WO2004053229A1

WO2004053229A1 - Filler-fiber composite

Info

Publication number: WO2004053229A1
Application number: PCT/US2003/038218
Authority: WO
Inventors: Geoffrey Lamar Hughes; Kyle James Mitchell
Original assignee: Specialty Minerals (Michigan) Inc.
Priority date: 2002-12-09
Filing date: 2003-12-03
Publication date: 2004-06-24
Also published as: CA2509514A1; KR20040050051A; CL2003002529A1; TW200500534A; US20040108081A1; UY28107A1; JP2006509118A; RU2005121567A; CN1723314A; EP1576236A1; AU2003293225A1; AR042328A1; NO20053138L; BR0316926A

Abstract

The present invention relates to a filler-fiber composite, a process for its production, the use of such in the manufacture of paper or paperboard products and to paper produced therefrom. More particularly the invention relates to a filler-fiber composite in which the morphology and particle size of the mineral filler are established prior to the development of the bond to the fiber. Even more particularly, the present invention relates to a PCC filler-fiber composite, wherein the desired optical and physical properties of the paper produced therefrom are realized.

Description

FILLER-FIBER COMPOSITE

FIELD OF THE INVENTION

The present invention relates to a filler-fiber composite, a process for its production, the use

of such in the manufacture of paper or paperboard products and to paper produced therefrom. More

particularly the invention relates to a filler-fiber composite in which the moφhology and particle size of the mineral filler are established prior to the development of the bond to the fiber. Even more particularly, the present invention relates to a PCC filler-fiber composite, wherein the desired optical and physical properties of the paper produced therefrom are realized.

BACKGROUND OF THE INVENTION

Loading particulate fillers such as calcium carbonate, talc and clay on fibers for the

subsequent manufacture of paper and paper products continues to be a challenge. A number of

methods, having some degree of success, have been used to address this issue. To insure that fillers remain with or within the fiber web, retention aids have been used, direct precipitation onto the

fibers have been used, a method to attach the filler directly to the surface of the fiber have been used,

mixing the fiber and the filler have been used, precipitation within never dried pulp have been used,

a method for filling the cellulosic fiber have been used, high shear mixing have been used, fiberous

material and calcium carbonate have been reacted with carbon dioxide in a closed pressurized container, fillers have been trapped by mechanical bonding, cationically charged polymers have been used and pulp fiber lumen loaded with calcium carbonate have all been used to retain filler in

fiber for subsequent use in paper. Most of the methods for fiber retention are both expensive and ineffective.

Therefore, what is needed is a filler fiber composite and a method for producing the same that is both effective in retaining the filler and inexpensive for the paper maker to utilize.

Therefore, an object of the present invention is to produce a filler/fiber composite. Another

object of the present invention is to provide a method for producing a filler/fiber composite. While

another object of the present invention is to produce a filler/fiber composite that maintains physical properties such as tensile strength, breaking length and internal bond strength. Still a further object

of the present invention is to produce a filler/fiber composite that maintains optical properties such as ISO opacity and pigment scatter. While still a further object of the present invention is to provide

a filler/fiber composite that is particularly useful in paper and paperboard products.

RELATED ART

U.S. Pat. No. 6,156,118 teaches mixing a calcium carbonate filler with noil fibrils in a size

ofP50 or finer.

U.S. Pat. No. 5,096,539 teaches in-situ precipitation of an inorganic filler with never dried pulp. U.S. Pat. No. 5,223,090 teaches a method for loading cellulosic fiber using high shear mixing of crumb pulp during carbon dioxide reaction.

U.S. Pat. No. 5,665,205 teaches a method for combining a fiber pulp slurry and an alkaline salt slurry in the contact zone of a reactor and immediately contacting the slurry with carbon dioxide and mixing so as to precipitate filler onto secondary pulp fibers.

U.S. Pat. No. 5,679,220 teaches a continuous process for in-situ deposition of fillers in

papermaking fibers in a flow stream in which shear is applied to the gaseous phase to complete the

conversion of calcium hydroxide to calcium carbonate immediately.

U.S. Pat. No. 5,122,230 teaches process for modifying hydrophilic fibers with a substantially

water insoluble inorganic substance in-situ precipitation.

U.S. Pat. No. 5,733,461 teaches a method for recovery and use of fines present in a waste water stream produced in a paper manufacturing process.

U.S. Pat. No. 5,731,080 teaches in-situ precipitation wherein the majority of a calcium

carbonate trap the microfibnl by reliable and non-reliable mechanical bonding without binders or retention aids. U.S. Pat. No. 5,928,470 teaches method of making metal oxide or metal hydroxide-modified cellulosic pulp.

U.S. Pat. No. 6,235,150 teaches a method of producing a pulp fiber lumen loaded with

calcium carbonate having a particle size of 0.4 microns to 1.5 microns.

The problem of insuring that filler materials, such as calcium carbonate, ground calcium carbonate, clay and talc, remain within fibers that are ultimately to be used in paper has been

subjected to a number of proofs. However, none of the prior related art discloses a filler fiber

composite where the moφhology of the filler is predetermined prior to introducing fibrils, a method

for its production nor its use in paper or paper products.

SUMMARY OF THE INVENTION

The present invention relates to a filler-fiber composite including feeding slake containing

seed to a first stage reactor, reacting the slake containing seed in the first stage reactor in the presence of carbon dioxide to produce a first partially converted calcium hydroxide calcium carbonate slurry,

reacting the first partially converted calcium hydroxide calcium carbonate slurry in a second stage

reactor in the presence of carbon dioxide to produce a second partially converted calcium hydroxide

calcium carbonate slurry and reacting the second partially converted calcium hydroxide calcium

carbonate slurry in a third stage reactor in the presence of carbon dioxide and fibrils to produce a

filler-fiber composite. In another aspect, the present invention relates to a filler-fiber composite including

feeding slake containing seed to a first stage reactor, reacting the slake containing seed in the first

stage reactor in the presence of carbon dioxide to produce a first partially converted calcium

hydroxide calcium carbonate slurry and reacting the first partially converted calcium carbonate slurry

in a second stage reactor in the presence of carbon dioxide and fibrils to produce a filler-fiber composite.

In a further aspect, the present invention relates to a filler-fiber composite including feeding

slake containing citric acid to a first stage reactor, reacting the slake containing citric acid in the first

hydroxide calcium carbonate slurry, reacting the first partially converted calcium hydroxide calcium

carbonate slurry in a second stage reactor in the presence of carbon dioxide to produce a second

partially converted calcium hydroxide calcium carbonate slurry, and reacting the second partially converted calcium hydroxide calcium carbonate slurry in a third stage reactor in the presence of

carbon dioxide and fibrils to produce a filler-fiber composite.

In yet a further aspect, the present invention relates to a filler-fiber composite Including

feeding slake containing citric acid to a first stage reactor, reacting the slake containing citric acid

in the first stage reactor in the presence of carbon dioxide to produce a first partially converted

calcium hydroxide calcium carbonate slurry, taking a first portion of the partially converted calcium

hydroxide calcium carbonate slurry adding fibrils and reacting such in a second stage reactor in the presence of carbon dioxide to produce a calcium carbonate\fιbril composite to serve as a heel and

taking a second portion of the partially converted calcium hydroxide calcium carbonate slurry adding

fibrils and surfactant and reacting in the presence of CO₂ to produce a second partially converted

Ca(OH) /CaCO₃/fιbril material and reacting the second partially converted Ca(OH)₂/CaCO /fibril

material in the presence of CO in a third stage reactor to produce a filler-fiber composite.

In still a further aspect, the present invention relates to a filler-fiber composite including

feeding slake containing citric acid to a first stage reactor, reacting the slake containing citric acid in the first stage reactor in the presence of carbon dioxide to produce a first partially converted

hydroxide calcium carbonate slurry adding fibrils and reacting such in a second stage reactor in the

presence of carbon dioxide to produce a calcium carbonate/fibril composite to serve as a heel and

fibrils and polyacrylamide and reacting in the presence of CO₂ to produce a second partially

converted Ca(OH)₂/CaCO₃/fibril material and reacting the second partially converted

Ca(OH)₂/CaCO /fibril material in the presence of CO in a third stage reactor to produce a filler/fiber composite.

In a final aspect, the present invention relates to a filler-fiber composite including feeding

stage reactor in the presence of carbon dioxide to produce a CaCO₃ heel and adding slake containing

sodium bicarbonate to the heel material of the first stage reactor in the presence of CO₂ to produce a partially converted calcium hydroxide calcium carbonate slurry and reacting the partially converted

calcium hydroxide calcium carbonate slurry in a second stage reactor in the presence of carbon

dioxide and fibrils to produce a filler-fiber composite.

DETAILED DESCRIPTION OF THE INVENTION

Precipitation of PCC with Varying Morphologies Continuous Flow Stir Tank Reactor (CFSTR)

Scalenohedral Morphology

The first step in this process involves making a high reactive Ca(OH)₂ rnilk-of-lime slake and

screening it at -325 mesh. This slake is then added to an agitated reactor, brought to a desired

reaction temperature, 0.1 percent citric acid is added to the slake to inhibit aragonite formation, and

reacted with CO₂ gas. The reaction proceeds 10 percent to 40 percent of the way through at which

point the reaction is stopped. This produces a partially converted Ca(OH)₂ /CaCO₃ slurry (approximately 20 percent solids by weight) which is then fed into a reaction vessel at a rate that

matches CO gassing to maintain a given conductivity (ionic saturation) to produce a scalenohedral

crystal. This reaction proceeds until stabilization of the process is achieved. The product made once

stabilization is achieved (approximately 95 percent converted) is then mixed with diluted fibrils

(approximately 1.5 percent concentration) and water. This mixture is then reacted with CO₂ gas to

endpoint pH 7.0. The product manufactured using this method can contain from about 0.2 percent

to about 99.8 percent scalenohedral PCC with respect to fibrils at 3 percent to 5 percent total solids. The product has a specific surface area from about 5 meters squared per gram to about 11

meters squared per gram; product solids from about 3 percent to about 5 percent and a PCC content

from about 0.2 percent to about 99.8 percent, and is predominantly scalenohedral in moφhology.

Aragonitic Morphology

The first step in this process involves making a high reactive Ca (OH) milk-of-lime slake and screened at -325 mesh. The concentration of this slake is approximately 15 percent by weight.

This slake is then added to an agitated reactor, brought to a desired reaction temperature, from about 0.05 percent to about 0.04 percent additive is added to direct moφhology and size, and reacted with

CO₂ gas. The reaction proceeds 10 percent to 40 percent of the way through at which point the

reaction is stopped. This produces a partially converted Ca (OH)₂ / CaCO₃ slurry which is then fed

into a reaction vessel at a rate that matches CO₂ gassing to maintain a given conductivity (ionic

saturation) to produce an acicular, aragonitic crystal. The reaction continues until process stabilization is achieved. The product made once stabilization is achieved, (approximately 95

percent calcium carbonate) is mixed with diluted fibrils (approximately 1.5 percent concentration) and water. The calcium carbonate and fibrils are then reacted with CO₂ gas to an endpoint of pH 7.0.

The product manufactured using this method contains from about 0.2 percent to about 99.8 percent

aragonitic PCC with respect to the fibrils at about 3 percent to about 5 percent total solids.

The product has a specific surface area of about 5 meters squared per gram to about 8 meters

squared per gram; product solids from about 3 percent to about 5 percent by weight and a PCC content from about 0.2 percent to about 99.8 percent with respect to fibrils and has a predominantly

aragonitic moφhology.

Rhombohedral Morphology

The first step in this process involves making a high reactive Ca (OH) milk-of-lime slake

which is screened at -325 mesh and has a concentration of approximately 20 percent by weight. 0.1 percent citric acid is added to inhibit aragonite formation. A portion of this slake is added to an agitated reactor, brought to a desired reaction temperature and carbonated with CO₂ gas. The

reaction proceeds to conductivity minimum producing a "heel". A "heel" is defined as a fully

converted calcium carbonate crystal with average particle size typically in the range of about 1

micron to about 2.5 micron with any crystal moφhology. Sodium bicarbonate is added to the

remainder of the slake not used in the manufacture of the "heel" material. This slake and CO₂ is

added to the "heel" material at a CO₂ gassing rate to maintain a given conductivity (ionic saturation)

to produce a rhombohedral crystal. The reaction is continued until process stabilization is achieved. Once stabilization is achieved, this product (approximately 90 percent to 95 percent converted) is

mixed with diluted fibrils (approximately 1.5 percent concentration) and water. Additional CO₂ is

added to an endpoint of pH 7.0. The product manufactured using this method contains from about

0.2 percent to about 99.8 percent rhombohedral PCC with respect to fibrils and is about 3 percent

to about 5 percent total solids.

The product has a specific surface area from about 5 meters squared per gram to about 8

meters squared per gram; product solids from about 3 percent to about 5 percent; and PCC content from about 0.2 percent to about 99.8 percent and has a predominantly rhombohedral moφhology:

EXAMPLES

The following examples are intended to exemplify the invention and are not intended to

limit the scope of the invention.

EXAMPLE 1

SCALENOHEDRAL PCC

Reacted 15 liters of water with 3 kilogram CaO at 50 degrees Celsius producing a 20 percent by weight Ca(OH)₂ slake. The Ca(OH)₂ slake was then screened at -325 mesh producing a screened

slake that was transferred to a first 30-liter double jacketed stainless steel reaction vessel with an

agitation of 615 revolutions per minute (φm). 0.1 percent citric acid, by weight of total theoretical

CaCO to be produced, was added to the screened slake in a 30-liter reaction vessel and the

temperature of the contents brought to 40 degrees Celsius. Began addition of 20 percent CO₂ gas in

air (14.83 standard liter minute CO₂/59.30 standard liter minute air) to the 30-liter reaction vessel to produce a 2:1 Ca (OH)₂/CaCO₃ slurry. At this point, CO₂ gassing was stopped and the slurry was

transferred to an agitated 20-liter storage vessel.

2 liters of the 2:1 Ca(OH)₂/CaCO₃ slurry was transferred to a first 4-liter agitated (1250 rpm)

stainless steel, double jacketed reaction vessel. The temperature was brought to 51 degrees Celsius

and 20 percent CO gas in air (1.41 standard liter minute CO₂/5.64 standard liter minute air) was

added to the first 4-liter reaction vessel until a pH of 7.0 was achieved producing a CaCO₃ slurry. Once apH 7.0 was achieved began addition of the 2:1 Ca(OH)₂/CaCO₃ slurry of the 20-liter storage

vessel to the first 4-liter reaction vessel while continuing to add 20 percent CO₂ gas in air (1.41

standard liter minute CO₂/5.64 standard liter minute air) to the first 4-liter reaction vessel to maintain

a conductivity of approximately 90 percent ionic saturation. The addition of Ca(OH)₂/CaCO₃ slurry

and CO₂ to the first 4-liter reaction vessel was continued for approximately 12 hours until product

physical properties remained essentially unchanged, producing a CaCO slurry that was approximately 98 percent converted. Transferred 0.18 liters of the 98 percent CaCO₃ slurry to a second 4- liter agitated (1250 φm), stainless steel, double jacketed reaction vessel, added 0.66 liters

of 3.8 percent by dry weight cellulosic fibers and diluted to 1.5 percent consistency. This mixture

of CaCO₃ slurry and fiber was reacted with 20 percent CO₂ in air (1.41 standard liter minute

CO₂/5.64 standard liter minute air) to produce a CaCO filler/fiber composite. The calcium

carbonate filler had a predominantly scalenohedral moφhology.

EXAMPLE 2

ARAGONITIC PCC

Reacted 10.5 liters of water with 2.1 kilograms CaO at 50 degrees Celsius producing a 15 percent by weight Ca(OH) slake. The Ca(OH)₂ slake was then screened at -325 mesh producing

a screened slake that was transferred to a 30-liter double jacketed stainless steel reaction vessel with

an agitation of 615φm. Added 0.1 percent by weight of a high surface area (HSSA) aragonitic seed

(surface area ~40 meters squared per gram, approximately 25 percent solids) to the 30-liter reaction

vessel and brought the temperature of the contents to 51 degrees Celsius. A "seed" is defined as a

fully converted aragonitic crystal that has been endpointed and milled to a high specific surface area (i.e. greater than 30 meters squared per gram and typically a particle size of 0.1 to 0.4 microns).

Began addition of 10 percent CO₂ gas in air (5.24 standard liter minute CO₂/47.12 standard liter

minute air) to the 30-liter stainless steel, double jacketed reaction vessel for a 15-minute period after

which the CO₂ concentration was increased to 20 percent in air (10.47 standard liter minute

CO₂/41.89 standard liter minute air) for an additional 15 minutes producing a 2.3:1 Ca (OH)₂/CaCO₃

slurry. At which time CO₂ gassing was stopped. The 2.3:1 Ca(OH)₂/CaCO slurry was transferred to an agitated 20-liter storage vessel. Transferred 2 liters of the 2.3:1 Ca(OH)₂/CaCO slurry to a first 4-liter agitated, double jacketed stainless steel reaction vessel with agitation set at 1250φm and

the temperature was brought to 52 degrees Celsius. Began addition of 20 percent CO₂ gas in air

(1.00 standard liter minute CO₂/3.99 standard liter minute air) to the first 4-liter reaction vessel and

the reaction was continued until a pH of 7.0 was achieved producing a 100 percent CaCO slurry.

The temperature of the 100 percent CaCO₃ slurry of the first 4-liter reaction vessel was brought to

63 degrees Celsius. Began addition of the 2.3:1 Ca(OH)₂/CaCO slurry of the 20-liter storage vessel

to the first 4- liter reaction vessel while continuing to add 20 percent CO₂ in air (1.00 standard liter minute CO₂/3.99 standard liter minute air) to the first 4-liter reaction vessel maintaining a

conductivity of approximately 90 percent ionic saturation. Continued the reaction for approximately

9 hours until the physical properties of the resultant product remained essentially unchanged,

producing a 98 percent by wt. CaCO₃ slurry.

Transferred 0.35 liters of the 98 percent CaCO₃ slurry to a second 4-liter agitated (1250 φm),

stainless steel, double jacketed reaction vessel, added 0.66 liters of 3.8 percent by wt. cellulosic fiber

and 1.0 liters water to the second 4-liter reactor producing a 1.5 percent by wt. CaCO₃/fiber mixture. Added an additional 20 percent CO₂ in air (1.00 standard liter minute CO₂/3.99 standard liter minute

air) to the second 4-liter reaction vessel until a pH of 7.0 was reached at which time the reaction was

completed producing a CaCO /fiber composite. The composite consisted of approximately 75

percent aragonitic PCC to fiber.

EXAMPLE 3

RHOMBOHEDRAL PCC

Reacted 15 liters of water with 3 kilograms CaO at 50 degrees Celsius producing a 20 percent by weight Ca(OH) slake. The Ca(OH)₂ slake was screened at -325 mesh producing a

screened slake that was transferred to an agitated 20-liter storage vessel. Transferred 2-liters of the

screened slake from the 20-liter storage vessel to a first 4-liter agitated, stainless steel, double

jacketed reaction vessel and began agitation at 1250φm. Added 0.03 percent citric acid by weight

of theoretical CaCO₃ to the first 4-liter reaction vessel and raised the temperature of the contents to

50 degrees Celsius. Added 20 percent CO₂ gas in air (1.44 standard liter minute CO₂/ 5.77 standard

liter minute air) to the first 4-liter reaction vessel until a pH of 7.0 was achieved producing alOO percent CaCO slurry. To the screened slake in the 20-liter storage vessel, added a solution of 1.3

percent by weight of Na₂CO , based on theoretical yield of CaCO₃, producing a Ca(OH)₂/ Na₂CO₃

slake. Increased the temperature of the contents of the first 4-liter reaction vessel to approximately

68 degrees Celsius and began addition of the Ca(OH)₂/ Na₂CO slake of the 20-liter storage vessel

to the first 4-liter reaction vessel while continuing to add 20 percent CO₂ in air (1.44 standard liter

minute CO / 5.77 standard liter minute air) to the first 4-liter reaction vessel maintaining a conductivity of approximately 50 percent ionic saturation. Addition of the Ca(OH)₂/ Na₂CO₃ slake and CO₂ was continued for approximately 12 hours until physical properties of the resultant product

remained essentially unchanged producing an approximate 98 percent by wt. CaCO slurry.

Transferred 0.22 liters of the 98 percent CaCO₃ slurry to a second 4-liter agitated (1250 φm)

dual jacketed, stainless steel reaction vessel and added 0.66 liters of 3.8 percent by weight cellulosic fiber and 1.0 liters water to the second 4-liter reactor producing a 1.5 percent by weight CaCO₃/fiber

mixture. Added an additional 20 percent CO₂ in air (1.44 standard liter minute CO₂/5.77 standard liter minute air) to the second 4-liter reaction vessel until a pH of 7.0 was reached at which time the

reaction was completed producing an approximate 3.4 percent by wt CaCO₃/fiber composite. The

calcium carbonate had a predominantly rhombohedral moφhology.

EXAMPLE 4

SCALENOHEDRAL - CFSTR

Reacted 15 liters of water with 3 kilograms CaO at 48 degrees Celsius to produce a Ca(OH)₂ slake, added an additional 6 liters of water producing a 20 percent by weight Ca(OH)₂ slake. The

20 percent Ca(OH)₂ slake was screened at -325 mesh and transferred to a 30-liter double jacketed,

stainless steel reaction vessel with an agitation of 615φm. Added 0.015 percent citric acid, by

weight of total theoretical CaCO to be produced, to the 30-liter reaction vessel and the temperature

of the contents brought to 36 degrees Celsius. Began addition of 20 percent CO₂ gas in air (13.72

standard liter minute CO₂ / 54.89 standard liter minute air) to the 30-liter reaction vessel to produce

a 5:1 Ca(OH)₂/CaCO₃ slurry. CO₂ gassing was stopped and the Ca(OH)₂/CaCO₃ slurry was transferred to an agitated 20-liter storage vessel. In a 4-liter agitated storage vessel, combined 0.25 liters of the Ca(OH)₂/CaCO₃ slurry with

0.66 liters of 3.8 percent by weight fibrils and with 1.09 liters of water making a Ca OH CaCO-s/fibril material. Transferred 2 liters of the Ca(OH)₂/CaCO₃/fibril material to a 4-liter

agitated (1250 revolutions per minute) reaction vessel and the temperature brought to 55 degrees

Celsius and carbonated with 20 percent CO₂ in air (1.30 standard liter minute CO₂ / 5.23 standard liter minute air) to a pH of 7.0 producing a CaCO₃/fibril composite. Prepared 16-liters of 1.5 percent by weight fibrils and a separate 10-liter vessel of water. To the 4-liter reaction vessel began addition

of the Ca(OH)₂/CaCO₃ slurry of the 20-liter agitated storage vessel, along with the 1.5 percent

consistency fibril mixture at 172.05 ml per minute, along with 31.21 ml per minute of additional

water while maintaining the flow of CO₂ gas (1.30 standard liter minute CO₂ / 5.23 standard liter

minute air) at a rate to maintain conductivity of approximately 90 percent ionic saturation, while

maintaining mass balance of approximately 4 percent to 5 percent total solids.

This reaction was continued until product physical properties remained essentially

unchanged. Addition of material from the storage vessel was stopped while CO₂ addition was

continued and the material in the 4-liter agitated reaction vessel was brought to a pH of 7.0 at which

time CO₂ addition was stopped producing a 2.2:1 CaCO₃/ fibril composite with the CaCO₃ having

a well defined scalenohedral moφhology. EXAMPLE 5

SCALENOHEDRAL CFSTR/RECYCLE/SURFACTANT

Reacted 15 liters of water with 3 kilograms CaO at 48 degrees Celsius to produce a Ca(OH)₂

slake, added an additional 6 liters of water producing a 20 percent by weight Ca(OH)₂ slake. The

20 percent Ca(OH)₂ slake was screened at -325 mesh and transferred to a 30-liter reaction vessel (615revolutions per minute). Added 0.015 percent citric acid, by weight of total theoretical CaCO3 to be produced, to the 30-liter reaction vessel and the temperature of the contents brought to 35

degrees Celsius. Began addition of 20 percent CO₂ gas in air (14.08 standard liter minute CO₂ / 56.30

standard liter minute air) to the 30-liter reaction vessel producing a 5:1 Ca(OH)₂/CaCO₃ slurry. At

this point, CO gassing was stopped and the Ca(OH)₂/CaCO₃ slurry was transferred to a 20-liter

agitated storage vessel.

In a 4-liter agitated storage vessel, combined 0.25 liters of the Ca(OH) /CaCO₃ slurry with

0.66 liters of 3.8 percent by weight fibrils and with 1.09 liters of water making 2 liters of

Ca(OH)₂/CaCO₃/fibril material.

Transferred 2 liters of the Ca(OH)₂/CaCO₃/fibril material to a 4-liter stainless steel, double

jacketed, agitated (1250 revolutions per minute) reaction vessel and the temperature was brought to

58 degrees Celsius. Reacted the Ca(OH)₂/CaCO₃/fibril material with 20 percent CO₂ in air (1.30 standard liter minute CO₂ / 5.23 standard liter minute air) to a pH of 7.0. At this point, prepared 16-liters of 1.5 percent by weight fibrils (6.32 liters of fibrils at 3.8

percent consistency and 9.68 liters of water) and a separate 10-liter vessel of water. Added 0.04

percent surfactant based on the volume of fibers at 1.5 percent consistency.

Once a pH of 7.0 was achieved in the 4-liter reaction vessel, began addition of the remaining

5:1 Ca(OH)₂/CaCO₃ slurry from the 20-liter agitated storage vessel, with a flow of the 1.5 percent fibril mixture at 176.48 ml per minute and with 32.00 ml per minute water from the 10-liter vessel

to the 4-liter reaction vessel while maintaining the flow of CO₂ gas (1.30 standard liter minute CO₂

/ 5.23 standard liter minute air) at a rate to maintain conductivity of approximately 90 percent ionic

saturation, while maintaining mass balance of approximately 4 percent to 5 percent total solids.

Continued addition of the material from the agitated storage vessel to the reaction vessel until

product physical properties remained essentially unchanged. At which point, addition of material

from the storage vessel was stopped while CO₂ addition was continued to a pH of 7.0 at which time CO₂ a ddition w as s topped. T his p roduced a 2.33:1 CaCO₃/fibril composite with the calcium

carbonate having a well defined scalenohedral moφhology.

EXAMPLE 6

SCALENOHEDRAL CFSTR/POLYACRYLAMIDE

Reacted 15 liters of water with 3 kilograms CaO at 48 degrees Celsius producing a Ca(OH)₂ slake, added an additional 6 liters of water producing a 20 percent by weight Ca(OH) slake. The

20 percent Ca(OH)₂ slake was then screened at -325 mesh producing a screened slake that was transferred to a 30-liter agitated (615φm) reaction vessel. Added 0.1 percent citric acid, by weight

of total theoretical CaCO₃ to be produced, to the 30-liter reaction vessel and the temperature of the

contents brought to 50 degrees Celsius. Began addition of 20 percent CO₂ gas in air (15.01 standard

liter minute CO₂ / 60.06 standard liter minute air) to the 30-liter reaction vessel producing a 5:1

Ca(OH)₂/CaCO slurry. CO₂ gassing was stopped and the slurry was transferred to a 20-liter agitated

storage vessel. To a 4-liter agitated vessel added 0.31 liters of the Ca(OH)₂/CaCO₃ slurry, 0.60 liters of fibrils at 3.8 percent consistency and 1.09 liters of water to produce a Ca(OH)₂/CaCO /fibril material. 2 liters of the Ca(OH)₂/CaCO₃/fibril material was transferred to a 4-liter agitated (1250

revolutions per minute) reaction vessel and the temperature was brought to 51 degrees Celsius. Began addition of 20 percent CO₂ in air (1.34 standard liter minute CO₂ / 5.34 standard liter minute

air) until a pH of 7.0 was reached producing a CaCO /fibril composite.

At this point, prepared 16-liters of 1.5 percent by weight fibrils (6.32 liters of fibrils at 3.8 percent consistency and 9.68 liters of water) and a separate 10-liter vessel of water. Added 0.05

percent cationic polyacrylamide (Percol 292) based on the volume of fibrils at 1.5 per cent

consistency.

5:1 Ca(OH) /CaCO₃ slurry from the 20-liter agitated storage vessel, with a flow of the 1.5 percent

fibril mixture at 90 ml per minute, along with 48.5 ml per minute of additional water to the 4-liter

agitated, double jacketed reaction vessel while maintaining the flow of CO₂ gas (1.30 standard liter minute CO₂ / 5.23 standard liter minute air) at a rate to maintain conductivity level of approximately 90 percent ionic saturation, and maintain mass balance of the reaction to maintain product

concentration at approximately 4 percent to 5 percent solids. Continued addition of the material

from the agitated storage vessel to the reaction vessel until product physical properties remained

essentially unchanged. Addition of material from the 20-liter storage vessel was stopped while CO₂

addition was continued until a pH of 7.0 was reached at which time CO₂ addition was stopped producing a 3.34:1 CaCO₃/fibril composite with the PCC having a well defined scalenohedral

moφhology.

DEFINITION OF FIBRIL A fibril is produced by refining (any pulp refiner known in the pulp processing industry)

cellulose and/or mechanical pulp fiber. The fibrils are typically 0.1 to 2 microns in thickness and

10 to 400 microns in length and are additionally prepared according to U.S. Pat. 6,251,222, which

is by this reference incoφorated herein.

The control fiber of the present invention was refined at the Empire State Paper Research

Institute (ESPRI) using an Escher-Wyss (conical) refiner to an 80° SR (freeness). Measured by a

fiber quality analyzer (using arithmatic means) the control fibril measured 200-400 microns

HOW CONTROL FILLER/FIBER WAS MADE Produce a 15% solids slake and mix with fibrils (~1.5% consistency) React in the presence

of CO2 to endpoint of pH of 7.0 producing a filler/fiber composite with a surface area of 6-11 m2/g

(-60 to 80% PCC but can have more or less in composite) TABLE 1

TABLE 2

TABLE 3

The moφhology controlled filler/fiber composite showed equivalent or greater physical

properties (i.e. tensil strength, breaking length, and internal bond strength) as compared with the control filler/fiber. TABLE 4

TABLE 5

The moφhology controlled filler/fiber composite showed equivalent optical properties

(i.e. ISO Opacity and Pigment Scatter) as compared with the control filler/fiber.

Claims

We claim:

1. A filler- fiber composite comprising:

(a) feeding slake containing citric acid to a first stage reactor

(b) reacting the slake containing citric acid in the first stage reactor in the presence of

carbon dioxide to produce a first partially converted calcium hydroxide calcium

carbonate slurry

(c) reacting the first partially converted calcium hydroxide calcium carbonate slurry

in a second stage reactor in the presence of carbon dioxide to produce a second partially converted calcium hydroxide calcium carbonate slurry and

(d) reacting the second partially converted calcium hydroxide calcium carbonate

slurry in a third stage reactor in the presence of carbon dioxide and fibrils to

produce a filler-fiber composite.

2. The filler- fiber composite of claim 1 wherein the fiber is from about 0.1 microns to

about 2 microns in thickness and from about 10 microns to about 400 microns in length.

3. The filler- fiber composite of claim 2 wherein the filler is scalenohedral having a

specific surface area of from about 5 meters squared per gram to about 11 meters

squared per gram.

4. The filler-fiber composite of claim 3 wherein the calcium hydroxide calcium carbonate

slurry is converted from about 20 percent to about 40 percent.

5. The filler-fiber composite of claim 4 wherein the first partially converted calcium

hydroxide calcium carbonate slurry is converted from about 41 percent to about 99

percent.

6. The filler-fiber composite of claim 5 wherein the second partially converted calcium

hydroxide calcium carbonate slurry is converted to a filler-fiber composite.

7. A method for producing a filler-fiber composite comprising:

(a) feeding slake containing citric acid to a first stage reactor

(b) reacting the slake containing citric acid in the first stage reactor in the presence of carbon dioxide to produce a first partially converted calcium hydroxide calcium

carbonate slurry

(c) reacting the first partially converted calcium hydroxide calcium carbonate slurry in a

second stage reactor in the presence of carbon dioxide to produce a second partially converted calcium hydroxide calcium carbonate slurry and

(d) reacting the second partially converted calcium hydroxide calcium carbonate slurry in

a third stage reactor in the presence of carbon dioxide and fibers to produce a filler-

fiber composite.

8. The method of producing the filler-fiber composite of claim 7 wherein the fiber is

from about 0.1 microns to about 2 microns in thickness and from about 10 microns

to about 400 microns in length.

9. The method of producing the filler-fiber composite of claim 8 wherein the filler is scalenohedral and has a specific surface area of from about 5 meters squared gram to about 11 meters squared per gram.

10. The method of producing the filler-fiber composite of claim 9 wherein the calcium

hydroxide calcium carbonate slurry is converted from about 20 percent to about 40

percent.

11. The method of producing the filler- fiber composite of claim 10 wherein the first partially converted calcium hydroxide calcium carbonate slurry is converted from

about 41 percent to about 99 percent.

12. The filler-fiber composite of claim 11 wherein the second partially converted calcium

hydroxide calcium carbonate slurry is converted to a filler-fiber composite.

13. The filler-fiber composite of claim 1 utilized in paper or paperboard

14. The filler-fiber composite of claim 7 utilized in paper or paperboard.

15. The paper produced utilizing the filler- fiber of claim 1.

16. The paper produced utilizing the filler-fiber of claim 7.

17. A filler- fiber composite comprising:

(a) feeding slake containing citric acid to a first stage reactor

carbon dioxide to produce a first partially converted calcium hydroxide calcium carbonate slurry

(c) taking a first portion of the partially converted calcium hydroxide calcium

carbonate slurry adding fibrils and reacting such in a second stage reactor in the presence of carbon dioxide to produce a calcium carbonate\fibril composite to serve

as a heel and

(d) taking a second portion of the partially converted calcium hydroxide calcium

carbonate slurry adding fibrils and surfactant and reacting in the presence of CO2 to

produce a second partially converted Ca(OH)2/CaCO3/fibril material and

(e) reacting the second partially converted Ca(OH)2/CaCO3/fibril material in the

presence of CO2 in a third stage reactor to produce a filler- fiber composite.

18. The filler-fiber composite of claim 17 wherein the fiber is from about 0.1 microns to

about 2 microns in thickness and from about 10 microns to about 400 microns in

length.

19. The filler- fiber composite of claim 18 wherein the filler is scalenohedral having a

squared per gram.

20. The filler-fiber composite of claim 19 wherein the calcium hydroxide calcium

carbonate slurry is converted from about 20 percent to about 40 percent.

21. The filler-fiber composite of claim 20 wherein the first partially converted calcium

percent.

22. The filler- fiber composite of claim 21 wherein the second partially converted calcium

hydroxide calcium carbonate slurry is converted to a filler-fiber composite.

23. A method for producing a filler-fiber composite comprising:

(a) feeding slake containing citric acid to a first stage reactor

carbonate slurry

(c) taking a first portion of the partially converted calcium hydroxide calcium

as a heel and

produce a second partially converted Ca(OH)2/CaCO3/fibril material and reacting the second partially converted Ca(OH)2/CaCO3/fibril material in the presence of CO2 in a third stage reactor to produce a filler-fiber composite.

24. The method for producing filler-fiber composite of claim 23 wherein the fiber is from

about 0.1 microns to about 2 microns in thickness and from about 10 microns to

about 400 microns in length.

25. The method for producing filler-fiber composite of claim 24 wherein the filler is

scalenohedral having a specific surface area of from about 5 meters squared per

gram to about 11 meters squared per gram.

26. The method for producing filler-fiber composite of claim 25 wherein the calcium

hydroxide calcium carbonate slurry is converted from about 20 percent to about 40 percent.

27. The method for producing filler-fiber composite of claim 26 wherein the first partially

converted calcium hydroxide calcium carbonate slurry is converted from about 41

percent to about 99 percent.

28. The method for producing filler-fiber composite of claim 27 wherein the second partially

converted c alcium h ydroxide calcium carbonate slurry is converted to a filler-fiber composite.

29. The filler-fiber composite of claim 17 utilized in paper or paperboard

30. The filler-fiber composite of claim 23 utilized in paper or paperboard.

31. The paper produced utilizing the filler-fiber of claim 17.

32. The paper produced utilizing the filler-fiber of claim 23.

33. A filler-fiber composite comprising:

(a) feeding slake containing citric acid to a first stage reactor

(c) taking a first portion of the partially converted calcium hydroxide calcium

carbonate slurry adding fibrils and reacting such in a second stage reactor in the

presence of carbon dioxide to produce a calcium carbonate/fibril composite to serve

as a heel and (d) taking a second portion of the partially converted calcium hydroxide calcium

carbonate slurry adding fibrils and polyacrylamide and reacting in the presence of

CO₂ to produce a second partially converted Ca(OH)₂/CaCO₃/fϊbril material and

(e) reacting the second partially converted Ca(OH)₂/CaCO₃/fibril material in the presence

of CO₂ in a third stage reactor to produce a filler/fiber composite.

34. The filler-fiber composite of claim 33 wherein the fiber is from about 0.1 microns to

35. The filler-fiber composite of claim 34 wherein the filler is scalenohedral having a

squared per gram.

36. The filler-fiber composite of claim 35 wherein the calcium hydroxide calcium

carbonate slurry is converted from about 20 percent to about 40 percent.

37. The filler-fiber composite of claim 36 wherein the first partially converted calcium

hydroxide calcium carbonate slurry is converted from about 41 percent to about 99 percent.

38. The filler-fiber composite of claim 37 wherein the second partially converted calcium

hydroxide calcium carbonate slurry is converted to a filler-fiber composite.

39. A method of producing a filler-fiber composite comprising:

(a) feeding slake containing citric acid to a first stage reactor

(b) reacting the slake containing citric acid in the first stage reactor in the presence of carbon dioxide to produce a first partially converted calcium hydroxide calcium carbonate slurry

(c) taking a first portion of the partially converted calcium hydroxide calcium

presence of carbon dioxide to produce a calcium carbonate/fibril composite to

serve as a heel and

(d) taking a second portion of the partially converted calcium

hydroxide calcium carbonate slurry adding fibrils and polyacrylamide and reacting in the presence of CO₂ to produce a second partially converted

Ca(OH)₂/CaCO₃/fibril material and

(e) reacting the second partially converted Ca(OH)₂/CaCO /fibril material in the

presence of CO₂ in a third stage reactor to produce a filler/fiber composite.

40. The method for producing filler-fiber composite of claim 39 wherein the fiber is from

about 0.1 microns to about 2 microns in thickness and from about 10 microns to

about 400 microns in length.

41. The method for producing filler- fiber composite of claim 40 wherein the filler is

scalenohedral having a specific surface area of from about 5 meters squared per gram to

about 11 meters squared per gram.

42. The method for producing filler- fiber composite o f claim 41 wherein the calcium

43. The method for producing filler-fiber composite of claim 42 wherein the first partially

converted calcium hydroxide calcium carbonate slurry is converted from about 41

percent to about 99 percent.

44. The method for producing filler-fiber composite of claim 43 wherein the second partially

converted calcium hydroxide calcium carbonate slurry is converted to a filler- fiber composite.

45. The filler-fiber composite of claim 33 utilized in paper or paperboard

46. The filler-fiber composite of claim 39 utilized in paper or paperboard.

47. The paper produced utilizing the filler-fiber of claim 33.

48. The paper produced utilizing the filler-fiber of claim 39.