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Amazon Papyrus Chemicals (Thailand) Co.

Ltd
12th Floor, Boonmitrr Building
138 Silom Road, Thailand
Tel: (66 02) 634 3495-8
Fax: (66 02) 634 3499

Activated Filler - Increasing Filler Levels


Presented at Asian Paper 2012, Bangkok
Peter de Clerck
Business Development Manager, Amazon-Papyrus Chemicals

Abstract:
The communications paper sector is under increasing price pressure, white paper producers are looking to
cheaper furnishes and higher filler contents. Increased filler addition leads to reduced retention and weaker paper.
The Activated Filler concept reduces these negative effects by directly treating the filler to
a) reduce interference with fibre-to-fibre bonding
b) make micro-agglomerated filler itself a bonding centre
As a result the filler retention is improved and white water becomes cleaner.
The principles behind these improvements and the effects on strength and optical properties are presented and
explained. The differing roles of GCC and PCC in such systems are examined.

Introduction
Mineral pigments are used to improve functional paper properties such as appearance, sheet formation,
smoothness, dimensional stability, brightness, opacity and printability. Pigments are also added as fillers or
adulterants to reduce the furnish costs by replacing more expensive fibre components.
Increasing filler content affects several areas of paper production, including runability, energy demand, retention,
formation, sheet strength, caliper, porosity, optical properties and so forth. Papermakers seeks to obtain the
benefits of increased filler content while minimising any negative impact.

AREA OF CONCERN
Wet end
Retention
Drainage
Formation
Chemical demand
Clothing
Dry end surface strength
PAPER PROPERTIES
Strength
Bulk
Stiffness
Two sidedness

EFFECT OF INCREASING FILLER CONTENT


Wet web strength reduced
FPR reduced
Increased drainage rate
Can be beneficial or detrimental
May increase due to larger surface area
Dramatically increased wire abrasion, felt filling.
Increased dusting and fluffing due to the
reduction in surface pick strength
Tensile and burst reduced
Decreased
Decreased
Increased difference

Table 1 Some problems associated with increased filler contents.


It is necessary to understand why increasing the filler loading affects these parameters.

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Effects of Filler
Increased Surface Area
Filler has a much higher specific surface area than fibre, so adding filler increases the specific surface area of the
furnish. This increased surface area reduces the efficiency of adsorbed wet end chemicals e.g. sizing chemicals
and strength agents. The greater the surface area increase, the greater the impact. This may be seen for example
in sizing demand.

Fig. 1 The effect of increased surface area on size efficiency (1)

Bonding Disruption
The most obvious effect of adding filler is the reduction in sheet strength.
Effect of Filler on Burst Strength
100%

Dispersed Clay
90%
80%

% of Original Burst

70%
60%
50%
40%
30%
20%
10%
0%
0%

5%

10%

15%

20%

25%

30%

35%

Clay loading

Fig. 2 The effect of increased filler loading on burst strength (2)

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The strength loss is particularly notable as there is both a decrease in the number of fibres in the sheet and a
reduction of fibre-fibre contact area.
Beazley, Dennison and Taylor (1979)(3) demonstrated a linear inverse relationship between tensile strength and
filler specific surface area.
Papermakers have long added starch and gums to increase paper strength, notably to compensate for the loss of
bonding when adding filler. An early Chinese formula for paper requires three materials fibre, kaolin and starch.
Strength agents were normally added to the thick stock and there adsorbed to the surfaces of the furnish
components. Selective treatment of furnish components has been proposed e.g. US patent 2,140,394 was issued
to Ruff in 1938 for cooking starch together with filler to improve paper strength(4).

Starch-Filler Composites
Starch was found to be highly effective in filler modification. It can be anchored on the filler surfaces or used to
encapsulate the filler particles to enhance fibre-filler bonding. Some patents call for filler to be mixed with starch
before cooking, the starch then being partially cooked. This procedure produces a sticky starch-pigment aggregate
and will generate fish-eyes if not well dispersed. Other patents call for the partially cooked starch-pigment gel to
be dried and then ground before being re-introduced to the furnish. Yet other patents call for the insolubilisation of
the starch in situ by adding cross-linking agents or stearates. (5 - 9).

Fig. 3 Coatd filler (10)


Optical properties such as opacity and brightness decrease when large amounts of starch are incorporated into
the sheet.
Filler modification using the starch-gel coating method can improve fibre-filler bonding but does not produce robust
filler flocs. When cationic starch is used in this process the generated composites will be of similar cationic charge
and so repel each other. Retention to the anionic fibre surfaces is favoured. When non-ionic starch is used to treat
fillers, retention is dominated by filtration mechanisms only.

Paper Strength
Paper strength is largely determined by the number, strength and distribution of bonds between the sheet
components. The most important of these is the contribution from inter-fibre bonding and the bonding distribution
network (i.e. formation).
Hydrogen bonds predominate in paper, forming and strengthening during sheet consolidation, dewatering and
drying. Fibre surfaces must come into close proximity for hydrogen bonds to form, filler particles may easily disrupt
fibre-fibre bond formation. Interference may come from both fibre separation (large particles may increase fibre
separation distances) and surface coverage (coverage of fibre surfaces occludes bonding sites).

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How the filler is located within the paper is important. Eklund at al. (1991)(11) stated that fillers can be incorporated
in a fibre structure in three different ways, each having a different impact on the paper properties.

Fig. 4 Fillers Incorporated in a Fibre Structure


1. Expansion: Filler expands the fibre network and thus lowers its density.
The expansion of the fibre network improves the light scattering properties of the paper. The filler particles
interfere with the fibre-fibre interactions and mechanical properties are lowered as a consequence.
2. Void Filling: Filler locates in the voids between the fibres
It does not interfere with fibre-fibre interactions. Mechanical properties are unaffected but the light
scattering will increase. There is no volume expansion of the fibre network and the density of the paper is
increased.
3. Insertion: Filler inserts between the fibres but does not result in full fibre separation
The insertion of filler does not affect the overall light scattering if there are no additional voids formed.
Fibre-fibre contact area is reduced, lowering the mechanical properties.
Hence the pore volume relative to unfilled papers may be higher (expansion), lower (void filling) or similar
(insertion).

Particle Size
Particle size has a significant effect. For pigment particles greater than 5m the impact is dominated by particle
shape and number as large particles disrupt points of interfibre bonding (expansion). For particles less than 2m
the surface coverage effects becomes more important as fibrils and fibres become coated, preventing fibril
collapse and consolidation on drying (insertion).
Papermakers are now using GCC having 60-70% particles less than 2 micron (70%<2 m) in pursuit of enhanced
optical properties of paper. Previously GCC of around 20%<2 m was normal. Furnish specific surface areas are
increased accordingly.
The selection of filler type is also important. PCC and calcined clay are aggregated fillers that have large internal
void volumes. By contrast, clay and GCC are dense fillers with a high packing density, resulting in decreased bulk.

Filler Incorporation:
Great ingenuity has been applied to increasing filler levels in paper. Various methods of incorporating filler in the
sheet have been explored, including lumen loading(12,13), cell wall loading(14,15), fines-filler composites(16), filler
modification(17,18), and fiber engineering (19,20) . The reader is referred to the literature for further details on these.

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Pre-flocculation Concept
One approach to reduce the negative effects of increased filler content is to preflocculate the filler prior to addition
to the paper stock(21-25). The interference with fibre-to-fibre bonding is reduced, the filler aggregates are more
easily retained in the web, drainage may be enhanced and less retention chemicals are needed.

Fig. 5 Reduced interference from pre-flocculated fillers


Mabee(26) reported that filler preflocculation could provide an approximate 26% increase in first pass ash retention
and 13% increase in the tensile strength when using the same amount of filler.
The reduced surface area of the furnish and improved filler retention result in lower chemical additive requirements.

Fig. 6 The effect of pre-flocculate filler loading on burst strength (2)

Optical Properties
Light scattering is due to the reflection and refraction of light at air/cellulose, air/filler and cellulose/filler interfaces.
With less coverage of the fibre surface and less air-filler interfaces, preflocculation will reduce the scattering
efficiency of the pigment.

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The opacifying effects of fillers such as PCC, calcined clay and TiO2 are greatly reduced by preflocculation.

Fig. 7 The effect of pigment on opacity (27)

As may be seen, both bonding and opacity are dependent on fibre-fibre bonding. There is an inverse relationship
between tensile strength and opacity.

Fig. 8 relationship between tensile and opacity

The strength/opacity relationship is maintained for both un-flocculated and pre-flocculated filler, confirming that the
prime effect of filler preflocculation is in maintaining fibre-fibre bonding.
Hence with pre-flocculated filler we may attain similar tensile strength and light scattering at higher filler levels.

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Preflocculating Filler:
The flocculation treatment and shear forces encountered determine the size distribution and stability of the flocs.
Generating filler flocs of a stable size under paper machine conditions is a significant challenge. A combination of
high shear stability and narrow floc size distribution is required for the success of filler preflocculation technology.
The size of the filler flocs have been shown to be very important for the tensile strength of the paper. Larger flocs
promote a higher tensile strength (z-direction strength has been shown to be much less affected).
A porous floc structure will enhance optical and printing properties.

Flocculation Mechanisms:
The correct type of flocculation is important. There are four recognised types of polymer-induced flocculation;
macromolecule bridging, charge neutralization, patch flocculation and network flocculation.
Coagulation
Coagulation or charge neutralization occurs when the repulsive forces separating particles are overcome by polyelectrolyte addition, allowing particles to come together under the influence of the weak van der Walls forces.
Bridging flocculation
The polymer has to reach across the electrical double layer of two similarly-charged particles. A polymer with high
molecular weight and low charge density is preferred.
Patch flocculation
Patches of the charged particle surfaces are covered by material with an opposite charge. These patches may
attract oppositely charged surfaces on other similarly partially-covered particles. Generally a compound with
moderate charge density and relatively low molecular weight is used.
Network flocculation
Network flocculation can be induced by electrostatic interaction or by hydrogen bonding between two interacting
components.
In filler pre-flocculation systems the flocculation mechanism will be either coagulation or patching. These flocs may
be disrupted by shear and subsequently reform when the shear is reduced.

Single-Polymer Flocculation(28)
Patching and charge neutralisation are the dominant floc types produced by low molecular weight polymers. Such
flocs tend to have a relatively small particle size and break down under the high shear forces of a modern paper
machine.
Bridging predominates in flocs formed by a high molecular weight flocculent. The flocs tend to have a broad floc
size distribution that is difficult to control due to poor mixing of viscous flocculent with the pigment slurry becoming worse at higher filler solids levels. High shear rates are needed to generate a regular floc-size
distribution.
When adding a single ionic agent the charge balance of the treated system is determined by the added charge.
Overall charge balance will limit the optimum treatment. This is a major concern in single-polymer systems.

Cationic Starch

(24,37)

Mention should be made of cationic starch treatment. Starch may be fully or partially dispersed (depending on the
starch type and cooking process) and so produces both bridging and charge neutralisation. Sheared flocs readily
reform and are more stable than those formed with C-PAM.

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Dual Polymer Flocculation(29-35)


Dual polymer systems comprises the addition of a flocculating agent to a filler dispersion, shearing of the
dispersion, addition of a second flocculating agent and then further shearing of the resultant flocs to the desired
particle size. Many sources propose a weak initial flocculation followed by a robust second flocculation, the
resulting slurry then being sheared to produce the desired floc size.
Dual polymer systems produce flocs with better shear stability and a narrower particle size distribution than flocs
from single polymer systems.

MicroPolymers(36)
Microparticles and micropolymers may also be used alone or with other polymers to produce flocculated pigment
slurries. Flocs formed by micro-particle bridging may have the same large, open structure as those formed by
bridging polymers but with the added advantage of floc reformation after shearing.

Reported Benefits of Preflocculation:


A series of benefits are reported for preflocculated filler, including
o
o
o
o
o
o
o

internal bonding is maintained / enhanced


equivalent strength and opacity achieved at higher filler contents
filler retention, formation and drainage are improved
energy savings in refining due to higher strength / less fibre
better press dewatering
energy savings in drying
improved wet web strength

Encapsulated Filler
Paper Strength
In papermaking practice, dry strength aids have long been used to compensate for the loss of paper strength due
to filler loading. Preflocculated filler alone allows for just a few percentage points increase in filler loading.
Filled paper is a composite material. Bonds between all furnish components play a contribution. Thus far we have
focused on fibre-fibre bonds. Fibre-filler bonds and filler-filler bonds also contribute to paper strength. Of these
bonds, filler-filler bonds will be the weakest.

fibre-filler
bonding

fibre-fibre
bonding

filler-filler
bonding

Fig. 9 Bonding Issues

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In a highly oriented paper the mode of failure in MD tensile is mainly the shearing of inter-fibre bonds. As bonding
increases fibre failure will eventually predominate. For Z-direction tensile the mode of failure is adhesive failure
(between two elements) or cohesive failure (within an element, layer or film). CD tensile is a combination of these
two failure modes.
Fibre-fibre bonds may be increased in a number of ways and are not reviewed here. Fibre-filler bonds may be
improved by starch and other dry strength additives previously adsorbed on the filler or fibre surface.
Filler-filler bonding is an obvious area of weakness. Improvement here is a more difficult task. Polymers used to
preflocculate fillers are often present in too low a concentration to generate significant inter-particle bonding.

Activated Filler
Activated Filler takes the prefloc process to the next level. AmiForm is a branched, amphoteric micropolymer.
Reaction with filler is by patching and particle bridging. When mixed with filler it partakes in particulate bridging,
generating robust, open flocs that will reform after shearing. The micro-polymer also acts as a binder in the dried
mineral floc. Being amphoteric there is no net contribution to the wet end charge balance and so addition rates
may be adjusted over a significant range. The amphoteric charge gives little interference with optical brighteners
added to the stock.

Untreated

2 kg/t AmiForm

3 kg/t AmiForm

5 kg/t AmiForm

Fig. 10 Activated Filler. Addition rates are per tonne of filler.


The pre-flocculated filler results in easier wire and press section dewatering, together with improved wet web
strength. The optimum average particle size appears to be about 40 to 75 m.

Conclusions:

Filler pre-treatment is receiving much renewed interest


Encapsulation and pre-flocculation are receiving most attention
Floc size and floc tenacity are important for pre-flocculated fillers
Poor filler-to-filler bonding is a potential weak point with pre-flocculated fillers
AmiForm Activated Filler addresses the issues of floc size, floc tenacity and filler-filler bonding

Further Developments:
Encapsulated Prefloc
but that is a topic for a future presentation.

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Case Study #1
Description
Asia, 900 t/d.
Gapformer
Plain Paper Copier, 80 gsm
Results
-

Reduced white water turbidity


Sheet ash rises from 22.7% to 23.8%
Filler addition reduced by 2%
Steady improvement in formation index
F ormation

WhitewaterTurbidity
68

2700

67

2600

66

F ormation Index

Turbidity (NTU)

2800

2500
2400
2300

65

64

2200

63

2100

62

2000
8:00 10:00 12:00 14:00 16:00 18:00 20:00 22:00 0:00

2:00

4:00

6:00

8:00 10:00 12:00

Time

61
06:00

12:00

18:00

00:00

06:00

12:00

18:00

T ime

Case Study #2
Description
Asia, 900 t/d.
Gapformer
Plain Paper Copier, 70 gsm
Results
-

Reduced white water turbidity


FPR increased 2%
Filler addition reduced by 4%
Filler content increased
Drainage improved
White Water Turbidity

4500
4300
4100

Turbidity (NTU)

3900
3700
3500
3300
3100
2900

AmiForm Trial
2700
2500
2:00

4:00

6:00

8:00

10:00

12:00

14:00

16:00

18:00

20:00

22:00

Remark

Before Trial

During Trial

Time
Dosage AmiForm 528 (kg/t CaCO3)
Particle Size (m)
W/W Turbidity (NTU)
Machine Speed (m/min)
Drainage Time (sec/500 ml)
FPR (%)
FPAR (%)
Filler Addition (l/min)
Filler Content (%)

06:00 - 09.00
0
2.54
4190
1281
31
74
44
75
21.8

09:00 - 12.00
5
4.17
3750
1270
29
76
47
72
22.4

0:00

Time

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References:
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
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23
24
25
26
27
28

Applications of Wet-End Paper Chemistry


Au and Thorn (Eds.). Blackie Academic, Glasgow, 1995
The Hylode System For Fibre Replacement
R.D. Mather PIRA Papermakers Conference, 1982
Influence of Mineral Fillers on Paper Strength: Its Mechanism and Practical Means of Modification
Beazley, K.M., Dennison, S. R., and Talyor, J. H 11th ESPRA European Meeting, 1979
Method of Preparing a Starch Enveloped Material
H.T. Ruff US Patent 2,140,394 Dec 13, 1938
Agglomerated Fillers Used in Paper
R.R. Davidson US Patent 4,115,187 Sep 19, 1978
Preflocculated Filler Compositions for Use in the Manufacture of Paper
L.E. Shiel US Patent 4,174,998 Nov 20, 1979
Compositions for Use With Papermaking Fillers
Brooks et al. US Patent 4,272,297 Jun 9, 1981
Paper Making Process Utilizing Fillers with Hardened Envelopes of Cationic Starch
Suden et al. US Patent 4,710,270 Dec 1, 1987
Improvement of paper properties using starch-modified precipitated calcium carbonate filler
Yulin Zhao, ZeShan Hu, Art Ragauskas & Yulin Deng February 2005 Vol 4, No 2, Tappi Journal
The effect of pre-flocculation of fillers on paper strength
Marcus Petersson Dissertation, Chalmers University of Technology Goteborg, Sweden 2011
Paper Chemistry - An Introduction
Eklund et al DT Paper Science Publications, 1991
Lumen-loaded paper pulp
Green, H. V., Fox, T. J., and Scallan, A. M. Pulp & Paper-Canada 83(7), 39-43, 1982
Filler loading in the lumen or/and cell wall of fibers - A literature review
Kumar, P., Negi, Y. S., and Singh, S. P. BioResources 6(3), 3526-3546, 2011
In-Situ Cellulose Fibres Loading With Calcium Carbonate Precipitated By Different Methods
Ciobanu et al Cellulose Chem. Technol., 44 (9), 379-387, 2010
The microporosity of pulp - The precipitation of inorganic fillers within the micropores of the cell-wall.
Allan et al Tappi Journal 75(1), 175-178, 1992
Improving the combinations of critical properties and process parameters of printing and writing
papers and paperboards by new paper-filling methods
Silenius, P. Dissertation/Thesis, Helsinki University of Technology, Helsinki, Finland, 2002
Clay-starch composites and their application in papermaking
Yoon, S. Y., and Deng, Y. L. J. Appl. Polym. Sci. 100(2), 1032-1038, 2006
The microporosity of pulp - The properties of paper made from pulp fibers internally filled with
calcium-carbonate. Allan, G. G., Negri, A. R., and Ritzenthaler, P. Tappi Journal 75(3), 239-244,
1992
Graft polymerization of vinyl acetate onto silica
Nguyen, V., Yoshida, W., and Cohen, Y. J. Appl. Polym. Sci. 87(2), 300-310, 2003
Preparation and application of cationic cellulose fibers modified by in-situ grafting of cationic PVA.
Sang, Y., and Xiao, H. Colloids and Surfaces - Aphysicochemical and Engineering Aspects 335(1-3),
121-127, 2009
Producing Dispersions of Preflocculated Fillers for Use in Papermaking
D.E. Smith US Patent 4,295,933 Oct 20, 1981
Preparation of Filler Compositions for Paper
Harvey, R.D. and Klem, R.E. US Patent 4,799,964 Jan 24, 1989
Method for Manufacturing Filler-containing Paper
G. Gavelin US Patent 4,889,594 Dec 26, 1989
Modification of Fillers to Allow Higher Retained Ash Contents
M.G. Riddell Paper, Jan 5, 1976
40% filler loaded paper dream or reality?
Mrs A.J. Hayes Paper Technology & Industry, Apr/May 1985
Controlled Filler Preflocculation: Improved Formation, Strength and Machine Performance
Mabee, S.W. TAPPI Papermakers Conference (2001)
Optimization of Pigment Performance in Paper
B.Alince Fundamentals of Papermaking, Trans. 9th Fund. Res. Symp., Cambridge, 1989
Cationic Polymer-modified Filler Material

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29

R.A. Gill US Patent 5,147,507 Sep 15, 1992


Pre-flocculation of GCC with cationic PAM and cationic Starch and the Influence of their dosage and
shear rate on prefloc size. Kyong Ho Lee and Hak Lae Lee Korea TAPPI Vol.38.No.4, 2006

30

Papermaking Using Cationic Starch and Carboxymethyl Cellulose or Its Additionally Substituted
Derivatives. Taggart et al. US Patent 5,061,346 Oct 29, 1991

31

Controllable Filler Preflocculation Using Dual a Polymer System


Cheng, W. and Gray, R.T. US Patent 8,088,213 B2 Jan 3, 2012
Pre-flocculation of fillers - Evaluation of different flocculation conditions
Sara Wiik, Thesis, Lulea University of Technology
Increasing Filler Content in Paper
Anuchate Saenkhot Paperex 2011
New Technology for Increased Filler Use and Fiber Savings in Graphics Grades
Cheng et al. TAPPI PaperCon 2011
Increasing ash without compromise - A comprehensive approach
Menard et al TAPPI PaperCon 2011
Paper Products Comprising Filler Materials Preflocculated Using Starch Granules and/or
Polymerized Mineral Networks. Palmer et al. US Patent 6,494,991 B1 Dec 17, 2002

32
33
34
35
36
37

Pre-flocculation of precipitated calcium carbonate filler by cationic starch for highly filled mechanical
grade paper. Yizhou Sang, Michael McQuaid and Peter Englezos BioResources 7(1), 354-373, 2012

The readers attention is also drawn to the following two additional works.
1

Bonding Material Coated Clay for Improving Paper Properties


Se-Young Yoon Dissertation, Georgia Institute of Technology May 2007

On the nature of joint strength in paper - a review of dry and wet strength resins used in paper manufacturing
Tom Lindstrom, Lars Wagberg and Tomas Larsson 13th Fundamental Research Symposium, Cambridge, Sept
2005

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