CHANGES TO PCC STRUCTURE IN PAPERMAKING

Thad C. Maloney*, Jos Ataide, Juha Kekkonen, Henrik Fordsmand, Henrik Hoeg-Petersen
*JM Huber, Telakkatie 5A, 49460 Hamina, Finland; tmaloney@huber.com
Abstract
For precipitated calcium carbonate (PCC), it is well known that the degree of structuring has a strong
influence on the performance of the pigment as a paper filler. Structuring refers to the aggregation of
small primary particles into a larger secondary structure. A high degree of pigment structure results in
high bulk and good optical performance. A long-standing question of papermakers concerns the
possible break-down of PCC from an aggregated structure into primary particles. This could
conceivably arise either from high shear forces in the wet end or from high structural pressure during
web consolidation. This study attempts to determine if such a break-down occurs for S-PCC in fine
paper production and to find out the implications for paper quality.
In the study, we demonstrate with lab sheets that when PCC structure breaks down there is a high
negative impact on paper properties. For example, two-sidedness increases and bulk decreases. In order
to examine the PCC particle properties on a paper machine, a new analytical technique was developed.
The technique is based on the oxidation of chemical pulp fibers under controlled conditions and the
subsequent analysis of the ash residues with particle size techniques. Our studies indicate that this is an
acceptable method to characterize fillers in pulp suspensions and paper handsheets. We go on to study
the filler properties from the PCC plant, through the approach flow system, to the couch of a modern
fine paper machine. Our analysis indicates that the S-PCC studied here did not break down to a
significant extent on full scale paper machines, though we did find evidence of breakdown on a pilot
machine. It was also found that the new test can give an indication of the amount of PCC flocs formed
in the wet end and in web consolidation.

Introduction
For uncoated woodfree copy paper, bulk is one of the most important quality parameters. Generally
speaking, the optical properties that can be reached with todays pulp bleaching methods, optical
brighteners and fillers are adequate. Likewise, strength of fine paper is less of an issue than in the
1980s and 1990s. There are several reasons why bulk (at a specified smoothness) is so important to
fine paper manufacturers. One reason is related to the manufacturing economies because high bulk
allows one to decrease grammages or to increase filler contents while maintaining adequate stiffness.
Precipitated calcium carbonate (PCC) has emerged as the filler of choice for todays fine paper. This is
because PCC gives excellent optics and bulk compared to its leading competing filler, ground calcium
carbonate (GCC). Also, the on-site solution allows one to synthesize several different morphologies
with different characteristics that can be used to help optimize a mills grade mix. Two of the important
morphologies for uncoated copy paper are rhombohedral PCC (R-PCC) and scalenohedral PCC (SPCC). R-PCC is not highly aggregated and has a low surface area-to-particle size ratio and thus gives
excellent drainage and high paper machine speed. However, even more important in fine paper
manufacture is S-PCC which is useful for manufacturing paper with high bulk.
Paper bulk at a given smoothness depends on several factors including the paper machine design and
pulp quality variables. The filler type and amount also has an important role. A large particle size and
narrow particle size distribution (PSD) increases paper bulk by decreasing the particle packing. Today,
both these variables have been optimized with PCC and there is very little room left for further
improvement by either of these appraoches. Another important variable for bulk is the amount of
structure or aggregation. The success that S-PCC enjoys is largely due to its high amount of structure.
The structure of S-PCC is shown in Figure 1. It its a useful view to consider the arrangement of PCC
in paper in terms of structural hierarchy. The arrangement of the crystal lattice in the primary level of
structural hierarchy determines certain material properties such as index or refraction and melting
point. For PCC used in paper manufacture the important crystalline types are aragonite and calcite. S-

PCC is the latter. The shape and size of the individual crystals influences the specific surface area,
which has a direct consequence on the consumption of wet end additives in papermaking. However, it
is the higher levels of structural hierarchy which are most important for paper bulk.

1
Crystal Structure

2
Crystal Morphology

3
Primary aggregation

4
Secondary aggregation

Figure 1. The levels of structural hierarchy in S-PCC: 1) molecular organization, 2) crystal

morphology, 3) primary aggregation and 4) secondary aggregation (PCC flocs).

In the synthesis of S-PCC, the cigar shaped crystals grow out of a calcium hydroxide core during the
carbonization reaction. After carbonization is complete, the single crystals are arranged in a 3dimensional star-shaped pattern attached at the original core through ionic bonding forces. In some
places on the S-PCC aggregate secondary nucleation may lead to further growth of cigar shaped
crystals. This third level of structural hierarchy is what is normally associate with the PCC particle size.
The size and structure of this aggregate has an important consequence for paper bulk.
We can also consider a fourth level of structure. In the paper machine wet end, colloidal and
hydrodynamic forces may cause the PCC aggregates to flocculate together. Thus, in paper, there is a
certain distribution of filler in the x, y an z directions that may be more or less homogenous (Karrila,
S. et al. 2002). The bonding of these larger filler aggregates is much weaker than the primary
aggregates, consisting mostly of electrostatic forces. It has been established through filler flocculation
experiments (Holm M. and Manner, H. 2003) that this highest level of filler structure can influence
paper properties e.g. optics, strength and bulk.
From the point that it is manufactured in the on-site plant to the finished paper PCC experience some
rather severe forces (Pelton, R. H. 1984) that may break down the aggregates into individual crystals.
In the wet end, the high shear in the pumps, cleaning units and in the formation zone (the highest shear
is normal at the fan pump and headbox screen) may be adequate to break apart the primary aggregates.
In press dewatering, the paper is subjected to high pressure, in the range of 10 MPa for a roll press,
which could crush the aggregated PCC structure causing a loss of bulk. Severe pressures in the
calender stack could also break apart the PCC structure causing a loss of bulk.
The objective of this study was to determine how deaggregation of S-PCC affects paper properties and
to determine if, in fact, S-PCC breaks down during fine paper manufacture.

Materials and Methods

In the first part of this study, S-PCC with a deliberately broken down structure was compared to
conventional in-tact S-PCC. The S-PCC used in the study is FS-240 and also a similar grade FS-270.
These are commercial grades of S-PCC produced by JM Huber with an average particle size of 2.4 m
and 2.7 m, respectively, as measured with a Sedigraph. A 70/30 hardwood/softwood mixture of
industrially prepared refined kraft pulp was used in handsheet making. A sample of the FS-240 was
broken down by exposing a 20% slurry to 12 hours in an Ultra-Turrax T50 mixer exposed to a shear of
1.83x104 s-1. Our experiments showed that this was adequate conditions to detach a significant fraction
of primary crystals from the aggregates.

80 g/m2 handsheets were prepared at different filler content in the range of 22-28% filler content on a
Fibertech dynamic sheet former. A cationic polymer micro particle retention system was used: 200
g/ton Kemira Fennopol K3400 R + 2500 g/ton bentonite. The pH was not adjusted and no other
additives were used. Sheets were calendered in a Gradek calender with 2+2 nips at 11 kN/m pressure at
room temperature. Sheets were tested with standard ISO methods.
Two different methods for particle size analysis were used. A Sedigraph 5100 measures particle size
distributions by sedimentation rate. The particle size by this method is especially effected by the
particle specific volume. Some measurements were also performed with a Horiba LA-920. This method
is also adequate to quantify PCC particle size distributions. However, because it is based on laser
diffraction the resulting PSD does not necessarily equal that from Sedigraph. The PCC or the ash
residues was first treated in a sonic bath for 30 minutes, followed by addition of a cationic dispersant,
Fennofix 40, before particle size measurements. We have found that for a conventional PCC particle
size distribution these are adequate dispersion conditions to break up flocs, but not to break down the
primary aggregates to individual PCC crystals.
The PSD of the PCC in either the pulp furnish or paper was determined as follows: A sample of the
dried furnish or paper was treated in a Leco TGA-601 thermo gravimetric analyzer under conditions
sufficient to oxidize the cellulosic fibers. An 8 gram sample of the dried furnish or paper was heated
first to 300oC and then held constant for 2 hours. The oven gas was air. These are sufficient conditions
to oxidize most of the organic material but not to cause the pulp to burst into flames. The temperature
was then increased to 500oC and held for 1 hour to remove any remaining organic material. However,
this is well below 900oC, at which temperature calcite decomposes. The ash residue was dispersed and
measured with Sedigraph as described above.
Results and Discussion
Handsheet experiments
The effect of the high sheer treatment on the PSD is shown in Figure 2. The node centered around 5
m is associated with the PCC primary aggregates. The small node at around 0.5 m is cause by the
primary crystals. In the unsheared PCC there is a very small amount of the individual crystals
detectable. After exposure to shear the amount of individual crystals increases significantly changing
the distribution from nearly mono- to bimodal. Furthermore the average size of the agglomerates also
decreases.

Mass Frequency (%)

14

PCC aggregates

12

Individual
PCC crystals

10
8

FS-240
Sheared FS-240

6
4
2
0
0.1

10

100

Particle Diameter (m)

Figure 2. The effect of shear treatment on the particle size distribution of FS-240 as measured
in a Horiba LA-920.
The deaggregation of the PCC has a distinct effect on most paper properties. Figure 3 shows that when
the S-PCC structure breaks down the bulk substantially decreases. Loss in bulk can be caused by either
a decrease in particle size or an increase in the width of the PSD. In this case, the break down of the
PCC agglomerates, resulting in the decreases in average particle size, contributes to the lower bulk. It
also seems reasonable, that an increase in the fraction of single PCC crystals has resulted in a higher
degree of PCC packing. The deagglomeration of the PCC has a substantial negative effect on optical

performance, shown in Figure 4. This is rather interesting, as the average particle size of FS-240 is
somewhat above the maximum for optimum light scattering. If the size of the PCC would have been
reduced by synthesizing a smaller S-PCC aggregate, then the light scattering would be expected to
increase. However, the individual PCC crystals in the size range about 0.1 m wide x 0.5-1.0 m long
(by SEM) are below the optimum size for light scattering. Therefore, when the PCC is broken down by
shear into individual crystals the light scattering decreases. Figure 5 shows that when the structure of
the PCC breaks down the tensile strength decreases. This is because a higher number of particles per
unit mass of PCC allows higher fiber surface coverage resulting in higher disruption of fiber bonds at a
given filler content. Figure 6 shows that break down of the PCC has had a fairly small effect on the
smoothness. However, the change to a bimodal distribution has increased the smoothness twosidedness. This is because the separated PCC crystals are preferentially pulled through the sheet by
dewatering forces and enriched on the wire side, increasing the smoothness of this side. Even-sidedness
is clearly favored by a homogenous and narrow distribution of particles.

60

Bulk (cm3/g)

Untreated S-PCC
Sheared S-PCC
1.20

1.15

Tensile Index (Nm/g)

1.25

1.10

Untreated S-PCC
Sheared S-PCC
50

40

30
20

22

24

26

28

30

20

22

Filler Content (%)

shear on PCC

28

30

Figure 5. The effect of deagglomeration

on the machine direction tensile index of
handsheets.
4.0

80

Untreated S-PCC

PPS Smoothness (m)

Light Scattering Coefficient (m /kg)

Figure 3. The effect of

used in handsheets.

24
26
Filler content (%)

Sheared S-PCC

75
70
65
60
20

22

24

26

28

30

Filler Content (%)

Figure 4.
The effect of PCC
deagglomeration on sheet light scattering.

3.0
2.0

Untreated S-PCC, TS
Untreated S-PCC, WS

1.0

Sheared S-PCC, TS
Sheared S-PCC, WS

0.0
1.10

1.12

1.14

1.16

1.18

1.20

1.22

Bulk (cm3/g)

Figure 6. The top (TS) and bottom (WS)

side smoothness vs. bulk for handsheets
made
from
normal
S-PCC
and
deagglomerated S-PCC.

Breakdown of PCC on the paper machine.

From the above study, it is seen that the break down of S-PCCs structure causes a highly negative
effect on the paper properties. In that study, rather severe conditions were used to breakdown the PCC.
Shear rates on a paper machine may be even higher than used in our lab experiment (Pelton, R. H. 84),
though exposure times to high shear typically much lower. The chemical conditions on a paper
machine may be more contusive to PCC deagglomeration than in our lab experiment. Partial
dissolution of the PCC will weaken the aggregate so that it may break down at low shear levels. In fact,
in the lab we have used pH shocks in the range of 3-4 to completely deaggregated S-PCC even in the
absence of a shear field. On a fine paper machine, exposure of the PCC to areas of low concentration,
especially in the long circulation, and pH shocks from e.g. alum used in connection with AKD sizing,
could weaken the aggregates and facilitate break down.
To our knowledge, a good method does not exist for the measurement of filler PSD after the
filler has been mixed with pulp or formed into a sheet. We attempted, in the first place, to

solve this problem by dissolving the pulp fibers with a cellulase enzyme. However, we were
not able to find an enzyme that could completely dissolve the fibers at a suitably high pH
within a reasonable time frame. Therefore, we developed the burning test described in the
experimental section. The validation of the test is shown in
Figure 7. In this experiment, the PSD of FS-270 measured with the Sedigraph was compared
to FS-270 that was heated under the conditions described in the experimental section. The
FS-270 was also mixed with pulp in the ratio 3:1 pulp:PCC, dewatered, , dried and then
heated under the above-mentioned conditions to completely oxidize the pulp fibers. The
results show that the heating of the PCC, or heating in the presence of pulp fib does not
significantly affect the PSD. SEM images of the ash residue shown PCC crystals that are
similar to unburned PCC, indicating that these have not physically changed during heating.
Also, the pH of the ash residue was 9.5 indicating that only a very small amount of CaCO3
had decomposed and formed CaO in the oxidation stage. The small amount of non-PCC
inorganic material in the pulp was assumed to have negligible influence on the PSD.

MassFrequency (%)

50

FS-270; Unburned
FS-270, Burned

40

FS-270 Mixed with pulp,

burned

30
20
10
0
0.1

1.0

10.0

Particle Diameter (m)

Figure 7. PSD of S-PCC, S-PCC heated under conditions of the oxidation test, and S-PCC
mixed with pulp then heated under the same conditions to oxidize and remove pulp. The
oxidation has no effect on the PSD.
The new PSD test was used to evaluate the possible breakdown of FS-270 in a pilot paper machine
trial. The pilot machine was running at 1600 m/min under typical European fine paper conditions; 80
g/m2 grammage, 20-22% filler content and no other fillers present than FS-270. The results in Figure 8
compare the PSD of the virgin filler (dosing tank sample) to the PSD of the PCC in the headbox. The
same analysis procedure was used for both samples. In Figure 8, a broadening of the distribution in
both directions is observed. There is a small increase in the amount of particle below 1 m, which is
associated with the existence of individual PCC crystals. This shows that under the conditions of the
pilot machine the FS-270 has begun to break down. Surprisingly, we also see the formation of a new
node at about 7 m. This indicates that some PCC flocs have formed that are roughly about the size of
2 primary PCC agglomerates.
Since the implementation of the fiber oxidation PSD test we have observed on many occasions the
existence of large PCC flocs. We believe that these are flocs that are present in the original sample, but
that the strength of the flocs is increased in the oxidation through a sintering-like process. Sintering
occurs when the temperature of packed particles is raised to a point near, but below, the bulk melting
temperature. The very high radius of curvature around sharp edges cause melting and welding at crystal
contact points. The melting point of calcite is 1339oC, which is well above the decarbonization point
around 900oC, which is also well above the test temperature of 500oC. Therefore, for this material and
under these conditions, we do not expect the same type of sintering that takes place in e.g. metal
powders. However, some sort of welding of the PCC particles takes place. This may be exacerbated by
the presence of organic and inorganic impurities in the sample. In any case, it is clear that in order for
the flocs to be bonded together the primary aggregates must be in intimate contact. Therefore the
amount of large particles 7 m and above- which is measured in the oxidation test gives information
of the state of PCC flocculation the original stock or paper sample.

Primary Aggregates

60

Mass Frequency (%)

50

Virgin SPCC
SPCC in Headbox

40
Primary
Crystals

30

PCC
Flocs

20
10
0
0.1

1.0

10.0

100.0

Partical Diameter (m)

Figure 8. The PSD for PCC leaving the PCC plant and in the headbox of a fine paper
machine. A broadening of the PSD is seen.
One of the topics we were interested in this study was the possible breakdown of PCC in calendering. It
seems possible that a high calendering load could cause the PCC structure to collapse causing a loss of
bulk. If this were an important mechanism in the sheet consolidation process, then we would expect the
amount of primary PCC crystals to increase with calendering pressure. In Figure 9, the PSD for PCC in
paper calendered in a single soft calender at 80 kN/m is compared to the PSD from paper calendered at
200 kN/m. The samples for this study were taken from the same pilot machine study mentioned above.
Figure 9 shows that the calendering has no effect on the amount of primary PCC crystals which are
present. The primary PCC crystals in the samples has already formed in the wet end. The high
calendering pressure has resulted in the formation of a small peak or large particles centered around 50
m. This may be due to tighter consolidation of filler flocs which are then sintered together in the
fiber oxidation step.
Primary
Aggregates

22
20
Mass Frequency (%)

18

Primary
Crystals

16

Heavy line
pressure

PCC
Flocs

14
12

Light line
pressure

10
8
6
4
2
0
0.1

1.0

10.0

100.0

Particle Diameter (m)

Figure 9. The PSD of FS-270 in a pilot machine soft nip calendar at low and high calendaring
pressures.
It seemed from the pilot study that some PCC deagglomeration and flocculation processes may take
place in fine paper manufacture. It was decided to investigate this phenomenon further on industrial
scale paper machines. We studied three different high speed modern fine paper machines by taking a
number of samples for the PCC plant through the approach flow all the way to the finished paper. The
results from all these surveys were consistent there is no evidence of significant PCC breakdown in
the approach flow or on the paper machine. This is illustrated in Figure 10 which shows results from

one of the machines. The slight increase in fine particles in the machine chest may be considered
negligible, especially since the primary particles are no longer visible in the headbox or on the paper
machine.
More detailed studies of the pumps and machinery in two PCC plants were also made and these
showed no evidence of significant PCC breakdown in either plant. We believe that the initial evidence
of PCC breakdown we found at the pilot machine headbox was due to the rather aggressive conditions
on this machine. On this machine, operating speeds thus sheer- were high and there is a significant
recirculation of broke. Thus the PCC is exposed to longer periods of high sheer than is normally seen
on an industrial fine paper machine. In Figure 10, it is seen that the amount of PCC agglomerates
increases from PCC plant, to wet end, to the pope. This is consistent with observations from other
paper machines. We believe that the formation of secondary PCC aggregates is caused primarily in the
wet end by homoflocculation of the PCC and is further enhanced in the consolidation process as the
PCC particles are brought into closer proximity.
40

Mass Frequency (%)

PCC storage tank

Machine chest

30

Headbox
Before calender
20

After calender

10

0
0.1

1.0

10.0

100.0

Particle Diameter (m)

Figure 10. The PSD from a full scale fine paper machine using PCC. Samples are taken
along the process from the PCC plant to the finished paper at the pope reel.
The test which was used in this study clearly gives useful information on the state of agglomeration of
PCC in stock suspensions and in paper. However, it is also apparent that there is some work remaining
to be done on the test development, especially in understanding the conditions that lead to the
formation of flocs or aggregates. Also, one should exercise caution in generalizing the results of the
study to other paper machines and grades of PCC. In fact, it if the authors experience that different
grades of PCC are aggregated with different bonding strengths, and it is clear that different paper
machines have widely different chemistries and shear profiles.
Conclussions
It was found that the breakdown of scalenohedral PCC to primary crystals causes a degradation in
handsheet properties including lower bulk, worse optics and more two-sidedness. A fiber oxidation test
was developed which seems to give a good indication of the state of agglomeration of PCC in pulp
suspensions or in finished paper. Under rather extreme conditions in a pilot paper machine, it was
found that the S-PCC begins to break down into primary crystals. However, in three industrial paper
machines was found that the PCC did not break down in the wet end or in consolidation. In both pilot
and full scale experiments it was found that flocs or secondary aggregates of PCC are formed. It is
believed that these are formed in the wet end by homoflocculation and in web consolidation.
References
Holm M. and Manner, H. (2003). APPITA anual conference: 337-342
Karrila, S., Susilo, A. and Champine, J. (2002). 2002 Progress in paper physics seminar: 114-117
Pelton, R. H. (84). TAPPI 1984 Papermakers Conference: 1-6