Chemically modified cellulose micro- and nanofibrils as paper-strength additives

Chemically modified cellulose micro- and nanofibrils were successfully used as paper strength additives. Three different kinds of cellulose nanofibrils (CNFs) were studied: carboxymethylated CNFs, periodate-oxidised carboxymethylated CNFs and dopamine-grafted carboxymethylated CNFs, all prepared from bleached chemical fibres of dissolving grade, and one microfibrillated cellulose from unbleached kraft fibres. In addition to mechanical characterization of the final paper sheets the fibril retention, sheet density and sheet morphology were also studied as a function of addition of the four different cellulose fibrils. In general, the cellulose fibrils, when used as additives, significantly increased the tensile strength, Young’s modulus and strain-at-break of the paper sheets. The effects of the different fibrils on these properties were compared and evaluated and used to analyse the underlying mechanisms behind the strengthening effect. The strength-enhancing effect was most pronounced for the periodate-oxidised CNFs when they were added together with polyvinyl amine (PVAm) or poly(dimethyldiallylammonium chloride) (pDADMAC). The addition of periodate-oxidised CNFs, with pDADMAC as retention aid, resulted in a 37% increase in tensile strength at a 2 wt% addition and an 89% increase at a 15 wt% addition (from 67 to 92 and 125 kNm/kg, respectively) compared to a reference with only pDADMAC. Wet-strong sheets with a wet tensile index of 30 kNm/kg were also obtained when periodate-oxidised CNFs and PVAm were combined. This significant increase in wet strength is suggested to be the result of a formation of cross-links between the aldehyde groups, introduced by the periodate oxidation, and hydroxyl groups on the lignocellulosic fibres and the primary amines of PVAm. Even though less significant, there was also an increase in wet tensile strength when pDADMAC was used together with periodate-oxidised fibrils which shows that the aldehyde groups are able to increase the wet strength without the presence of the primary amines of the PVAm. As an alternative method to strengthen the fibre network, carboxymethylated CNFs grafted with dopamine, by an ethyl dimethylaminopropyl carbodiimide coupling, were used as a strength additive. When used as an additive, these CNFs showed a strong propensity to form films on and around the fibres and significantly increased the mechanical properties of the sheets. Their addition resulted in an increase in the Young´s modulus by 41%, from 5.1 to 7.2 GPa, and an increase in the tensile strength index of 98% (from 53 to 105 kNm/kg) with 5 wt% retained dopamine-grafted CNFs.     

Influence of non-singular stress terms and specimen geometry on small-scale yielding at crack tips in elastic-plastic materials

The plane strain elastic-plastic state at a crack tip is determined for compact tension, bend, double edge-cracked and centre-cracked specimens using a finite element method with triangular constant-strain elements. The solutions are found to differ by 10 to 30 per cent at the ASTM-limit as regards fracture surface displacement, normal stress and plastic zone size. In order to bring the boundary layer solution for the crack problem into agreement with the solution for a specific specimen one has to modify this solution. The modification consists of an addition to the boundary tractions for the boundary layer problem of tractions corresponding to the non-singular, constant second term in a series expansion of the normal stress parallel to the crack plane.     

An automated micromethod for the separation of monosaccharides by partition chromatography

Summary The conditions for a separation of monosaccharid.es and their automatic determination on the microscale have been studied. The separation is based upon partition chromatography on an anion-exchange resin in its sulphate form with ethanol -water as the eluent. The eluate is analysed colorimetrically with orcinol as the colour reagent. Microgram quantities in complicated mixtures of monosaccharides can be determined in less than three hours.

---

Zusammenfassung Die Arbeitsbedingungen für die Trennung und automatische Bestimmung von Monosacchariden im Mikromaßstab wurden untersucht. Die Trennung wird verteilungschromatographisch an einem Anionenaustauscherharz in Sulfatform mit Äthanol-Wasser als Eluent ausgeführt. Das Eluat wird kolorimetrisch mit Orcin als Farbreagens durchgeführt. In Monosaccharidgemischen lassen sich Mikrogrammengen in weniger als 3 Stunden bestimmen.

---

Résumé On a étudié les conditions de séparation des monosaccharides et leur dosage automatique à l'échelle micro. La séparation repose sur la Chromatographie de partage sur une résine échangeuse anionique sous sa forme sulfate, avec le mélange éthanol-eau comme éluant. On analyse par colorimétrie l'éluat avec l'orcinol comme réactif coloré. On peut doser des quantités de l'ordre du microgramme dans des mélanges complexes de monosaccharides en moins de 3 heures.

---

---

The financial support of the Swedish Technical Research Council is gratefully acknowledged. Thanks are also due to Dr.H. W. Holy, Teehnicon Instruments Co., Chertsey, Great Britain, for a gift of specially prepared ion-exchange resin.     

Crossing numbers of sequences of graphs II: Planar tiles

We describe a method of creating an infinite family of crossing‐critical graphs from a single small planar map, the tile, by gluing together many copies of the tile together in a circular fashion. This method yields all known infinite families of k‐crossing‐critical graphs. Furthermore, the method yields new infinite families, which extend from (4,6) to (3.5,6) the interval of rationals r for which there is, for some k, an infinite sequence of k‐crossing‐critical graphs all having average degree r. © 2003 Wiley Periodicals, Inc. J Graph Theory 42: 332–341, 2003     

High-resolution VUV spectroscopy using pulsed laser sources

The resonance spectroscopic techniques - level-crossing, optical double resonance and quantum-beat spectroscopy - have been employed following pulsed laser excitation. The use of pulsed lasers has enabled spectroscopic studies of atomic structures and radiative lifetimes in the UV/VUV spectral region.     

Gas permeability and n‐butane solubility of poly(1‐trimethylgermyl‐1‐propyne)

The gas permeability and n‐butane solubility in glassy poly(1‐trimethylgermyl‐1‐propyne) (PTMGP) are reported. As synthesized, the PTMGP product contains two fractions: (1) one that is insoluble in toluene and soluble only in carbon disulfide (the toluene‐insoluble polymer) and (2) one that is soluble in both toluene and carbon disulfide (the toluene‐soluble polymer). In as‐cast films, the gas permeability and n‐butane solubility are higher in films prepared from the toluene‐soluble polymer (particularly in those films cast from toluene) than in films prepared from the toluene‐insoluble polymer and increase to a maximum in both fractions after methanol conditioning. For example, in as‐cast films prepared from carbon disulfide, the oxygen permeability at 35 °C is 330 × 10^?10 cm³ (STP) cm/(cm² s cmHg) for the toluene‐soluble polymer and 73 × 10^?10 cm³ (STP) cm/(cm² s cmHg) for the toluene‐insoluble polymer. After these films are conditioned in methanol, the oxygen permeability increases to 5200 × 10^?10 cm³ (STP) cm/(cm² s cmHg) for the toluene‐soluble polymer and 6200 × 10^?10 cm³ (STP) cm/(cm² s cmHg) for the toluene‐insoluble polymer. The rankings of the fractional free volume and nonequilibrium excess free volume in the various PTMGP films are consistent with the measured gas permeability and n‐butane solubility values. Methanol conditioning increases gas permeability and n‐butane solubility of as‐cast PTMGP films, regardless of the polymer fraction type and casting solvent used, and minimizes the permeability and solubility differences between the various films (i.e., the permeability and solubility values of all conditioned PTMGP films are similar). © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2228–2236, 2002     

Correlation effects in the electronic coupling between π electrons through a cyclohexane spacer

The electronic coupling between symmetrically placed π electrons through a cyclohexane spacer is calculated using ab initio methods. In particular we have performed a multiconfigurational configuration interaction study involving the broken symmetry Hartree—Fock solutions. The value of Δ, in a simplified model the splitting between the symmetric and antisymmetric π orbitals, is moderately changed compared to the Koopmans theorem value. The influence of the basis set on the calculated splittings is also analyzed.     

Energy transport in one-dimensional thermoelectric systems

The efficiency of thermoelectric power generators and the coefficient of performance of thermoelectric refrigerators increase rapidly in the region of small ZT, and then level off to a flat curve in the region of large ZT, where ZT is the figure of merit. Therefore, simply because one-dimensional thermoelectric materials have high ZT predicted theoretically does not imply that efficient thermoelectric devices can be built with such one-dimensional systems. Our numerical analysis, based on the fundamental thermodynamics which is independent of material systems, with emphasis on energy transport has confirmed this conjecture.