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50 °C, is illustrated graphically in Fig. 11.29.

0 2 4 6 8

0

5

10

15

20

HW-Sulfite HW-PHK

Chain Scissions [104/DP

w,t

-104/DP

w,0

]

Ageing time at 50 °C [h]

Fig. 11.29 Course of chains scissions (based on weighted

molecular weight) of alkali celluloses prepared from hardwood

sulfite and PHK dissolving pulps as a function of time

at 50 °C.

The ageing of alkali cellulose follows a pseudo zero-order reaction kinetics

based on the number-average degree of polymerization DPn, according to the following

expression [56]:

104

DPn_t _

104

DPn_0 _ _ kA t _1_

where kA is the reaction rate of the ageing process.

1057

11 Pulp Properties and Applications

The deviation from linearity, which is particularly discernible for alkali cellulose

made from a hardwood sulfite pulp, can be attributed to the change (decrease) in

polydispersity during degradation. Based on today’s knowledge of the reaction

mechanism, chain scission is initiated by the reducing endgroups. In agreement

with these considerations, oxidative alkaline degradation of sulfite pulp proceeds

faster as compared to the more narrowly distributed PHK dissolving pulp (see

Fig. 11.29).

The arguments in favor of electron beam treatment of dissolving pulp are a better

control of viscosity degradation following a strict random scission mechanism,

which results in better reactivity towards derivatization due to a better accessibility

In the crystalline regions.

Hardwood sulfite and PHK dissolving pulps were irradiated by means of a 10 MeV

accelerator, applying dosages of between 0 and 30 kGy (Fig. 11.30).

0 10 20 30

0

5

10

15

20

25

HW-Sulfite: untreated after steeping

HW-PHK: untreated after steeping

Chain Scissions [104/DP

w,j

-104/DP

w,0

]

Radiation dose [kGy]

Fig. 11.30 Course of chain scissions (based on weighted

molecular weight) of hardwood sulfite and PHK dissolving

pulps, before and after steeping as a function of radiation

dose.

After irradiation, the molecular weight was determined without any further

treatment and after alkalization with a caustic solution of 17.5% NaOH (steeping).

Degradation kinetics can be described by means of zero order, whereby using the

model equation from Sakurada:

104

DPn_t _

104

DPn_0 _ _ kD Dn _2_

1058

11.3 Dissolving Grade Pulp

where kD is the reaction rate of the radiation degradation.

The exponent n takes into account the fact that the polydispersity changes during

radiation degradation. According to Fig. 11.30, the course of chain scissions is

comparable for both pulps investigated. Because of a larger amount of carbonyl

groups (including reducing end groups), the degradation rate of a sulfite pulp is

more enhanced after a subsequent steeping step as compared to a PHK pulp. As

mentioned previously, the statistical character of molecular weight degradation

has been proposed as one important advantage of the electron beam treatment

compared to chemical degradation processes. If random chain scission is

assumed, then nonuniformity (U = PDI – 1) would approach unity, as indicated

by Kuhn [89].

The data in Fig. 11.31 show that the MWD curves through progressive degradation

are practically equal for both degradation processes, namely electron beam

treatment followed by steeping and oxidative alkaline ageing. Furthermore, the

results suggest that the statistical degradation performance applies to both degradation

processes. The conclusion is that radiation degradation and alkaline ageing

successively reduce the molecular weight, making the MWD progressively narrower.

In both processes, the reaction kinetics is governed by the content of carbonyl

groups, indicating that the degradation rate of sulfite pulps is higher than

that of PHK pulps.

600 500 400 300 200

1

2

3

4

5

6

HW-Sulfite: Ageing E-beam&steeping

HW-PHK Ageing E-beam&steeping

Polydispersity Index [M

w

/M

n

]

Viscosity [ml/g]

Fig. 11.31 Polydispersity index (PDI) as a function

of cellulose viscosity indicating the course

of degradation: comparison of electron beam

treatment with oxidative alkaline

treatment for both hardwood sulfite and PHK

dissolving pulps. The PDI was determined

from GPC-MALLS measurement (according to

[68]).

1059

11 Pulp Properties and Applications

11.3.2.8 Overview of Pulp Specification

As stated previously, the suitability of dissolving pulps can be adequately determined

simply by simulating the conversion processes to the final products, at

least on a laboratory scale. The most important property of virtually all dissolving

pulps can be expressed by the term “chemical reactivity”. Pulp reactivity, however,

cannot be described by a single structural feature, but rather by both the physical

structure of the cellulosic material and the type of chemical interaction with the

reagent. Additionally, all three structural levels – the molecular, supramolecular,

and fibrillar – must be considered when using the term reactivity [90].

Reactivity is related to the accessibility of chemicals to the cellulose, which

means the relative ease by which the hydroxyl groups can be reached by the reactants.

Structure and morphology of the fiber determines the homogeneity of the

conversion process and final product quality [91].

One of the most informative parameters in commercial specification sheets

(quality card) is that of alkali solubility tests at room temperature. Here, the pulps

are subjected to extractions with 10% (highest alkaline solubility) and 18% NaOH

(concentration of steeping lye), respectively. Thereby, differentiation must be

made between methods based on the gravimetric determination of the extraction

residue (R-values) and determination of the soluble fraction (S-values) using

potassium dichromate oxidation of the filtrate, followed by titration. The results

are specified as a percentage based on the dry starting material. The concentration

of NaOH is given as a subscript index (R10, R18 or S10, S18). The alkali resistances

are directly related to alkaline processing of dissolving pulps, as for viscose and

etherification processes. There, the R18 or (in some cases preferred) R21.5 values

have been cited as being representative of the yield of alkaline-processed products

(viscose fiber and cellulose ether) [92]. It has been shown that the cellulose content

corresponds well with the R18 value. For sulfite pulps with low molecular

weight, the R18 value lies below the cellulose content, because low molecularweight

material becomes dissolved. For PHK pulps and high-viscosity sulfite

pulps (ether application), the R18 value exceeds the cellulose content because high

molecular-weight, alkali-stable hemicelluloses remain in the pulp [93]. The difference

between the two extraction results is sometimes used as a measure for low

molar mass cellulose (R18 – R10 or S10 – S18).

Moreover, the S18 or (100 – R18) values are good indicators for estimating the

organic wastewater load associated with the production of viscose fibers or cellulose

ethers.

The data in Tab. 11.16 represents a simplified specification profile of the most