Note: Descriptions are shown in the official language in which they were submitted.
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CONTROLLABLE FILLER PREFLOCULATION
USING A DUAL POLYMER SYSTEM
Crosg-Reference to Related Applications
This Application is a Continuation-in-part of pending US Patent Application
serial
number 11/854,044 filed on September 12, 2007,
Statement Regarding Federally Sponsored Research or Development
Not Applicable.
Background of the Invention
This invention relates to the preflocculation of fillers used in papermaking,
particularly, the production of shear resistant filler flocs with a defined
and controllable size
distribution at high filler solids is disclosed.
Increasing the filler content in printing and writing papers is of great
interest for
improving product quality as well as reducing raw material and energy costs.
However, the
substitution of cellulose fibers with fillers like calcium carbonate and clay
reduces the strength of
the finished sheet. Another problem when the filler content is increased is an
increased difficulty
of maintaining an even distribution of fillers across the three-dimensional
sheet structure. An
approach to reduce these negative effects of increasing filler content is to
preflocculate fillers
prior to their addition to the wet end approach system of the paper machine.
The definition of the term "preflocculation" is the modification of filler
particles
into agglomerates through treatment with coagulants and/or flocculants prior
their addition to the
paper stock. The flocculation treatment and shear forces of the process
determine the size
distribution and stability of the flocs prior to addition to the paper stock.
The chemical
environment and high fluid shear rates present in modern high-speed
papermaking require filler
flocs to be stable and shear resistant. The floc size distribution provided by
a prefiocculation
treatment should minimize the reduction of sheet strength with increased
filler content, minimize
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the loss of optical efficiency from the filler particles, and minimize
negative impacts on sheet
uniformity and printability, Furthermore, the entire system must be
economically feasible.
Therefore, the combination of high shear stability and shall) particle size
distribution is vital to the success of filler preflocculation technology.
However, filler floes
formed by a low molecular weight coagulant alone, including commonly used
starch, tend to
have a relatively small particle size that breaks down under the high shear
forces of a paper
machine. Filler flocs forrned by a single high molecular weight flocculant
tend to have a broad
particle size distribution that is difficult to control, and the particle size
distribution gets worse at
higher filler solids levels, primarily due to the poor mixing of viscous
flocculant solution into the
.10 slurry. Accordingly, there is an ongoing need for improved
preflocculation technologies.
The art described in this section is not intended to constitute an admission
that any
patent, publication or other infimmation referred to herein is "prior art"
with respect to this
invention, unless specifically designated as such. In addition, this section
should not be construed
to mean that a search has been made or that no other pertinent information as
defined in 37
C.F.R. 1.56(a) exists,
Brief Summary of the Invention
At least one embodiment is directed towards a method of preparing a stable
dispersion of flocculated filler particles having a specific particle size
distribution for use in
__ papei making processes comprising a) providing an aqueous dispersion of
filler particles; b)
adding a first flocculating agent to the dispersion in an amount sufficient to
mix uniformly in the
dispersion without causing significant flocculation of the filler particles;
c) adding a second
flocculating agent to the dispersion in an amount sufficient to initiate
flocculation of the filler
particles in the presence of the first flocculating agent; and d) optionally
shearing the flocculated
dispersion to provide a dispersion of filler flocs having the desired particle
size.
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At least one embodiment is directed towards a method of making paper products
from pulp comprising folining an aqueous cellulosic papermaking furnish,
adding an aqueous
dispersion of filler flocs prepared as described herein to the furnish,
draining the furnish to form
a sheet and drying the sheet. The steps of forming the papermaking furnish,
draining and drying
may be carried out in any conventional manner generally known to those skilled
in the art.
At least one embodiment is directed towards a paper product incorporating the
filler flocs prepared as described herein.
Brief Description of the Drawings
A detailed description of the invention is hereafter described with specific
reference being made to the drawings in which:
FIG. 1 is an illustration of an MCL time resolution of a flocculating
reaction.
Detailed Description of the Invention
The following definitions are provided to determine how terms used in this
application, and in particular how the claims, are to be construed. The
organization of the
definitions is for convenience only and is not intended to limit any of the
definitions to any
particular category. For purposes of this application the definition of these
terms is as follows:
"Coagulant" means a composition of matter having a higher charge density and
lower molecular weight than a flocculant, which when added to a liquid
containing finely divided
suspended particles, destabilizes and aggregates the solids through the
mechanism of ionic
charge neutralization.
".Floccuirant" means a composition of matter having a low charge density and a
high molecular weight (in. excess of 1,000,000) which when added to a liquid
containing finely
3
=
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divided suspended particles, destabilizes and aggregates the solids through
the mechanism of
interparticle bridging.
".Flocculating Agent" means a composition of matter which when added to a
liquid destabilizes, and aggregates colloidal and finely divided suspended
particles in the liquid,
flocculants and coagulants can be flocculating agents,
"GCC' means ground calcium carbonate, which is manufactured by grinding
naturally occurring calcium carbonate rock
"FCC' means precipitated calcium carbonate which is synthetically produced.
In the event that the above definitions or a description stated elsewhere in
this
application is inconsistent with a meaning (explicit or implicit) which is
commonly used, in a
dictionary, or stated in a source incorporated by reference into this
application, the application
and the claim terms in particular are understood to be construed according to
the definition or
description in this application, and not according to the common definition,
dictionary definition,
or the definition that was incorporated by reference. In light of the above,
in the event that a term
can only be understood if it is construed by a dictionary, if the term is
defined by the Kirk-
Othmer Encyclopedia of chemical Technology, 5th Edition, (2005), (Published by
Wiley, John &
Sons, Inc.) this definition shall control how the term is to be defined in the
claims.
The fillers useful in this invention are well known and commercially
available.
They typically would include any inorganic or organic particle or pigment used
to increase the
Opacity or brightness, increase the smoothness, or reduce the cost of the
paper or paperboard
sheet. Representative fillers include calcium carbonate, kaolin clay, talc,
titanium dioxide,
alumina .trihydrate, barium sulfate, magnesium hydroxide, and the like.
Calcium carbonate
includes GCC in a dry or dispersed slurry form, chalk, PCC of any morphology;
and PCC in a
dispersed slurry form. Some examples of GCC and PCC slurries are provided in
co-pending US
Patent Application Serial Number 12/323,976, The dispersed slurry forms of GCC
or PCC are
typically produced using polyacrylic acid polymer dispersants or sodium
polyphosphate
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dispersants. Each of these dispersants imparts a significant anionic charge to
the calcium
carbonate particles, Kaolin clay slurries may also be dispersed using
polyacrylic acid polymers
or sodium polyphosphate.
In an embodiment, the fillers are selected from calcium carbonate and kaolin
clay
and combinations thereof.
In an embodiment, the fillers are selected from precipitated calcium
carbonate,
ground calcium carbonate and kaolin clay, and mixtures thereof.
The first flocculating agent is preferably a cationic polymeric floceidant
when
used with cationically charged fillers and anionic when used with anionically
charged fillers,
However, it can be anionic, nonionic, zwitterionic, or amphoteric as long as
it will mix uniformly
into a high solids slurry without causing significant flocculation.
The definition of "without causing significant flocculation" is no
flocculation of
the -filler in the presence of the first flocculating agent or the formation
of floes which are smaller
than those produced upon addition of the second flocculating agent and
unstable under conditions
of moderate shear. Moderate shear is defined as the shear provided by mixing a
300 ml sample
in a 600 ml beaker using an IKA RE16 stirring motor at 800 rpm with a 5 cm
diameter, four-
bladed, turbine impeller. This shear should be similar to that present in the
approach. system of a
modern paper machine.
Suitable flocculants generally have molecular weights in excess of 1,000,000
and
often in excess of 5,000,000.
The polymeric flocculant is typically prepared by vinyl addition
polymerization of
one or more cationic, anionic or nonionic monomers, by copolymerization of one
or more
cationic monomers with one or more nonionic monomers, by copolymerization of
one or more
anionic monomers with one or more nonionic monomers, by copolymerization of
one or more
cationic monomers with one or more anionic monomers and optionally one or more
nonionic
monomers to produce an amphoteric polymer or by polymerization of one or more
zwitterionic
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- monomers and optionally one or more nonionic monomers to form a
zwitterionic polymer. One
or more zwitterionic monomers and optionally one or more nonionic monomers may
also be
copolymerized with one or more anionic or cationic monomers to impart cationic
or anionic
charge to the zwitterionic polymer. Suitable flocculants generally have a
charge content of less
than 80 mole percent and often less than 40 mole percent.
While cationic polymer flocculants may be formed using cationic monomers, it
is
also possible to react certain nonionic vinyl addition polymers to produce
cationically charged
polymers. Polymers of this type include those prepared through the reaction of
polyacrylamide
with dimethylamine and formaldehyde to produce a Marmieh derivative.
Similarly, while anionic polymer flocculants may be formed using anionic
monomers, it is also possible to modify certain nonionic vinyl addition
polymers to form
anionically charged polymers. Polymers of this type include; for example,
those prepared by the
hydrolysis of polyacrylamide.
The flocculant may be prepared in the solid form, as an aqueous solution, as a
water-in-oil emulsion, or as a dispersion in water. Representative cationic
polymers include
copolymers and terpolymers of (ineth)acrylamide with dimethylaminoethyl
methaerylate
(DMAEM), dimethylaminoethyl aerylate (DMAEA), diethylaminoethyl aerylate
(DEAEA),
diethylaminoethyl metham4ate (DEAEM) or their quaternary ammonium forms made
with
dimethyl sulfate, methyl chloride or benzyl chloride. Representative anionic
polymers include
copolymers of acrylamide with sodium acrylate and/or 2-acrylamido 2-
methylpropane sulfonie
acid (AMPS) or an acrylamide homopolymer that has been hydrolyzed to convert a
portion of the
acrylamide groups to acr lie acid.
In an embodiment, the flocculants have a RSV of at least 3 dL/g.
In an embodiment, the flocculants have a RSV of at least 10 dL/g.
In an embodiment, the flocculants have a RSV of at least 15 dLlg.
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As used herein, "RSV" stands for reduced specific viscosity. Within a series
of
polymer homologs which are substantially linear and well solvated, "reduced
specific viscosity
(RSV)" measurements for dilute polymer solutions are an indication of polymer
chain length and
average molecular weight according to Determination of Molecular Weights, by
Paul J. Flory,
pages 266-316, Principles of Polymer Chemistry, Cornell University Press,
Ithaca, NY, Chapter
VII (1953), The RSV is measured at a given polymer concentration and
temperature and
calculated as follows:
RSV = [(rilrk,)-1]/c where n = viscosity of polymer solution, rj, viscosity of
solvent at the same
temperature and c = concentration of polymer in solution.
The units of concentration "c" are (grams/I00 ml or gldeciliter). Therefore,
the
units of RSV are dLlg. Unless otherwise specified, a 1.0 molar sodium nitrate
solution is used
for measuring RSV. The polymer concentration in this solvent is 0.045 g/dL.
The RSV is
measured at 30 C. The viscosities tl andio are measured using a Cannon
Ubbelohde semi-micro
dilution viscometer, size 75. The viscometer is mounted in a perfectly
vertical position in a
constant temperature bath adjusted to 30 0.02 C. The typical error inherent
in the calculation
of RSV for the polymers described herein is about 0.2 dila. When two polymer
homologs
within a series have similar RSV's that is an indication that they have
similar molecular weights.
As discussed above, the first flocculating agent is added in an amount
sufficient to
mix uniformly in the dispersion without causing significant flocculation of
the filler par. ides. In
an embodiment, the first flocculating agent dose is between 0.2 and 6,0 lb/ton
of filler treated. In
an embodiment, the flocculant dose is between 0.4 and 3,0 lb/ton of filler
treated. For purposes
of this invention, "lb/ton" is a unit of dosage that means pounds of active
polymer (coagulant or
flocculant) per 2,000 pounds of filler.
The second flocculating agent can be any material that can initiate the
flocculation
of filler in the presence of the first flocculating agent. In an embodiment,
the second flocculating
agent is selected from microparticles, coagulants, flocculants and mixtures
thereof
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Suitable microparticles include siliceous materials and polymeric
microparticles.
Representative siliceous materials include silica based particles, silica
microgels, colloidal silica,
silica sols, silica gels, polysilicates, cationic silica, aluminosilicates,
polyaluminosilicates,
borosilicates, polyborosilicates, zeolites, and synthetic or naturally
occurring swelling clays. The
swelling clays may be bentonite, hectorite, smectite, montmorillonite,
nontronite, saponite,
sauconite, marmite, attapulgite, and sepiolite.
Polymeric microparticles useful in this invention include anionic, cationic,
or
amphoteric organic microparticles. These microparticles typically have limited
solubility in
water, may be crosslinked, and have an unswollen particle size of less than
750 mu.
Anionic organic microparticles include those described in US 6,524,439 and
made
by hydrolyzing acrylamide polymer microparticles or by polymerizing anionic
monomers as
(meth)acr,ylic acid and its salts, 2-aculamido-2-methylpropane sulfonate,
sulfoethyl-
(meth)acrylate, vinylsulfonic acid, styrene sulfanic acid, maleic or other
dibasic acids or their
salts or mixtures thereof These anionic monomers may also be copolymerized
with nonionic
monomers such as (meth)acrylamide, N-alkylacrylamides, N,N-dialkylacrylamides,
methyl
(meth)acrylate, acrylonitrile,
methylacetamide. N-vinyl methyl formamide, vinyl acetate,
N-vinyl pyrrolidone, and mixtures thereof.
Cationic organic microparticles include those described in US 6,524,439 and
made by polymerizing such monomers as diallyidialkylammonium halides,
acryloxyaikyltrimethylammonium chloride, (meth)acrylates of
dialkylainirioalkyl compounds,
and salts and quaternaries thereof and, monomers of N,N-
dialkylaminoalkyl(meth)acrylamides,
(meth)acrylamido.propyltrimethylammonium chloride and the acid or quaternary
salts of N,N-
dimethylaminoethylacrylate and the like. These cationic monomers may also be
copolymerized
with nonionic monomers such as (meth)acrylamide, N-alkylacrylamides, N,N-
dialkylacrylamides, methyl (meth)aorylate, acrylonitrile, N-vinyl
methylacetamide, N-vinyl
methyl fonuamide, vinyl acetate, N-vinyl pyrrolidone, and mixtures thereof.
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Amphoteric organic microparticles are made by polymerizing combinations of at
least one of the anionic monomers listed above, at least one of the cationic
monomers listed
above, and, optionally, at least one of the nonionic monomers listed above.
Polymerization of the monomers in an organic microparticle typically is done
in
the presence of a polyfunetional crosslinking agent. These crosslinking agents
are described in
US 6,524,439 as having at least two double bonds, a double bond and a reactive
group, or two
reactive groups. Examples of these agents are N,N-
methylenebis(meth)aciylamide,
polyethyleneglycol di(meth)acrylate, N-vinyl acrylamide, divinylbenzene,
triallyiammonium
salts, N-methylallylacrylamide glycidyl (meth)acrylate, aerolein,
methylolacrylamide,
dialdehydes like glyoxal, diepoxy compounds, and epiehlorohydrin.
in an embodiment, the rnicroparticle dose is between 0.5 and 8 lb/ton of
filler
treated. In an embodiment, the microparticle dose is between 1.0 and 4.0
lb/ton of filler treated.
Suitable coagulants generally have lower molecular weight than flocculants and
have a high density of cationic charge groups. The coagulants useful in this
invention are well
known and commercially available. They may be inorganic or organic.
Representative inorganic
coagulants include alum, sodium aluminate, polyaluminum chlorides or PACs
(which also may
be under the names aluminum chlorohydroxide, aluminum hydroxide chloride, and
polyaluminum hydroxychloride), sulfated polyaluminum chlorides, polyaluminum
silica sulfate,
ferric sulfate, ferric chloride, and the like and blends thereof
Many organic coagulants are formed by condensation polymerization. Examples
of polymers of this type include epichlorohydrin-dimethylamine (EPI-DMA)
copolymers, and
EPI-DMA copolymers crossiir3ked with ammonia.
Additional coagulants include polymers of ethylene dichloride and ammonia, or
ethylene dichloride and dimettrylamine, with or without the addition of
ammonia, condensation
polymers of multifunctional amines such as diethylenetriamine, tetraethyl
enepentamine,
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hexamethylenediamine and the like with ethylenedichloride or polyfunctional
acids like adipic
acid and polymers made by condensation reactions such as melamine formaldehyde
resins.
Additional coagulants include cationically charged vinyl addition polymers
such
as polymers, copolymers, and terpolymers of (meth)acrylamide, diallyl-N,N-
disubstituted
ammonium halide, dimethylaminoethyl methacrylate and its quaternary ammonium
salts,
dimethylaminoethyl acrylate and its quaternary ammonium salts,
methacrylamidopropyltrimethylammonium chloride, diallylmethyl(beta-
propionamido)ammonium chloride, (beta-methacryloyloxyethyptrimethyl ammonium
methylsulfate, quatemized polyvinyllactam, vinylamine, and acrylamide or
methacrylamide that
has been reacted to produce the Mannich or quaternary Mannich derivatives.
Suitable quaternary
ammonium salts may be produced using methyl chloride, dimethyl sulfate, or
benzyl chloride.
The terpolymers may include anionic monomers such as acrylic acid or 2-
acrylamido 2-
methylpropane sulfonic acid as long as the overall charge on the polymer is
cationic. The
molecular weights of these polymers, both vinyl addition and condensation,
range from as low as
several hundred to as high as several million.
Other polymers useful as the second flocculating agent include cationic,
anionic,
or amphoteric polymers whose chemistry is described above as a flocculant. The
distinction
between these polymers and flocculants is primarily molecular weight.
The second flocculating agent may be used alone or in combination with one or
more additional second flocculating agents, in an embodiment, one or more
microparticles are
added to the flocculated filler slurry subsequent to addition of the second
flocculating, agent.
The second flocculating agent is added to the dispersion in an amount
sufficient to
initiate flocculation of the filler particles in the presence of the first
flocculating agent, in an
embodiment, the second flocculating agent dose is between 0.2 and 8,0 lb/ton
of filler treated, in
an embodiment, the second component dose is between 0.5 and 6.0 lb/ton of
filler treated.
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in an embodiment, one or more micropartieles may be added to the flocculated
dispersion prior to shearing to provide additional flocculation and/or narrow
the particle size
distribution.
In an embodiment, the second flocculating agent and first flocculating agent
are
oppositely charged.
In an embodiment, the first flocculating agent is cationic and the second
flocculating agent is anionic.
In an embodiment, the first flocculating agent is selected from copolymers of
acrylamide with dimethylaminoethyl methacrylate (DMAEM) or dimethylaminoethyl
acrylate
(DAUM and mixtures thereof
In an enibodiment, the first -flocculating agent is an acrylamide and
dimethylaminoethyl acrylate (DMAEA) copolymer with a cationic charge content
of 5-50 mole
% and an RSV of > 15 &/g.
In an embodiment, the second flocculating agent is selected from the group
consisting of partially hydrolyzed acrylamide and copolymers of acrylamide and
sodium amylate.
In an embodiment, the second flocculating agent is acrylamide-sodium acrylate
copolymer having an anionic charge of 5-40 mole percent and a RSV of 0,3-5
dig.
In an embodiment, the first flocculating agent is anionic and the second
flocculating agent is cationic,
In an embodiment, the first flocculating- agent is selected from the group
consisting of partially hydrolyzed acrylamide and copolymers of acrylamide and
sodium acrylate.
In an embodiment, the first flocculating agent is a copolymer of acrylamide
and
sodium acrylate having an anionic charge of 5-75 mole percent and an RSV of at
least 15 &/g.
In an embodiment, the second flocculating agent is selected from the group
consisting of epiehlorohydrin-dimethylamine (EN-DMA) copolymers, EPI-DMA
copolymers
crosslinked with ammonia, and homopolymers of diallyl-N,N-disubstituted
ammonium halides.
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in an embodiment, the second flocculating agent is a homopolymer of diallyi
dimethyl ammonium chloride having an RSV of 0.1-2 &!g.
in an embodiment, the second flocculating agent is selected from copolymers of
acrylamide with dimethylarninoethyl methacrylate (DklAEM) or
dimethylaminoethyl acrylate
(DMARA) and mixtures thereof.
In an embodiment, the second flocculating agent is an acrylamide and
ditnethylaminoethyl acrylate (DM.AEA) copolymer with a cationic charge content
of 5-50 mole
(.'/* and an RSV of > 1.5 dfig.
Dispersions of filler flocs according to this invention are prepared prior to
their
addition to the papermaking furnish. This can be done in a batch-wise or
continuous fashion.
The filler concentration in these slurries is typically less than 80% by mass.
It is more typically
between 5 and 65% by mass.
A batch process can consist of a large mixing tank with an overhead, propeller
mixer, The filler slurry is charged to the mix tank, and the desired amount of
first flocculating
agent is fed to the slurry under continuous mixing. The slurry and flocculant
are mixed for an.
amount of time sufficient to distribute the first flocculating agent uniformly
throughout the
system, typically for about 10 to 60 seconds, depending on the mixing energy
used. The desired
amount of second flocculating agent is then added while stirring at a mixing
speed sufficient to
break down the filler flocs with increasing mixing time typically from several
seconds to several
minutes, depending on the mixing energy used. Optionally, a microparticle is
added as a third
component to cause reflocculation and narrow the floc size distribution. When
the appropriate
size distribution of the filler flocs is obtained, the mixing speed is lowered
to a level at which the
floes are stable. This batch of flocculated filler is then transferred to a
larger mixing tank with.
sufficient mixing to keep the filler flocs uniformly suspended in the
dispersion. The flocculated
filler is pumped from this mixing tank into the papermaking furnish.
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In a continuous process the desired amount of first flocculating agent is
pumped
into the pipe containing the filler and mixed with an in-line static mixer, if
necessary. A length
of pipe or a mixing vessel sufficient to permit adequate mixing of filler and
flocculant may be
included prior to the injection of the appropriate amount of second
flocculating agent, The
second flocculating agent is then pumped into the pipe containing the filler
and mixed with an in-
line static mixer, if necessary. Optionally, a microparticle is added as a
third component to cause
reflocculation and narrow the floe size distribution. High speed mixing is
then required to obtain
the desired size distribution of the filler floes. Adjusting either the shear
rate of the mixing
device or the mixing time can control the floe size distribution. A continuous
process would lend
itself to the use of an adjustable shear rate in a fixed volume device. One
such device is
described in US Patent 4,799,964. This device is an adjustable speed
centrifugal pump that,
when operated at a back pressure exceeding its shut off pressure, works as a
mechanical shearing
device with no pumping capacity. Other suitable shearing devices include a
nozzle with an
adjustable pressure drop, a turbine-type emulsification device, or an
adjustable speed, high
intensity mixer in a fixed volume vessel. After shearing, the flocculated
filler slurry is fed
directly into the papermaking furnish.
In both the batch and continuous processes described above, the use of a
filter or
screen to remove oversize filler flocs can be used. This eliminates potential
machine runnability
and paper quality problems resulting from the inclusion of large filler flocs
in the paper or board.
In an embodiment, the median particle size of the filler flocs is at least 10
p.m. In
an embodiment, the median particle size of the filler floes is between 10 and
100 p.m. In an
embodiment, the median particle size of the filler flocs is between 10 and 70
p.m.
In at least one embodiment the invention is practiced using at least one of
the
compositions and/or methods described in US Patent Application 12/975,596. In
at least one
embodiment the invention is practiced using at least one of the compositions
and/or methods
described in US Patent 8,088,213.
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EXAMPLES
The foregoing may be better understood by reference to the following Examples,
which are presented for purposes of illustration and are not intended to limit
the scope of the
invention:
Examples 1-7
The filler used for each example was either undispersed or dispersed,
sealenohedral PCC (available as Albacar HO from Specialty Minerals Inc,,
Bethlehem, PA
USA). When undispersed PCC is used, the dry product was diluted to 10% solids
using tap
water. When dispersed PCC was used, it was obtained as 40% solids slurry and
is diluted to 10%
solids using tap water. The size distribution of the PCC was measured at three
second intervals
during flocculation using a Lasentec! S400 FBRM (Focused Beam Reflectance
Measurement)
probe, manufactured by Lasentec, Redmond, WA. A description of the theory
behind the
operation of the FBRM can be found in US Patent 4,871,251. The mean chord
length (MCP of
the PCC floes is used as an overall measure of the extent of flocculation. The
laser probe is
inserted in a 600 triL beaker containing 300 aiL of the 10% PCC slurry. The
solution is stirred
using an IKA RE16 stirring motor at 800 rpm for at least 30 seconds prior to
the addition of
flocculating agents.
The first flocculating agent is added slowly over the course of 30 seconds to
60
seconds using a syringe. When a second flocculating agent is used, it is added
in a similar
manner to the first flocculating agent after waiting 10 seconds for the first
flocculating agent to
mix. Finally, when a microparticle is added, it is added in a similar manner
to the flocculating
agents after waiting 10 seconds for the second flocculating agent to mix.
Flocculants are diluted
to a concentration of 0.3% based on solids, coagulants are diluted to a
concentration of 0,7%
based on solids, starch is diluted to a concentration of 5% based on solids,
and microparticles are
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diluted to a concentration of 0.5% based on solids prior to use. A typical MCL
time resolution
profile is shown in FIG. 1.
The MCL time resolution profile of FIG. 1 was recorded by Lasentec S400
FBRM. At point one, the first flocculating agent is introduced into the slurry
and the MCL
increases then quickly decreases under 800 rpm mixing speed, indicating that
the filler floes are
not stable under the shear. At point two, the second flocculating agent is
introduced, and the
MCL also increases then decreases slightly under 800 rpm mixing. At point
three, a
microparticle is introduced and the MCL increases sharply then reaches a
plateau, indicating that
the filler floes are stable under 800 rpm mixing. Once the shear is raised to
1500 rpm, MCL
starts to decrease.
For every filler flocculation experiment, the maximum MCL after addition of
the
flocculating agent is recorded and listed in Table IL The maximum MCL
indicates the extent of
flocculation. The slurry is then stirred at 1500 rpm for 8 minutes to test the
stability of the filler
flocs under high shear conditions, The MCL values at 4 minutes and 8 minutes
are recorded and
listed in Tables III and IV, respectively.
The particle size distribution of the filler flocs is also characterized by
laser light
scattering using the Mastersizer Micro from Malvern Instruments Ltd.,
Southborough, MA USA.
The analysis is conducted using a polydisperse model and presentation 4PAD.
This presentation
assumes a 1.60 refractive index of the filler and a refractive index of 1.33
for water as the
continuous phase. The quality of the distribution is indicated by the volume-
weighted median
floe size, D(V,0.5), the span of the distribution, and the uniformity of the
distribution. The span
and uniformity are defined as:
....................
,0,5)
D(V,0.5)
uniformity _____
D(17 ,0.5)IV,
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Here D(v, 0,1), D(v,0.5) and D(v, 0.9) are defined as the diameters that are
equal or larger than
10%, 50% and 90% by volume of filler particles, respectively. Vi and R are the
volume fraction
and diameter of particles in size group i. Smaller span and uniformity values
indicate a more
uniform particle size distribution that is generally believed to have better
performance in
papennaking. These characteristics of filler flocs at maximum MCIõ 4 minutes
and 8 minutes
under 1500 rpm shear are listed in Tables 11, III and IV for each example, The
PCC type,
flocculating agents, and doses of flocculating agents used in each example are
listed in Table
Example 8
This experiment demonstrates the feasibility of using a continuous process to
flocculate the PCC slurry. A batch of 18 liters of 10% solids undispersed PCC
(available as .
Albaear HO from Specialty Minerals Inc., Bethlehem, PA USA) in tap water was
pumped using
a centrifugal pump at 7.6 Llmin into a five gallon bucket. A 1.0 lb/ton active
dose of 0.3% solids
floeculant A solution was fed into the PCC shiny at the centrifugal pump inlet
using a
progressive cavity pump. The PCC was then fed into a static mixer together
with 1.0 lb/ton
active dose of a 0.7% solids solution of coagulant A. The size distribution of
the filler flocs was
measured using the Mastersizer Micro and reported in Table ff. 300 mil, of the
resultant slurry
was stirred in a beaker at 1500 rpm for 8 minutes in the same manner as in
Examples 1-7. The
characteristics of the filler flocs at 4 minutes and 8 minutes are listed in
Tables III and IV,
respectively.
Example 9
The filler slurry and experimental procedure was the same as in Example 8,
except
that coagulant A was fed into the centrifugal pump and floceulant A was fed
into the static mixer.
The size characteristics of the filler floes are listed in Tables II, III and
IV,
16
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Table I. PCC type, flocculating agent descriptions, and flocculating
agent doses for
examples I through 9.
Polymer 1
Polymer 2
Micropartiele
PCC Dose Dose Dose
Ex Type Name (113/ton) Name (lb/ton) Name (lb/ton)
1 Undispersed Stalok 400 20 None None
2 Undispersed Flocculant A 1 Coagulant A I None
3 Undispersed Coagulant A 1 Flocculant A 1 None
4 1 Undispersed Flocculant B 1 Coagulant B 3 B
2
1 Undispersed Coagulant B 3 Flocculant B I B 2
6 Dispersed Flocculant A 1,5 Coagulant A 4 None
7 Dispersed Coagulant A I
Flocculant A 1.5 None
: ..
¨ "
8 Undispersed Flocculant A 1 Coagulant A I None
9 : Undispersed Coagulant A : 1 : Flocculant A 1 None
Stalok 400 Cationic starch available from Tate & Lyle, Decatur, IL USA
Flocculant A. Anionic sodium actylate-acrylamide copolymer fiocculant with
an RSV of
about 32 dLig and a charge content of 29 mole % available from Nalco Co.,
Naperville, IL -USA.
: Flocculant B Cationic acrylamide-dimethylaminoethyl methaerylate-methyl
chloride
quaternary salt copolymer flocculant with an RSV of about 25 dig and a
charge content of 20 mole % available from Nalco Co., Naperville, IL USA,
Coagulant A Cationic poly(diallyidimethylaramonium chloride) coagulant
with an RSV of
about 0.7 dLig available from Nalco Co., Naperville, IL USA.
: Coagulant B Anionic sodium acrylate-actylamide copolymer with an RSV of
about 1.8
diLlg and a charge content of 6 mole % available from Nalco Co., Naperville,
IL USA.
õõ.
Microparticle B Anionic colloidal boro¨silicate mieroparticle available
from Nalco Co.,
Naperville, IL USA.
5
17
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Table IL Characteristics of filler flocs at maximum MCL or 0 min under
1500 rpm shear.
Example MCL (gm) D(v,0.1) (pm) D(v,0.5) (pm)1D(v' 0.9) (pm) Span niformity
1
I 12.52 10.42 3.07 46.48 1.56 .49
___________________ .---. -
2 16.81 13.48 2.08 "8.92 12.66 .83
_______________________________________________________________________ -.1
30.13 53.94 130.68 P28,93 1.34 $.41
.=-= 18.52 - ---
14 il 9.46 43.91 . 0.86 1.63 $.51
38.61 j67.2 147.73 40.04 11.17 .36
16 34.39 3.21 111.48 09.04 11.40 0,43
1
7 45.63 4.17 125.68 240.63 64.
4.4
i
......... *
tfi INA 4.4 8.17 125.47 1.74 b.52
INA 9.62 132.79 23462 1.54 10.46
. . ........ .... ......... - .........
Table III. Characteristics of filler flocs after 4 minutes under 1500 rpm
shear,
- ........................................
1 xample MCI, (p.m) P(v,0.1) (nn) D(v,0.5) (pin) rD(v,0.9) (pm) Span
Uniformity
1 746 14.76 ..).51 17.39 t1.33 p.41
i1---- 1
IP 13.21 11,29 = 7.26 '1.78 12.95 0.92
,t .......................................................................
16.13 13.25 42,73 142.37 3.02 0.92
-------------------------------------------- 1 ....... = ....
............................... - ........ ,
4 13.86 14.91 8.46 51.63 1.29 .4
5 17.66 1.8 158.08 14131 2.09
................... --
6 1 -t14.77 15.77 35.62 85.29 L95 1.6
1
=
7 '21.26 12.88 Ts.o0 197.46 .10 1.24
8 NA 14.91 5.88 16.29 1.71 t53
19 NA :.08 8.64 152.89 298 .93
:
=.
5
18
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Table IV. Characteristics of filler floes after 8 minutes under 1500 rpm
shear.
....................................................................... =
,,, - == _________________________________________
:Example MCI, (pm) 1D(v,0.1) (pin) P(v,0.5) (pm) f:)(v,0.9) (pm) Span
Uniformity
r----- õ.. .......
1. 1.02 4.01 18.03 15 '1.37 .. .43
:
............................... 1 ......
2 :12.43 18.57 I0.47 48.67 1.96 ..67
1
. ............. I . .....
13.62 19.46 :.28.93 (110.3 13.49 1.06
1 ==== ==
:4 12.88 12.483.48 142.36 :11, .27
:15.30 15.64 4116 106.73'217
0.7
..
......................................................................... :=
1
= 112.06 == == 10.41 .. .,' 3.88 --t----
52 1:7
.81 .'1.62
7 117.42 .2 30.37 il 76 5.49 :1.53
_________________________________________________________________________ 4
. .. -
0 NA 12.67 30.84 I 5.95 1.73 To.53
, .................................................... = .... - ..
9 .SIA ;.66 134.82 116.3 3.15
" I =""" = .,. =
As shown in Tables II-1V, filler flocs formed in Example 1, where only
cationic
starch was used, are not shear stable. On the other hand, filler flocs formed
by multiple polymers
5 exhibit
enhanced shear stability, as demonstrated in Examples 2 to 9. Examples 2, 4, 6
and 8
show filler flocs prepared according to this invention and Examples 3, 5, 7
and 9 show filler flocs
prepared using existing methods. The filler flocs prepared according to the
invention generally
have narrower particle size distributions after beim., sheared down (as shown
by the smaller
values of span and uniformity in Tables 111 and IV) compared with those formed
by existing
methods.
Example 10
The purpose of this example was to evaluate the effects of different sizes of
PCC
flocs on the physical properties of handsheets, The PCC samples were obtained
using the
procedure described in Example 2, except that the PCC solids level was 2%.
Four samples of
preflocculated filler flocs (10-A, 10-B, 10-C and 10-1)) were prepared with
different particle
sizes by shearing at 1500 rpm for different times. The shear times and
resulting particle size
characteristics are listed in Table V.
19
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Thick stock with a consistency of 2.5% was prepared from 80% hardwood dry lap
pulp and 20% recycled fibers obtained from American Fiber Resources (AFR) LLC,
Fairmont,
WV, The hardwood was refined to a freeness of 300 mL Canadian Standard
Freeness (TAPP1
Test Method T 227 om-94) in a Valley Beater (from Voith Sulzer, Appleton, WI).
The thick
stock is diluted with tap water to 0.5% consistency.
Hand.sheets were prepared by mixing 650 mL of 0.5% consistency furnish at 800
rpm in a Dynamic Drainage Jar with the bottom screen covered by a solid sheet
of plastic to
prevent drainage. The Dynamic Drainage Jar and mixer are available from Paper
Chemistry
Consulting Laboratory, Inc., Carmel, NY. Mixing was started and 1 g of one of
the PCC samples
was added after 15 seconds, followed by 6 lb/ton (product based) of GC7503
palyaluminum
chloride solution (available from Gulbrandsen Technologies, Clinton, NJ, USA)
at 30 seconds, 1
lb/ton (product based) of a sodium acrylate-acrylamide copolymer floceulant
with an RSV of
about 32 dLig and a charge content of 29 mole ",/ii (available from Nalco
Company, Naperville, IL
USA) at 45 seconds, and 3,5 Ibiton. (active) of a borosilicate microparticle
(available from Nalco
Company, Naperville, IL USA) at 60 seconds.
Mixing was stopped at 75 seconds and the furnish was transferred into the
deckle
box of a Noble 8z, Wood handsheet mold. The 8"x 8" handsheet was formed by
drainage through
a 100 mesh forming wire. The handsheet was couched from the sheet mold wire by
placing two
blotters and a metal plate on the wet handsheet and roll-pressing with six
passes of a 25 lb metal
roller, The forming wire and one blotter were removed and the handsheet was
placed between
two new blotters and the press felt and pressed at 50 psig using a roll press.
All of the blotters
were removed and the handsheet is dried for 60 seconds (top side facing the
dryer surface) using
a rotary drum drier set at 220T. The average basis weight of a handsheet was
84 Wm-, The
handsheet mold, roll press, and rotary drum dryer are available from
Adirondack Machine
Company, Queensbury, NY, Five replicate handsheets are produced for each PCC
sample tested.
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The finished handsheets were stored overnight at TAPPI standard conditions of
50% relative humidity and 23 C. For each sheet, the basis weight was
determined using TAPPI
Test Method T 410 om-98, the ash content was determined using TAPPI Test
Method T 211 oin-
93, brightness is determined using ISO Test Method 2470:1999, and opacity was
determined
using ISO Test Method 2471:1998. Sheet formation, a measure of basis weight
uniformity, was
determined using a Kajaani Formation Analyzer from Metso Automation,
Helsinki, Ft The
results from these measurements are listed in Table VI. The tensile strength
of the sheets was
measured using TAPPI Test Method T 494 om-01, Scott Bond was measured using
TAPPI Test
Method T 569 pm-00, and z=-directional tensile strength (ZDT) was measured
using TAPPI Test
Method T 541 om-89. These results are listed in Table VII.
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Table V. Filler floc size characteristics for samples 10-A through 10-E,
The 10.-E sample is
an untreated FCC slurry.
................... . ___________
.Shear ......
..
Time 1.1.)(v, 0.1) D(v,0.5) D(v, 0.9)
Example (s) MCI, (urn) ..1.1r0 flim) (pm).pan Inifonnity
...................................... + ....
10-.A 210 F70.4 . 0.4 83.6 181,2 1.8 17.55
_____________________________________ I 1
10-B 330 49.3 p9.2 '4.0 129.1 1.6 ' .49
10-C 450- 39,4 .22.5 - 45.1 187.4 1.4 .44 .
......
10-D 1500 t29.8 13.8 25.8 = 6 3 1.3
.39
L110-E = ...".TA .24 0.64 1.54 3.28 1.7
'J.66
..
Table VI. The optical properties of sheets with different size filler
floes.
.. . ...................................... .
.................... i
FCC from Basis weight ksh contentOpacity at Brightness =Formation
Ex, No. (g/m2) ..%)6(-)g/in ' - (% ISO) % ISO) . Index
== .......................... 1
10-A 43 15.0 189.6 87.8
.......... + = - = - = ... 4---
10--B 83.8 113.3 79.1 87.8 = 3.3
.. ...................................................
10-C 4:84.6 14.4 t 9.6 .7.9 ' 4.3
. ............................................................ ,
10-D 83.5 13.9 :9.8 87.8 102.6
10-E 83.0 14.5 2.8 87.6 101.2
.............................................................. =
Table VII. Mechanical strength properties of sheets with different size
filler flocs.
.............................................. - ...................
[ t echanical Strength .mprovement (%)
.. I . ..
FCC fro).: ZDT Scott Bond Tensile IndexTEA Scott Tensile
,Ex. No. kPa) (psi) . N=nalg) . N.cm/cm2) ZDT Bond Index TEA
................ i . ---------- . .. .
10-A 33.2 1,226.3 *2.9 .6 14 :06 13.8 44
+... + ==
10-B p09.7 1254..8 "1.7 ., .2 10 2 .3 0
1
10-C *75.9 217.2 :,..3.0 Ø5 4.8 -9 .9 )6
................ 1 = . ............... ..-4.:.
10-D ,,f- 81.4 R19.6 '55 :...L.3 5.7 31 /.0
30
110.-B , 44.9 -179.0 9.9 1.8 0 . ) .
.. ................. ....
22
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As shown in Table V, the size of the filler flocs decreases as the time under
1500
rpm shear increases, demonstrating the feasibility of controlling the size of
filler flocs by the time
under high shear. Handsheets prepared from each of the four preflocculated
fillers (10-A through
10-D) and the untreated filler (10-E) have roughly equivalent ash contents and
basis weight, as
listed in Table VI increasing the floc size did not hurt brightness, but
decreased the formation
and opacity of the sheets slightly. The mechanical strength of the sheets, as
measured by z-
directional tensile strength, Scott Bond, tensile index, and tensile energy
absorption (TEA)
increased significantly with increasing filler floc size. This is shown in
Table VII. In general,
higher median PCC floc size lead to increased sheet strength. In practice, the
slight loss of
opacity could be compensated for by increasing the PCC content of the sheet at
constant to
improved sheet strength.
In at least one embodiment, a method of preflocculating filler particles for
use in
papennaking processes comprises: a) providing an aqueous slum, of filler
particles; h) adding a
first flocculating agent to the dispersion under conditions of high mixing; d)
adding a second
flocculating agent under conditions of high mixing in an amount sufficient to
initiate flocculation
of the filler particles in the presence of the first flocculating agent; and
c) optionally shearing the
-flocculated dispersion to provide a dispersion of filler floes having the
desired particle size.
Preferably, the first flocculating agent is one of the previously described
anionic flocculants.
Preferably, the second flocculating agent is one of the previously described
cationic flocculants.
The two flocculants may each have a high molecular weight and low to medium
charge density.
Without being limited by theory or design it is believed that the first high
molecular weight flocculating agent forms an evenly distributed mixture
through the slurry
before absorption. This evenly distributed mixture aids the cationic second
flocculating agent in
efficiently pulling together the mass to form the floc particles. As the
following examples
demonstrate, this embodiment's novel use of two high molecular weight
flocculating agents to
23
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control the particle size distribution through the slurry produces
unexpectedly efficient floc
production. This embodiment can best be understood with reference to Examples
11-16.
Example 11-12
Scalenohedral PCC (available as Syncarb S NY from Omya) was diluted to 10%
solids using tap water, The size distribution of the filler was measured at
three second intervals
during flocculation using a Lasentee S400 FBRIVI. The laser probe was
inserted in a 600 mL,
beaker containing 300 mi., of the 10% PCC slurry, The solution was stirred
using an WA RE16
stirring motor at 800 rpm for at least 30 seconds prior to the addition of
flocculating agents.
The first flocculating agent was added, as a dilute solution, slowly over the
course
of several minutes using a syringe. When a second flocculating agent is used,
it was added in a
similar manner to the first flocculating agent after waiting 10 seconds for
the first flocculating
agent to mix, The slurry is then stirred at 1500 rpm for 2-4 minutes to test
the stability of the
filler floes under high shear conditions, The PCC type, flocculating agents,
and doses of
flocculating agents used in these examples are listed in Table VIII, and the
resulting
characterization of the particles is given in Table IX.
Examples 13-16
This experiment demonstrated the feasibility of using a continuous process to
flocculate the PCC slurry, A hatch of 18 liters of 10% solids undispersed PCC
(available as
Albacar HO from Specialty Minerals Inc., Bethlehem, PA USA) in tap water is
pumped using a
centrifugal pump at 7,2 kg PCC/min into a five gallon bucket. The appropriate
dosage of the first
flocculating agent solution is fed into the PCC slurry at the centrifugal pump
inlet using a
progressive cavity pump. The PCC is then fed into a static mixer together with
the appropriate
dosage of the second flocculating agent. The size distribution of the filler
flocs is measured
using the Mastersizer Micro and reported in Table X. The resulting sample is
exposed to
additional shear by circulating the sample through a centrifugal pump; the
results are also given
in Table X.
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The results shown in Tables IX-X highlight the advantages of the dual
flocculant
treatment. Examples 12, 14-16 demonstrate improved shear stability as
indicated by a lower
volume percent of particles with size less than 10 micron, These samples were
found to be
superior to Examples 11 and 13.
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Table VIII. Calcium carbonate type, flocculating agent descriptions, and
flocculating agent
doses for examples.
............
Polymer 1 Polymer 2 Micropartiele
======== ========= :==: .=
==== ====:. = 1
Calcium carbonate Dose : Dose Dose
Ex Type Name (lb/ton) Name ::
(lb/ton) Name (lb/ton)
= "
====: = ' ""=:":""===='
:ii Undispersed PCC Flocculant A . 2 Coagulant A
1 None =
12 Iindispersed PCC Flocculant A 1.5 Floceulant B 1.5
None
=
13 Undispersed PCC Flocculant A 1.5 Coagulant A 1.5 1, None
==== = = = =
14 Undispersed PCC Flocculant A 1 Flocculant B 1 None
_____________ ----------------------- -----------------------------------
-==
15 Undispersed PCC Flocculant .A 1 Flocculant C 1
A
== == == ==== ==
== =:== ===== =====.
16 Undispersed FCC = Flocculant A 1 = Flocculant B I
A 1
==================== == =
Flocculant A Anionic sodium
acrylate-aerylamide copolymer floeculant with an RSV of about 32
dilg and a charge content of 29 mole % available from Nalco Co., Naperville,
IL
USA.
Flocculant B Cationic
acrylamide-dimethylaminoethyl aerylate-methyl chloride quaternary salt
copolymer flocculant with a RSV of about 25 dijg and a charge content of 10
mole
% available from Nalco Co., Naperville, IL USA.
....... ==== =
Flocculant C Cationic
acrylamide-dimethylaminoethyl acrylate-inethyl chloride quaternary salt:
copolymer floccuiant with a RSV of about 25 dig and a charge content of 20
mole
% available from Nalco Co., Naperville, IL USA.
Coagulant A Cationic
poly(diallyldimethylartnnonium chloride) coagulant with an R.SV of about
0.7 didg available from Nalco Co., Naperville, IL USA.
. ................::
Microparticle A Anionic
colloidal borosilicate microparticle available from Nalco Co., Naperville, IL
USA.
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Table IX, Characteristics of flocculated calcium carbonate samples in Examples
11-12 as
prepared at 800 rpm and upon subsequent shear under 1500 rpm.
= ...,
Ex , Time at 1500 D(v, 0.1) .., D(v, 0.5) D(v, 0.9) Vol % <
10 Span
:
= rpm (min) (urn) (pm) (11m) (ltm)
...... .....
11 0 28,6 70.9 . 149.4 0.9 1.7
..............
12 0 55.4 109.1 : 201,9 0.2 1.3
.... .. ..... - 4 - - . =
:
....
= -
: 11 2 14.4 37.7 87.5 3.8 1.9
.... .......... ...................
.... ......
12 2 20.3 45.3 . 94A 1,3 1.6
........................................... = ..................
11 4 11.4 28.6 70.0 : 6.7 2.0
. ....... ....
12 4 14.9 ' 33.8 73.4 ; 2.9
1.7
27
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Table X. Characteristics of flocculated calcium carbonate samples in Examples
13-16.
Ex No. circulations D(v, 0,1) D(v, 0.5) I D(v., 0.9)
Vol % < 10 Span
(.tm)
through pump (,1m) (i.un) (Pm)
...................................... ---6-" __
13 0 18.6 36.8 68.6 1.47 1.36
L
14 0 57.3 115.0 211.5 0.18 1.34
............................. 1 ................. - ___________________ ,
15 0 49.1 99.6 1910 0.62 1.43
õ. .......................................................................
16 0 36.8 76.2 148.6 0.77 1.47
,
, .....................................
13 3 10.9 21.5 39.6 6.94 1.34
,
14 3 23.7 45.1 81.1 1.22 L27
15 3 17,3 34.5 63.7 2.04 1.35
16 3 16.0 35.2 69.0 2.83 1.51
õ.......4.õ_ ................................................. ..,,... ...
13 6 9.0 18.0 33.3 12.44 1.35
14 6 16.7 32.2 1- 58.3 1.76
1.29
................... : ..............................................
15 6 12.2 26.0 5L1 5,26 1.50
,=
õ_,_._..., , ________________________________________________________
...........
=
..;
16 6 13.7 30.1 59.0 4,14 1.51
1
13 9:
. 8.0 16.2 30.0 17.28 1.36
:
,
................... f ------------------
14 9 14.0 27.3 49.9 2.89 1.31
; ...........................
15 9 1 10.2 21.7 42.3 8.87 1.48
,=
16 9 11.7 26.2 52.1 6.27 I 1.54
I .,. .......
28
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At least one embodiment is a method of preflocculating filler that has been
dispersed using a high charge, low molecular weight, anionic dispersing agent.
The method
consists of a) providing an aqueous slurry of anionically dispersed filler
particles; 11) adding a low
molecular weight coagulant to the dispersion in order to completely or
partially neutralize the
charge in the system; c) adding a first flocculating agent to the dispersion
under conditions of high
mixing; d) adding a second flocculating agent (can be a coagulant or
flocculant) to the dispersion
under conditions of high mixing; and c) optionally shearing the flocculated
dispersion to provide a
dispersion of filler flocs having the desired particle size.
Preferably, the low molecular weight, charge-neutralizing component is a
coagulant, as previously described. Preferably, the first flocculating agent
is an anionic or
cationic flocculant, as previously described. Preferably, the second
flocculating agent is either a
coagulant or a flocculant with the opposite charge of the first flocculating
agent. This can best be
understood with reference to the following Examples 17-20:
Examples 17-20
The dispersed ground calcium carbonate ((iCC) used in the examples is either
Hydmcarb HO G-ME or Omyafil 90 from Oliva. The dispersed GCC, obtained as a
65% solids
slurry, is diluted to 10% solids using tap water. The size distribution of the
filler is measured at
three second intervals during flocculation using a Lasentec 8400 FBRM
(Focused Beam
Reflectance Measurement) probe, as described in Examples 1-7, The laser probe
is inserted in a
600 mIL beaker containing 300 nit, of the 10% PCC slurry. The solution is
stirred using an IKA
RE16 stirring motor at 800 rpm for at least 30 seconds prior to the addition
of flocculating agents.
The neutralizing polymer is added slowly over the course of approximately a
few
minutes. The first flocculating agent is then added slowly over the course of
several minutes
using a syringe. When a second flocculating agent is used, it is added in a
similar manner to the
first flocculating agent after waiting 10 seconds for the first flocculating
agent to mix. The
CA 02867598 2014-09-16
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slurry is then stirred at 1500 rpm for 2-4 minutes to test the stability of
the filler floes under high
shear conditions.
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Table XL Ground calcium carbonate source, flocculating agent descriptions, and
flocculating
agent doses for examples 17-20.
Polymer A Polymer 1
Polymer 2
.
=
Source of Dispersed
Ground Dose Dose Dose
Ex Calcium Carbonate Name (lb/ton) :
Name (lb/ton) Name (lb/ton)
= = = = = r = = = = =
= = = = = =
17 Hydrocarb HO Cf-ME, None Coagulant A 4
Flocculant A 1.5
..................
18 Hydrocarb HO G-ME Coagulant A : 4 Flocculant A 1.5
Coagulant A I
. ............................. , ............
19 Hydrocarb HO G-ME None
Coagulant B 2 Flocculant B
1.4
=
...= .= ====" """"" ===
20 Omyafil 90 Coagulant A 1.5 Flocculant A 1 Coagulant A
0.5
Flocculant A Anionic sodium acrylate-acrylarnide copolymer flocculant with an
RSV of about
32 &Lig and a charge content of 29 mole % available from Nalco Co.,
Naperville, IL USA.
==========
Flocculant B Cationic acrylamide-dimethylamitmethyl aciylate-methyl chloride
quaternary:
salt copolymer flocculant with an RSV of about 25 dLlg and a charge content of
mole % available from Nalco Co., Naperville, IL USA.
Coagulant A Cationic poly(diallyidimethylammonium chloride) coagulant with an
RSV of
about 0.7 dLlg available from Nalco Co., Naperville, IL USA.
Coagulant B Cationic epichlorohydrin-dimethylamine copolymer crosslinked with
ammonia
with a RSV of about 0.3 dL/g available from Nalco Co., Naperville, IL, USA.
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Table XII. Characteristics of flocculated ground calcium carbonate samples in
Example 17-20,
as prepared at 800 rpm and upon subsequent shear under 1500 rpm.
................................ ..=,= ...................................
Ex Time at 1500 D(v, 0.1) D(v, 0.5) D(v, 0.9) , Vol A) < 10
Span
rpm urn
.: ....
1 12.2
17 0
.. 1 35.1 113.2 5.2 2.9
:õ..õõõ, --------------------------------------------------------------------
18 0 59.9 139.5 235.9 0.0 L3
...................................................... 4. .........
=
19 ' 0 24.9 101.8 211.9 1.1 1.8
=
............................................ - . .... 4 ....................
20 0 27.4 77.4 171.3 0.1 1 1.9
____________________ -õõõõ,,,,. = .............................. .
:
................................................................. +, -------
17 2 mins. 8.4 21.5 62.6 14.0 ,. 2.5
18 : 2 mins. 34.7 74.2 148.7 0.6 1.5
=
:
.... ............................ ...... ........... =
19 2 mins. 7.5 36,1 130.6 13.9 3.4
............................................ + . .. .
20 2 mins. 18.4 45.3 101.9 1.4 1,8
___________________________________________________________________ .... :
-
18 4 mins. :
27.6 57.6 46.8 0.7 0.3
(mistake
here)
õ..õõõõõõõ_..4 ........................................... .. ..
=
20 4 mins; 14.6 35.9 84.2 3.2 1,9
:: ....................................... . ____
I
I ..... =
.................... =44 t
18 8 mins, 22.6
1 46.9 91.7 0.7 1.5
,.. ......
As shown in Table XI, Examples 18 and 20 demonstrate the invention disclosed,
namely, an initial treatment with a charge-neutralizing polymer followed by
two flocculating
polymers. Examples 17 and 19 represent the use of a coagulant followed by a
flocculant. As
shown in Table XII, the preflocculated GCC in Examples 18 and 20 show improved
shear
32
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WO 2013/158811 PCT/US2013/037048
stability indicated by larger median particle size D(vA5) at the same amount
of shear. Examples
18 and 20 also have an improved particle size distribution, indicated by
smaller span and lower
percent by volume less than 10 microns.
Example 21
The purpose of these examples was to evaluate the impact of the prefloeculated
ground calcium carbonate on the physical properties of paper sheets. The
preflocculated sample
from Example 20 was used for this purpose, and compared against untreated
Omyafil 90.
Thick stock with a consistency of 2.3% was prepared from 75% hardwood dry lap
pulp and 25% softwood dry lap pulp. Both woods were refined to a freeness of
400 mi., Canadian
Standard Freeness (TAPPI Test Method T 227 om-94) in a Valley Beater (from
Voith Sulzer,
Appleton, WI), The thick stock was diluted with tap water to 0.5% consistency.
Handshects were prepared by mixing 650 int of 0.5% consistency furnish at 800
rpm in a Dynamic Drainage Jar with the bottom screen covered by a solid sheet
of plastic to
prevent drainage. The Dynamic Drainage Jar and mixer are available from Paper
Chemistry
Consulting Laboratory, Inc., Cannel, NY. Mixing was started and the GCC sample
was added,
followed by 11 lb/ton cationic starch and 3 lb/ton of Nalco 7542 sizing agent
at 15 seconds, and
finally 0.6 lb/ton (product based) of a sodium acrylate-acrylamide copolymer
fiocculant with an
RSV of about 32 cilig and a charge content of 29 mole % (available from Nalco
Company,
Naperville, IL),
Mixing was stopped at 45 seconds and the furnish was transferred into the
deckle
box of a Noble elk. Wood handsheet mold. The 8"x 8" handsheet was formed by
drainage through
a 100 mesh forming wire. The handsheet was couched from the sheet mold wire by
placing two
blotters and a metal plate on the wet handsheet and roll-pressing with six
passes of a 25 lb metal
roller. The forming wire and one blotter were removed and the handsheet was
placed between
two new blotters and the press felt and pressed at 50 psig using a flat press.
All of the blotters
were removed and the handsheet was dried for 60 seconds (top side facing the
dryer surface)
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PCT/US2013/037048
using a rotary drum drier set at 220 F. The handsheet mold, roll press, and
rotary drum dryer are
available from Adirondack Machine Company, Glens Falls, NY, Five replicate
handsheets were
produced for each PCC sample tested.
The finished handsheets were stored overnight at TAPPI standard conditions of
50% relative humidity and 23 C. The basis weight (TAPPI Test Method T 410 om-
98), ash
content (TAPPI Test Method T 211 om-93) for determination of PCC content,
brightness (ISO
Test Method 2470:1999), opacity (ISO Test Method 2471:1998), formation,
tensile strength
(TAPPI Test Method T 494 om-01), Scott Bond (TAPPI Test Method T 569 pm-00),
and z-
directional tensile strength (ZDT, TAPPI Test Method T 541 am-89) of the
handsheets were
tested. The formation, a measure of basis weight unifonnity, was determined
using a Kajaani
Formation Analyzer from lvietso Automation, Helsinki, FL
Table XII. Properties of sheets containing untreated ground calcium carbonate
or
a preflocculated sample as described in Example 20,
= ==
Basis weight Ash content ZDT TEA
Tensile Index
= GCC source
(g/m2) (Niulg)
(kPa)
(Jim')
Ornyafil 90 86.0 12.6 562 49.3 135
. = .. - ..
Omyafil 90 81.4 18.4 553 44.0 102
...... : . ..................................................................
Example 20 91.4 17.8 608 53.7 163
. . == ..........
*
Example 20 91,4 27.7 598 45.4 129
======== = == -,=== == " " == ........ õ . .
The mechanical strength data in Table XII indicates a 20% increase in tensile
index and 10% increase in internal bond strength at a level 18% ash for the
sheets containing the
preflocculated filler produced in Example 20, compared to the sheets
containing untreated GCC.
While this invention may be embodied in many different forms, there described
in
detail herein specific preferred embodiments of the invention. The present
disclosure is an
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WO 2013/158811 PCT/US2013/037048
exemplification of the principles of the invention and is not intended to
limit the invention to the
particular embodiments illustrated. All patents, patent applications,
scientific papers, and any
other referenced materials mentioned herein are incorporated by reference in
their entirety.
Furthermore, the invention encompasses any possible combination of some or all
of the various
embodiments described herein and/or incorporated herein, In addition the
invention
encompasses any possible combination that also specifically excludes any one
or some of the
various embodiments described herein and/or incorporated herein.
The above disclosure is intended to be illustrative and not exhaustive. This
description will suggest many variations and alternatives to one of ordinary
skill in this art. Aft
these alternatives and variations are intended to be included within the scope
of the claims where
the term "comprising" means "including, but not limited to, Those familiar
with the art may
recognize other equivalents to the specific embodiments described herein which
equivalents are
also intended to be encompassed by the claims.
All ranges and parameters disclosed herein are understood to encompass any and
all subranges subsumed therein, and every number between the endpoints. For
example, a stated
range of "I to 10" should be considered to include any and all subranges
between (and inclusive
of) the minimum value of I and the maximum value of 10; that is, all subranges
beginning with a
minimum value of I or more, (e.g.. Ito 6.1), and ending with a maximum value
of 10 or less,
(e.g. 2.3 to 9.4, 3 to 8, 4 to 7), and finally to each number 1, 2, 3, 4, 5,
6, 7, 8, 9, and 10 contained
within the range.
This completes the description of the preferred and alternate embodiments of
the
invention. Those skilled in the art may recognize other equivalents to the
specific embodiment
described herein which equivalents are intended to be encompassed by the
claims attached
hereto.
35
