole milk or orange juice, the thickening agent will typically be
present in the
composition at weight percent of 0.1 weight percent, based on the total weight
of the
composition, when the composition is a concentrate having about 5-25% total
solids. The
viscosity of the concentrate may be varied, primarily by the incorporation of
more or less
thickener. If a more viscous concentrate is desired, the addition of more
thickening agent
will provide for a more viscous composition. Alternatively, a more effective
thickening
agent may be utilized, i.e., a thickening agent that achieves the same
increase in viscosity
but at a lower concentration.
[0086] In one aspect, the thickening agent may be a polyhydroxy polymer,
e.g., a
polysaccharide such as a cellulosic or a functionalized cellulosic. When the
thickening agent
is a polysaccharide, the polysaccharide may have at least 50, or at least 100,
or at least 150,
or at least 200 saccharide units per polymer chain. The number average
molecular weight
of the polysaccharide may be at least 13,000 or at least 17,000 or at least
21,000 or at least
25,000.
[0087] In one aspect, the thickening agent is a polyhydroxy small molecule,
such as
glycerol. A polyhydroxy small molecule has a molecular weight of less than 500
g/nnol and
has at least three hydroxyl groups.
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[0088] In one aspect, the thickening agent is a cellulosic, which includes
derivatives
of cellulosic resins. A suitable cellulosic is hydroxyethylcellulose (HEC).
HEC is a derivative
of cellulose wherein the ¨CH2OH groups are converted to ¨CH2OCH2CH2OCH2CH2OH
groups,
and -OH groups are converted to--OCH2CH2OH groups. HEC is commercially
available in
many grades, which vary as to molecular weight and degree of derivatization,
which in turn
lead to different solution viscosities (typically measured at 2% solids in
water). Suitable HEC
is CellosizeTM from Dow Chemical (Midland, MI) and AqualonTM from Ashland
Chemical
(Covington, KY).
[0089] Other suitable cellulosic thickening agents include methyl
cellulose, ethyl
cellulose, nnethylhydroxyethylcellulose, nnethylhydroxypropylcellulose,
hydroxypropylcellulose, and anionic (salt) forms such as sodium
carboxynnethylcellulose,
dihydroxypropyl ethers of cellulose (see, e.g., U.S. Pat. No. 4,096,326),
[0090] Suitable polyhydroxy polymers other than cellulosics include corn
starch or
modified corn starch, potato starch or modified potato starch, and pectin or
modified
pectin.
[0091] The thickening agent may be a polyacrylannide. Suitable
polyacrylannide
thickening agents may be selected from copolymers of acrylannide and ammonium
acrylate;
copolymers of acrylannide or nnethacrylannide and
nnethacryloyloxyethyltrinnethylannnnoniunn
halide, for example chloride; and copolymers of acrylannide and 2-acrylannido-
2-
nnethylpropanesulphonic acid. These copolymers may be prepared in the presence
of a
crosslinking agent, where exemplary crosslinking agents include
divinylbenzene,
tetraallyloxyethane, nnethylenebisacrylannide, diallyl ether,
polyallylpolyglyceryl ethers or
allylic ethers of alcohols of the sugar series, such as erythritol,
pentaerythritol, arabitol,
nnannitol, sorbitol and glucose. See, e.g., U.S. Pat. Nos. 2,798,053 and
2,923,692. The
polyacrylannide may be ionic and neutralized with a neutralizing agent such as
sodium
hydroxide, potassium hydroxide, aqueous ammonia or an amine such as
triethanolannine or
nnonoethanolannine. Ionic polyacrylannides may be prepared by copolymerizing
acrylannide
and sodium 2-acrylannido-2-nnethylpropanesulphonate via a radical route using
initiators of
the azobisisobutyronitrile type and by precipitation from an alcohol such as
tert-butanol. A
crosslinked copolymer of acrylannide and nnethacryloyloxyethyltrinnethyl-
ammonium
chloride may be obtained by copolymerization of acrylannide and
dinnethylanninoethyl
nnethacrylate quaternized with methyl chloride, followed by crosslinking with
a compound
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containing olefinic unsaturation, such as nnethylenebisacrylannide.
[0092] The thickening agent may be a polyacrylic acid. Suitable polyacrylic
acid
thickening agents are commercially available. For example, Lubrizol
(Wickliffe, Ohio) sells
their CarbopolTM synthetic thickeners that are made from polyacrylic acid. The
polyacrylic
acid may be neutralized in order to adjust its thickening behavior. For
example, polyacrylic
acid may be neturalized with ammonium ions using, e.g., ammonium hydroxide.
Ashland
Chemical markets their CarbomerTM line of crosslinked polyacrylic acids.
Again, these
polymers need to be neutralized in order to provide effective thickening
behavior.
[0093] The thickening agent may be a gum or a derivative thereof. Examples
include
locust bean gum and derivatives, guar gum and derivatives, and xanthan gum and
derivatives. Exemplary gum derivatives include sulfonated gum, e.g.,
sulfonated guar,
hydroxypropyl derivatized gum, e.g., hydroxypropyl guar, cationic derivatives,
e.g., cationic
guar,
[0094] The thickening agent may be a hydrophobically modified thickening
agent. In
one aspect, the thickening agent comprises a hydrophobic group such as a
hydrophobic alkyl
chain, where suitable examples of such thickening agents include
hydrophobically modified
ethylene oxide urethane (HEUR) polymer, hydrophobically modified alkali
soluble emulsion
(HASE) polymer, hydrophobically modified hydroxyethyl cellulose (HMHEC), and
hydrophobically modified polyacrylannide (HMPA). HEUR polymers are linear
reaction
products of diisocyanates with polyethylene oxide end-capped with hydrophobic
hydrocarbon groups. HASE polymers are honnopolynners of (meth)acrylic acid, or
copolymers of (meth)acrylic acid, (nneth)acrylate esters, or nnaleic acid
modified with
hydrophobic vinyl monomers. HMHEC refers to hydroxyethyl cellulose modified
with
hydrophobic alkyl chains. HMPA refers to copolymers of acrylannide with
acrylannide
modified with hydrophobic alkyl chains (N-alkyl acrylannide).
[0095] In one aspect, the fluid composition of the present disclosure
includes an
inorganic salt of an organic or inorganic acid. Suitable inorganic salts of
organic acids
include ammonium citrate, calcium acetate, copper acetate, copper citrate,
magnesium
citrate, melamine phosphate salt, nickel acetate, potassium acetate, potassium
citrate,
sodium acetate, sodium bitartrate, strontium acetate, urea phosphate, and zinc
acetate.
[0096] The amount of inorganic component present in the composition may be
varied over a wide range. Based on the total weight of the solids present in
the
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composition, the inorganic component may constitute from 1% to about 15% of
that weight.
In various embodiments, the inorganic component is at least 2%, or at least
3%, or at least
4%, or at least 5%, or at least 6%, or at least 7%, or at least 8%, or at
least 9%, or at least
10%, or at least 11%, or at least 12%, or at least 13%, or at least 14%, or at
least 15% of the
total weight of the solid components of the composition. In various
embodiments, the
inorganic component contributes not more than 30%, or 25% or 20% or 15% or not
more
than 10% of the total weight of the solids present in the composition. As
mentioned
previously, in one embodiment the inorganic component is an inorganic salt.
[0097] In one aspect, the fluid composition of the present disclosure
includes a non-
volatile organic solvent that is miscible with water. As used herein, a non-
volatile material
or solvent that is a liquid has a boiling point of greater than water, i.e.,
greater than 100 C.
An exemplary organic solvent is ethylene glycol nnonobutyl ether, also known
as BUTYL
CELLOSOLVETM.
[0098] As mentioned previously, the present disclosure provides a
concentrate
composition comprising water and solids, the solids comprising a first
surfactant selected
from annphoteric surfactants, a second surfactant selected from anionic
surfactants, and a
third surfactant selected from an annphoteric and an anionic surfactant, the
third surfactant
being different from the first and second surfactants. Optionally, the third
surfactant, but
neither of the first or second surfactants, is a fluorosurfactant. The third
surfactant may be
a fluorinated or perfluorinated anionic fluorosurfactant while the second
(anionic)
surfactant of the concentrate is non-fluorinated. Alternatively, the third
surfactant may be
a fluorinated or perfluorinated annphoteric surfactant while the first
(annphoteric) surfactant
of the concentrate is non-fluorinated. A fluorinated surfactant will contain
some C-F bonds
and may contain only C-F bonds (in which case it is perfluoronated) and may
contain some
C-H bonds (in which case it is a hydrofluorocarbon-containing molecule).
[0099] In addition to fluorinated versions of the annphoteric and anionic
surfactants
identified herein, other exemplary fluorosurfactants that may be included in a
concentrate
or composition of the present disclosure include the CaptstoneTM
fluorosurfactants and the
ForafacTM fluorosurfactants, both from DuPont (Wilmington, DE). Other
exemplary
fluorosurfactants are those disclosed in any of US Patent Publication No. US
20130112908;
US 20120255651; US20110232924; US 20110091408; US 20100168318; and US. Patent
No.
US 8,287,752; US 8,039,677; US 7,977,426; and US 7,989,568.
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[00100] However, in another embodiment, the third surfactant is not a
fluorosurfactant. Fluorine-containing compounds should be used with caution
since they
may have an undesirable bio-persistence profile, and/or they may break down to
hazardous
materials. In one embodiment, the present concentrates and compositions do not
contain
any fluorocarbons, while in another embodiment the present concentrates and
compositions do not contain any halocarbons.
Formulations
[00101] The present disclosure provides material fabrication fluids, e.g.,
metal cutting
fluids, in concentrated form as well as in diluted (ready-to-use) forms. The
concentrated
form may be described in terms of the amounts of the various components, where
these
amounts are relative to the total amount of surfactant present in the
concentrate.
[00102] For example, for each weight part of surfactant (e.g., for each 1g,
or each 1kg,
etc. of surfactant) the concentrate may contain 1-10 weight parts of anti-rust
agent. Thus, if
the concentrate contains 10 grams of surfactant, the concentrate may also
contain from 10-
100 grams of anti-rust agent. Optionally, the concentrate contains at least 1,
or at least 2,
or at least 3, or at least 4, or at least 5 weight parts of anti-rust agent
(relative to 1 weight
part of surfactant), and may contain less than 10, or less than 9, or less
than 8, or less than
7, or less than 6, or less than 5 weight parts of anti-rust agent. In
exemplary embodiments,
the concentrate contains 1-10, or 2-8, or 3-7, or 4-6 weight parts of anti-
rust agent such as
sodium nitrite, for each 1 gram of total surfactant present in the
concentrate.
[00103] For each weight part of surfactant, the concentrate may contain 0.1-
0.5
weight parts of thickener. Thus, if the concentrate contains 10 grams of
surfactant, the
concentrate may also contain 1-5 grams of thickener. Optionally, the
concentrate contains
at least 0.1 or at least 0.2, or at least 0.3, or at least 0.4 weight parts of
thickener (relative to
1 weight part of surfactant(s)), and may contain less than 0.5, or less than
0.4, or less than
0.3 weight parts of thickener. In exemplary embodiments, the concentrate
contains 0.1-0.5,
or 0.2-0.4 weight parts of thickener such as hydroxyethylcellulose, for each 1
gram of total
surfactant present in the concentrate.
[00104] For each weight part of surfactant, the concentrate may contain
0.05-0.25
weight parts of inorganic salt. Thus, if the concentrate contains 10 total
grams of surfactant,
the concentrate may also contain 0.5-2.5 grams of inorganic salt. Optionally,
the
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concentrate contains at least 0.05, or at least 0.1, or at least 0.15, or at
least 0.2 weight
parts of inorganic salt (relative to 1 weight part of surfactant(s) present in
the concentrate),
and may contain less than 0.25, or less than 0.2, or less than 0.15, or less
than 0.1 weight
parts of inorganic salt. In exemplary embodiments, the concentrate contains
0.05-0.25, or
0.1-0.2 weight parts of inorganic salt such as calcium chloride.
[00105] For each weight part of surfactant, the concentrate may contain
0.01-0.1
weight parts of non-volatile, water-soluble organic solvent. Thus, if the
concentrate
contains 10 total grams of organic solvent, the concentrate may also contain
0.1-1 grams of
organic solvent. Optionally, the concentrate contains at least 0.01, or at
least 0.02, or at
least 0.03, or at least 0.04, or at least 0.05, or at least 0.06, or at least
0.07 weight parts of
organic solvent (relative to 1 weight part of surfactant(s) present in the
concentrate), and
may contain less than 0.1, or less than 0.09, or less than 0.08, or less than
0.07, or less than
0.06, or less than 0.05 weight parts of organic solvent. In exemplary
embodiments, the
concentrate contains 0.01-0.1, or 0.02-0.9, or 0.03-0.8 weight parts of
organic solvent such
as ethylene glycol butyl ether.
[00106] For each weight part of surfactant, the concentrate may contain 0.2-
1.0
weight parts of defoanner. Thus, if the concentrate contains 10 total grams of
surfactant,
the concentrate may also contain 2-10 grams of defoanner. Optionally, the
concentrate
contains at least 0.2, or at least 0.3, or at least 0.4, or at least 0.5
weight parts of defoanner
(relative to 1 weight part of surfactant(s) present in the concentrate), and
may contain less
than 1.0, or less than 0.9, or less than 0.8, or less than 0.7, or less than
0.6 weight parts of
defoanner. In exemplary embodiments, the concentrate contains 0.2-1.0, or 0.3-
0.8, or 0.4-
0.6 weight parts of defoanner such as a silicone defoanner.
[00107] The concentrate will also contain water. The amount of water may
vary, but
is typically in the range of 5-50% of the weight of the concentrate. In other
words, 100
grams of concentrate will include between 5 and 50 grams of water. In optional
embodiments, the concentrate is at least 5%, or at least 10%, or at least 15%,
or at least
20%, or at least 25% by weight water, while in other optional embodiments, the
concentrate
is less than 50%, or less than 45%, or less than 40%, or less than 35%, or
less than 30% by
weight water.
[00108] The present disclosure also provides for diluted forms of the
concentrate,
which are ready to use in a material fabrication process, such as a metal
cutting operation.
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In optional embodiments, the diluted forms of the concentrate have been
diluted
sufficiently that their water content is from 75-99%. Dilute forms of the
concentrate may be
diluted by combining the concentrate with an equal volume of water (a lx
dilution), or be
prepared by 2x, or 3x, or 4x, or 5x, or 6x, or 7x, or 8x, or 9x, or 10x, or
11x, or 12x, or 13x, or
14x, or 15x, or 16x, or 17x, or 18x, or 19x, or 20x dilution, as well as
ranges providing by
selecting any two of these values. For example, the diluted form may be
prepared by a
dilution of from 5x-15x, i.e., adding 5-15 volumes of water to each volume of
concentrate,
or by adding 5-15 weights of water to each weight of concentrate.
[00109] In one embodiment, the present disclosure provides a composition
comprising water and solids, the solids comprising at least one surfactant,
such as an
annphoteric first surfactant, an anionic second surfactant, and a third
surfactant selected
from an annphoteric and an anionic surfactant, the third surfactant being
different from the
first and second surfactants. In optional embodiments: the water comprises 75
to 95 wt%
of the composition; e.g., the water comprises 75 to 80 wt% of the composition
or the water
comprises 80 to 85 wt% of the composition or the water comprises 85 to 90 wt%
of the
composition or the water comprises 95 to 95 wt% of the composition. In
optional
embodiments: the annphoteric surfactant(s) comprises 10 to 30 wt% of the
solids or 15 to
25 wt% of the solids; e.g., the annphoteric surfactant(s) comprises 10 to 15
wt% of the solids
or the annphoteric surfactant(s) comprises 15 to 20 wt% of the solids or the
annphoteric
surfactant(s) comprises 20 to 25 wt% of the solids or the annphoteric
surfactant(s) comprises
25 to 30 wt% of the solids. In an optional embodiment, the annphoteric
surfactant(s)
comprise 1 to 5 wt% of the composition. In optional embodiments, the anionic
surfactant(s)
comprise 45 to 85 wt% of the solids; e.g., the anionic surfactant(s) comprise
45-55 wt% of
the solids or the anionic surfactant(s) comprise 55-65 wt% of the solids or
the anionic
surfactant(s) comprise 65-75 wt% of the solids or the anionic surfactant(s)
comprise 75-85
wt% of the solids. In an optional embodiment, the anionic surfactant(s)
connprise 5 to 25
wt% of the composition.
[00110] In additional optional embodiments, the annphoteric surfactant is
one or
more betaines selected from cocodinnethyl sulphopropyl betaine, lauryl betaine
and
cocannidopropyl betaine; the anionic surfactant is one or more surfactants
selected from
ammonium lauryl sulfosuccinatenn, sodium lauryl sulfate, sodium laureth
sulfate, sodium
lauryl ether sulfate, ammonium lauryl ether sulfate, triethanolannine
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dodecylbenzenesulfonate, sodium lauryl sarcosinate, ammonium lauryl sulfate,
sodium oleyl
succinate, sodium dodecyl sulfate, sodium decyl sulfate, sodium octyl sulfate,
and sodium
dodecylbenzene sulfonate; the composition further comprises an inorganic salt,
where
optionally the inorganic salt comprises 2 to 20 wt% of the solids; the
composition further
comprises a thickening agent, where optionally the thickening agent comprises
0.1 to 5 wt%
of the solids.
[00111] As mentioned previously, the compositions of the present disclosure
may
include both of an annphoteric surfactant (and optionally more than one
annphoteric
surfactant) and an anionic surfactant (and optionally more than one anionic
surfactant). In
one aspect, the one or more annphoteric surfactant(s) contribute about an
equal weight to
the composition as do the one or more anionic surfactant(s). In other aspects,
and again as
measured on a weight basis, the annphoteric surfactant(s) contribute a lesser
weight to the
total weight of the composition than do the anionic surfactant(s), where in
various
embodiments the annphoteric surfactant(s) contribute from 1 to 50%, or from 5
to 40%, or
from 10 to 30% or from 15 to 25% of the total weight of the anionic and
annphoteric
surfactants.
[00112] When the composition contains two of an annphoteric surfactant, or
two of
an anionic surfactant, the two surfactants are not necessarily present in
equal weight
amounts. In various embodiments, the composition comprises a first and a
second anionic
surfactant, where the first surfactant provides 1 to 50% of the total weight
of the first and
second surfactant. In additional embodiments, the first surfactant provides 1-
40%, or 1-
30%, or 1-20%, or 1 to 10%, or 1 to 5% of the total weight of the first and
second anionic
surfactants. Likewise, in various embodiments, the composition comprises a
first and a
second annphoteric surfactant, where the first annphoteric surfactant provides
1 to 50% of
the total weight of the first and second surfactant, and in additional
embodiments, the first
annphoteric surfactant provides 1-40%, or 1-30%, or 1-20%, or 1 to 10%, or 1
to 5% of the
total weight of the first and second annphoteric surfactants.
[00113] In one embodiment, a mixture of two annphoteric surfactants are
included in
a material fabrication fluid, e.g., a metal cutting fluid composition, of the
present disclosure.
For instance, mixtures of any of the previously mentioned annphoteric
surfactants may be
used. When two annphoteric surfactants are present in a composition, those two
surfactants will be present in relative amounts, based on the weight of each
the surfactants
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in the composition. For example, if the composition contains equal weights of
the two
annphoteric surfactants, then those two surfactants are present in a weight
ratio of 1:1. If
the composition contains twice as much of a first surfactant than of a second
surfactant,
then those two surfactants are present in a weight ratio of 1:2. If the second
surfactant is
present within a range of permissible weights, relative to the weight of the
first surfactant,
and that range is between "equal to the weight of the first surfactant" and
"twice as much
as the weight of the first surfactant" such that those two surfactants are
present in a weight
ratio of 1:(1-2).
[00114] As mentioned above, in one embodiment the present disclosure
provides for
the presence of two annphoteric surfactants in a composition. In various
embodiments,
those two annphoteric surfactants may be present at any of the following
relative amounts:
1:1; 1:(1-5); 1:(1-10); 1:(1-15); 1:(1-20); 1:(1-25); 1:(1-30); 1:(5-10); 1:(5-
15); 1:(5-20); 1:(5-
25); 1:(5-30); 1:(10-15); 1:(10-20); 1:(10-25); 1:(10-30); 1:(15-20); 1:(15-
25); 1:(15-30); 1:(20-
25); and 1:(25-30).
[00115] In one embodiment, a mixture of two anionic surfactants are
included in a
material fabrication fluid, e.g., a metal cutting fluid composition, of the
present disclosure.
For instance, mixtures of any of the previously mentioned anionic surfactants
may be used.
When two anionic surfactants are present in a composition, those two
surfactants will be
present in relative amounts, based on the weight of each the surfactants in
the composition.
For example, if the composition contains equal weights of the two anionic
surfactants, then
those two surfactants are present in a weight ratio of 1:1. If the composition
contains twice
as much of a first surfactant than of a second surfactant, then those two
surfactants are
present in a weight ratio of 1:2. If the second surfactant is present within a
range of
permissible weights, relative to the weight of the first surfactant, and that
range is between
"equal to the weight of the first surfactant" and "twice as much as the weight
of the first
surfactant" such that those two surfactants are present in a weight ratio of
1:(1-2).
[00116] As mentioned above, in one embodiment the present disclosure
provides for
the presence of two anionic surfactants in a composition. In various
embodiments, those
two anionic surfactants may be present at any of the following relative
amounts: 1:1; 1:(1-
5); 1:(1-10); 1:(1-15); 1:(1-20); 1:(1-25); 1:(1-30); 1:(5-10); 1:(5-15); 1:(5-
20); 1:(5-25); 1:(5-
30); 1:(10-15); 1:(10-20); 1:(10-25); 1:(10-30); 1:(15-20); 1:(15-25); 1:(15-
30); 1:(20-25); and
1:(25-30).
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[00117] In one embodiment the present disclosure provides a material
fabrication
fluid, e.g., a metal cutting fluid concentrate composition, that contains 10-
25 wt% of a first
anionic surfactant, optionally a sulfonate surfactant such as sodium
dodecylbenzene
sulfonate, optionally 12-23 wt% or optionally 15-20 wt% of the first anionic
surfactant; 5-15
wt% of an annphoteric surfactant, optionally a betaine surfactant such as
cocannidopropyl
betaine, optionally 7-13 wt% or optionally 7-11 wt% of the betaine surfactant;
1-10 wt% of a
second anionic surfactant, optionally a sulfate surfactant such as sodium
laureth sulfate or
sodium dodecyl sulfate, optionally 2-8 wt% or 3-7 wt% of the second anionic
surfactant; up
to about 5 wt% of an organic solvent, optionally a glycol ether such as
ethylene glycol butyl
ether, optionally 1-4 wt% or 2-3 wt% of glycol ether; 2-15 wt% of a thickener
such as a
cellulosic thickener, e.g., hydroxyethyl cellulose, optionally 4-12 wt% or 6-
10 wt% of the
thickener; up to about 10 wt% of calcium chloride, optionally 2-7 wt% or 3-6
wt% of calcium
chloride. Optionally the concentrate may contain a third anionic surfactant,
such as sodium
octyl sulfate, in an amount of up to about 5 wt%. Water will also be present
in the
concentrate. The total non-aqueous content of the concentrate is about 25-75
wt%, or
about 30-70 wt%, or about 35-55 wt%, or about 40-50 wt% (in the last case the
water
content is 50-40 wt%).
[00118] In one embodiment, the present disclosure provides a composition
including
a first anionic surfactant at a concentration of 0.1-0.3 wt% (i.e., 0.1-0.3 g
of first anionic
surfactant in 100 g of the composition, i.e., 1000-3000 ppnn of first anionic
surfactant), a
second anionic surfactant different from the first anionic surfactant at a
concentration of
0.01-0.10 wt% (i.e., 100-1000 ppnn of second anionic surfactant), an
annphoteric surfactant
at a concentration of 0.05-0.15, (i.e., 500-1500 ppnn of annphoteric
surfactant), and anti-rust
agent at a concentration of 0.1-0.3 wt% (i.e., 1000-3000 ppnn of anti-rust
agent). The
composition optionally also contains thickening agent at a concentration of
0.05-0.15 wt%
(500-1500 ppnn of thickening agent), and/or inorganic salt at a concentration
of 0.01-0.1
wt% (100-1000 ppnn of inorganic salt), and/or non-volatile organic solvent at
a
concentration of 0.01-0.1 wt% (100-1000 ppnn of non-volatile organic solvent),
and/or
defoanning agent at a concentration of 0.05-0.2 wt% (i.e., 500-2000 ppnn of
defoanning
agent). In one embodiment, the composition contains each of these components,
i.e., each
of first anionic surfactant, second anionic surfactant, annphoteric
surfactant, anti-rust agent,
thickening agent, inorganic salt, non-volatiles organic solvent and defoanning
agent. In one
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embodiment, the composition contains each of these components, i.e., each of
first anionic
surfactant which is a sulfonate-containing surfactant, second anionic
surfactant which is a
sulfate-containing surfactant, annphoteric surfactant which is a betaine-
containing
surfactant, anti-rust agent, thickening agent which is a cellulosic thickening
agent, inorganic
salt, non-volatiles organic solvent and defoanning agent. In one embodiment,
the
composition contains each of these components, i.e., each of first anionic
surfactant which
is a sulfonate-containing surfactant, second anionic surfactant which is a
sulfate-containing
surfactant, annphoteric surfactant which is a betaine-containing surfactant,
anti-rust agent
which is sodium nitrite, thickening agent which is a hydroxyethyl cellulose,
inorganic salt
which is calcium chloride, non-volatiles organic solvent which is ethylene
glycol butyl ether,
and defoanning agent which is a silicone defoanning agent.
[00119] In one embodiment, the present disclosure provides a composition
including
a first anionic surfactant at a concentration of about 0.2 wt% (i.e., about
0.2 g of first anionic
surfactant in 100 g of the composition, i.e., about 2000 ppnn of first anionic
surfactant), a
second anionic surfactant different from the first anionic surfactant at a
concentration of
about 0.05 wt% (i.e., about 500 ppnn of second anionic surfactant), an
annphoteric
surfactant at a concentration of about 0.09 wt% (i.e., about 900 ppnn of
annphoteric
surfactant), and anti-rust agent at a concentration of about 0.2 wt% (i.e.,
about 2000 ppnn of
anti-rust agent). The composition optionally also contains thickening agent at
a
concentration of 0.05-0.15 wt% (500-1500 ppnn of thickening agent) or about
800 ppnn
thickening agent, and/or inorganic salt at a concentration of 0.01-0.1 wt%
(100-1000 ppnn of
inorganic salt) or about 400 ppnn inorganic salt, and/or non-volatile organic
solvent at a
concentration of 0.01-0.1 wt% (100-1000 ppnn of non-volatile organic solvent)
or about 200
ppnn of non-volatile organic solvent, and/or defoanning agent at a
concentration of 0.05-0.2
wt% (i.e., 500-2000 ppnn of defoanning agent) or about 1000 ppnn of defoanning
agent. In
one embodiment, the composition contains each of these components, i.e., each
of first
anionic surfactant, second anionic surfactant, annphoteric surfactant, anti-
rust agent,
thickening agent, inorganic salt, non-volatiles organic solvent and defoanning
agent. In one
embodiment, the composition contains each of these components, i.e., each of
first anionic
surfactant which is a sulfonate-containing surfactant, second anionic
surfactant which is a
sulfate-containing surfactant, annphoteric surfactant which is a betaine-
containing
surfactant, anti-rust agent, thickening agent which is a cellulosic thickening
agent, inorganic
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salt, non-volatiles organic solvent and defoanning agent. In one embodiment,
the
composition contains each of these components, i.e., each of first anionic
surfactant which
is a sulfonate-containing surfactant, second anionic surfactant which is a
sulfate-containing
surfactant, annphoteric surfactant which is a betaine-containing surfactant,
anti-rust agent
which is sodium nitrite, thickening agent which is a hydroxyethyl cellulose,
inorganic salt
which is calcium chloride, non-volatiles organic solvent which is ethylene
glycol butyl ether,
and defoanning agent which is a silicone defoanning agent.
[00120] The following are some additional exemplary embodiments of the
compositions of the present disclosure, where metal cutting composition and
metal cooling
composition are used interchangeably:
1) A metal cutting composition comprising water, a first surfactant, a
thickening agent
such as a cellulosic thickening agent, and an anti-rust agent.
2) A metal cutting composition comprising water, a first surfactant, an
inorganic salt
such as calcium chloride, and an anti-rust agent.
3) A metal cooling composition of any of embodiments 1-2 wherein the first
surfactant
is an anionic surfactant.
4) The composition of any of embodiments 1-3 wherein the first surfactant is
an anionic
surfactant comprising a sulfonate group.
5) The composition of any of embodiments 1-4 wherein the first surfactant is
sodium
dodecylbenzene sulfonate.
6) The composition of any of embodiments 1-5 comprising a second
surfactant,
wherein the second surfactant is an annphoteric surfactant.
7) The composition of any of embodiments 1-6 comprising a second surfactant,
wherein the second surfactant is an annphoteric surfactant comprising a
betaine
group.
8) The composition of any of embodiments 1-7 comprising a second surfactant,
wherein the second surfactant is cocannidopropyl betaine.
9) The composition of any of embodiments 1-8 comprising a third surfactant,
wherein
the third surfactant is an anionic surfactant.
10) The composition of any of embodiments 1-9 comprising a third surfactant,
wherein
the third surfactant is an anionic surfactant comprising a sulfate group.
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11) The composition of any of embodiments 1-10 comprising a third surfactant,
wherein
the third surfactant is sodium laureth sulfate.
12) The composition of any of embodiments 1-11 wherein the anti-rust agent is
sodium
nitrite.
13) The composition of any of embodiments 1-12 comprising a thickening agent
which is
a cellulosic thickening agent, wherein the cellulosic thickening agent is
hydroxyl ethyl
cellulose.
14) The composition of any of embodiments 1-13 comprising a defoanning agent.
15) The composition of any of embodiments 1-14 comprising a defoanning agent,
wherein the defoanning agent is a silicone polymer.
16) The composition of any of embodiments 1-15 comprising a first surfactant
that
comprises a sulfonate group and a second surfactant that comprises a sulfate
group.
As discussed below, the present disclosure also provides a method of machining
metal,
comprising applying a composition comprising a composition of any of
embodiments 1-16 to
a piece of metal being machined, in an amount and time that are effective to
dissipate heat
from the metal being machined. The machining process may achieve cutting of
the metal,
and thus be referred to as a cutting process. The machining process may be any
of
broaching, tapping, hobbing, cutting, drilling, milling, turning, sawing,
honing or grinding,
which are examples of the machining processes that may be used in the method
of the
present disclosure.
[00121] The following are some additional exemplary embodiments of the
compositions of the present disclosure. A composition comprising water, a
first surfactant,
a thickening agent, and an anti-rust agent. The first surfactant may be an
anionic surfactant,
such as a sulfonate- or sulfate-containing surfactant. Optionally, the first
surfactant is
sodium dodecylbenzene sulfonate. Optionally, the first surfactant is sodium
laureth sulfate.
Rather than being an anionic surfactant, the first surfactant may be an
annphoteric
surfactant, such as a betaine-containing surfactant, e.g., cocannidopropyl
betaine.
Optionally, the composition may include two surfactants, where each is an
anionic
surfactant, e.g., wherein the two surfactants are a sulfate-containing
surfactant and a
sulfonate-containing surfactant such as sodium laureth sulfate and sodium
dodecylbenzene
sulfonate. Optionally, the composition may include two surfactants, where one
is an anionic
surfactant and the other is an annphoteric surfactant, such as a sulfate-
containing anionic
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surfactant and a betaine-containing annphoteric surfactant where the sulfate-
containing
anionic surfactant may be sodium laureth sulfate and the betaine-containing
annphoteric
surfactant may be cocannidopropyl betaine. Optionally, the composition may
include two
surfactants, where one is an anionic surfactant and the other is an
annphoteric surfactant,
such as a sulfonate-containing anionic surfactant and a betaine-containing
annphoteric
surfactant, where the sulfonate-containing anionic surfactant may be sodium
dodecylbenzene sulfonate and the betaine-containing annphoteric surfactant may
be
cocannidopropyl betaine. Optionally, the composition may include three
surfactants, two of
the three surfactants being non-identical anionic surfactants and one of the
three
surfactants being an annphoteric surfactant, where these three surfactants may
optionally
be a sulfate-containing surfactant, a sulfonate-containing surfactant, and a
betaine-
containing surfactant, e.g., sodium dodecylbenzene sulfonate, sodium laureth
sulfate, and
cocannidopropyl betaine. When present, the sulfonate-containing surfactant may
be
present at a concentration of about 1800 ppnn, e.g., 1000-3000 ppnn. When
present, the
sulfate-containing surfactant may be present at a concentration of about 500
ppnn, e.g.,
100-1000 ppnn. When present, the annphoteric surfactant may be present at a
concentration of about 900 ppnn, e.g., 500-1500 ppnn. The composition will
contain an
effective amount of an anti-rust agent as described herein, where the anti-
rust agent may
be, e.g., sodium nitrite. The concentration of the anti-rust agent may be
about 100-5000
ppnn, or about 1000-3000 ppnn, or about 2000 ppnn. The thickening agent is
described
herein, and may be, e.g., a cellulosic thickening agent such as hydroxyl ethyl
cellulose. The
concentration of the thickening agent in the composition may be about 100-2000
ppnn, or
about 500-1500 ppnn, or about 800 ppnn. The composition may optionally
contain, and in
one embodiment does contain, a defoanning agent as described herein. An
exemplary
defoanning agent is a silicone polymer. When present, the defoanning agent may
be present
at a concentration of about 100-5000 ppnn, or about 500-2000 ppnn, or about
1000 ppnn.
[00122] The following are some additional exemplary embodiments of the
compositions of the present disclosure. A composition comprising water, a
first surfactant,
an inorganic salt, and an anti-rust agent. The first surfactant may be an
anionic surfactant,
such as a sulfonate- or sulfate-containing surfactant. Optionally, the first
surfactant is
sodium dodecylbenzene sulfonate. Optionally, the first surfactant is sodium
laureth sulfate.
Rather than being an anionic surfactant, the first surfactant may be an
annphoteric
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surfactant, such as a betaine-containing surfactant, e.g., cocannidopropyl
betaine.
Optionally, the composition may include two surfactants, where each is an
anionic
surfactant, e.g., wherein the two surfactants are a sulfate-containing
surfactant and a
sulfonate-containing surfactant such as sodium laureth sulfate and sodium
dodecylbenzene
sulfonate. Optionally, the composition may include two surfactants, where one
is an anionic
surfactant and the other is an annphoteric surfactant, such as a sulfate-
containing anionic
surfactant and a betaine-containing annphoteric surfactant where the sulfate-
containing
anionic surfactant may be sodium laureth sulfate and the betaine-containing
annphoteric
surfactant may be cocannidopropyl betaine. Optionally, the composition may
include two
surfactants, where one is an anionic surfactant and the other is an
annphoteric surfactant,
such as a sulfonate-containing anionic surfactant and a betaine-containing
annphoteric
surfactant, where the sulfonate-containing anionic surfactant may be sodium
dodecylbenzene sulfonate and the betaine-containing annphoteric surfactant may
be
cocannidopropyl betaine. Optionally, the composition may include three
surfactants, two of
the three surfactants being non-identical anionic surfactants and one of the
three
surfactants being an annphoteric surfactant, where these three surfactants may
optionally
be a sulfate-containing surfactant, a sulfonate-containing surfactant, and a
betaine-
containing surfactant, e.g., sodium dodecylbenzene sulfonate, sodium laureth
sulfate, and
cocannidopropyl betaine. When present, the sulfonate-containing surfactant may
be
present at a concentration of about 1800 ppnn, e.g., 1000-3000 ppnn. When
present, the
sulfate-containing surfactant may be present at a concentration of about 500
ppnn, e.g.,
100-1000 ppnn. When present, the annphoteric surfactant may be present at a
concentration of about 900 ppnn, e.g., 500-1500 ppnn. The composition will
contain an
effective amount of an anti-rust agent as described herein, where the anti-
rust agent may
be, e.g., sodium nitrite. The concentration of the anti-rust agent may be
about 100-5000
ppnn, or about 1000-3000 ppnn, or about 2000 ppnn. The inorganic salt is
described herein,
and may be, for example, calcium chloride. The concentration of the inorganic
salt in the
composition may be about 50-2000 ppnn, or about 100-1000 ppnn, or about 400
ppnn. The
composition may optionally contain, and in one embodiment does contain, a
defoanning
agent as described herein. An exemplary defoanning agent is a silicone
polymer. When
present, the defoanning agent may be present at a concentration of about 100-
5000 ppnn, or
about 500-2000 ppnn, or about 1000 ppnn.
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Methods of Manufacture
[00123] In one aspect, the present disclosure provides methods of preparing
the
material fabrication fluid, e.g., the metal cutting fluid concentrate
compositions and the
corresponding metal cutting fluid compositions as identified herein. In
general, the
concentrates are prepared by combining water with one or more surfactants
selected from
anionic and annphoteric surfactants, along with optional ingredients. The
compositions are
prepared by diluting the concentrate with water or aqueous solution.
[00124] In one embodiment, a concentrate is prepared by combining a first
surfactant
which is an annphoteric surfactant, a second surfactant which is an anionic
surfactant, and a
third surfactant selected from an annphoteric and an anionic surfactants,
where the third
surfactant is other than the first or second surfactants. The concentrate may
optionally
contain additional surfactant(s), i.e., a fourth, fifth, etc. surfactant. In
addition, or
alternatively, the concentrate may contain active ingredient(s) other than
surfactant, e.g.,
inorganic components, organic solvents and thickening agents. The compositions
are water
based, in other words, they are aqueous compositions in that the carrier is
primarily water.
The compositions may be prepared by any of the following methods.
[00125] In one embodiment, a container of water is provided. This container
holds
between about 5 and 20 Kg of water. This method may be scaled up or down so as
to
provide the desired amount of fluid concentrate. The initial amount of water
is about 5-
40%, or about 10-30% of the total amount of water in the concentrate. The
water may be at
ambient temperature or it may be at an elevated temperature. Elevated
temperatures of
below the boiling point of water, i.e., below 100 C, or below 90 C, or below
80 C, or below
70 C may be used. Elevated temperatures in excess of the ambient temperature,
e.g.,
above 25 C, or above 30 C, or above 40 C, or above 50 C, or above 60 C, or
above 70 C may
be used.
[00126] The one or more surfactants are then added to the water. In one
embodiment an annphoteric surfactant is added to the water, followed by the
sequential
addition of a first and second anionic surfactant. In an alternative
embodiment, an anionic
surfactant is added first to the water, followed by an annphoteric surfactant,
which in turn is
followed by the addition of either a second anionic surfactant or a second
annphoteric
surfactant. In another embodiment, the first and second anionic surfactants
are added
sequentially, followed by the addition of an annphoteric surfactant.
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[00127] After the addition of a surfactant to the water, the resulting
mixture is stirred
to provide a homogeneous or near homogeneous state. Stirring may be performed
leisurely
or vigorously, however in either event it is preferred that undue amounts of
foam are not
created. Foam typically results from the entrapment of air in the mixture,
where air tends
to become entrapped when there is a significant vortex created during the
mixing process
and/or when the stirring device repeated enters and exits the mixture. Foam
retention also
tends to be greater when the viscosity of the mixture is greater. These
situations are
preferably avoided in order to minimize foam production. In order to assure
good mixing, a
stirring time of about 15-60 minutes may be employed after the addition of
each surfactant.
[00128] Depending on the presence or absence of insulation surrounding the
container in which the concentrate is being prepared, the temperature of the
mixture may
drop during the surfactant addition and stirring steps. Alternatively, the
temperature of the
mixture may be maintained at or nearly at the original temperature of the
water by, for
example, maintaining gentle heating directed to the sides and/or the bottom of
the
container which holds the concentrate. Alternatively, or additionally, heating
coils may be
positioned within the container to add or withdraw heat from the concentrate
as desired.
[00129] As surfactant is added to the water, the viscosity of the mixture
will tend to
increase. A solution of increased viscosity will tend to entrap air more
readily than does a
lower viscosity solution, all other factors being equal. In order to reduce
the viscosity of a
mixture, additional water may be added to the mixture after the addition of
any of the first,
second or third surfactants. For example, an amount of water which is about 5-
40%, or
about 10-30% of the total amount of water in the concentrate may be added to
the mixture
after the first addition of surfactant. In addition, or alternatively, an
amount of water which
is about 5-40%, or about 10-30% of the total amount of water in the
concentrate may be
added to the mixture after the second addition of surfactant.
[00130] After all of the surfactants have been added and thoroughly mixed
into the
water, optional ingredient(s) may be added to the resulting mixture. For
example, an
inorganic component, e.g., an inorganic salt, may be added to the mixture,
followed by
stirring to completely dissolve the inorganic component. The optional
ingredient(s) may be
added to the warm or hot mixture, or to the mixture after it has cooled down
to room
temperature. Since the concentrate will typically be stored and used at room
temperature,
any optional ingredients that will significantly impact the viscosity or flow
properties of the
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mixture are typically added to the mixture at room temperature.
[00131] The surfactants and optional ingredients may be added to the water
in a neat
form, i.e., without being in contact with a solvent, or may be added in a
diluted form, i.e., in
contact with a solvent so as to provide a solution, paste, dispersion, etc. of
the ingredient.
In one embodiment, the surfactants are added to water in the order of their
solids content
in water, with the more concentrated ingredient being added first. In other
words, if a
surfactant is at 50% solids and another surfactant is at 25% solids, then the
surfactant at
50% solids is added to water before the surfactant at 25% solids is added to
the mixture.
[00132] The concentrate may be prepared in a batch, continuous or semi-
continuous
mode. In a batch mode, ingredients are added sequentially to a container of
water, until all
of the ingredients have been added, in which case a batch of concentrate has
been
prepared. In a continuous mode, water is propelled through a pipe or other
conduit, and
various ingredients are added to the water at various points along the
conduit. For
example, the conduit may be fitted with T-valves, where an ingredient may be
fed into the
water, or aqueous mixture, through the T-valve. The conduit may also contain
mixers within
the conduit, either static or inline mixers, to facilitate the creation of a
homogenous mixture
after an ingredient has been added to the water or aqueous mixture. For
example, water
and a first surfactant may be fed into a pipe and pass through a mixer.
Typically a static
mixer is adequate if the surfactant is pre-dissolved in water. Otherwise, an
inline mixer is
typically preferred. Thereafter, a second surfactant is added to the conduit
downstream of
the mixer, which again goes through a mixing process. Finally, a third
surfactant is added to
the aqueous mixture, following by mixing as needed, so as to provide an
aqueous mixture
comprising three surfactants. Thereafter, additional, optional ingredients may
be added to
the conduit, through a T-valve for example, following by suitable stirring, to
form the final
concentrate.
[00133] To facilitate mixing of the various ingredients, and to minimize
vortex
formation and consequently foam formation, baffles may be installed within the
batch or
continuous reactor. Suitable mixing equipment, such as agitators, impellers,
static mixers,
colloid mills, and homogenizers are made and sold by, e.g., Chennineer
(Dayton, Ohio) and
Sulzer (Winterthur, Switzerland).
[00134] In an alternative embodiment for a continuous process, three T-
valves are
located at the beginning of the conduit, at a location after water has already
been added to
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the conduit. The first, second and third surfactants are each delivered into
the conduit
through one of the three T-valves. In this manner, all of the three
surfactants are combined
essentially at the same time, and then the resulting mixture is passed through
an inline or
static mixer within the conduit, to provide a homogenous aqueous mixture.
Optional
ingredients are then added to the homogeneous aqueous mixture as desired, to
provide the
final concentrate.
[00135] In either a continuous or batch process, the water and/or aqueous
mixture
may be heated to a temperature in excess of ambient temperature, e.g., a
temperature
between 50 C and 90 C. Heating may be accomplished by routine methods known in
the
art. The elevated temperature may be maintained as needed to facilitate prompt
mixing of
the ingredients to form a homogeneous mixture.
[00136] Accordingly, in one embodiment, the present disclosure provides a
continuous
process for making a material fabrication fluid, e.g., a metal cutting fluid
concentrated
composition. The process comprises providing a continuous reactor, charging
water to the
continuous reactor, adding to the water in the continuous reactor the desired
one or more
surfactants, e.g., a) a first anionic surfactant, b) a second annphoteric
surfactant, and c) a third
surfactant selected from an anionic surfactant and a cationic surfactant, the
third surfactant
being different from the first surfactant and the second surfactant; and
mixing components
a), b) and c) to provide a homogeneous mixture. Optionally, the continuous
reactor is
maintained at a temperature in excess of 50 C. Also optionally, a mixer
selected from an in-
line mixer and a static mixer is present in the continuous reactor.
Method of Use
[00137] The present disclosure provides fabrication fluids, e.g., fluids
useful in metal
cutting, that may be used in the course of materials fabrication, e.g.,
cutting metal. In one
embodiment, the fluid concentrate of the present disclosure is diluted with
water to provide
a composition that may be applied to tooling involved in material fabrication,
e.g., a metal
cutting fluid composition that is applied directly to the metal. The
concentrate will have a
solids level or content, measured as the sum of the weights of the non-aqueous
components in the concentrate, divided by the total weight of the concentrate.
When
water is combined with concentrate so as to form a metal cutting fluid
composition, the
metal cutting fluid composition will likewise have a solids level or content,
which will be less
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than the solids level or content of the concentrate. In various embodiment,
the
composition is formed by combining sufficient water with the concentrate so as
to provide a
metal cutting fluid composition having a weight percent solids, based on the
total weight of
composition, of 0.1%, or 0.5%, or 1%, or 1.5%, or 2%, or 2.5%, or 3%, or 3.5%,
or 4%, or
4.5%, or 5%, or 5.5%, or 6%, or 6,5%, or 7%, or 7.5%, or 8%, or 8.5%, or 9%,
or 9.5%, or 10%,
or 10.5%, or 11%, or 11.5%, or 12%, or 12.5%, or 13%, or 13.5%, or 14%, or
14.5%, or 15%,
or 15.5%, or 16%, or 16.5%, or 17%, or 17.5%, or 18%, or 18.5%, or 19%, or
20%, or a
concentration within a range provided any of the two aforesaid solids percent
values, e.g.,
0.5% to 4%.
[00138] In one aspect, the prepared person will have a supply of metal
cutting fluid
concentrate in storage, readily available when needed to cut metal, and with
access to a
method of combining the concentrate with water so as to form a metal cutting
fluid
composition. Optionally, the metal cutting fluid concentrations as disclosed
herein may be
diluted with water to create a metal cutting fluid composition.
[00139] Cutting fluid maintenance involves checking the concentration of
soluble oil
emulsions (using refractonneters), pH (using a pH meter), the quantity of
tramp oil (hydraulic
oil leaking into the cutting fluid system) and the quantity of particulates in
the fluid. Action
taken to maintain the fluid includes adding make-up concentrate or water,
skimming of
tramp oil, adding biocides to prevent bacterial growth and filtering the
particulates by
centrifuging.
[00140] The cutting fluid within a coolant system degrades with time due to
bacterial
growth and contamination with tramp oil and fine metal swarf from the
machining
operation. When it becomes uneconomical to maintain the fluid by regular make-
up
operations it is dumped. Prior to letting the fluid flow into a sewer system,
it should be
treated to bring the fluid composition to safe disposal levels.
[00141] Some metals are more difficult to machine than others. Stainless
steel, exotic
alloys and very hard metals demand a very high level of performance from the
cutting fluid.
Other metals, like brass and aluminum, are easy to machine with general-
purpose oils.
Where tough, low-nnachinability metals are involved, it is advantageous to use
highly
additized cutting oil with excellent extreme-pressure (EP) and anti-weld
capability. Most
often, these oils contain active sulfur and chlorine to protect the tooling
and ensure good
parts finish. In one embodiment, the cutting fluid of the present invention
include active
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sulfur and/or chlorine.
[00142] For brass, aluminum, many carbon steels and low-alloy steels, a
cutting oil
with lubricity additives, friction modifiers and mild EP/anti-weld performance
is sufficient.
These oils are generally formulated with sulfurized fat (inactive) and/or
chlorinated paraffin.
Active cutting oils (containing active sulfur) should not be used for brass
and aluminum, as
they will stain or tarnish the finished parts. Oils formulated for brass and
aluminum are
often called "non-staining" oils. In one embodiment, the cutting fluid of the
present
invention includes one or more of lubricity additives, friction modifiers,
sulfurized fat
(inactive) and chlorinated paraffin.
[00143] Easy machining operations (turning, forming, drilling, milling,
etc.) can be
performed at higher speeds and require high levels of cooling with only modest
EP
capability. The milder operations can be performed with lower viscosity,
lightly additized
fluids. Difficult machining operations must be run at lower speeds and require
a great deal
of anti-weld protection. Oils designed specifically for the most difficult
operations, like
thread-cutting or broaching, are generally higher in viscosity and loaded with
EP additives
like active sulfur and chlorine.
[00144] The type of machinery will also dictate some of the cutting oil
characteristics.
For example, screw machines experience heavy cross-contamination between the
lube oil
and cutting oil. For this reason, these machines frequently run on dual-
purpose or tri-
purpose oils that can be used in the lube boxes, hydraulics and cutting oil
sumps.
[00145] Grinders, gun drills and deep-hole drilling machines require
lighter viscosity
oils for high rates of cooling, good chip and swarf flushing, through-the-tool
delivery and
high-pressure application without foaming. CNC OEMs may place restrictions on
the cutting
oil due to potential incompatibility between the cutting fluid and machine
components,
such as seals. Centerless grinders may require a tougher fluid than surface
grinders.
[00146] In general, the compositions of the present disclosure, in a ready-
to-use
form, may be applied during a material fabrication process. As used herein,
material
fabrication, which may also be referred to as machining, is a process whereby
a tool makes
contact with, and is used to modify the shape or surface of, a material by any
suitable
method, and heat is generated at the contact point between the material and
the tooling.
Examples include cutting into the material with a blade, drilling a hole in
the material with a
drill bit, and removing a surface layer of the material with a lathe. Another
example of
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material fabrication is stamping. The composition may be applied to the
material being
fabricated and/or the tooling that comes into contact with the material being
fabricated.
Examples of the application process include flooding, spraying, dripping,
misting, and
brushing the composition onto the part being fabricated and/or the associated
tooling that
contacts the part being fabricated. The material being fabricated may be, for
example,
metal, stone or plastic. The composition, after application, will maintain the
tooling/material interface at a relatively cool temperature so that harm,
e.g., warpage, is
avoided for each of the material being fabricated and the tooling doing the
fabricating. The
composition may also provide lubricating properties.
[00147] For example, when the fabrication fluid is a metal cutting fluid,
the fluid
provides coolant and lubricant properties as need for metal working processes,
such as
machinery and stamping. Metal cutting generates heat due to friction, which
can deform
the material. Coolants work to remove the heat from the machinery and
materials so it can
speed the cutting process, making the machines more productive. Besides
cooling, cutting
fluids also aid the cutting process by lubricating the interface between the
tool's cutting
edge and the chip. By preventing friction at this interface, some of the heat
generation is
prevented. This lubrication also helps prevent the chips from being welded
onto the tool,
which would interfere with subsequent cutting. Most metal working and
machining
processes can benefit from the use of cutting fluids, depending on the
workpiece material.
[00148] The compositions of the present disclosure provide one or more of
the
following benefits in materials fabrication: keeping the workpiece at a stable
temperature
(which is critical when working to close tolerances); maximizing the lifetime
of the cutting
tip by lubricating the working edge and reducing the top welding; ensuring
safety for the
people handling it (toxicity, bacteria, and fungi) and for the environment
upon disposal; and
preventing rust on machine parts and cutters.
[00149] A portion of the fabricating equipment will come into contact with
the
workpiece being fabricated. For example, the fabricating equipment may have a
blade that
cuts the material during fabrication. The blade may be metal, e.g., stainless
steel, or it may
be diamond encrusted. Alternatively, the fabricating equipment may be a
turning tool such
as a latche or a drill, or a polishing or sanding device.
[00150] Thus, the present disclosure provides methods of delivering a
fabrication
fluid, e.g., a metal cooling composition, as described herein. In one
embodiment, the
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present disclosure provides a method comprising providing a fabrication
composition of the
present disclosure, applying that composition to one or both of the material
being
fabricated and the tooling that is being used to fabricate the material, and
fabricating the
material with the tooling in the presence of the composition of the present
disclosure. The
method affords cooling and temperature control at the interface where the
tooling contact
the fabricated material, and/or provides lubrication at that interface.
[00151] For example, the present disclosure provides a method for
fabricating a solid
material such as metal, stone, plastic, the method comprising providing a
composition of
the present disclosure, such as a composition comprising water, a first
surfactant, a
thickening agent, and an anti-rust agent; applying that composition to the
material being
fabricated, e.g., by brushing, spraying, or pouring the composition onto the
material and/or
onto the tooling that does the fabricating, where the composition will
transfer to the
interface of the tooling/ material during the fabrication process; and
fabricating that
material with tooling in the presence of the composition.
[00152] As another example, the present disclosure provides a method for
fabricating
a solid material such as metal, stone, plastic, the method comprising
providing a
composition of the present disclosure, such as a composition comprising water,
a first
surfactant, an inorganic salt, and an anti-rust agent; applying that
composition to the
material being fabricated, e.g., by brushing, spraying, or pouring the
composition onto the
material and/or onto the tooling that does the fabricating, where the
composition will
transfer to the interface of the tooling/ material during the fabrication
process; and
fabricating that material with tooling in the presence of the composition.
[00153] The stone may be, for example, any of granite, limestone, marble,
sandstone,
slate, basalt, tavertine or quartzite. Other stones may also be fabricated
using the
compositions of the present disclosure.
[00154] The plastic may be, for example, a pure polymer such as
polypropylene and
polyethylene, or a plastic composite, such as a composite of polymer and
stone, e.g.,
CORIANTM. The plastic may be a silicon chip or other silicon product such as a
silicon wafer
or other silicon material used in the semiconductor industry.
[00155] The composition and methods of use thereof according to the present
disclosure achieve one or both of a) a reduction in the heat being generated
on the cutting
surface to improve the quality of the product (e.g., fewer burrs, smoother
cut, less
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deformation (in the case of plastic); and b) increasing the longevity of the
fabricating device.
In one embodiment, the compositions of the present disclosure contain little
or no oil, and
accordingly their use eliminates the problem of disposing of toxic oil-based
waste that is
associated with alternative fabricating fluids.
[00156] The following examples are provided to illustrate embodiments of
the
present disclosure and are not to be construed as limiting thereon.
Examples
[00157] In the following examples, the indicated commercial products may
not have
the solids content or the neutralization indicated as being used in the
example. In such a
case, the commercial product may be diluted with water to the indicted solids
content
and/or neutralized with acid or base as needed to provide the indicated
neutralized form.
The thickening agent is added to provide a final viscosity approximately that
of whole milk
or orange juice.
Example 1
[00158] To about 10 kg of heated water (about 75 C) is sequentially added
the
following ingredients, each ingredient addition being followed by stirring for
a period of
about 30 minutes in a manner that minimizes foam formation: first anionic
surfactant
solution (about 9 kg at about 60% solids in water of branched chain sodium
dodecylbenzene
sulfonate, e.g., SULFONIC 100 from Stepan Company, after neutralization with
sodium
hydroxide), annphoteric surfactant solution (about 4.5 kg at about 35% solids
in water of
cocannidopropylbetaine, e.g., AMPHOSOL CA from Stepan Company), heated water
(about 9
kg), second anionic surfactant solution (about 11 kg at about 3% solids in
water of sodium
lauryl ether sulfate, e.g., CALFOAM ES-703 from Pilot Chemical Co.), and
inorganic salt
solution (about 2 kg at about 30% solids in water of calcium chloride, where
calcium
chloride in both solid and solution forms is available from e.g., OxyChenn,
Ludington, MI).
The resulting mixture is allowed to cool to ambient temperature (about 8
hours) and then
thickening agent (about 4 kg of about 1.5% solids in water of sodium carboxy
methyl
cellulose, e.g., AQUALON, Ashland Chemicals, Covington, KY) is added. To this
mixture is
added a desired amount of anti-rust agent, and optionally further added are
one or both of
defoanner and colorant, to provide the final metal cutting fluid concentrate.
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Example 2
[00159] To about 10 kg of heated water (about 75 C) is sequentially added
the
following ingredients, each ingredient addition being followed by stirring for
a period of
about 30 minutes in a manner that minimizes foam formation: first anionic
surfactant
solution (about 9 kg at about 53% solids in water of triethanolannine
dodecylbenzene
sulfonate, CALSOFT T60 (Pilot Chemical), annphoteric surfactant solution
(about 4.5 kg at
about 35% solids in water of sodium cocoannphoacetate, AMPHITOL 20Y-B (Kao
Chemicals),
heated water (about 6.5 kg), second anionic surfactant solution (about 14 kg
at about 7%
solids in water of ammonium lauryl sulfate, EMAL AD-25R (Kao Chemicals)), and
inorganic
salt solution (about 2 kg at about 30% solids in water of calcium chloride,
where calcium
chloride in both solid and solution forms is available from e.g., OxyChenn,
Ludington, MI).
The resulting mixture is allowed to cool to ambient temperature (about 8
hours) and then
thickening agent (about 4 kg of about 1.5% solids in water of sodium carboxy
methyl
cellulose, e.g., WALOCEL CRT, Dow Chemical) is added. To this mixture is added
a desired
amount of anti-rust agent, and optionally further added are one or both of
defoanner and
colorant, to provide the final cutting fluid concentrate.
Example 3
[00160] To about 8 kg of heated water (about 75 C) is sequentially added
the
following ingredients, each ingredient addition being followed by stirring for
a period of
about 30 minutes in a manner that minimizes foam formation: first anionic
surfactant
solution (about 8.5 kg at about 53% solids in water of sodium lauryl
sulfoacetate, LATHANOL
LAL flake (Stepan Co.), annphoteric surfactant solution (about 6.3 kg at about
30% solids in
water of lauryl hydroxysultaine, AMPHITOL 20HD, Kao Chemicals), heated water
(about 6.5
kg), second anionic surfactant solution (about 14 kg at about 7% solids in
water of sodium
octyl phenol ethoxylate sulfate, POE-3, POLY-STEP C-OP3S (Stepan Co.)), and
inorganic salt
solution (about 2 kg at about 30% solids in water of calcium chloride, where
calcium
chloride in both solid and solution forms is available from e.g., OxyChenn,
Ludington, MI).
The resulting mixture is allowed to cool to ambient temperature (about 8
hours) and then
thickening agent (about 4 kg of about 1.5% solids in water of sodium carboxy
methyl
cellulose, e.g., AQUALON, Ashland Chemicals, Covington, KY) is added. To this
mixture is
added a desired amount of anti-rust agent, and optionally further added are
one or both of
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defoanner and colorant, to provide the final cutting fluid concentrate.
Example 4
[00161] To about 8.5 kg of heated water (about 75 C) is sequentially added
the
following ingredients, each ingredient addition being followed by stirring for
a period of
about 30 minutes in a manner that minimizes foam formation: first anionic
surfactant
solution (about 9 kg at about 53% solids in water of polyoxyethylene (10)
nonylphenol
phosphate, FOSFODET 90/22 (Kao Chemicals)), annphoteric surfactant solution
(about 5.3 kg
at about 35% solids in water of disodiunn cocoannphodipropionate, CRODATERIC
CADP 38
(Croda)), heated water (about 6 kg), second anionic surfactant solution (about
14 kg at
about 7% solids in water of sodium dioctyl sulfosuccinate, STEPWET DOS-70
(Stepan Co.)),
and inorganic salt solution (about 3.3 kg at about 30% solids in water of
calcium chloride,
where calcium chloride in both solid and solution forms is available from
e.g., OxyChenn,
Ludington, MI). The resulting mixture is allowed to cool to ambient
temperature (about 8
hours) and then thickening agent (about 4 kg of about 1.5% solids in water of
sodium
carboxy methyl cellulose, e.g., WALOCEL CRT, Dow Chemical) is added. To this
mixture is
added a desired amount of anti-rust agent, and optionally further added are
one or both of
defoanner and colorant, to provide the final cutting fluid concentrate.
Example 5
[00162] To about 15 kg of heated water (about 75 C) is sequentially added
the
following ingredients, each ingredient addition being followed by stirring for
a period of
about 30 minutes in a manner that minimizes foam formation: first anionic
surfactant
solution (about 5 kg at about 53% solids in water of polyoxyethylene (8) octyl
ether
carboxylic acid, AKYPO LF2 (Kao Chemical)), annphoteric surfactant solution
(about 8.3 kg at
about 30% solids in water of cocannidopropylannine oxide, CALOXAMINE CPO
(Pilot
Chemical)), heated water (about 14 kg), second anionic surfactant solution
(about 7.5 kg at
about 20% solids in water of sodium lauroyl sarcosinate, MAPROSYL 30-13
(Stepan Co.)), and
inorganic salt solution (about 3.3 kg at about 30% solids in water of calcium
chloride, where
calcium chloride in both solid and solution forms is available from e.g.,
OxyChenn, Ludington,
MI). The resulting mixture is allowed to cool to ambient temperature (about 8
hours) and
then thickening agent (about 4 kg of about 1.5% solids in water of sodium
carboxy methyl
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cellulose, e.g., AQUALON, Ashland Chemicals, Covington, KY) is added. To this
mixture is
added a desired amount of anti-rust agent, and optionally further added are
one or both of
defoanner and colorant, to provide the final cutting fluid concentrate.
Example 6
[00163] To about 14 kg of heated water (about 75 C) is sequentially added
the
following ingredients, each ingredient addition being followed by stirring for
a period of
about 30 minutes in a manner that minimizes foam formation: first anionic
surfactant
solution (about 5.6 kg at about 50% solids in water of potassium oleate,
ICTEOL K-50 (Kao
Chemicals)), annphoteric surfactant solution (about 8.3 kg at about 30% solids
in water of
cocannidopropyl betaine, CALTAINE C-35 (Pilot Chemical), heated water (about
15 kg),
second anionic surfactant solution (about 6 kg at about 20% solids in water of
disulfonated
diphenyl oxide with linear decyl substitution, DOWFAX C1OL, (Dow Chemical)),
and inorganic
salt solution (about 3.3 kg at about 30% solids in water of calcium chloride,
where calcium
chloride in both solid and solution forms is available from e.g., OxyChenn,
Ludington, MI).
The resulting mixture is allowed to cool to ambient temperature (about 8
hours) and then
thickening agent (about 4 kg of about 1.5% solids in water of sodium carboxy
methyl
cellulose, e.g., WALOCEL CRT, Dow Chemical) is added. To this mixture is added
a desired
amount of anti-rust agent, and optionally further added are one or both of
defoanner and
colorant, to provide the final cutting fluid concentrate.
Example 7
[00164] To about 15 kg of heated water (about 75 C) is sequentially added
the
following ingredients, each ingredient addition being followed by stirring for
a period of
about 30 minutes in a manner that minimizes foam formation: first anionic
surfactant
solution (about 5 kg at about 50% solids in water of isopropylannine
dodecylbenzene
sulfonate, NINATE 411 (Stepan Co.)), annphoteric surfactant solution (about 10
kg at about
30% solids in water of cocannidopropyl hydroxysultaine, AMPHOSOL CS-50
(Stepan), heated
water (about 15 kg), second anionic surfactant solution (about 5 kg at about
30% solids in
water of sodium dodecylbenzene sulfonate, MELIOSOL 50X (Kao Chemical), and
inorganic
salt solution (about 3.3 kg at about 30% solids in water of calcium chloride,
where calcium
chloride in both solid and solution forms is available from e.g., OxyChenn,
Ludington, MI).
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The resulting mixture is allowed to cool to ambient temperature (about 8
hours) and then
thickening agent (about 4 kg of about 1.5% solids in water of sodium carboxy
methyl
cellulose, e.g., AQUALON, Ashland Chemicals, Covington, KY) is added. To this
mixture is
added a desired amount of anti-rust agent, and optionally further added are
one or both of
defoanner and colorant, to provide the final cutting fluid concentrate.
Example 8
[00165] To about 20 kg of heated water (about 75 C) is sequentially added
the
following ingredients, each ingredient addition being followed by stirring for
a period of
about 30 minutes in a manner that minimizes foam formation: first anionic
surfactant
solution (about 8.4 kg at about 50% solids in water of disulfonated
diphenyloxide with alkyl
substitution, DOWFAX C1OL (Dow Chemical)), annphoteric surfactant solution
(about 6.7 kg
at about 30% solids in water of laurannidopropylbetaine, AMPHITOL 20AB (Kao
Chemicals),
heated water (about 12 kg), second anionic surfactant solution (about 4 kg at
about 20%
solids in water of sodium C14-C16 olefin sulfonate, ALFANOX 46 (Kao Chemical),
and
inorganic salt solution (about 1.7 kg at about 30% solids in water of calcium
chloride, where
calcium chloride in both solid and solution forms is available from e.g.,
OxyChenn, Ludington,
MI). The resulting mixture is allowed to cool to ambient temperature (about 8
hours) and
then thickening agent (about 4 kg of about 1.5% solids in water of sodium
carboxy methyl
cellulose, e.g., WALOCEL CRT, Dow Chemical) is added. To this mixture is added
a desired
amount of anti-rust agent, and optionally further added are one or both of
defoanner and
colorant, to provide the final cutting fluid concentrate.
Example 9
[00166] To about 10 kg of heated water (about 75 C) is sequentially added
the
following ingredients, each ingredient addition being followed by stirring for
a period of
about 30 minutes in a manner that minimizes foam formation: first anionic
surfactant
solution (about 9 kg at about 60% solids in water of linear chain sodium
dodecylbenzene
sulfonate, e.g., CALSOFT F90 (Pilot Chemical)), annphoteric surfactant
solution (about 4.5 kg
at about 35% solids in water of cocannidopropylbetaine, e.g., AMPHOSOL CA from
Stepan
Company), heated water (about 9 kg), second anionic surfactant solution (about
11 kg at
about 3% solids in water of sodium lauryl ether sulfate, e.g., CALFOAM ES-703
from Pilot
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Chemical Co.), and inorganic salt solution (about 2 kg at about 30% solids in
water of
calcium chloride, where calcium chloride in both solid and solution forms is
available from
e.g., OxyChenn, Ludington, MI). The resulting mixture is allowed to cool to
ambient
temperature (about 8 hours) and then thickening agent (about 4 kg of about
1.5% solids in
water of sodium carboxy methyl cellulose, e.g., AQUALON, Ashland Chemicals,
Covington,
KY) is added. To this mixture is added a desired amount of anti-rust agent,
and optionally
further added are one or both of defoanner and colorant, to provide the final
cutting fluid
concentrate.
Example 10
[00167] To about 10 kg of heated water (about 75 C) is sequentially added
the
following ingredients, each ingredient addition being followed by stirring for
a period of
about 30 minutes in a manner that minimizes foam formation: first anionic
surfactant
solution (about 9 kg at about 60% solids in water of linear chain sodium
dodecylbenzene
sulfonate, e.g., CALSOFT F90 (Pilot Chemical)), annphoteric surfactant
solution (about 4.5 kg
at about 35% solids in water of cocannidopropyl betaine, e.g., AMPHOSOL CA
from Stepan
Company), heated water with dissolved ethylene glycol butyl ether (about 9 kg
water and
about 1 kg ether), second anionic surfactant solution (about 11 kg at about 3%
solids in
water of sodium laureth sulfate, e.g., CALFOAM ES-703 from Pilot Chemical
Co.), and
inorganic salt solution (about 2 kg at about 30% solids in water of calcium
chloride, where
calcium chloride in both solid and solution forms is available from e.g.,
OxyChenn, Ludington,
MI). The resulting mixture is allowed to cool to ambient temperature (about 8
hours) and
then thickening agent (about 4 kg of about 1.5% solids in water of sodium
carboxy methyl
cellulose, e.g., AQUALON, Ashland Chemicals, Covington, KY) is added. To this
mixture is
added a desired amount of anti-rust agent, and optionally further added are
one or both of
defoanner and colorant, to provide the final cutting fluid concentrate.
Example 11
[00168] The present disclosure provides cutting fluids of high solids
content (also
referred to as high solids centration), which are called concentrates (or
cutting fluid
concentrates), and which may be diluted with water prior to being used in a
machining or
fabricating operation. Table 1 identifies various machining operations
characterized by the
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metal being machined and the process being applied to the metal. The processes
are
exemplary of the processes used in metal working, such as broaching, tapping,
hobbing,
cutting, drilling, milling, turning, sawing, honing and grinding. Each of
these processes
benefits from the application of cutting fluid to the metal during the metal
working or
machining process, where the desired amount of cutting fluid depends not only
on the
specific process, but also on the identity of the metal being subjected to the
process. In
addition to identifying various processes, Table 1 identifies 8 common metals,
namely,
aluminum (Al) alloy, brass, casting iron (also known as cast iron), bronze,
low carbon steel,
stainless steel, alloy steel and titanium (Ti) alloy. For each process and
metal selected, Table
1 indicates the parts of water that may be added to 1 part of a cutting fluid
concentrate of
the present disclosure in order to create an effective cutting fluid. For
example, bronze may
be broached using a cutting fluid prepared from 10 parts of water and 1 part
of cutting fluid
concentrate of the present disclosure. As another example, titanium alloy may
be turned
using a cutting fluid prepared by combining anywhere from between 5 to 10
parts of water
for each 1 part of cutting fluid concentrate of the present disclosure.
Table 1
Low- Stain-
Casting Alloy Ti
Process Al alloy Brass Bronze Carbon less
Iron Steel Alloy
Steel Steel
Broaching 10-15 10-15 10 10 10 5 5 5
Tapping 10-15 10-15 10 10 10 5 5 5
Hobbing 10-15 10-15 10 10 10 5 5 5
Cutting 10-15 10-15 10-15 10-15 10-15 5-10 5-10 5
Drilling 10-15 10-15 10-15 10-15 10-15 5-10 5-10 5
Milling 15 15 10-15 10-15 10-15 5-10 5-10 5-10
Turning 15 15 10-15 10-15 10-15 10 10 5-10
Sawing 15 15 15 15 15 10 10 5-10
Honing 15 15 15 15 15 10 10 5-10
Grinding 15 15 15 15 15 10 10 5-10
[00169] Tablet 1 is based on diluting a concentrate of the present
disclosure with
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water. For example, when the desired operation is broaching with bronze, a
dilution of the
concentrate of the present disclosure with 10-15 parts water is recommended.
[00170] For example, utilizing a concentrate having 18 wt% sodium dodecyl
benzene
sulfonate, 9 wt% cocannidopropyl betaine, 8 wt% hydroxyethyl cellulose, 5 wt%
sodium
laureth sulfate, 4 wt% calcium chloride, 2 wt% ethylene glycol butyl ether and
54 wt%
water, this is diluted times 10 with water. Anti-rust agent is added at 1.5 x
the concentrate/
10000 ppnn based on 1:150 ratio mix. De-foaming agent is added at 0.15 x the
concentrate/
1000 ppnn based on 1:150 ratio mix. Colouring agent is added at 0.0000095 x
the
concentrate (litres) /10 ppnn of 1:150 ratio mix. The anti-rust agent is based
on 1% of fully
dilution of the concentrate (1:150 ratio mix). The de-foaming agent is based
on 0.01% of
fully dilution of the concentrate (1:150 ratio mix). An antibacterial agent
may optionally be
added.
[00171] The efficacy of the metal cutting fluid concentrations and
compositions of the
present disclosure may be evaluated by one or more test methods that indicate
the
effectiveness of the composition during a metal cutting operation.
[00172] For example, a vibration test was performed, comparing a cutting
fluid
composition as described in Example 11, to a commercial emulsion oil. The
cutting occurred
during a milling operation at a blade movement of 3,000 rotations per minute,
and 250
nnnn/nnin. Along the x axle, the vibration was measured to be 0.08179268 for a
commercial
emulsion oil, vs. 0.056828924 for the metal cutting fluid of Example 11, for a
30.5%
decrease in vibration amplitude. Along the y axle, the vibration was measured
to be
0.07328386 for the same commercial emulsion oil, vs. 0.044023185 for the metal
cutting
fluid of Example 11, for a 39.9% decrease in vibration amplitude. Along the z
axle, the
vibration was measured to be 0.077851914 for the same commercial emulsion oil,
vs.
0.059323387 for the metal cutting fluid of Example 11, for a 23.8 decrease in
vibration
amplitude.
[00173] When a roughness test was performed using a milling operation on
medium
carbon steel, a commercial emulsion oil provided a roughness of 4.972 as the
average Rmax
(unn), while the metal cutting fluid of Example 11 provided a roughness of
3.913 Rmax (unn).
Thus, the metal cutting fluid of the present disclosure provided a 21.3%
decrease in the
roughness of the cut part compared to a commercial emulsion based oil.
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Example 12
[00174] As shown in Table 1, a 5 to 15-fold dilution of a material
fabrication
concentrate of the present disclosure is suitably used for a large variety of
metal and other
machining operations. In one embodiment, the present disclosure provides
compositions
resulting from 5 to 15 fold dilution of a concentrate of the present
disclosure. In one
embodiment, the present disclosure provides compositions resulting from a 5-
fold dilution
of a concentrate of the present disclosure. In another embodiment, the present
disclosure
provides compositions resulting from a 15-fold dilution of a concentrate of
the present
disclosure.
[00175] In one embodiment, the present disclosure provides a composition
resulting
from a 10-fold dilution of a concentrate of the present disclosure. This
composition has 0.2
wt% of sodium dodecylbenzene sulfonte, 0.05 wt% sodium laureth sulfate, 0.09
wt%
cocannidopropyl betaine, 0.08 wt% hydroxyethyl cellulose, 0.04 wt% calcium
chloride, 0.02
wt% ethylene glycol butyl ether. To this diluted solution is added anti-rust
agent to a 0.2
wt% amount and defoanning agent to a 0.1 wt% amount.
[00176] This composition can be used in each of the machinery operations
identified
in Table 1, i.e., broaching, tapping, hobbing, cutting, drilling, milling,
turning, sawing, honing
or grinding of any of aluminum (Al) alloy, brass, casting iron (also known as
cast iron),
bronze, low carbon steel, stainless steel, alloy steel and titanium (Ti)
alloy.
[00177] Any of the various embodiments described above can be combined to
provide further embodiments. All of the U.S. patents, U.S. patent application
publications,
U.S. patent applications, foreign patents, foreign patent applications and non-
patent
publications referred to in this specification and/or listed in the
Application Data Sheet are
incorporated herein by reference, in their entirety. Aspects of the
embodiments can be
modified, if necessary to employ concepts of the various patents, applications
and
publications to provide yet further embodiments. These and other changes can
be made to
the embodiments in light of the above-detailed description. In general, in the
following
claims, the terms used should not be construed to limit the claims to the
specific
embodiments disclosed in the specification and the claims, but should be
construed to
include all possible embodiments along with the full scope of equivalents to
which such
claims are entitled. Accordingly, the claims are not limited by the
disclosure.
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