Raymond A. Young

Swelling of wood. Part II. Swelling in organic liquids

The rate and maximum swelling of several North American wood species in 40 organic liquids have been obtained with a computer interfaced linear variable displacement transformer. Since wood swells very fast in some organic liquids, even at room temperature, this apparatus made it possible to obtain accurate rate data on the swelling of wood in organic liquids. It was found that many similarities existed between wood and cellulose maximum swelling within various solvent chemical classes. Hence, it appears that cellulose is the primary wood polymer responsible for the major amount of swelling of wood (...)

Swelling of wood

SummaryThe rate and maximum swelling of several North American wood species in water have been obtained with a computer interfaced linear variable displacement transformer. Since wood swells extremely fast in water even at room temperature, this apparatus made it possible for the first time, to obtain accurate rate data on the swelling of wood in water. The strict linear dependence of swelling on the temperature suggests a chemical mechanism. The activation energies obtained from Arrhenius plots ranged from 32.2 KJ/mole for sitka spruce to 47.6 KJ/mole for sugar maple. Although the two hardwoods exhibited greater maximum tangential swelling compared with the two softwoods, the maximum swelling appears to be correlated with the wood density. Generally both the rate and maximum swelling of the woods were increased by removal of extractives and the activation energies were reduced.

Swelling of compressed cellulose fiber webs in organic liquids

Maximum liquid-holding capacities of various compressed fibers in water and in a series of various organic liquids have been investigated. The maximum liquid-holding capacity versus bulk density relationships gave polynomial curves, generally with a peak. Good relative correlations for cellulose, compressed fiber pellets and wood were found for the series of liquids tested. In general, liquids that swelled wood to a low to medium range (up to 6%) did not swell appreciablyα-cellulose and sulfite pulp, while good to excellent wood-swelling agents swelled all the fibers very significantly. It was also found that the hydrogen-bonding parameter of the swelling liquid was the most important factor. The swelling rate of various compressed fiber systems in organic liquids was dramatically increased by raising the temperature. Activation energies and molar volume of the swelling liquid were linearly correlated.

Efficacy of Pinosylvins against White-Rot and Brown-Rot Fungi

Summary Three stilbenes, pinosylvin (PS), pinosylvin monomethyl ether (PSM) and pinosylvin dimethyl ether (PSD), were extracted from white spruce (Picea glauca), jack pine (Pinus banksiana), and red pine (Pinus resinosa) pine cones, and their structures were confirmed by spectroscopic and chromatographic (HPLC, GC/MS, NMR and FTIR) analysis. PS, PSM, PSD or a 1:1:1 mixture of these stilbenes at concentrations of 0.1 % and 1.0 % were examined for their fungal inhibitory activity by two bioassay methods. Growth of white-rot fungi (Trametes versicolor and Phanerochaete chrysosporium), and brown-rot fungi (Neolentinus lepideus, Gloeophyllum trabeum and Postia placenta) on agar media in the presence of each of the stilbenes or a 1:1:1 mixture inhibited growth of white-rot fungi, but slightly stimulated growth of brown-rot fungi. Soil-block assays, conditions more representative of those found in nature, did not correlate with those from the screening on agar media. PS, PSM, PSD or a 1:1:1 mixture of the three compounds at concentrations of 0.1 % and 1.0 % did not impart any significant decay resistance to white-rot fungi inoculated on a hardwood (Red maple). However under the same conditions, decay resistance was observed against brown-rot fungi on a softwood (Southern yellow pine). It appears that stilbenes at least partially contribute to wood decay resistance against brown-rot fungi.

Properties and treatments of pulps from recycled paper. Part I. Physical and chemical properties of pulps

The mechanical, physical, and chemical properties of recycled pulps were evaluated after a series of treatments designed to improve and/or modify the pulp characteristics. Tensile strength, bursting strength, and apparent density of the pulps decreased with recycling. However, the tear strength, in most cases, increased after the first recycle and then decreased after the second recycle. Carboxyl content and WRV of pulps also decreased with recycling. Chemical treatments did not increase the bonding ability of recycled pulps and, in most cases, decreased the physical properties of the pulps. Altering the physical state of the cellulose microstructure through additional swelling did not appear to be a significant factor for strength restoration. It may be that the hemicelluloses plan a greater role in recycling than originally thought.

Comparison of the properties of chemical cellulose pulps

The literature related to differences between chemical cellulose pulps produced by different pulping processes has been reviewed. Kraft pulps tend to be stronger, particularly in tear strength, while sulfite pulps hydrate and beat more readily. Organosolv pulps tend to mirror the properties of sulfite more than those of kraft pulps. A number of theories have been offered to explain the different properties of the chemical pulps; however, none has been universally accepted. It may be that acidic processes develop weak points in the fibers which are magnified in tear strength losses since, at a constant tensile strength, a 10% loss in fiber strength can lead to a 25–30% loss in tear strength. The effects of acidic pulping may also be magnified in greater fiber breakage and damage in the subsequent refining stages. However, strength improvements for inferior pulps can be realized through post-chemical treatments. Caustic treatments appear to give the greatest improvements, presumably due to increases in acidic group content which results in enhanced swelling properties, and possible subtle reorientation of cell wall polymers. The strength of hornified, recycled fibers can also be enhanced with such treatments, although simple beating will restore considerable strength, but at the expense of drainage rates. It is clear that the processes are complex and involve both the chemistry and physics of the fibers and how these attributes combine to affect the subsequent beating of the fibers for bonding and strength development.

Wetting of wood

SummaryThermodynamic work of adhesion, contact angle, wettability and acid-base contributions of the wetting of four North American wood species were determined using the Wilhelmy technique. The wetting angles with water varied from 60° for Sitka spruce to 74° for Douglas-fir. The wood surfaces had a strong acidic character since the greatest interactions for all the wood species occurred with formamide (basic probe) while lesser interactions were obtained with ethylene glycol (acidic probe). In addition, dispersive and polar surface free energies of wood, γds and γps respectively, were determined using Wus simultaneous equations. In general, 75 to 80% of the total surface free energy of wood was due to dispersion forces. Specific wettabilities of wood and advancing contact angles in thirty various organic liquids were also evaluated.

Surface fluorination of paper in CF4-RF plasma environments

Plasma-based technologies are an exciting alternative for cellulose andpaper modification. Barrier coatings and surface functionalization of celluloseenhances properties and creates new possibilities for cellulose-based products.A parallel plate radio frequency (RF)-plasma reactor was used to modify papersubstrates under discharge parameters such as power, time and pressure. Carbontetrafluoride RF-plasma treatment of paper caused intense fluorination and itwas demonstrated that the fluorination reaction mechanisms can be controlled bythe external plasma parameters. Fluorine contents as high as 51.3% (contactangle=147°) were obtained for the treated cellulose. It was shown that eventreatment times as low as 30 s can generate relative surface fluorineatomic concentrations as high as 30%. High resolution ESCA and ATR-FTIRanalysisindicated covalently bound CFx functional groups with CF4treatment. It was found that under certain experimental conditionssuper-hydrophobic paper surfaces are created by combining the high surfacefluorine atomic concentrations with specific plasma-generated surfacetopographies.

Highly hydrophobic sisal chemithermomechanical pulp (CTMP) paper by fluorotrimethylsilane plasma treatment

Fluorinated thin layers were created on chemithermomechanical pulp (CTMP) sisal paper surfaces with fluorotrimethylsilane (FTMS) radio frequency-plasma conditions. It was found that the FTMS-discharge environments caused implantation of fluorine and –Si(CH3)x groups into the surface layers of the paper substrates. Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy and Electron Spectroscopy for Chemical Analysis, as well as Atomic Force Microscopy and Scanning Electron Microscopy analyses revealed a smooth surface for the FTMS plasma-treated paper, apparently covered completely with a cross-linked polymerized network. Although the plasma reaction takes place with the cellulose, hemicelluloses and lignin, it appears that the chemical linkage is mainly to the lignin component on the CTMP paper surface by means of mainly C–O–Si–F, with some C–Si–F structures. The CTMP fibers apparently have a high lignin surface concentration. The water absorption for the plasma-treated CTMP paper was reduced from greater than 300 to 17 g of water/m2 and the contact angle increased from less than 15° to greater than 120° the strength properties were only slightly reduced and the brightness was essentially unaffected with the FTMS plasma treatment.

Interphase effects on the mechanical and physical aspects of natural fiber composites

The interaction and adhesion between the fiber and matrix has a significant effect in determining the mechanical and physical behavior of fiber composites. The effect of the interface and interphase depends on several factors such as chemical composition (functional groups), molecular structure characteristics (branching, molecular weight distribution, cross-linking), and details of its physical state (above or below Tg, nature and degree of crystallinity). Natural fibers have complex and varying chemical structures that have uneven surface topographies. This creates difficulties in using single fiber composite testing to accurately evaluate the interfacial shear strengths, except for comparisons. A review of our interphase related research in natural fiber composites is presented. When using coupling agents it is well known that the tensile and flexural strengths increase dramatically in natural fiber reinforced composites. However, in the case of modulus, the results are more complex. For two ethylene-propylene impact copolymers, the uncoupled systems had much higher Youngs moduli than the coupled systems. The dynamic storage moduli of the uncoupled impact polymers were higher than the coupled composites at temperatures up to about 50°C. At higher temperatures the presence of the coupling agent resulted in higher storage moduli. Transcrystallinity may play an important role in this phenomenon. Creep and other long-term properties are also affected by the quality of the interphase, although the level of improvement decreases with an increase in the molecular weight of the matrix polymer. Coupling agents reduced the rate of water absorption and the moduli were less affected in blends with a higher concentration of coupling agents.