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Bution. The decrease in molar mass of the wood polymers during pulping and
Bleaching procedures is normally estimated by measuring the intrinsic viscosity
Of the pulp fibers. Since celluloses from natural sources and after chemical treatment
Are always polydisperse, the determination of intrinsic viscosity is insufficient
To predict specific fiber properties. Additional information is provided by
Measuring the molecular weight distribution of paper pulps. The results of GPC
measurements of cellulose solutions in LiCl/DMAc with MALLS/RI detection
according to Schelosky et al. [23] are provided in Tab. 11.2 and Fig. 11.3.
3 4 5 6 7
HW-SULFITE
SW-SULFITE
HW-KRAFT
SW-KRAFT
Log Molecular Weight
dW/d(log M)
Fig. 11.3 Molar mass distribution of a representative selection
of fully bleached commercial paper pulps [17].
The typical pattern of molecular weight distribution of the four different categories
Of chemical paper grade pulps is clearly demonstrated in Fig 3. The kraft
Pulps can easily be distinguished from the sulfite pulps by a hemicellulose distribution
Centered at a rather high molecular weight. The bimodal character of the
Molecular weight distribution is particularly pronounced for the hardwood pulps,
Comprising a clear minimum between the cellulose and hemicellulose distributions.
The polydispersity index (PDI) calculated from the ratio of mass-weighted (Mw)
and number-weighted (Mn) molar masses (PDI = Mw/Mn), as shown in Tab. 11.2.
Is significantly higher for the sulfite as compared to the kraft pulps, and indicates
Paper-Grade Pulp
Tab. 11.2 Numerical evaluation of molecular weight distribution
of fully bleached commercial paper pulps [17].
Parameter Pine Spruce Eucalyptus Beech Spruce Spruce Beech
Kraft Kraft Sulfite Sulfite
ECF TCF ECF ECF TCF ECF TCF
DPv (Cuen) 2207 1648 2355 2240 3074 2486 3489
DPw 2827 2251 2847 2636 3648 3144 4050
DPn 659 650 612 590 572 504 517
PDI 4.3 3.5 4.6 4.5 6.4 6.2 7.8
DP < 120 wt% 3.5 3.1 3.0 3.5 5.4 6.3 7.4
DP < 200 wt% 8.2 7.9 8.2 10.7 8.8 8.7 12.8
DP > 2000 wt% 38.7 29.7 40.5 39.5 49.8 44.0 53.4
Zero-span tensile strength
dry Nm·g–1 130.8 133.7 147.1 n.d. 113.1 103.6 98.8
wet Nm·g–1 116.2 109.4 n.d. n.d. 96.5 82.9 84.4
A broader distribution of the former. The high PDI of the sulfite pulps originates
From rather high molecular-weight cellulose and very low molecular-weight hemicellulose
Fractions owing to the heterogeneous degradation of the wood pulp constituents
Across the cell wall layers. Intrinsic strength properties from a polymeric
Material are always related to the weakest part in the polymer, which is represented
By the short-chain molecules. A detailed evaluation of the numerical data from
GPC measurement revealed that zero-span tensile strength correlates well with
the weight percent of the DP <120 fraction, as illustrated in Fig. 11.4.
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By the water retention value (WRV). The data in Tab. 11.1 indicate that the | | | The intrinsic viscosity as well as standard information from GPC measurements |