NBSIR 73-274 00

Evaluation of Currency and

Stamp Papers

E. L. Graminski and E. E. Toth

Paper Evaluation Section

Institute for Materials Research

National Bureau of Standards

Washington, D. C. 20234

August 15, 1973

Progress Report covering the period

January 1 - June 30, 1973

Prepared for Bureau of Engraving and Printing

U.S. Department of the Treasury

Washington, D. C. 20401

CONTENTS

Page

1. SUMMARY 1

2. DEVELOPMENT OF A BEATER SCHEDULE FOR

A LABORATORY BEATER 3

2 . 1 Background 3

2.2 Experimental 5

2.3 Results and Discussion 5

3. EFFECT OF MELAMINE RESIN ON THE RETENTION OF

STIFFNESS OF CURRENCY PAPER WITH FLEXING .... 6

3.1 Background 6

3.2 Experimental 6

3.3 Results and Discussion 7

4. MODIFICATION OF WOOD PULP HANDSHEETS BY

TREATMENT WITH ACRYLIC LATEXES 8

4 . 1 Background 8

4.2 Experimental 8

4.3 Results and Discussion 9

5. MODIFICATION OF HANDSHEETS MADE FROM CURRENCY

STOCK BY TREATMENT WITH ACRYLIC LATEXES 11

5.1 Background 11

5.2 Experimental 11

5.3 Results and Discussion 12

6. BIBLIOGRAPHY 13

1. SUMMARY

As part of a continuing study for the Bureau of Engraving

and Printing of the U.S. Department of the Treasury, the

effect of melamine resin on the retention of bending stiffness with flexing and the possibility of improving the stiffness retention of paper by treatment with acrylic resins was

studied. Work was initiated on the development of a method,

using a commercial laboratory beater, for refining rag pulp

to produce a high degree of fibrillation with minimum cutting

of the fibers.

Several years ago it was demonstrated that currency

printed on dry-print paper has a longer circulation life than

currency printed on wet-print paper. The latter is no longer

in use. The fiber furnish of dry-print paper differs from

that of the old wet-print paper and, in addition, dry-print

paper contains melamine resin and glycerine. It was not known

up to now which change (s) was responsible for the improved

circulation life.

The effect of one of the constituents--melamine resinon the retention of bending stiffness with flexing was evaluated. Handsheets were prepared from currency paper beater

stock and were treated with various quantities of the same

wet strength resin used in currency paper. The retention of

stiffness was determined by flexing the handsheets on the

NBS paper flexing apparatus and measuring the decrease in

stiffness after flexing. The results demonstrate that the

wet strength resin improves stiffness retention to a marked

degree and indicates that the wet strength resin may be

singularly responsible for most, if not all, of the improvements in circulation life of dry-print currency paper. The

results also suggest that even greater improvements in stiffness retention might be possible by a more deliberate development of physical properties by mechanical refinement of the

pulp in combination with wet strength resin.

Previous work on improving retention of cantilever stiffness with flexing by treatment of paper with acrylic latexes

indicated a relationship between the retention of bending

stiffness and the stiffness of the polymer used to modify the

paper. Therefore, a group of acrylic resins, having a wide

range of film stiffness, was used to modify wood pulp handsheets and to determine their effect on stiffness retention

with flexing. The retention of stiffness was evaluated with

2

the aid of the NBS paper flexing apparatus. The results

indicate that there is a good correlation between polymer

stiffness and retention of stiffness of paper with flexing,

but beyond a certain polymer film stiffness little, if any,

improvement in retention of paper stiffness is produced.

In addition to the work with wood pulp handsheets , the

performance of handsheets made from currency stock saturated

with acrylic polymers was evaluated. The polymers investigated had a wide range of film stiffness. Modification of

the handsheets and test evaluations were the same as those

used on the wood pulp handsheets. The results were in good

agreement with those obtained with wood pulp handsheets,

indicating that it should be possible to improve the stiffness retention of currency type paper with acrylic resins.

The work performed in developing a method for beating

rag pulps with a laboratory beater was inconclusive, and

additional work must be done. More work also is needed on

optimizing the retention of bending stiffness with flexing

by treatment of paper with acrylic resins.

3

2. DEVELOPMENT OF A BEATER SCHEDULE FOR

A LABORATORY BEATER*

2 . 1 Background

The term "beating" is used in the paper industry to

describe the mechanical treatment of fibers in a water medium.

Beating involves fiber separation, fiber cutting, and "fibrillation," or fraying, of the fibers. The term beating originated from the practice, in the early days of papermaking, of

impacting a wet mass of pulp in a machine similar to the

familiar laboratory mortar and pestle.

The laboratory beater used in this study is similar to

the so-called Hollander beater. This beater and its action

has been well described by Casey [1]

"The Hollander beater consists of an elongated tub with

a dividing partition, or midfeather, which stops short of

both ends of the tub. A beater roll equipped with metal bars

set across the width of the roll circulates the stock in the

tub, and at the same time works the fibers against bars set

in a bedplate under the roll. The amount of action is controlled by raising or lowering the beater roll relative to

the bedplate. There have been many modifications of this

basic design of the old Hollander beater over the years, but

none of the radical changes have proven to be very practical.

"The beater has a number of functions: it can beat or

fibrillate the stock; it can be used to cut the fibers; or it

can be used for mixing and blending the stock and the nonfibrous materials. The beater is sometimes used as a washing

device and as a bleacher. However, the action of the beater

is primarily of a rubbing or crushing nature whereby the

fibers are subjected to a succession of hammer-like blows

or impacts

.

"Dull beater roll bars, high consistency of stock, and

low temperature favor the rubbing or brushing action. On the

other hand, if the consistency is low, the knives sharp, and

the beater roll is put down hard on the bedplate, the action

becomes predominantly of a cutting nature. In general, beaters

with dull bars produce papers with higher bursting, tensile,

and tearing strengths than beaters with sharp bars. Special

beater rolls made of basalt lava can be used to produce a high degree of bruising action or "wet" beating such as is

required for glassine.

4

". . .In general, beating improves some properties and

has a bad effect on others. Thus, the papermaker must select

the proper beating conditions to bring out certain properties

without detracting too much from other properties. Beating

must not be carried out so that any one property is emphasized

too much, since this may detract from another property. By

changing the beating procedure, it is possible to produce

papers from the same pulp possessing radically different

properties

.

"In general, increased beating within the commercial

range increases bursting strength, tensile strength, and

folding endurance, but generally tends to decrease tearing

resistance. Stretch increases on beating, with the greatest

increase obtained by beating at the highest consistency. Increased beating tends to increase smoothness, hardness, and

amount of fiber bonding of the fibers, but on the other hand,

tends to decrease the opacity and lower the bulk and dimensional stability of the paper."

The purpose of developing a beater schedule for rag

pulps with a laboratory beater is to obtain handsheets with

good strength properties with minimum cutting of fibers. To

achieve this, the pressure on the bedplate must be applied

gradually over a period of time. If the pressure on the bedplate is applied too rapidly, serious degradation of the fiber

occurs. The resulting handsheets may have good strength, but

their ability to withstand flexing will be poor. The general

procedure is described in reference [2].

Current work has been directed toward obtaining information on changes in fiber length distribution with beating.

The relationship between beater schedule and sheet properties

will be done later.

Changes in fiber length were estimated with a laboratory

fiber classifier [3] . One change was made in the fiber classification procedure reported previously [4]. Five instead

of 10 grams of dry fiber were used for each determination, as

the reduced quantity of fibers permitted full water flow

through the classifier. Otherwise, the longer-f ibered masses

acted as filters and retained part of the shorter fibered

fractions that normally would have passed through this size

screen

.

5

2 . 2 Experimental

The beating procedure was as follows: The cotton pulp

(360 grams) was torn into pieces approximately 2 inches

square, and soaked overnight in 20 liters of water in an 88

liter stainless steel container. The following day, the

mixture was agitated for 1 hour with a propeller stirrer.

The mixture was then transferred to the beater, and the

stainless steel container was rinsed with 1 to 1 1/2 liters

of water. The water level in the beater was then brought

to 23 liters, which had been previously determined and marked.

The roll was started while the bedplate lever arm was

supported so that no possible contact with the roll could

occur. After circulation had proceeded for 1 to 2 minutes,

the bedplate lever arm was released, but no weight was placed

on it. The lever arm was counterbalanced so no force was

exerted on the roll when the beater contained 23 liters of

water. The time of beating was considered to have started

at the moment the bedplate lever arm was released.

Aliquots were removed from the beater at definite time

intervals of beating under varying load conditions. Just

prior to taking aliquots, the bedplate lever arm was raised

to stop the beating action while the roll continued to rotate

to ensure good mixing. Three samples were taken at each

interval, two for fiber classification and one for the weight

control

2 . 3 Results and Discussion

The results of two beater runs are given in Table 1A.

The only difference between the two runs was the time of

beating at each load level, but the results are greatly different. Of significance is the gradual decline in fraction V

in run 2 during the first 3 hours of beating, accompanied by

a slight increase in fractions I through IV. As beating continued, fraction I declined and fractions II through V increased.

The gradual decline in fraction V during the first hours

of run 2 could be due to fibrillation. As the fibers are

fibrillated, the formation of a mat on the screen occurs

sooner and is more complete at an earlier time than with unfibrillated fibers. More small fibers and debris are trapped

on the larger screens, resulting in a decline in fraction V.

This will be verified in subsequent work on developing a beater schedule.

6

3. EFFECT OF MELAMINE RESIN ON THE RETENTION OF

STIFFNESS OF CURRENCY PAPER WITH FLEXING

3 . 1 Background

Previous work [5] with wet strength resins indicated

that the increase in circulation life between the mill wetand dry-print currency paper may be due to the melamine resin

used in the dry print paper and, to a lesser degree, to the

fiber content. More work has been done to determine whether

the wet strength resin was indeed the major factor in increased

circulation life.

3 . 2 Experimental

Some beater stock for currency paper was obtained from

the manufacturer of currency paper, and handsheets (70 g/m ) containing different quantities of wet strength resin were

prepared from the stock.

The beater stock came in two containers labeled cotton

and flax. It was assumed that the containers consisted of

100 percent of each pulp. The stock was mixed accordingly to

produce handsheets containing 75 percent cotton and 25 percent linen. However, it was later determined that the container marked flax consisted of a 1-1 mixture of cotton and

linen. Consequently, the resulting handsheets contained 87

percent cotton and 13 percent linen. Since the purpose of

this investigation was to determine the effect of melamine

resin on the retention of stiffness of currency paper, the

difference in the fiber composition from regular currency

paper was not considered to be an important factor.

Sufficient water was added to the stock in a stainless

steel container to make a 1 percent consistency. Aliquots

were taken (approx. 650 cm^) , diluted with- 1000 cm^ tap water,

and disintegrated for 7500 revolutions with a British disintegrator [2]. The contents were then transferred to 2-liter

beakers and enough 12 percent solution of melamine resin was

added to each beaker so that it contained either 3 or 9 percent resin based on the weight of fiber. The pH of the

mixture was 4.15 with 3 percent resin and 3.45 with 9 percent

resin. The mixture was stirred frequently during a 30

irinute interval. Since no change in pH was observed during

the time of treatment, no adjustment of the pH with aluminum

sulfate was necessary in order to obtain good resin adsorption.

7

The mixture was then transferred to the deckle box of

the handsheet machine and a sheet was formed. A quick check

on the wet strength of the handsheets indicated that the

resin was insufficiently cured. Therefore, the handsheets

were placed in an oven at 105°C and cured for 1 hour. Following curing, the wet strength was approximately 50 percent

of the dry strength. One half of each 12 x 12 inch handsheet

was flexed 1000 times over 1/8 inch rollers, and the other

half was used as an unflexed control.

3 . 3 Results and Discussion

The results of the physical tests of flexed and unflexed

paper are given in Tables 2 and 3, and the standard deviations

of the data are given in Tables 4 and 5.

The wet strength resin produced a significant improvement in the retention of cantilever stiffness. These results

strongly indicate that the increase in circulation life of

currency printed on dry-print currency paper is due to the

melamine resin added to the paper and not to the change in

fiber composition.

There is a marked decrease in air permeability of the

sheets containing melamine resin. It is unlikely that the

resin forms a film during sheet formation which could account

f or the decline in air permeability. In any case, the addition of the melamine resin must, in some way, increase sheet

density or affect the structure of the sheet. Perhaps the

resin causes the debris and fibrils to form a network in the

interstices of the sheet and produce a film-like material in

currency paper, as has been shown in earlier reports [4, 6, 7].

With the exception of wet strength, melamine resin has

the greatest effect on folding endurance of all the physical

properties evaluated. The increase in folding endurance is

almost 10 fold at the highest level of treatment. Previous

work performed at NBS [8, 9, 10] showed that currency type

paper, which has a folding endurance equal to or exceeding

that of the present currency paper, can be produced without

melamine resin. Limited work with melamine resin on some

experimental currency-type papers [10] indicated that the

folding endurance of the high fold paper could be increased

further with the addition of melamine resin. It would be of

great interest to evaluate the durability of a currency-type

paper whose folding endurance is developed to a maximum through

mechanical refinement followed by treatment with melamine resin.

8

4. MODIFICATION OF WOOD PULP HANDSHEETS BY

TREATMENT WITH ACRYLIC LATEXES

4 . 1 Background

In the last NBS Report [11] to BEP , it was shown that

modification of paper with acrylic latexes, either by beater

addition or paper saturation, improves the retention of

stiffness with flexing. Paper saturation was superior to

beater addition, and there appeared to be a correlation

between the retention of stiffness of the paper with flexing

and the film stiffness of the polymer. In order to confirm

this, wood pulp handsheets were treated with four acrylic

latexes having a wide range of film stiffnesses.

4 . 2 Experimental

Four acrylic latexes were used in this investigation

and are designated as K— 3, HA— 8, HA— 16, and AC— 201. A relative parameter of film stiffness is the temperature (T3Q0

)

at which the torsional modulus of an air dried film is

300 kg/cm 2 . The respective temperatures for ^200' which were

estimated by the manufacturer for the four latexes used in

this investigation, are as follows:

Latex K-3 HA8

HA- 15 AC-201

T °c 300' U -32 -14 33 45

This represents a much wider range of film stiffness than

was investigated previously [11].

A bleached kraft wood pulp was beaten in a PFI laboratory mill at 10 percent consistency, with no clearance between

bedplate and roll, for 5,000 revolutions at 3.4 kilograms

force and a relative velocity of roll to bedplate of 6 m/sec.

The beating was done in distilled water. A total of 920 g

pulp was beaten in 23 separate charges and then combined in

a large stainless steel container. The pulp was diluted with

sufficient distilled water to make a 1 percent suspension and

was stirred vigorously for 1 hour prior to handsheet preparation. Aliquots of the 1 percent suspension were treated in

9

the British disintegrator for 7,500 revolutions, transferred

to the deckle box of the handsheet mold, and sheets were made

in the usual way. Each sheet was weighed after drying and

only those sheets whose weight per unit area was 70 g/m^ + 5

percent were retained. The sheets were then separated into

10 groups of 6 sheets each by a random selection.

The paper saturation was performed as follows: The

felts which are used in wet pressing of handsheets were

saturated with either a 5 or 10 percent emulsion of the

acrylic. A handsheet was placed between felts and passed

through the calender rolls on the sheet machine. The excess

latex was squeezed out, saturating the paper with latex. As

the felt and paper proceeded through the rolls, the excess

latex in the paper was squeezed out. The wet sheet saturated

with acrylic was lifted from the felt and dried on the drying

drum at 95°C for approximately 3 minutes. The weight of the

sheet was determined after drying and by difference the percent of polymer in the sheet was determined.

The effect of acrylic resins on the retention of physical

properties was evaluated by determining the decline in physical properties after 1000 double flexes over 1/8 inch rollers

on the NBS paper f lexer.

4 . 3 Results and Discussion

The results are given in Tables 6-9, and the standard

deviation of the results are given in Tables 10-13.

The effect of the acrylic latexes on the extensional

and plastic stiffn€?ss of wood pulp handsheets was dependent

on the film stiffness of the acrlyic polymers. Handsheets

treated with polymers having a T3QQ less than 0°C had an

extensional stiffness lower than the control, while handsheecs

treated with the two latexes having a T 30 q above 0°C resulted

in an increase in extensional stiffness. The other tensile

properties behaved similarly except that handsheets treated

with AC-201 (T3QQ = 45°) showed no increase or a slight decrease in properties over those treated with HA-16 (T 3 qq = 33)

.

In other words, as T 3 qq increased above 33°C, the relationship between film stiffness and tensile properties did not

hold.

10

In general, Elmendorf tear decreased with increasing

film stiffness. There appeared to be little if any relationship between film stiffness and folding endurance. Sonic

modulus increased with torsional stiffness, but the increase

appeared to level off as ISqq increased above 33°C. Cantilever

stiffness decreased when the handsheets were modified with

soft acrylic latexes and approached the stiffness of handsheets prepared in the regular manner as the polymer stiffness

increased. As expected, air permeability declined after

saturation with acrylic latexes.

The polymers having a T-^qq below 0°C did not produce

satisfactory improvements in stiffness retention with flexing.

It is quite apparent that the very soft polymers are unsatisfactory for improving stiffness retention. Both of the

polymers having T^qq above 0°C did improve stiffness retention significantly (two sided t test). However, stiffness

retention was appreciably better with HA-16 (T-^qq =' 33°) than

with AC-201 (T 300 = 45°), which is the stiffest polymer that

has been evaluated. Apparently, AC-201 forms a brittle film

that cracks during flexing as indicated by the substantial

increase in air permeability after flexing. The cracking of

the polymer film would be analagous to the cracking of the

matrix in currency paper [4],

The above results indicate that there is a relationship

between the stiffness of the acrylic polymer used in paper

saturation and the retention of stiffness with flexing. However, there apparently is an optimum polymer stiffness beyond

which little if any improvement in stiffness retention occurs.

11

5. MODIFICATION OF HANDSHEETS MADE FROM CURRENCY

STOCK BY TREATMENT WITH ACRYLIC LATEXES

5 . 1 Background

All of the evaluations of acrylic latexes so far have

been performed on wood pulp handsheets. As cotton and linen

are used in the manufacture of currency paper and as different

pulps respond differently to latex treatments, it was necessary to determine the effect of acrylic latexes on the retention of stiffness of handsheets made from currency stock.

The latexes chosen for this study had been used previously

on wood pulp handsheets.

5 . 2 Experimental

Five acrylic resins having a wide range of film stiffness were used in this investigation. The designations of

the five latexes and their T^

nf) temperatures are as follows:

Latex K-3 P-339 AC-61 HA- 16 AC-201

T °C -32 3 16 33 45

Each of the latexes has been evaluated previously on wood

pulp handsheets and the results were reported either in

section 4 of this report or in the last NBS Report [11]

.

The method of treatment is described in section 4.2 of

this report, except that the handsheets were made from currency stock. The fiber composition was 8 7 percent cotton

and 13 percent linen. The results before and after flexing

1000 times over 1/8 inch rollers are given in Tables 14 and 15,

and the standard deviation of the data are given in Tables

16 and 17.

12

5 . 3 Results and Discussion

The best improvement in stiffness retention occurred

with the polymers having a T^qq of 16°C or higher. Of the

three latexes falling into this category, AC-61 (T^qo = 16°)

appeared to produce the greatest improvement in stiffness

retention. Handsheets treated with AC-61 also contained a larger amount of polymer, and this factor may be partially

responsible for the better performance. Nevertheless, it is

apparent that modification of handsheets with acrylic latexes

can lead to an improvement in stiffness retention with

flexing. Still another factor to be considered is that none

of the handsheets were treated with melamine resin. Conceivably, a combination of wet strength resin and acrylic latex

may result in still further improvement of stiffness retention .

13

6. BIBLIOGRAPHY

1. Casey, James P., Pulp and Paper, Vol II: Papermaking,

Interscience , Second Edition, pages 582, 583, 595, and

596 (1960).

2. TAPPI Method T 200 os-70, Laboratory Processing of Pulp

(Beater Method)

3. TAPPI Method T 233 su-64, Fiber Length of Pulp' by

Classification.

4. Graminski, E. L. and Toth, E. E., Evaluation of Currency

and Stamp Papers, NBS Report 10 336, September 17, 1970.

5. Graminski, E. L. and Toth, E. E., Evaluation of Currency

and Stamp Papers, NBS Report 10 912, October 2, 1972.

6. Graminski, E. L. and Toth, E. E., Evaluation of Currency

and Stamp Papers, NBS Report 10 465, August 9, 1971.

7. Graminski, E. L. , Toth, E. E., and Smith, M. A., Evaluation of Currency and Stamp Papers, NBS Report 10 802,

February 15, 1972.

8. Shaw, M. B. and Bicking, G. W. , Research on the Production

of Currency Paper in the Bureau of Standards Experimental

Paper Mill, Tech. Pap. BS 21, 89 (1926-27) T329.

9. ^haw, M. B. and Bicking, G. W. , Further Experimental

Production of Currency Paper in the Bureau of Standards

Paper Mill, NBS J. Res. 3, 899 (1929) RP 121.

10. Carson, F. T. and Shaw, M. B., Wearing Quality of Experimental Currency-Type Paper, J. Res. NBS 3_6 , 249 (1946),

RP 1701.

11. Graminski, E. L. and Toth, E. E., Evaluation of Currency

and Stamp Papers, NBSIR 73-124 (January 30, 1973).

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