Bunichiro Tomita

Analysis on residue formation during wood liquefaction with polyhydric alcohol

Liquefactions of cellulose powder, steamed lignin, alkali lignin, and their mixtures were carried out to analyze the reaction process of wood using polyhydric alcohol. The liquefaction of wood proceeded immediately and wood components were converted to N,N-dimethylformamide (DMF)-soluble components. After that, the condensation reaction occurred with increasing reaction time. However, none of cellulose powder, steamed lignin, and alkali lignin condensed by themselves during their liquefaction. The mixture of cellulose and lignin was also liquefied, and condensed after a long reaction time. The results of analysis showed that the behavior of the mixture resembled that of wood with respect to molecular weight distribution and the main functional groups. Lignin was converted to DMF-soluble compounds in the initial stage of wood liquefaction, followed by cellulose gradually being converted into soluble compounds. After that, condensation reactions took place among some parts of depolymerized and degraded compounds from cellulose and lignin, and were converted into DMF-insoluble compounds. It was concluded that the rate-determining step of wood liquefaction was the depolymerization of cellulose. Furthermore, it was suggested that the condensation reaction was due to the mutual reaction among depolymerized cellulose and degraded aromatic derivatives from lignin or due to the nucleophilic displacement reaction of cellulose by phenoxide ion.

Hydration behavior of wood cement-based composite I: evaluation of wood species effects on compatibility and strength with ordinary Portland cement.

As an essential preliminary evaluation for understanding the hydration behavior of wood-cement-water mixtures, an isothermal calorimetry and experimental method were used to measure the hydration heat of woodcement-water mixtures. The compatibility of 38 wood species with ordinary portland cement was studied using this procedure. Based on the results, all the wood species tested were classified into two groups. The 24 species included in the first group showed a moderating influence on the hydration reaction of cement, and a maximum temperature (Tmax) peak during the exothermic reaction while the cement set appeared within 24h for each species. The other 14 species inhibited cement hydration completely. According to the maximum hydration temperature (Tmax) and the time (Tmax) required to reach the maximum temperature of the mixture, the suitability of each species in the first group was estimated when used as a raw material during production of cement-bonded particleboard. By testing mechanical properties [modulus of rupture (MOR) and internal bonding strength (IB)] during the board-making experiment using the same composition of wood-cement-water, a positive correlation was found betweenTmax andtmax and MOR and IB. The results imply that the method can be used as a predictor of the general inhibitory properties and feasibility of using wood species as raw materials prior to manufacture of cement-bonded particleboard.

Study of hydration behavior of wood cement-based composite II: effect of chemical additives on the hydration characteristics and strengths of wood-cement composites

The influence of the 30 chemical additives on the hydration characteristics of birch wood-cement-water mixture was determined by measuring the maximum hydration temperature (Tmax) and the time (tmax) required to reach the temperature. The chemical additives were tested and divided into two types depending on the pattern of exothermic reaction peak within the 24-h observation period. The wood-cement-water mixtures with additions of each of the 11 type I chemical additives showed a two-peak temperature-time curve similar to that for neat cement. CaCl2, FeCl3, and SnCl2 reached the highestTmax above 50°C. When the 19 type II chemical additives were included, the mixtures offered only one peak hydration temperature-time curve. Among them, the 10 chemical additives caused an obvious temperature increase at the beginning of the hydration reaction. The most significant effect was with the addition of diethanolamine, where the mixture produced aTmax above 50°C. The strength values (modulus of rupture, internal bond strength) of word-cement board were tested with separate additions of the 10 chemical additives arranged by the highestTmax. There was a good positive correlation betweenTmax and the strength values. In addition, the composite chemical additives were preliminarily examined to determine if they accelerated the hydration reaction of blast-furnace slag cement. The results revealed that composite chemical additives evidently accelerated the hydration reaction and the setting of blast-furnace slag cement mixed with wood. Blast-furnace slag cement can thus be considered for use as an acceptable inorganic bonding material for wood-cement panel manufacture.

Effect of ozone treatment of wood on its liquefaction

The effects of ozone treatment were investigated to improve the process of liquefaction of wood with polyhydric alcohol solvents. The liquefied wood having a high wood to polyhydric alcohol ratio (W/P ratio) could be prepared by using the wood treated with ozone in the liquid phase. The liquefied wood with a W/P ratio of 2 : 1 had enough fluidity to act as a raw material for chemical products. To get some information about the effects of ozone treatment toward the wood components, cellulose powder and steamed lignin were treated with ozone and liquefied. In particular, ozone treatment in the liquid phase was found to be effective for wood and cellulose powder. On the other hand, steamed lignin self-condensed during liquefaction after treatment with ozone in the liquid phase. Thus, ozone treatment provided lignin with reactive functional groups, and caused the subsequent condensation reaction. Although lignin was converted to a more condensable structure by ozone treatment, the condensation reaction was found to be suppressed for wood during its liquefaction. The wood liquefied products displayed good solubilities in N,N-dimethyl formamide (DMF) even after treatments of long duration. It was suggested that one of the main effects of ozone treatment toward wood was the decomposition of cellulose.

Effects of five additive materials on mechanical and dimensional properties of wood cement-bonded boards

There is a growing desire to improve the properties and use of nonwood plant materials as supplements to wood materials for wood cement-bonded boards (WCBs). This study was conducted to determine the comparative properties of WCBs containing various amounts of discontinuous inorganic fiber materials, such as alkali-resistant glass fiber, normal glass fiber, mineral wool, and nonwood plant materials such as retted flax straw and wheat straw particles. Tested cement-bonded boards were made at wood/additive compositions of 100/0, 90/10, 80/20, 70/30, 60/40, and 50/50 (weight percentages). Seventy-eight laboratory-scale WCBs were produced. Various board properties, such as the modulus of rupture (MOR), internal bonding strength (IB), water absorption (WA), thickness swelling (TS), and linear expansion (LE), were studied. The test results showed that three types of discontinuous inorganic fiber used as reinforcing materials in composites significantly enhanced and modified the performance of WCBs. The mechanical properties and dimensional stability of cement-bonded board were significantly improved with increasing amounts of the additives. MOR and IB were increased; and WA, TS, and LE of boards were reduced by combination with the inorganic fiber materials. The results also indicated that combination with retted flax straw particles only slightly increased the MOR of boards, and wheat straw particles led to marked decreases in all the mechanical properties and the dimensional stability of WCBs.

Hydration behavior and compressive strength of cement mixed with exploded wood fiber strand obtained by the water-vapor explosion process

Poor compatibility was found between exploded wood fiber strand (WFS) and cement due to the excessive presence of water-soluble degraded polysaccharides in extractives of exploded WFS obtained from weathered wood waste treated by the water-vapor explosion process (WVEP). This study presents some comparative results from a continuing investigation on the compressive strengths of exploded WFS–cement mixtures. Based on results previously obtained with the hydration test, the relation between hydration behavior and compressive strength of the mixture was explored. In addition, the effect of the curing age on compressive strength development of the mixture with selected additive chemicals was examined. The results supported the results of early studies with hydration tests indicating that adding MgCl2 to the mixtures of exploded WFS mixed with quick-curing cement or ordinary Portland cement and a composite of MgCl2 + CaO added to the mixture of exploded WFS and furnace-slag cement effectively improved the hydration behaviors; it greatly enhanced the compressive strengths of mixtures as well. Compressive strengths were strongly correlated to maximum hydration temperatures (Tmax) of wood–cement mixtures influenced by the cement type, wood wastes (treated or not with WVEP), additive chemicals, and their content levels. The results also indicated that adding selected chemicals had no significant effect on compressive strength among the mixtures of exploded WFS mixed, respectively, with three types of cement at a curing age of 180 days. X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray spectroscopy were used to identify the hydration products and to probe the element distribution of the mixture in the wood–cement interface zone from a fractured surface.

A preliminary investigation on microstructural characteristics of interfacial zone between cement and exploded wood fiber strand by using SEM-EDS

The hydration behavior and strength performance of cement mixed with exploded wood fiber strand (WFS) obtained by the water-vapor explosion process have been studied previously. In the current study, the microstructural characteristics of cement–exploded WFS interfacial zone were examined using scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS). The Ca/Si ratios at the interfacial zones and the elemental compositions of hydration products deposited in the tracheid lumen were investigated. In addition, the morphological differences and compositional variations of hydration products that developed on the wood surfaces were examined. The results revealed that the Ca/Si ratios at the interfacial zones were strongly influenced by the mixture compositions, and that the elemental compositions of the hydration products that filled the tracheid lumen were significantly different from those of the cement paste in the mixtures. Differences in morphology and composition of hydration products at the wood surfaces were also observed to correspond to the different mixture compositions. These characteristics are considered to be directly related to the bond property, and thus, to the mechanical performance of WCM.

Influence of moisture content on the vibrational properties of hematoxylin-impregnated wood

The vibrational property of hematoxylinimpregnated wood was investigated from the aspect of moisture content dependence. The specific dynamic Youngs modulus (E/γ) and loss tangent (tanδ) of hematoxylin-impregnated wood were determined in the relative humidity (RH) range of 0%–97%, and were compared with those of the untreated and some conventional chemically treated woods. The changes in theE/γ and tanδ of wood with increasing RH were suppressed by acetylation and formaldehyde treatment because of a marked reduction in the hygroscopicity of the wood. Although the hematoxylin impregnation did not significantly affect the hygroscopicity of the wood, its influence onE/γ and tanδ were similar to that of formaldehyde treatment at low RH and of acetylation at medium RH. It was supposed that at low to medium RH hematoxylin restrains the molecular motion of amorphous substances in the cell wall because of its bulkiness and rigidity. On the other hand, at high RH it seems to work as a plasticizer with adsorbed water molecules.

Dimensional stability of wood acetylated with acetic anhydride solution of glucose pentaacetate

Five wood species were acetylated with acetic anhydride (AA) solution of glucose pentaacetate (GPA) at 120°C for 8h, and the effect of GPA on the dimensional stability of the acetylated wood was investigated. Some GPA was introduced into the wood cell wall during acetylation. The GPA remaining in the cell lumen penetrated the cell wall effectively after heating to more than 140°C for 10min. The bulking effects of GPA resulted in a 10%–30% increase in the anti-swelling efficiency of the acetylated wood with 20% GPA/AA solution in place of AA. Hydrophobic GPA did not deliquesce under highly humid conditions and it remained in the cell wall after boiling in water.

Study of hydration behaviors of wood-cement mixtures: compatibility of cement mixed with wood fiber strand obtained by the water-vapor explosion process

To provide information on the feasibility of using exploded wood fiber strand (WFS) obtained by the water-vapor explosion process in wood-cement mixtures, the compatibility between cement and exploded WFS and its improvement with various additive chemicals were investigated by observation and analysis on hydration behaviors in terms of hydration characteristics: maximum hydration temperature (Tmax) and required time (tmax). The three types of cement, six additive chemicals, and exploded WFS (sugi, air-dried and water-soaked) were employed as raw materials in this study. The hydration behaviors of mixtures demonstrated that exploded WFS had strong retarding effects on cement hydration and completely prevented mixtures from setting. The analysis of sugar revealed that the sugar contents of exploded WFS were much higher than those in unexploded wood and increased to about 20-fold (air-dried) and 10-fold (water-soaked), respectively. The degraded polysaccharides became a major factor and played an important role in inhibiting the setting of cement. Moreover, high-performance liquid chromatography analysis proved that the main peaks representing the molecular weight of polysaccharides in extractives of exploded WFS shifted markedly to a lower range of polymerization. MgCl2 was determined to be an effective additive chemical for restraining the inhibitory influences. Addition contents of 2%–3% and 4%–5% were available and acceptable for quick-curing cement and ordinary Portland cement, respectively. As for the furnace-slag cement, the composite additive chemicals of MgCl2 (4%) and CaO (2%) were found to have an obvious accelerating effect.