NORTHERN DIVISION

MEETING HELD AT THE ENGINEERS' CLUB, MANCHESTER

6th MARCH 1959
Mr. P.A. DUXBURY in the Chair
THE APPLICATION
OF MODIFIED STARCHES
AT THE SIZE PRESS
A. HARSVELDT
Synopsis
The paper gives a survey of a number of important factors that
must be borne in mind in the application of modified starches at the
size press. The causes of the coating pattern or tracking are discussed
and methods are given to eliminate this pattern. The conversion
methods of starches are discussed and advantages and disadvantages
in connection with special applications are indicated.
Purpose of surface sizing
Surface s1zmg imparts to writing papers increased strength,
improved rattle and better surface smoothness. For printings, the
size press is principally used for coating to obtain higher gloss and
better smoothness after supercalendering.
A correctly located size press may also contribute essentially to a
production increase of the machine-for example, writings can be
made with free-beaten stuff and consequently at higher speed;
strength and rattle in this case are obtained by surface sizing in the
size press.
Printings will benefit also by the higher speed made possible by
use of free-beaten stuff. Part of the fillers can now be added in the
size press and the addition of filler to the beater can be reduced in
quantity or dropped altogether.
If one wanted the fibres to absorb the fillers added in the beater,
none at the size press, the degree of beating would have to be
increased, which would mean lower operational speeds and troubles
like cockling and wrinkling.
Mr. Harsveldt is Research and Laboratory Director, /
N.V., Holland t) I \:S l 1 U I H 1.... ..__ '\
399 Nuaml. Vennootscnap
W. A.
CHEM\SCHE FABfilt:i\FN
F 0 X H <2_L__ _ __ ,
-----
400 MODIFIED STARCHES AT THE SIZE PRESS
The modem size press
Fig. 1 shows the size press mounted between the first and second
drying sections and indicates a number of particulars that are
important for size press operation as follows.
I. Feeding the paper into the size press
The feeding-in angle shall not be greater than 25 to the horizontal.
If the angle is greater, the surface area available for impregnation
with the same quantity of size delivered will be reduced, the size
flowing quickly to both sides in the direction of the upper cylinder
of the size press.
If the angle is too acute, the size will flow on the sheet in the
opposite direction of travel and the area of paper coated with starch
solution will be greater.
FIG. 1
SIZEPRESS
IN T/IE
PAPERMACll/tYE
2. Feeding of the paper into the drying section
Three important things are to be observed here-
J. The paper, when emerging from the size press, should not adhere
too long to the upper roller.
2. The paper shall be given sufficient time for expansion-in other
words, the run after the size press should not be too short. In this
respect, fine papers will present greater difficulties than medium
grade and mechanical papers.
3. The paper should not be dried too quickly; in the first two
cylinders, therefore, the steam pressure should be kept low and
these cylinders are run without dryer felts in a number of
papermills.
After the size press, but not long before the paper enters the
second drying section, a Mount Hope cylinder should be provided
to smooth out any wrinkles. This cylinder should be located so that
the paper contacts the cylinder at an angle less than 30.
MODIFIED STARCHES AT THE SIZE PRESS 401
The rolls of the size press are generally located one vertically
above the other, but the top roll may also be placed a little out of
vertical with the bottom roll, as a consequence of which the surface
area covered with starch solution is somewhat larger on the upper
side of the paper. The pressure per linear inch will be lower in
this case.
A size press with horizontally mounted rolls has been designed.
This requires little space on the papermachine, which is certainly
an advantage.
Hardness of rubber rolls
Little can be found in the literature.on the degree of roll hardness
in size presses. It will be quite clear that two non-resilient rolls
(like cast iron) are unsuitable, as the line of contact will be very thin.
From a very good article on size presses,<1) we learn that there are
85 per cent. equipped with a rubber-clad bottom roll and a top roll
of stonite or copper. The degrees of hardness of the rubber roll are
indicated as 3 0 ~ 5 P & J.
Today, hard top rolls are preferred almost everywhere, as a doctor
can be mounted on a hard roll, whereas a soft surface would become
rough and cracked on prolonged exposure to doctoring; bottom
rolls never have doctors.
For the practical significance of the difference in hardness of the
two rolls, the question to be asked first is whether the objective is
only surface sizing with starch or coating. In the latter case, the
best plan will be to work with two hard rolls, a metal top roll and
a hard rubber bottom roll or two hard rubber rolls. To explain this,
we have to make clear what happens when coating colour is
transferred to paper.
402 MODIFIED STARCHES AT THE SIZE PRESS
This transfer is dependent upon an interplay of coating colour
and paper properties and controls to a great extent the quality of
the resulting coated paper (Fig. 2). When the paper is fed through
the nip of the applicator rolls, its surface will absorb water and
adhesive out of the coating colour with the result that a certain
amount of coating colour is immobilised on the paper by loss of
20-30 per cent. of its water by drainage and 3-4 per cent. of the
starch binder. This layer may be fairly strongly held to the paper
by penetration into coarse pores or surface roughness. The im-
mobilisation capacity should increase with-
J. Increasing porosity of the sheet.
2. Increasing pressure between the applicator rolls.
3. Longer contact between coating colour and paper.
4. Decreasing coating colour viscosity.
FI G. 2
Between applicator roll and immobilised coating layer, there is
still free coating colour of low plastic viscosity, which splits to
transfer some constant fraction to the paper, roughly 50 per cent.
In the process of splitting, the free coating film is elongated.
The diameter of a filament is gradually reduced in the middle by
slow elongation (necking down), causing the originally near-
cylindrical form to change into a shape resembling an hourglass. A
break occurs when the thinnest part of the filament gives way.
The shorter the necks, the less the coating pattern. We have already
MODIFIED STARCHES AT THE SIZE PRESS 403
used a rheological approach for the property of length. A short
coating colour-possessing a low plastic viscosity and a high yield
value-will show shorter necks. A long coating colour-with too
high a plastic viscosity-will tend more to form necks and produce
a heavier pattern on the coated paper.
In the case of a coating with very low water retention applied to
the same paper, the penetration of adhesive and water into the
paper will cause a substantial increase in solids and flow resistance
of the coating next to the paper, with the result that the film will
split rather close to the roll surface. Hence, the web will carry away
a film much heavier than that left on the roll. When water retention
is extremely low, coating may become inoperable over the whole
area-the solids content of the film become so high that dilatant
behaviour occurs, resulting in erratic film splitting in the dilatant
layer and a sharply ribbed pattern. The applicator roll then emerges
from the nip carrying deposits of unsized pigment. A series of
experiments were undertaken on our laboratory size press to estab-
lish the dependency of water retention and patterning.
For these trials, starch/clay colours at 40 per cent. solids with
varying percentages of a thin, oxidised starch were applied on a full
rosin-sized mechanical printing.
Water retention and viscosities of 40 per cent. solids
starch/clay colours
TABLE 1
Per cent. of starch Water retention, Viscosity,
on the china clay sec. centipoises
15 36 15
18 48 17
21 57 24
24 67 28
27 82 31
The data given in Table 1 indicate an increase in the plastic
viscosities with increasing percentages of starch. All the coating
colours gave Newtonian rheograms, so that patterning could only be
correlated to viscosity and wet film thickness. It appears that in-
creasing the proportion of starch, which means increasing the water
retention, reduced the sharply ribbed coating pattern to a minimum.
404 MODIFIED STARCHES AT THE SIZE PRESS
As soon as the wet film thickness and the viscosities increased
too much, the normal coating pattern appeared again. The ex-
planation of this phenomenon is that the higher percentages of starch
inhibit excessive drainage of adhesive and water in the paper, so
leaving enough fluid colour to give reasonably satisfactory film
splitting. Too high a percentage of starch, however, increases the
viscosity too much, giving longer necks and more coating pattern.
Application to the paper surface
In operating a size press, it is imperative for its economic perform-
ance to have an adequate after-section to remove the water taken up
(up to 30 g./sq. m.).
1. Effect of the weight per unit area
The pick-up per unit area is fairly uniform over the paper sheet
and is independent of the weight applied.
When increasing the weight, the drying section before the size
press will as a rule be heavily loaded, whereas the after-section is
loaded to a smaller extent. With low weights per unit area, a higher
speed will usually be chosen; the drying section before the size press
will be sufficient, but the after-section will now have to evaporate
more water, because a larger surface of paper passes through the
size press in a given time.
2. Effect of rosin siZing
An unsized paper will absorb much more water than will a sized
paper. There is decreasing absorption with increasing degree of
sizing.
3. Viscosity and solids content of the starch solution
These two characteristics are closely related. The viscosity of the
starch solution will increase hyperbolically in higher concentrations,
when the temperature remains unaltered.
Fig. 3 shows the increase in viscosity for three different tem-
peratures, if the concentration is also increased. When the
concentration is graphed against the logarithm of the viscosity, a
straight line (Fig. 4) is obtained.
At higher starch concentrations, the viscosity and also the starch
absorption by the paper will increase. Furthermore, the starch
absorption by the paper increases more than one would expect from
the increase in the solids content of its solutions.
MODIFIED STARCHES AT THE SIZE PRESS
12
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8
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.,
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....
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Increase in l/i.s'cosity
o /' modif'led .starch
FI G. 3
by increasing' concentro;c1on
60 C
70C
% sol/ds content
lo
Increase in viscosit!I
of' modil'ied .sfCJre>h
j.z
by inc-reasinq concencr<9t/on
171' As
FIG. 4
% so/ids content
2 3 4- 5 ~ 7 8 9 lo II 13 /J I ~ Hi ,t,
18
405
406 MODIFIED STARCHES AT THE SIZE PRESS
This explains why, when working with higher solids, more water
has to be evaporated than when working with lower solids. With
water only, the amount absorbed is at a minimum: as soon as
starch has been dissolved in it, the amount of water absorbed by
the paper will increase with advancing viscosity.
/.8.
I.
FIG. 5
.Orf,' p/ck,u,o ci'9'cSl/nS't vlS'co.r/t51
(sized , b<>' se pcS1pers)

' ISO
Dry pick- vp ag-CJ/nsc /ofT. ol' viscosity
(s./zed .601.se ,bc>1j:1er.s)
FI G. 6
loq. oF v/sco.s-ity /n c,J;>.
4567891o" 4 5 6 7 8 '9 10'-
To confirm this conclusion further on an experimental size press,
trials were run with starches of different viscosities in a single
concentration.
I
MODIFIED STARCHES AT THE SIZE PRESS
407
With a 11! in. paper width, the machine was run at speeds of
9 ft./min.; on two different offset papers of approximately 90 g./m.,
quantities of 1-2 g./sq. m. were applied (Fig. 5).
The curves show the characteristic hyperbolic relationship between
absorption and viscosity. The steeper line in Fig. 6 shows the small
increase of the absorption with the viscosity, if the offset paper is
also engine-sized with 2 per cent. starch.
4. Effect of the degree of beating
When beaten to a low degree, the porosity of a paper will be higher
and the absorption of a starch solution in the size press will naturally
be higher.
5. Temperature of the starch solution
As the viscosity of starch solutions rises with falling temperature,
the paper will absorb more of the solution upon cooling.
Generally speaking, at least 30-35 per cent. of the total drying
capacity should be found in the after-section.
The requiremen.ts for a starch
Any native starch is composed of two components-linear
macromolecules called amylose and branched macromolecules called
amylopectin. Chemically, both polymers consist of units of glucose
that are linked to one another. In such glucose chains, the hydroxyl
groups of one molecule have a strong affinity for the hydroxyl groups
in a second molecule, especially if the two molecules are closely
adjacent. This is possible with amylose, because straight chains can
lie parallel to one another. This occurs in a starch solution upon
cooling and ageing-the linear chains gravitate towards each other
and the hydroxyl groups keep the chains close together like bridges.
If the starch solution is diluted, the chain bundles will settle as an
insoluble precipitate; if the solution is a concentrated one, however,
the whole substance will gel. This phenomenon is called retro-
gradation, going back to the solid form. With the branched
component, the amylopectin, only a few hydroxyl groups can come
into proximity, as parallel orientation is not easy: therefore, solutions
that contain amylopectin exclusively cannot gel.
Native starches cannot be used in the size press, because of their
rather high viscosity, either for starch coating or for surface sizing.
It is necessary to have starches that are carefully converted to the
required degree with low viscosity, but still having good adhesive
power.
408 MODIFIED STARCHES AT THE SIZE PRESS
A low viscous solution penetrates more deeply into the paper than
does a highly viscous one and will consequently better meet the
requirements. One can work with a higher solids content and obtain
greater tensile strength improvement, though decomposition should
not proceed too far, otherwise the film-forming properties of the
starch and its adhesive power will be lost.
There are various processes to decompose native starches. One of
them is the hydrolytic decomposition under the influence of acids.
It has been found, however, that these thin-boiling starches retain
a great deal of amylose and consist of very little amylopectin. This
accounts for the high tendency to retrogradation.
This is a disadvantage, if a deeper penetration into the paper is
wanted or if a coating colour with a long period of stability is
required. Hydrolytically decomposed starches, however, may also
have their advantages-for example, optimum closing of the paper
surface with low penetration depth is required.
In another process of conversion, oxidation is the principle in-
volved. Thin-boiling starch types, possessing very high stability,
result. The oxidising agent, sodium hypochlorite, does not destroy
the chained amylopectin molecule, but introduces highly soluble
carboxyl groups and carbonyl groups into the chains, which repress
the tendency to retrogradation. This method enables the preparation
of the ideal types for normal surface sizing and for starch pigment
coating.
In the third place, roasted dextrins are known. Brimhall (1943)
proved that dextrinising is accompanied by a diminishing of the
linear chain molecule and that the number of chained molecules
increases. During the dextrinising process, however, chain fragments
will also come into existence and, being so small, they dissolve even
in cold water.
As a result, it is not advisable to use roasted dextrins for the
surface sizing of offset papers and writing papers, because the starch
film is in contact with dampening water on the offset press and
because too high a sensitiveness to water in writings may cause the
detrimental feathering. Finally, the papermaker can decompose
the native starch himself by means of enzymes. This method
requires careful control, but will give good filming properties and
adhesive power if well conducted. Unfortunately, the low molecular
sugars also formed cause non-drying films.
In recent years, other starch derivatives have found some interest
for surface sizing-etherified and esterified starches, in which the
hydroxyl groups in various places have been substituted by other
MODIFIED STARCHES AT THE SIZE PRESS 409
chemical groups. The advantages brought about by such sub-
stitutes are-
J. By substitution of the hydroxyl groups, the orientation of parallel
amylose chains is hampered. This means improved stability.
2. The kind of group introduced may have an essential effect on the
filming properties.
Apart from the fact that films of etherified and esterified starches
are generally less brittle, a polar substituent (like carboxyl, sulphonic
acid, glycollic acid) will make starch films more resistant to oil and -
grease, which makes these products interesting for greaseproof
papers and boards.
On the other hand, it will be understood that the substitution of
hydroxyl groups by hydrophobic ether groups or ester groups will
impart to the films improved oil absorptivity, as it is known that
higher rosin sizing of a paper will also give this.
I have attempted to summarise the principles of size press work.
Although much depends on the mechanics of the size press, the
particular type of starch used plays an important role, too.
REFERENCE
1. Currie, D. C., Wyatt, M. C. and Taylor, J. E., 'A Short Discussion of Size
Pressing and Tub-sizing': Pulp and Paper Mag. Can., 1956, 57 (3), 274
410 MODIFIED STARCHES AT THE SIZE PRESS
DISCUSSION
MR. J. WINTERBURN: Do the horizontally mounted rolls not give a
better nip condition, owing to less camber being needed and the
same natural deflection being present in both rolls?
I object to the expander roll being called a Mount Hope cylinder,
as this type of expander was invented by William Mycock of
Littleborough and has been known for a great number of years in the
textile trade as the Mycock expander.
MR. A. HARSVELDT: If we consider the case of a pair of rubber-
covered rolls that have been ground straight face and that are loaded
by a force being applied to their journals, the result will be a bending
of the rolls under the application of the load, resulting in increased
pressure near the ends of the roll. This gives rise to a nip with small
width at the centre of the roll and wider at the ends of the roll.
The simplest method of correcting this situation is to increase the
thickness of the rubber in the centre of the roll, tapering it out
towards the ends. When this is dom\ we have equal pressure across
the nip and an even nip is obtained.
Mounting the rolls horizontally or vertically doe!" not change the
fact that we have to compensate for the deflection of the rolls under
load by increasing the thickness of the cover in the centre of the roll.
Thank you for the comment on the expander roll.
MR. F. BRIDGE: Has Mr. Harsveldt investigated the effect offurnish
on the quality of the starch to be used in the size press operation?
Hardwood pulps are now being used more extensively along with
softwood pulps aDd it would be interesting to know whether this fact
has to be taken into account when deciding the most suitable type
of starch.
What is Mr. Harsveldt's opinion on the best type of surface for
the drying cylinder immediately following the size press? In this
connection, l am particularly interested in the reduction of sticking
troubles and fouling of the cylinder surface by starch and clay
deposits.
MR. HARSVELDT: The composition of the furnish of the base paper
can alter the starch pick-up. In papers containing esparto, the pick-
up is normally higher than in those grades when hardwood pulps
are used. Softwood pulps will pick up more than will hardwood
pulps. Another factor plays a role, too. It will depend on the
make-up of the furnish to what degree the base sheet has to be
DISCUSSION
411
-------------------------------
rosin-sized. We have seen that the degree of rosin sizing in the base
paper can alter the starch pick-up. Generally, the composition of the
furnish together with the degree of rosin sizing decide the strength
of the starch solution and the molecular magnitude of the starch
to be used.
I think the best surface for the drying cylinder immediately
following the size press would be a chrome-plated finish. This is
seldom done; usually, the first two dryers following the size press
require doctors to remove the build-up of coating material from their
surface. Sometimes a baby dryer, operating at reduced temperature
to avoid sticking and provided with an oscillating doctor, is installed
immediately after the size press.
MR. J. A. HAAS: Could Mr. Harsveldt indicate how pick-up of the
starch solution is influenced by its contact time with the paper web
and also by the moisture content of the web entering the size press?
MR. HARSVELDT: In a fully rosin-sized base paper, the pick-up of
the starch solution is not affected by the moisture content of the sheet
as it enters the size press. If the rosin sizing is dec1 eased, the moisture
content of the sheet plays an important role. The most favourable
web moisture content is 6-20 per cent. Below and above this
moisture content, absorption of size decreases. In U.S.A. practice,
the sheet is fed in at 3-17 per cent. moisture content.
With the same quantity of starch solution present for impregnation,
the pick-up will increase with its contact time with the paper web.
MR. F. GLEDHILL: What angle does Mr. Harsveldt recommend for
the sheet entering the starch press on a papermachine making fine
papers at, say, 400 ft./min.?
MR. HARSVELDT: The angle at which the paper web enters the press
nip affects the height of the size barrier on the top side of the sheet;
Each mill must decide by trial and error the angle most suited to
its own conditions. Making the angle more acute gives greater
pick-up, making it steeper gives less pick-up. Nobody can recom-
mend a particular angle without having tried it out.
MR. R. TOMLINSON: What diameter would you make the starch
press rolls?
MR. HARSVELDT: The average diameter of the size press rolls is
24 in. Small diameter rolls give splashing troubles, but give less
coating pattern when starch/clay coatings are applied.
412 MODIFIED STARCHES AT THE SIZE PRESS
MR. B. H. TURNER: J. What is the most effective method of con-
trolling the starch pick-up on the papermachine?
2. ls it usual to drive both the top and bottom rolls in a size press?
3. Should the expander roll be driven and, if so, at what speed in
relation to the paper?
MR. HARSVELDT: J. The most effective method of controlling the
starch pick-up in the size press on a given base paper is controlling
the solids and viscosity of the starch solution.
A direct measurement on the paper could be done by incorporating
radioactive tracers in the size and measuring them in the sheet with
radioactive counting techniques.
2. Usually, the bottom roll of the size press is driven and the top
roll is driven by contact with the bottom roll and the paper. lt is a
good practice to drive both the top and bottom roll. When the press
is loaded and speeds are high, the top roll has a tendency to slip
on tbe starch size or coating on the paper. This can be avoided by
driving the top roll individually: if so, the roll speed is normally
maintained slightly below paper speed.
3. The task of the expander roll is to eliminate wrinkles and
creases in the sheet and to ensure that the sheet is correctly presented
to the first after-drying cylinder.
There should be as little tension on the paper as possible, so it
would appear a good practice to drive the expander roll in-
dependently at a slightly higher speed than the paper.
MR. A. L. OKELL: Did Mr. Harsveldt find that, despite the lower
speed of the paper (9 ft./min.) through his experimental size press
installation, he was able to correlate the results obtained on the
experimental press with those obtained at normal speeds on a full
size papermachine?
MR. HARSVELDT: The logarithmic proportion between viscosity and
pick-up has been established in papermachine practice. This is
referred to in a paper given by Dr. Arneberg in summer 1957 at
Baden-Baden, Germany (not yet published).
MR. A. BIRTWISTLE: What type of size press would Mr. Harsveldt
prefer to use for applying a clay coating-vertical or horizontal?
If a horizontal press is preferred, what type of rolls would he suggest
be used?
DISCUSSION 413
MR. HARSVELDT: For applying starch/clay coating, I prefer a size
press with hard rolls (one metal roll and one hard rubber roll or
two hard rubber rolls) that can be loaded up to a pressure of
350 lb./linear in. In the classical type of size press with vertically
mounted rolls, it is quite usual to apply high pressure. The horizontal
size press does not allow pressure at the moment; but, if the
horizontally mounted rolls are both hard and it is designed to apply
high pressures, a horizontal size press would do very well for
starch/clay coatings.
MR. J. H. POTTER: When starch is oxidised by sodium hypochlorite,
carboxyl groups are introduced into the molecule. The introduction
of these groups into the starch makes films of such starches more
hydrophilic than a modified starch with no carboxyl groups intro-
duced. Furthermore, there is a chemical reaction between electrolytes
and oxidised starches resulting in a marked fall in pH value. Such
a reaction will occur when oxidised starches are applied to papers
containing even minute traces of electrolytes. In advocating the use
of oxidised starches for general size press application, are you not
going against two of the primary requirements of the lithographer-
namely, a paper surface not unduly weakened by water and a stable
pH value greater than 4.8? .
The speaker's statements on roasted dextrins cannot be allowed
to pass without comment. Present day materials, produced by
roasting, do in fact possess film solubilities much lower than starches
converted by hydrochlorite oxidation. I must disagree therefore with
statements that roasted starches are unsuitable for sizing offset
papers and writing papers.
I should also like to point out to the papermakers present that the
low powder solubility of oxidised starches beam no relationship to
the solubility of its film when applied to paper.
MR. HARSVELDT: It is perfectly right that introducing carboxyl
groups into the starch molecule makes the starch more hydrophilic;
however, on the average, only one carboxyl g1oup is introduced into
ten glucose units, just sufficient to eliminate the set-back properties
of the starch. Work can then be done with a starch having as high
a molecule magnitude as possible and still possessing a good
stability. Because of the size of the molecule, the water resistance is
sufficient for offset printing.
Oxidised starches are supplied at a pH value between 6.5 and 7.
This means that the carboxyl groups are neutralised, giving partly
the sodium salt of a carboxylic acid; when electrolytes are present
414 MODIFIED STARCHES AT THE SIZE PRESS
in fair quantities, the sodium salt cannot behave like a cation
exchanger as the carboxylic acid would certainly behave. The
conclusion is that starches having a small part of their hydroxyl
groups substituted by carboxylic groups do not give any noticeable
exchange of sodium ions with hydrogen ions when neutralised.
On the use of roasted dextrins that contain a certain percentage of
coldwater soluble fragments of starch, 1 stressed that these small
fragments effect the film solubility. ln an oxidised starch, the
molecular size is homogeneous because of the wet manufacturing
process.