- -

0
0
M 0

Conference
AiIkai unie Paper]nnlak unig
ini ]Rapeir ][]ftd[t][S t]r tleS

THE ADSORPTION OF CATIONIC STARCH

Author
Peter de Clerck
AVEBE FAR-EAST PTE LTD, SINGAPORE

Jakarta, September 19 20, 1995-

Shangri-La Hotel,
BNI City Complex, Jl.Jend.Sudirman Kav.1,
Jakarta 10220, Indonesia

Ministry of Industry
Directorate General of Chemical Industry
Directorate of Pulp, Paper, and Paper Product Industry
 Autltor

PETER DE CLERCK

Mr. Peter de Clerck is a papermaker specialist from Avebe office for the Far East
region based in Singapore since 1987. He graduated from the School of Paper
Science at U.M.I.S.T., Manchester in 1983 and has worked for a leading recycling
paper mill of the International Paper Group in UK as paper technologist, and followed

W
by a term as technical manager and later on as process engineer at Kimberly Clark
paper mill.

Abstract

In the conservation from rosinlalum to neutral or alkaline sizing, several significant

changes occur in the wet-end chemistry. This paper examines the sequence of
chemical additives used, while reducing effluent emissions. Chemical and physical
criteria are reduced to a simple framework to enable the mill to evaluate its own
additions sequences and the likely consequences.

Jakarta - Indonesia. September 19 - 20; 1995

Conference on Alk~!inePape.makin&in Puper ~dusm'es,
Theddsolption of Cationic Starch Page 1 of 8

INTRODUCTION

The adsorption of cationic starch is of great importance to the papermaker as only filly
retained starch will contribute to the strengthening of the paper sheet. Unretained starch
will contribute to effiuent problems and may also cause slime and deposits in the machine
system.

ADSORPTION ONTO CELLULOSE

Cationic starch reacts with charged sites on fibre surfaces. The negative surface charge of
cellulose results 6om the dissociation of uronic and saccharinic acid groups. This charge is
decreased at lower pH due to protonation of the carboxyl groups (Figure 1). Low pH then
reduces the zeta potential of the fibre and its mt
y for cationic starch.

cellulose-COOH 5 cellulose-COO-+ H'

t

low pH

Figure 1. The effect of pH on cellulose surface charge

Increasing the number of reactive - COOH groups on the fibre increases the adsorption of
cationic starch. However not all of these charged sites are accessible to the starch molecule
as the high molecular weight cationic starch cannot penetrate the smaller capillaries of the
fibre. Only a proportion of the total fibre surface is then available for starch adsorption.

Both electrostatic (ionic) bonding and hydrogen bonding play a part in starch adsorption on
cellulose. Electrostatic bonding is the dominant force - if a non-ionic starch is used, over

Conference on =IlkslineFapermaki~gin Paper Indus;n'es, Jakarta - Indonesia, September 19 - 20. I995

The Adsorption of Cationic Starch Page 2 of 8

80% of the adsorbed starch can be removed simply by washing with hot water. Cationic
starch adsorption is virtually irreversible.

Starch adsorption is limited. Under ideal condition fibre can adsorb up to 4%-5% cationic
starch. The relationship of adsorption to cationic starch addition is of the form shown in
Figure 2. Chemists refer to this shape of adsorption curve as a Langmuir adsorption
isotherm

0 20 40 60 80 lW 120
CATIONIC STARCH ADDED, mglg of adsorbent

Figure 2. Adsorption of cationic starch on cellulose

The plateau (flat) region of the curve represents the saturation value (G),i.e. the maximum
possible adsorption.

Conference on Alkuline Pupemtukir~gin Baper Indristries, Jakarta - Indonesia, September 19 - 20, 1995
The Adsovtion of Cationic Starch Page 3 of 8

ADSORPTION ON FURNISH COMPONENTS

Adsorption curves for cationic starch may be produced for any adsorbing material. Typical
curves for a cationic potato starch of d.s. 0.035 (Amylofax PW) are given in Figure 3.

100% RETENTlqN
PREMIUM COATING CLAY
/

N0.2 CLAY
-

TiO RUTILE

0 40 W 80 100 120
CATIONIC STARCH ADDED. rnglg ol adsorbent

Figure 3. Adsorption Isotherms at pH5 (ref.4)

SPECIFIC SURFACE AREA

Adsorption is a surface phenomena. The greater the available (accessible) surface, the
greater may be the starch adsorption. Refining allows greater starch adsorption by
increasing the accessible surface area of the fibres. The surface area per gram of material is
referred to as the speciJicsuface area.

The specific areas of typical alrnish components are given in table 1. The corresponding
adsorption saturation values obtained fiom Figure 3 are given for some of the components.

C'onference on slllialine Papennahing in Paper Indusrn'es, Jcliarto - Indonesia, September 19 - 20, 1995
TheAdsorption of Cationic Starch Page 4 of 8

Hydrodynamic Saturation
surface area value
Material (m2/g) (amdg)

Fibte fraction
Pulp blend
Fines fraction

Filler Clay
No.2 coating clay
Calcined clay
Premium coating clay

Ground CaC0:
Precipitated CaCO;
Talc

Table 1. Specific surface area and adsorption saturation values.

STARCH DISTRIBUTION

In papermaking practice, cationic starch is normally used at between 0.3% and 2.5% on
furnish, i.e. 3-25 mg/g. Most of the addition is below 12 mg/g. Refening to figure 3, at
these low addition levels the adsorption efficiencies are close to 100% i.e. 100% overall
starch retention.

Cationic starch is usually added to a blend of furnish materials and, so ends up distributed
between them. It has been concluded that the a, saturation values give a good estimate of
the relative reaction rates of the starch with the individual fbrnish components. This relative
reaction rate may also be termed the relative adsorption intensity.

.h-- --
Co~fermcea,? . - l l C ~ f i ;Prrpe.mcXing
;~ i i Pu'pe~
~ Jakartu - I~donesicl,Seprmzber i9 - 26, I995
I??r?l:st;ies,
The Adsorotion of Cationic Starch Page 5 of 8

Work has shown that the relative adsorption intensities for fibre, fines and clay are in the
ratios 1:5:4 respectively. Considering a typical hmish we can calculate the contribution of
the adsorption potential of each hrnish component to the total hrnish. We would expect
cationic starch (or other additives) to be distributed accordingly between the hrnish
components. Taking a typical hmish,

Relative Expected
Adsorption distribution
Component Composition Intensity Value ratio

axb mb
2.08

Fibre 69%

Pulp fines 15%

Clay 16%

Furnish 1OOYo

Table 2. Distribution of a 1% addition of cationic starch at pH 5

Note that the fibre, comprising 69% of the furnish, adsorbs only 33% of the starch. The
rest is distributed between the fines and the fillers. Hence the presence of large quantities of
fines and fillers is detrimental to starch adsorption by the fibre.

Conference on Alkaline PapemaXing in P a p r Industries, Jakartc - Indonesia, September 19 - 20, 1335

The Adsorption of Cationic Starch Page 6 of 8

From Table 2 we can calculate the expected starch concentration on each hrnish
component. If we add 1.2% (12mg/g) cationic potato starch the following results are
found.

Component Composition Relative expected starch

distribution concentration
on component

Fibre

Pulp fines

Clay

Furnish 100% - -

From this table we note the high cancentration of starch on the fines and filler components
of the furnish. Naturally if the first-pass retention of fines and fillers is low, then the overall
starch retention and efficiency wiH be low. Good first-pass retention is crucial for good
total starch retention.

Co~ljerenceon Alkaline Papemaki~tgil?Paper industries, Jakarta - Indonesia, September 19 - 20, I995

The Adsolption of Cationic Starch Page 7 of 8

POINT OF ADDITION

It is recommended that the cationic'starch be added to the thick stock of the papemachine,
as such stock contains a higher relative proportion of fibres with less fines and filler when
compared to the thin stock. Starch is more efficient at promoting strength when adsorbed
onto long fibres rather than onto other &sh components. Hence starch addition should
idealy be before filler addition.

High turbulence promotes the deposition of high molecular weight polymers onto the
fibres. Thus a good point for starch addition is to the outlet of the stuff pump in the thick
stock system.

When the level box has been selected as the starch addition point, then in order to achieve a
faster response on the paper machine to changes in starch addition, it is recommended that
the overflow from the thick stock headbox (level box) is returned to the inlet of the stuff
pump rather than to the machine chest. This reduces the buffering capacity of the system.
Good pumps are required to ensure a steady flow of starch to the stock.

The starch solution should be diluted to a maximum of 1% concentration before being

added to the stock. Clean water - not backwater - must be used for cationic starch dilution.
A dual injection.point is recommended i.e. two tappings to the pipe instead of the normal
one. This ensures better mixing and distribution.

CONCLUSIONS

By consideration of simple adsorption phenomena, it is possible to considerably improve

the efficiency of cationic starch additions. The basic principles can be extended to other
performance additives.

Jakartcl - hZd~iit%S&i,
hrfermce on Albline Papemiding in Paper Industntnes, September 19 - 20, 1995
TheAdsorption of Cationic Starch Page 8 of 8

REFERENCES

1. Sjostrom E. et.al.,Journal of Polymer Science, 11(c)(1965), 2 1 l .

2. Britt, K.W. & Unbehend, J.E., Tappi, 57(12)(1974), 8 1.

3. Roberts, J.C. (ed), Paper Chemistry, 1991,63.

4. Marton, J., Tappi, 63 (4)(1980), 87.

Jakarta - Indonesia, September 19 - 20, 1995

Conference on Alkaline Papemking in P q e r Jndndustries,