IMPACT OF COOKING CONDITIONS ON PHYSICAL STRENGTH OF EUCALYPTUS PULP

Nam Hee Shin and Bertil Stromberg

Andritz Inc
13 Pruyn’s Island Drive
Glens Falls, NY 12801

ABSTRACT

Laboratory studies using multiple white liquor additions and multiple black liquor extractions were
carried out to investigate the impact of cooking conditions on the physical strength of Eucalyptus pulp.
Results of these studies indicate that the bleached pulp tensile index cannot be predicted by
unbleached pulp tensile index. The variation of cooking conditions does not affect unbleached pulp
tensile index, but they do have an effect on bleached pulp tensile index. Both unbleached pulp cellulose
yield and pulp viscosity show a linear relationship with tensile index. However, unbleached pulp
cellulose yield shows a better correlation than pulp viscosity. Xylan content of pulp does not show any
effect on tensile index of either unbleached or bleached pulps. In contrast to tensile index, tear index
decreases with increasing both cellulose yield or pulp viscosity. In addition, the bleached pulp tear index
can be predicted by the unbleached pulp tear index.

Key words: White liquor profile, Unbleached, Bleached, Viscosity, Xylan, Cellulose yield

INTRODUCTION

Since the introduction of Lo-Solids® cooking in 1993, there are over 60 digesters around world using this
innovative cooking process. These mills reported many benefits such as better digester runability,
higher pulp yield and better bleachability. In addition, both hardwood and softwood mills reported a pulp
strength improvement as results of using the Lo-Solids cooking process. Especially hardwood mills
reported a significant improvement of tensile strength.

The mechanical properties of paper depend primarily on the morphological character of the individual
fiber and on the interaction between them. The general relationship between fiber morphology and
paper strength properties has been studied for various wood species (1, 2, 3). Fiber length has been
shown to have a significant impact on tear strength. At a given apparent density, the tear strength
increases with increasing fiber length. Meanwhile, the fiber length shows a minor influence on tensile
strength. In addition to the fiber length, fiber coarseness also has a morphological influence on the
paper properties. At similar fiber length and strength, coarser fibers form bulky sheets of high tear
strength but low tensile strength.

Another factor affecting the paper strength properties is fiber strength. The fiber strength is measured as
the wet zero-span tensile strength. A lower wet zero-span tensile strength measurement is often
obtained by either a lower cellulose content or a higher fiber damage. The correlation between fiber
strength and cellulose content was found up to 70~80% cellulose content. However, above that level,
factors other than cellulose content were found to be more important. In laboratory cooking, the fiber
damage usually indicates chemical damage which can be measured by the DP or viscosity of fiber.

There have been many attempts to compare softwood pulp strength properties with the varying
carbohydrate composition of pulp (especially hemicellulose content). One of the widely accepted
concepts is that increasing pulp yield with increasing hemicellulose yield decreases the tear index at a
given tensile index. A lower tear index is explained by a lower number of fibers per unit weight of paper
or higher rigidity in the fiber bonding due to higher hemicellulose content. However, this higher
hemicellulose yield was obtained mainly by the addition of additives instead of by changing the cooking
conditions.
As previously published paper (International Colloquium on Eucalyptus Kraft Pulp, 2003), the white
liquor profilings significantly affect not only pulp yield and viscosity but also delignification rate. The pulp
yield depends mainly on cellulose yield, and cellulose yield is significantly affected by alkali
concentration in the beginning of the cook. A higher cellulose yield is obtained by decreasing the EA
concentration. However, this lower alkali concentration negatively affects the delignification rate. This
study also indicated clearly that the xylan yield is varied to a minor extent and the variation in xylan
content does not reflect the variation in the pulp yield.

In this study, the effect of cooking conditions on Eucalyptus pulp strength is investigated.

RESULTS AND DISCUSSIONS

As described in the previous paper, Eucalyptus Urograndis chips from Brazil were cooked to different
kappa levels using the laboratory counter-current Lo-Solids cooking process. The total white liquor
addition was divided into three charges with varying total EA charges (18 to 24% EA charges) at
different cooking temperatures (145, 150, and 155oC) and a 680 H-factor. One more set of cooks was
done at 155oC and 1000 H-factor. Pulps of kappa range from 13.9 to 17.6 were oxygen delignified to a
10 kappa number and then bleached to 90%ISO using a D-E-D bleaching sequence.

Tensile Index

In order to study the impact of cooking conditions on pulp strength, the tensile index at 3000 PFI
revolutions was plotted as a function of unbleached pulp kappa number (Figure 1). For unbleached
pulps, all pulps show a similar tensile index. This means the variation of cooking conditions does not
affect unbleached pulp tensile index. On the other hand, bleached pulps show a very different trend.
The bleached pulp tensile index is significantly affected by the conditions in the cook. A decrease in
kappa number from 17.6 to 13.9 during the cook decreases the bleached tensile index by 14% from 101
Nm/g to 87 Nm/g. Evidently, low kappa number pulps lose more tensile strength during bleaching than

Unbleached pulp Bleached Unbleached pulp Bleached pulp

120 120
Tensile index @ 3000 rev., Nm/g
Tensile index @ 3000 rev., Nm/g

110 110

100 100

90 90

80 80

70 70

60 60
12 13 14 15 16 17 18 19 20 14.0 14.5 15.0 15.5 16.0 16.5

Unbleached pulp kappa number Xylan content, % in the pulp

Figure 1. Impact of degree of cooking on tensile Figure 2. Impact of xylan content of pulp on
strength. tensile strength.

high kappa pulps. This finding was unexpected because both 13.9 and 17.6 kappa unbleached pulps
have a similar tensile index and the 13.9 kappa unbleached pulp is oxygen delignified to the same
target kappa number under milder conditions than the 17.6 kappa pulp. In addition, both oxygen
delignified pulps were bleached to 90% ISO under identical bleaching conditions. This clearly indicates
that the variation of cooking conditions has a great influence on the bleached pulp strength properties.

The variation of kappa number with varying cooking conditions affects the carbohydrate compositions of
pulp (4) which is commonly believed to influence the tensile and tear strength. The improvement of the
pulp tensile strength is often explained by improving bonding strength and bonding area. Higher
bonding strength is usually obtained by maintaining a higher hemicellulose content in the fiber. For this
case, hemicellulose apparently acts to increase bonding strength. However, as shown in Figure 2, the
variation of xylan content of both unbleached pulp and bleached pulps does not affect the tensile index.
For the unbleached pulp, despite a variation of xylan content of the pulp from 16.1 to 14.9%, the same
tensile index is obtained. A similar trend can also be observed with the fully bleached pulps. The
variation of xylan content from 15.4 to 14.5% does not affect tensile index. All bleached pulps show a
similar tensile strength. This finding can be possibly explained by noting that the xylan content of pulp
may exceed a critical value that affects bonding strength, and as a result, xylan no longer impacts the
tensile index. As compared to unbleached pulp, the bleached pulp shows a wider variation of tensile
index at a given xylan content. The range of variation in the tensile index is from 87 to 100 Nm/g. This
clearly indicates that factors other than xylan content significantly affect tensile strength of pulp.

Since the variation of pulp yield depends mainly on the cellulose yield under different cooking
conditions, its impact on tensile strength of the bleached pulp is plotted in Figure 3. The bleached pulp
tensile strength shows a good linear correlation with the unbleached pulp cellulose yield. A higher
tensile index of bleached pulp is obtained from a higher unbleached pulp cellulose yield. When
unbleached pulp cellulose yield increases from 41 to 43%, the tensile index of bleached pulp increases
from 86 to 101 Nm/g.

The effect of pulp viscosity as a fiber strength indicator (5, 6) on the tensile index was evaluated. Figure
4 clearly demonstrates that pulp viscosity significantly affect the tensile index, especially the bleached
pulp tensile index. For unbleached pulps of different yields, tensile strength decreases slightly as pulp

Unbleached pulp Bleached pulp

120
Tensile index @ 3000 rev., Nm/g

120
Tensile index @ 3000 rev., Nm/g

110

110
100
100
90
90

80
80

70 70

60 60
40.0 40.5 41.0 41.5 42.0 42.5 43.0 43.5 44.0 1000 1100 1200 1300 1400 1500 1600 1700

Unbleached pulp cellulose yield, % on wood Pulp viscosity, dm3/kg

Figure 3. Impact of unbleached pulp cellulose Figure 4. Effect of pulp viscosity on tensile
yield on tensile strength of the bleached pulp. strength.

viscosity decreases from 1640 to 1340 dm3/kg. However, bleached pulps show a quite different trend.
Tensile strength of pulp is directly proportional to pulp viscosity. Changing bleached pulp viscosity from
1310 to 1100 dm3/kg decreases the tensile strength by 15 units from 101 to 86 Nm/g. This clearly
indicates that decreasing the viscosity value below a certain level significantly affects the tensile
strength due to a loss of fiber strength.
The positive impact of cooking to a higher kappa number on the bleached pulp tensile index seen in
Figure 1 can be explained by the higher bleached pulp viscosity. Due to the fact that the viscosity loss
during the bleaching is affected in a similar way for both high and low kappa pulps, a higher bleached
viscosity is obtained from a high kappa pulp (Figure 5).

These results clearly indicate that the selection of cooking conditions which produce higher pulp
viscosity and higher cellulose yield is the key factor to produce a higher tensile index bleached pulp.

Unbleached pulp Bleached 145 C 150 C 155 C

1700 45

Cellulose yield, % on wood

1600 44
Pulp viscosity, mPa.s

1500 43

1400 42

1300 41

1200 40

1100 39

1000 38
12 13 14 15 16 17 18 19 20 0 2 4 6 8 10 12 14

Unbleached pulp kappa number EA concentration at the end of lower cook, g/l

Figure 5. Effect of bleaching on pulp viscosity. Figure 6. Effect of black liquor concentration at the
end of lower cook on cellulose yield.

As described in the previous paper (4), the black liquor EA concentration at the end of the lower cook
zone (at the end of bulk delignification) shows a good correlation with cellulose yield. Cellulose yield
increases by decreasing the black liquor EA concentration (Figure 6) regardless of cooking temperature.
When the tensile strength of bleached pulps is plotted as a function of PFI revolutions at a given white
liquor charge and H-factor (Figure 7), it demonstrates clearly there is no effect of cooking temperature
on the bleached pulp tensile strength. All three cooking temperatures of 145, 150, and 155oC show the

145 C-680H 150 C-680H 155 C-680H 18% 20% 22% 24%

120 120
110
100
100
Tensile index, Nm/g

Tensile index, Nm/g

90
80
80
60 70
60
40
50
40
20
30
0 20
0 1000 2000 3000 4000 5000 6000 0 1000 2000 3000 4000 5000 6000

PFI, revolutions PFI, revolutions

Figure 7. Impact of cooking temperature on tensile Figure 8. Impact of alkali charge on tensile
strength. strength.

same tensile strength development. On the other hand, a variation in cooking chemical charge shows a
significant effect on the bleached pulp tensile strength (Figure 8). At 145oC cooking temperature and
680 H-factor, an increase in the white liquor charges decreases the bleached pulp tensile strength. This
result clearly indicates that a higher bleached pulp tensile strength can be obtained by reducing the
white liquor charge.

145-D1-BL-680 155-D1-BL-1000 145-D1-BL-680 155-D1-BL-1000

1500 120
Bleached pulp viscosity, dm3/kg

BL pulp tensile index, Nm/g

1400 110

1300 100

1200 90

1100 80

1000 70

900 60
10 11 12 13 14 15 16 17 18 19 20 900 1000 1100 1200 1300 1400 1500

Kappa number Bleached pulp viscosity, dm3/kg

Figure 9. Effect of H-factor on bleached pulp Figure10. Effect of bleached pulp viscosity on
viscosity. bleached pulp tensile strength.

In order to cook to the same target kappa number, decreasing white liquor charge requires an increase
in H-factor. Since cooking temperature did not show any negative effect on the bleached pulp tensile
strength, in this study, H-factor was increased only by increasing cooking temperature.

As shown in Figure 9, a higher H-factor cooking at a higher temperature does not show any negative
impact on the bleached pulp viscosity. Pulps produced from 1000 H-factor at 155oC show the same
bleached pulp viscosity at a given kappa number as pulps produced from 680 H-factor at 145oC.
Bleaching the same kappa number pulps should show no difference in the bleached pulp tensile
strength due to the same bleached pulp viscosity. However, results in Figure 10 show an unexpected
trend. Bleached pulps produced from high H-factor cooking show a higher tensile index at a given

145-D1-BL-680 155-D1-BL-1000 145-D1-BL-680 155-D1-BL-1000

44 120
BL pulp tensile index, Nm/g
Cellulose yield, % on wood

110
43
100

42 90

80
41
70

40 60
10 11 12 13 14 15 16 17 18 19 20 40 41 42 43 44

Kappa number UBL pulp cellulose yield, % on wood

Figure 11. Effect of H-factor on unbleached pulp Figure12. Effect of unbleached pulp cellulose yield
cellulose yield. on bleached pulp tensile strength.

bleached pulp viscosity than those produced from low H-factor cooking. The positive impact of a high H-
factor on the bleached pulp tensile strength can be explained by a higher unbleached pulp cellulose
yield (Figure 11). The results shown in Figure 12 clearly demonstrate that the bleached pulp tensile
strength show a better correlation with the unbleached pulp cellulose yield than the bleached pulp
viscosity. This finding leads us to believe that the cellulose yield may have a greater influence on tensile
index than pulp viscosity. However, this cellulose yield can be used only as a guiding factor to improve
tensile index. It is still not clear which fiber characteristics are modified or changed with the variation of
cellulose yield and how these characteristics affect the tensile strength.

Tear Index

In contrast to tensile index, tear index shows quite a different trend when the tear index at 3000 PFI
revolutions is plotted against unbleached pulp kappa number. For unbleached pulp, a linear correlation
is found between tear index and unbleached pulp kappa number. Unbleached pulp tear index increases
from 10 to11 mNm2/g with decreasing kappa number from 17.6 to 13.9. A similar trend is also obtained
from the bleached pulp (Figure 13). Another interesting finding is the bleached pulp shows a higher tear
index than unbleached pulp and the bleached pulp increases one unit of tear index regardless of
unbleached pulp kappa number. This means that the bleached pulp tear index can be predicted from
the unbleached pulp tear index.

Pulp viscosity and cellulose yield are an indirect measure of fiber strength. As previously discussed,
tensile index decreases with decreasing pulp viscosity below a critical value. Above this critical value,
pulp viscosity does not affect tensile index. In addition, the cellulose yield also shows a similar trend as
pulp viscosity. This means fiber strength shows an important role on tensile index.

Unbleached pulp Bleached Unbleached pulp Bleached pulp

14 14
Tear index @ 3000 rev., mNm2/g

Tear index @ 3000 rev., mNm2/g

13 13

12 12

11 11

10 10

9 9

8 8
12 13 14 15 16 17 18 19 20 1000 1100 1200 1300 1400 1500 1600 1700

Unbleached pulp kappa number Pulp viscosity, dm3/kg

Figure 13. Effect of degree of cooking on tear Figure 14. Effect of pulp viscosity on tear strength.
strength.

The effect of pulp viscosity on tear index is shown in Figure 14. Both brown and bleached pulps show
that tear index increases with decreasing pulp viscosity. This finding is also true when tear index is
plotted as a function of cellulose yield (Figure 15). Tear index decreases with increasing cellulose yield.
Both results suggest that fiber strength does not have any significant role in the improvement of tear
index. The trend shown in Figure 15 is consistent with the fact that a lower yield pulp contains more
fibers per unit weight of pulp. A lower pulp yield is obtained with a lower cellulose yield.

The effect of xylan content in pulp on tear index is shown in Figure 16. The general trend is that tear
index increases with decreasing xylan content. Unbleached pulps show the range of tear index from 10
to 11.5 mNm2/g with xylan content ranging from 16.2% to 14.8%. After bleaching, the pulps show a
higher tear index range from 11 to 12.2 mNm2/g at a lower xylan content from 15.3% to 14.4%.
However, the variation of tear index at a given xylan content is too large to conclude that xylan content
significantly affects tear index.
 Unbleached pulp Bleached pulp Unbleached pulp Bleached pulp

14 14
Tear index @ 3000 rev., mNm2/g

Tear index @ 3000 rev., mNm2/g

13 13

12 12

11 11

10 10

9 9

8 8

7 7
40 41 42 43 44 14.0 14.5 15.0 15.5 16.0 16.5

Unbleached pulp cellulose yield, % on wood Xylan content, % in the pulp

Figure 15. Effect of unbleached pulp cellulose Figure 16. Effect of xylan content on tear strength.
yield on tear strength.

Mill Results

Lo-Solids Cooking is a unique cooking method maintaining both lower dissolved wood solids and lower
alkali concentration throughout the cook. As shown in a four screen single vessel digester (Figure 17),
post impregnation liquor which is relatively high in dissolved wood solids is removed through the first set
of extraction screens. The first white liquor charge which is added through the chip feed system is
controlled mainly by maintaining the black liquor EA concentration between 3 and 8 g/L as NaOH.

White Liquor
Chip In

Impregnation Extraction
Liquor Out

Upper Cook White

Liquor

Lower Cook
Cold Blow

Extraction
Liquor Out

Wash zone
White
Liquor

Cold Blow
Pulp Out

Figure 17. Four screen single vessel Lo-Solids

digester configuration.
The second white liquor and cold blow are added into the lower cooking circulation: the second set of
extraction screens. Makeup liquor is uniformly distributed throughout the column by means of the
counter-current flow in the upper cook zone and bulk delignification is continued in the lower cooking
zone between the second and main extraction (the third set) screens.
The final white liquor charge is added at the bottom of digester with the counter-current flow in the wash
zone or into the main extraction circulation with the con-current flow in the wash zone.

As discussed previously, the laboratory study clearly demonstrated that the black liquor EA
concentration at the end of lower cook has a significant impact on cellulose yield and
bleached pulp tensile strength. An increase in black liquor EA concentration results in decreasing both
cellulose yield and bleached pulp tensile strength. An interesting finding is that mill bleached pulp
produced from the same Eucalyptus using other cooking processes also shows the same linear
relationship between the bleached pulp tensile strength and black liquor EA concentration at the end of

Lab bleached pulp Mill bleached pulp Lab bleached pulp Mill bleached pulp

120 120
Tensile index @ 3000 rev., Nm/g

Tensile index @ 3000 rev., Nm/g

110 110
Other processes
100 100

90 90

80 80
Lo-Solids
Cooking
70 70

60 60
0 2 4 6 8 10 12 14 16 800 900 1000 1100 1200 1300 1400

EA concentration at the end of lower cook, g/l Pulp viscosity, dm3/kg

Figure 18. Effect of black liquor EA concentration at Figure 19. Comparison of mill and lab pulps
the end of lower cook on mill pulp tensile strength. tensile strength against pulp viscosity.

the lower cook stage as the lab produced pulp. The mill using this other cooking process maintains 14
to 16 g/L EA concentration at the end of the lower cook stage compared to 5 to 10 g/L in a Lo-Solids
cook. As shown in Figure 18, an increase in black liquor concentration to 14 g/L at the end of the lower
cook stage results in decreasing the bleached pulp tensile strength. The pulp viscosity of mill bleached
pulp also shows a good correlation with the bleached pulp tensile strength (Figure 19).

CONCLUSIONS

• A higher bleached pulp tensile index is obtained from higher kappa unbleached pulp.
• Xylan content in pulp does not affect tensile index.
• Unbleached pulp cellulose yield shows a better correlation with bleached pulp tensile index than
pulp viscosity.
• Selection of cooking conditions that produce a higher unbleached pulp cellulose yield and pulp
viscosity is the key factor to improve bleached pulp tensile index. The cooking chemical charge
is a more critical parameter to be controlled than the cooking temperature.
• Higher tear index is obtained from pulp that has a lower pulp viscosity and cellulose yield.
• As compared to unbleached pulps, bleached pulps show a lower xylan content and higher tear
index but this higher tear index can not be explained by lowering the xylan content due to a
large variation of tear index at a given xylan content.
• In the mill, lowering black liquor EA concentration at the end of lower cook is the key factor for
improving the bleached pulp tensile strength.
REFERENCES

1. Francisco N. Tamolang, Frederick F. Wangaard, Robert M. Kellogg, Tappi Journal, 51:1, 19-25
(1968).
2. N. Gurnagul, D.H. Page, R.S. Seth, Journal of pulp and paper science, 16:1, J36-J41 (1990).
3. R.S. Seth, D.H. Page, Tappi Journal, 71:1, 103 – 107 (1988).
4. Nam Hee Shin, Bertil Stromberg, International Colloquium on Eucalyptus Kraft Pulp, September
4 and 5 2003, Vicosa, Brazil.
5. Norayr Gurnagul, D.H. Page, Michael G. Paice, , Nordic Pulp and Paper Research Journal no.
3/1992, 152-154.
6. Jian Li, Geoffery Moeser, Laura Roen, Ind. Eng. Chem. Res. 2000, 39, 916-921.