Professional Documents
Culture Documents
Papermaking
Se-Young Yoon, Yulin Deng
School of Chemical and Biomolecular Engineering, IPST, Georgia Institute of Technology,
N.W. Atlanta, Georgia 30332-0620
Received 9 July 2005; accepted 18 August 2005
DOI 10.1002/app.23007
Published online 12 January 2006 in Wiley InterScience (www.interscience.wiley.com).
ABSTRACT: Claystarch composites with different aggregate sizes and starch to clay ratios were prepared by a
simple precipitation method. The aggregates of the composites were used as llers to improve the paper properties. The
experimental results showed that the paper strengths increased more than 100% for starch-modied clay compared
to untreated clay at 20 30% clay loading. The increase in
paper strengths of claystarch composite-lled handsheets
was mainly due to two reasons, i.e., the relatively large
aggregate size and the improved internal bonding. The op-
INTRODUCTION
For many years, the increase in ller content in papers
has been driven by the reduction in papermaking cost,
the improvement in optical properties, paper formation, printability, and the water removal rate during
papermaking. However, as ller loading is increased,
the paper strength, bulk, and stiffness are usually
decreased. To increase the proportion of ller without
sacricing paper properties, various methods have
been explored. Preocculation method prior to addition to the paper stock have been well studied in the
past.13 From pilot plant trials, Marbee reported that
occulation method could provide an 26% increase
in rst pass ash retention and 13% increase in the
tensile strength when the same amount of ller was
used.4 Lumen loading method that held ller mainly
within the lumens of bers have been studied for
many years.57 Filler modication with polymers,
such as chemically bonded poly(acrylic acid) and
poly(vinyl acetate) to llers, was also reported.8 Gill
modied precipitated calcium carbonate (PCC) surface by introducing catioinic groups on PCC using
epichlorohydrin and polyamino-amide or polyamine.9
The result showed that the breaking length was improved about 10% at the same brightness (89%) using
1% polymer-treated PCC. Silenius recently reported a
Correspondence to: Y. Deng (yulin.deng@chbe.gatech.
edu).
Journal of Applied Polymer Science, Vol. 100, 10321038 (2006)
2006 Wiley Periodicals, Inc.
1033
EXPERIMENTAL
Materials
Dry Branch Kaolin (Dry Branch, GA) provided the
calcined kaolin clay. Raw corn starch was used for this
experiment. Ammonium sulfate was obtained from
Aldrich. Bleached hardwood and softwood pulps
were each rened in a Valley beater to a freeness of
400 CSF. Equal proportions of the two pulps were
mixed, and the mixture was used as the base pulp
furnish for the handsheets. Percol-175 (cationic polyacrylamide retention aid) was obtained from Ciba
Specialty Chemicals (Suffolk, VA). Crosslinker, Eka
AZC 5800LN (Ammonium zirconium carbonate, 30%
solution), was procured from Eka Chemical (Marietta,
GA).
1034
1035
Figure 1 Morphology of claystarch composite from the optical microscope and SEM. (a) SEM picture of pure clay; (b) and
(c) Optical microscope picture of the aggregates prepared at clay to starch ratio of 1 : 1; and (d) SEM picture of claystarch
composite with starch ratio of 1 : 1.
improve paper-strength properties compared to conventional papermaking ller. As the content of pure
clay increased, the tensile strength of the handsheet
made from unmodied clay decreased signicantly as
1036
Figure 4 ZDT (Zero Directional Tensile) strength as a function of ller content for pure clay and the claystarch composites with different clay to starch ratios.
strength and number of interber bonds. Thus, increased clay content in handsheets caused a greater
reduction in tensile strength. Our previous research15
proposed that the reduced interber bonding by the
increasing clay content could be compensated through
the improvement of the clayber bonding by the
starch that was coated on ller. It is reported that the
starch-coated PCC could improve the tensile strength
up to 30%, compared to the same amount of pure
PCC. As shown in Figure 3, the tensile strengths of the
handsheets made from three different claystarch
composites increased about 110% compared to original clay at 20 and 30% clay doses. As shown in the
Page equation,20 the tensile strength of paper combines the intrinsic ber strength, the bonding strength,
and the contact area. Since the ber intrinsic strength
was the same for all handsheets, the increase in the
paper strength should be contributed from the in-
1037
From ZDT tests, it was determined that internal bonding was improved by adding claystarch composite
compared to using pure clay. To investigate the bonding between wood ber and composites, the surface of
handsheets lled with claystarch composites was observed by SEM. Some of the claystarch composites
were stuck on the wood ber surface and have almost
no individual clay particles on ber surface or between bers, as shown in Figure 9(a). At higher magnication (b), we could observe the bonding structure
between ber and claystarch composite in detail. The
brils from the ber are strongly bound with the
composites so the boundaries of them could not been
clearly observed. Appearance of claystarch composites was also changed during pressing and drying. As
can be seen from Figure 9(b) the thermoplasticization
makes swollen starch penetrate into bril network to
form a smooth bonding area. Obviously, this will help
the bonding of composites with brils or bers.
CONCLUSIONS
This study provided a method of claystarch composite preparation. The composite such prepared can be
Figure 9 SEM pictures of claystarch composites lled handsheets (a) Clay : Starch 1 : 0.25 and (b)1 : 0.5.
1038
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