Penkin A., Vetokhin S., Dubodelova E., Solovyova T.

Modified GCC Fillers in Printing Paper Production

MODIFIED GCC FILLERS IN PRINTING PAPER PRODUCTION

Penkin A., Vetokhin S., Dubodelova E., Solovyova T.

Belarusian State Technological University, Minsk, Belarus

Email: [email protected]

ABSTRACT

Ground calcium carbonates (GCC) are most effective natural fillers for papermaking
by the cost/performance ratio. They improve the optical and printing properties of paper as
well as reduce its cost. But they like all the fillers significantly decrease mechanical strength
of paper and give it higher two-sidedness. To overcome these drawbacks the filler
modification was used by cationic starch solution, which leads to positively charged flocs’
formation from its particles. We used chalk and marble suspension of 5 and 15%
concentrations as GCC, and cationic starch with approximate degree of substitution 0.035
under 4% of GCC was a modifier. Physical properties of the produced samples were studied
by standard methods as well as by electron microscopy and zeta potential measurement.
Application of the modified filler in the manufacture of fine printing paper resulted in the
increase of first pass retention by 18% and tensile strength by 7%. Paper containing the
modified filler has a lower two-sidedness for such parameters as roughness, smoothness,
surface strength and black optical density approximately by 10–30%.

Key words: ground calcium carbonate, modification, cationic starch, filler retention,
mechanical strength, two-sidedness.

INTRODUCTION

The use of fillers in fine printing paper production enables to attain the required
optical properties and printability like high brightness and opacity, good ink receptivity etc. In
addition fillers improve to some extent the sheet microformation and reduce its manufacturing
cost by partial substitution of fibrous raw materials with cheaper minerals [1–4].
Ground calcium carbonates are most effective natural fillers by cost/performance ratio.
They include some commercial products that are derived by grinding and classification of
three major geological modifications: chalk, limestone, and marble [5]. Brightness of GCC
fillers from chalk is low and it is generally in the range 80-88%. Limestone and marble are
chalk that was recrystallized by geological transformation and thermal metamorphosis being
exposed to high pressures and high temperatures [5]. Due to these processes the carbonate
fillers from marble and limestone contain a little of impurities (less than 1%), high brightness
(up to 96%), and good shade. This is the most important for special kinds of printing paper,
which can’t contain optical brightener.
It is well known that in addition to the positive influence of carbonate fillers on the
optical and printing properties of the paper they like all the fillers significantly reduce
mechanical strength of paper [5-7]. Industrial research runs to overcome the adverse effects of
fillers and to enhance printability of paper and to increase filler retention through preliminary
filler modification by various methods and materials [8-14].
In this way the authors tried to modify the GCC fillers by cationic starch that is one of
the most widely used papermaking additives. We used cationic starch as the filler modifying

Industrial Technology and Engineering. 2016, 3(20): 47-53 47

Penkin A., Vetokhin S., Dubodelova E., Solovyova T. Modified GCC Fillers in Printing Paper Production

an additive for two goals that are high level of filler retention in paper web during its
formation from aqueous slurry and maximizing filler retention in the top and especially in
wire side of surface layers of paper, which are further subjected for surface sizing with water-
soluble binders for strengthening. It was expected to decrease two-sidedness of paper and to
improve its printability and mechanical strength.

MATERIALS AND METHODS

GCC fillers. We used for our experiments the powdery GCC fillers that contained
chalk of 82% brightness («MTD-2», Russia), marble of 95% brightness («Hydrocarb 40 UR»,
OOO «Omya Ural», Russia), and marble of 96% brightness («Normcal», Som Deniz Sanayi
ve Ticaret AS, Turkey).
Cationic starch. For fillers modification we used the cationic starch with approximate
degree of substitution 0.035 («Hi-Cat C 323 A», «Roquette», France). It was claimed by the
supplier to be suitable for use as strength/retention additive for papermaking.
GCC filler modification. There were three following stages in the process of GCC
filler modification:
– preparation of well dispersed unmodified filler suspension;
– preparation of cationic starch solution by conventional procedure of cooking the
starch;
– filler modification by it suspension treatment by cationic starch solution.
Filler suspensions of 5.0 and 15.0% concentrations were prepared in a glass container
by vigorous stirring for 10 minutes at 20°C in laboratory conditions. An aqueous solution of
cationic starch was prepared typically for hot cooking starches’ temperature regime, which
included heating the aqueous 1.0% suspension of cationic starch up to 95°C under constant
stirring, holding-off at this temperature for 20 minutes, cooling the solution to the temperature
20°C. Filler suspension modification was carried out by stirring in a glass vessel for 15 min at
20°C. Dosage of cationic starch was from the series of 0, 0.5, 1.0, 1.5, 2.0 and 4.0 % of the
filler for both 5.0 and 15.0 % concentration.
Later, preparation of the modified filler was carried out at UE «Paper Mill» of
Goznak, Republic of Belarus, by a specially designed production line. It included units for
preparation of cationic starch solution and unmodified filler suspension and a unit for filler
modification equipped with controlled rotation speed stirrer that provided the required size of
filler flocs.
GCC filler properties. Electrokinetic potential (Zeta potential) of GCC filler aqueous
suspensions in the presence and absence of the cationic starch were measured at 20°C by the
micro electrophoresis method. The measurements were made with a Zetaphoremeter IV
(CAD Instruments, France). This apparatus converts the electrophoretic mobility into the zeta
potential according to the Helmholtz-Smoluchowsky equation. The measurements were
carried out on a 0.025 mass % filler dispersions.
Determination of particle size distribution was performed by gravitational liquid
sedimentation method. The particle size was measured for 0.8 mass % filler aqueous
suspensions before and after modification at different solid and starch content. As the particle
size was given the mode diameter value was corresponded to the peak of the frequency size
particle distribution. It represents the particle size most commonly found in the size particle
distribution. The particle size values in the figures are given as relative values. As a whole it
was taken the particle size value for the suspensions at 20°C without starch added.

48 Industrial Technology and Engineering. 2016, 3(20): 47-53

Penkin A., Vetokhin S., Dubodelova E., Solovyova T. Modified GCC Fillers in Printing Paper Production

Optical properties of GCC fillers in the initial (unmodified) and modified state after
drying such as brightness and shade were measured by photometer «Kolir» («Trigla»,
Ukraine).
Papermaking and paper properties determination. The industrial samples of printing
paper were manufactured at UE «Paper Mill» of Goznak by Fourdrinier paper machine under
enterprise’s regulations and instructions. Printing paper was based on furnish consisting of
hardwood and softwood pulp (60/40). They didn’t contain any optical brightener. Paper
sampling was made under ISO 186 requirements.
Tensile strength and breaking length of paper samples were measured according to
ISO 1924-2 standard method by tensile tester (Lorentzen and Wettre, Sweden).
Paper ash content was defined by ISO 2144 standard method. Percentage of first pass
retention was calculated as the ratio of ash content of paper to ash content of paper slurry,
which samples were taken from the head box of a paper machine,.
To evaluate the influence of the modified GCC filler on two-sidedness of a printing
paper we measured the indicators of roughness (according to Bendtsen, ISO 8791-2),
smoothness (according to Bekk, ISO 5627), surface strength (according to Dennison wax pick
test, TAPPI T459) and black optical density for two sides of a paper samples (top and wire).
Paper surface structure was visualized by a Scanning Electron Microscope JSM 5610
LV (JEOL, Japan).

RESULTS AND DISCUSSION

Fig. 1 shows the influence of cationic starch/GCC filler dry weight ratio on zeta
potential of filler particles in aqueous suspensions at modification.

Fig. 1. Influence of cationic starch/GCC filler dry weight ratio on zeta potential of filler
particles in aqueous suspensions at modification

The presented data (Fig. 1) shows that the particles of chalk suspension in the initial
state have low negative zeta potential (- 17 mV) whereas marble filler particles have low
positive charge (+ 5 mV).
It is well known that the calcium carbonate particles at various conditions in water
may have a different charge both positive and negative one [15]. Са2+, СО32– [16, 17] and
HCO3– ions [18] are potential depending ions of the calcium carbonate-water system.

Industrial Technology and Engineering. 2016, 3(20): 47-53 49

Penkin A., Vetokhin S., Dubodelova E., Solovyova T. Modified GCC Fillers in Printing Paper Production

Additionally SiO32– и PO43– ions contained in impurities impact significantly on the sign and
value of the zeta potential of the calcium carbonate particles [19, 20]. According to the
technical data of the studied GCC fillers the content of impurities in the chalk is about 4% and
it is less than 1% in the marble. Therefore at the relative constancy of electrokinetic
measuring conditions it can be assumed that the negative charge of the chalk particles is
associated with high content of impurities. This is also reflected in the low brightness of the
used chalk (82%).
It is also shown that cationic starch addition increases the zeta potential level of the
suspension recharging chalk particles from -17 to +9 mV and making it higher for marble
from +5 to +13 mV. Such a change of electrokinetic properties of carbonate fillers under the
action of the modifying treatment may be explained by the adsorption of the cationic starch
macromolecules on the surface of the filler particles.
It was flocculation of calcium carbonate particles [21–23] estimated in the
modification process. The results shown in Fig. 2 allowed to confirm that the size of modified
filler particles is approximately 2–2.5 times larger than the original particles size.
Both Figures 1 and 2 demonstrate that the most intensive charge rising and flocs’ size
growth are observed till cationic starch/GCC filler dry weight ratio attains 1%. Therefore pilot
testing fillers’ modification was performed at a rate of 1% cationic starch.
Main properties of produced original and modified GCC fillers’ paper samples of 75
g/m2 grammage are presented in the Table below.

Fig. 2. Influence of cationic starch/GCC filler dry weight ratio to relative particle size of
aqueous suspensions at different solid content at modification

Table – Properties of the paper containing unmodified and modified GCC filler based on
marble
GCC filler
Paper properties
unmodified modified
Ash content, % 6.7 8.2
First pass retention, % 62.8 80.6
Tensile strength, kN/m 4.94 5.28
Breaking length, km 6.72 7.18
Surface strength, Dennison wax stick number TS/WS (Δ, %) 20/16 (20) 20/18 (10)

50 Industrial Technology and Engineering. 2016, 3(20): 47-53

Penkin A., Vetokhin S., Dubodelova E., Solovyova T. Modified GCC Fillers in Printing Paper Production

Table continuation
Black optical density, top side (TS)/wire side (WS) (Δ, %) 1.39/1.10 (21) 1.32/1.23 (7)
Roughness, ml/min TS/WS (Δ, %) 244/395 (62) 263/342 (30)
Smoothness, s TS/WS (Δ, %) 39/30 (23) 40/36 (10)

It could be seen that filler modification leads to the increase of first pass retention that
is accompanied by ash content growth without tensile strength losing. These may be
explained by the presence of a filler in the paper stock in the form of positive charged flocs
which are well retained mechanically and electrostatically. Moreover the flocs demonstrate
lower screening effect relative to the surface of the cellulose fibers due to a controlled particle
aggregation. The location of filler particles in the paper structure is shown in Fig. 3.
Apparently the particles of the unmodified filler are more evenly distributed along the
paper surface as modification by cationic starch works some grouping of the particles, thus
preventing the reduce of the surface of fiber to fiber bonding.
The data presented in the table also shows a significant decrease of paper two-
sidedness for the samples with modified filler adding. This appears as a reduction of the
difference of paper parameters measured for top and wire sides of the paper by approximately
10–30%. The result the most probably is due to less washing out of a paper mat of modified
filler particles because of stronger electrostatic adhesion and fixation of the filler onto the
cellulose fibers.

b
Fig. 3. SEM images of paper surface with unmodified (a) and modified (b) GCC filler

Industrial Technology and Engineering. 2016, 3(20): 47-53 51

Penkin A., Vetokhin S., Dubodelova E., Solovyova T. Modified GCC Fillers in Printing Paper Production

CONCLUSION

Modification of GCC fillers by cationic starch solution leads to formation of positively

charged flocs from its particles. At a dry weight ratio of cationic starch/GCC filler of 1% the
zeta potential of chalk is 7 mV and zeta potential of marble is 12 mV. Size of the modified
filler particles at these conditions is approximately 2–2.5 times larger than the original particle
size.
Application of the modified filler in the manufacture of fine printing paper at UE
«Paper Mill» of Goznak resulted in the increase of first pass retention by 18% and tensile
strength by 7%. The paper containing the modified filler has a lower two-sidedness for such
parameters as roughness, smoothness, surface strength and black optical density
approximately by 10–30%.

REFERENCES

1 Doelle K., Amaya J.J. Application of calcium carbonate for uncoated digital printing
paper from 100% eucalyptus pulp. TAPPI Journal. 2012, vol. 10, no. 1, pp. 51–59.
2 Wanhee Im, Hak Lae Lee, Hye Jung Youn, Dongil Seo. Structure characterization of
ground calcium carbonate flocs by fractal analysis and their effects on handsheet properties.
TAPPI Journal, 2013, vol. 12, no. 3, pp. 17–23.
3 Zhao, Hu Z., Deng Y., Ragauskas A. Improvement of paper strength with starch modified
clay. Journal of Applied Polymer Science, 2005, vol. 97, pp. 44–55.
4 Se-Young Yoon, Yulin Deng. Clay-Starch composites and their application in
papermaking. Journal of Applied Polymer Science, 2006, vol. 100, pp. 1032–1038.
5 Herbert Holik Handbook of Paper and Board. 2013. Weinheim: WILEY-VCH Verlag
GmbH &Co, 992 p.
6 Hubbe M.A., Gill R.A. Filler particle shape vs. paper properties. Proceedings of spring
technical and international environmental conference TAPPI Paper Summit. Atlanta, 2004.
TAPPI Press, Atlanta, pp. 141–150.
7 Li L., Collis A., Pelton R. A new analysis of filler effects on paper strength. Journal of
Pulp and Paper Science, 2002, vol. 28, no. 8, pp. 267–273.
8 Shen J., Song Z, Qian X., Liu W. Filler modification for papermaking. BioResources,
2009, 4 (no. 3), pp. 1190–1209.
9 Dongil Seo, Wan Hee Im, Hye Jung Youn and Hak Lae Lee. The effects of process
variables for GCC pre-flocculation on floc and handsheet properties. Nordic Pulp and Paper
Research Journal, 2012, vol. 27, no. 2, pp. 382–387.
10 Ana F. Lourenço, José A.F. Gamelas, João Sequeria, Paulo J. Ferreira, José L. Velho.
Increase of the filler content in papermaking by using a silica-coated PCC filler. Nordic Pulp
and Paper Research Journal, 2014, vol. 2, no. 2, pp. 242–247.
11 José A.F. Gamelas, Ana F. Lourenço, Marco Xavier, Paulo J. Ferreira. Modifica-tion of
precipitated calcium carbonate with cellulose esters and use as filler in papermaking.
Chemical Engineering Research and Design, 2014, vol. 92, no. 11, pp. 2425–2430.
12 Sang Y., McQuaid M., Englezos P. Pre-flocculation of precipitated calcium carbonate
filler by cationic starch for highly filled mechanical grade paper. BioResources, 2012, 7 (no.
1), pp. 354–373.
13 Yulin D., Phil J., Leslie M., Ragauskas Art J. Starch-modified fillers for linerboard paper
grades: A perspective review. TAPPI Journal, 2010, vol. 9, no. 4, pp. 31–36.

52 Industrial Technology and Engineering. 2016, 3(20): 47-53

Penkin A., Vetokhin S., Dubodelova E., Solovyova T. Modified GCC Fillers in Printing Paper Production

14 Pang P., Englezos P. Application of pretreated ground calcium carbonate in mechanical

pulp suspensions. Pulp and Paper of Canada, 2003, vol. 104, no. 6, pp. 37–39.
15 Vanerek, A., Alince, B., van de Ven, T.G.M. Colloidal behavior of ground and
precipitated calcium carbonate fillers: effect of cationic polyelectrolytes and water quality.
Journal of Pulp and Paper Science, 2000, vol. 26, no. 4, pp. 135–139.
16 Nyström R., Linden M., Rosenholm J.B. The influence of Na+, Ca2+, Ba2+ and La3+ on the
ζ potential and the yield stress of calcite dispersions. Journal of Colloid and Interface
Science, 2001, vol. 242, pp. 259–263.
17 Eriksson R., Merta J., Rosenholm J.B. The calcite/water interface I. Surface charge in
different electrolyte media and the influence of low-molecular-weight polyelectrolyte.
Journal of Colloid and Interface Science, 2007, vol. 313, pp. 184–193.
18 Moulin P., Roques H. Zeta potential measurement of calcium carbonate. Journal of
Colloid and Interface Science, 2003, vol. 261, pp. 115–126.
19 Houbin Li, Yumin Du, Xiaojun Wu, Huaiyu Zhan. Effect of molecular weight and degree
of substitution of quaternary chitosan on its adsorption and flocculation properties for
potential retention-aids in alkaline papermaking. Colloids and Surfaces A: Physicochemical
and Engineering Aspects, 2004, vol. 242, pp. 1–8.
20 Hołysz L., Chibowski E., Szcześ A. Influence of impurity ions and magnetic field on the
properties of freshly precipitated calcium carbonate. Water Research, 2003, vol. 37,
pp. 3351–3360.
21 Sableviciene D., Klimaviciute R., Bendoraitiene J., Zemaitaitis A. Flocculation properties
of high-substituted cationic starches. Colloids and Surfaces A: Physicochemical and
Engineering Aspects, 2005, vol. 259, pp. 23–30.
22 Nyström R., Backfolk K., Rosenholm J.B., Nurmi K. Flocculation of calcite dispersions
induced by the adsorption of highly cationic starch. Colloids and Surfaces A:
Physicochemical and Engineering Aspects, 2003, vol. 219, pp. 55–66.
23 Nyström R., Backfolk K., Rosenholm J.B., Nurmi K. The effect of pretreatment of calcite
dispersions with anionic sodium polyacrylate on their flocculation behavior induced by
cationic starch. Journal of Colloid and Interface Science, 2003, vol. 262, pp. 48–54.

Industrial Technology and Engineering. 2016, 3(20): 47-53 53