To clarify liquefaction ratios and their construction variations of the main chemical compositions of wood in phenol using phosphoric acid as a catalyst, the chemical ingredients of wood such as holocellulose, cellulo...To clarify liquefaction ratios and their construction variations of the main chemical compositions of wood in phenol using phosphoric acid as a catalyst, the chemical ingredients of wood such as holocellulose, cellulose and lignin, were measured and extracted according to GB methods. With Fourier transform infrared （FTIR）, the product identification of reactant before and after liquefaction in phenol was investigated. The molecular weights and their distributions of the liquefaction results （acetone soluble parts） were studied by gel permeation chromatography （GPC）. Results show that the molecular weights and their distributions of poplar and Chinese fir are almost the same. In poplar, the distribution of cellulose is the largest, and that ofholocellulose the smallest after liquefaction. For Chinese fir, the distribution of holocellulose is the largest, and that of cellulose the smallest. After liquefaction of poplar cellulose, the change bands of FTIR spectrum observed below 1 600 cm^-1, can be attributed to new substitute groups. The same is true for poplar lignin. For Chinese fir, the spectra of liquefaction results of all chemical compositions differ from that of wood meal. This reveals the more activity groups were produced because of the reactions between Chinese fir and phenol. The research shows that the liquefaction ratios of poplar decrease in the following order： holocellulose 〉 lignin 〉 cellulose, and those of Chinese fir in the order： lignin 〉 cellulose 〉 holocellulose.展开更多
To investigate value in use of liquefied wood-based resin applications in molding material, Chinese fir （Cunninghamia lanceolata） and poplar （Populus tomentosa） wood meal were liquefied in phenol. The reactant was...To investigate value in use of liquefied wood-based resin applications in molding material, Chinese fir （Cunninghamia lanceolata） and poplar （Populus tomentosa） wood meal were liquefied in phenol. The reactant was co-condensed with formaldehyde to obtain liquefied wood-based resin. For this paper, we investigated the characterization of the resin and its application in molding material. The result shows that the basic properties of liquefied wood-based resin were satisfactory; the bonding strength of plywood prepared with liquefied Chinese fir and liquefied poplar resin can reach 1.54 and 1.00 MPa, respectively. The compression strengths of the molding material prepared with two kinds of liquefied wood resin were 73.01 and 73.58 MPa, almost the same as that of PF resin molding material. The limiting volume swelling of molding material made with liquefied Chinese resin and liquefied poplar resin were 8.5% and 8.3%, thickness swelling rates of water absorption were 3.3% and 4.2%, and the maximum weight ratios of water absorption were 25.9% and 26.2%, respectively. The soil burial test result shows that the weight loss rate of the molding materials made with liquefied Chinese resin and liquefied poplar resin were 8.3% and 9.1% and that of the PF resin molding material was 7.9%. After the soil internment test, the reduction ratio of compression strength of the two kinds of molding material achieved 16.9% and 17.7%, while that of the PF resin molding material was 15.4%. The test results of wood fungi inoculation on the three surfaces of the molding material indicate the breeding rate of molding material prepared with liquefied Chinese resin and liquefied poplar resin were at level 4 and that of PF resin molding material was at level 1 of the ISO standard.展开更多
The increase in the residue content resulting from polycondensation would be adverse to the utilization of lignocellulose and to the quality of products obtained from liquefied lignocellulosic material.The yield of th...The increase in the residue content resulting from polycondensation would be adverse to the utilization of lignocellulose and to the quality of products obtained from liquefied lignocellulosic material.The yield of the residue formed from liquefaction and the mechanism of polycondensation were reported mainly by Lin,Yamada and Kobayashi.The major products of cellulosic liquefaction are levulinic acid and hydroxymethylfurfural（HMF） derivatives under polyhydric alcohols and phenolated compounds under phenols.The cleavage of the β-O-4 bonds is the major reaction pathway of lignin liquefaction under various liquefying reagents regardless of whether they contain acid catalysts or not.The break up compounds by decomposition are polymerized to substances with high molecular weight by polycondensation in lignocellulosic liquefaction.The molecular weight of condensed residues increases almost linearly as a function of liquefaction time at the later stage of lignocellulosic liquefaction.The longer the time required,the greater the content of new residue generated by polycondensation during the entire process of liquefaction.We conclude that the condensed residues may stem from the interaction of degraded lignin and cellulose components in wood or from the products of two major components reacting with liquefying reagents.展开更多
In order to investigate the shrinking and swelling behavior of wood at a non-equilibrium state, the moisture sorptlon processes of wood under constant and changing conditions were studied. For the static sorption expe...In order to investigate the shrinking and swelling behavior of wood at a non-equilibrium state, the moisture sorptlon processes of wood under constant and changing conditions were studied. For the static sorption experiment, Chinese fir （Cunninghamia lanceolata） specimens were subjected to the adsorption processes at 25℃, 10 different relative humidity environments and the moisture contents were measured at distinct time intervals of adsorption processes. For the dynamic sorption experiment, the specimens were exposed to periodically and linearly varying relative humidity between 45% and 75% at 25℃. Moisture content as well as radial and tangential dimensional changes in response to the changing relative humidity were measured. The main results from the experiments indicated that： the moisture sorption isotherms of Chinese fir at equilibrium state and different stages of adsorption processes could be characterized by S-shape curves. From the non-equilibrium state to the equilibrium state, the sigmoid moisture sorption isotherms changed from smooth, gradually increasing values to a steep rise at 100% humidity. Furthermore, under dynamic conditions with a constant temperature and a linearly and periodically varying relative humidity, the moisture content as well as radial and tangential dimensional changes of the specimens generally waved but lagged behind the relative humidity change.展开更多
Wood of Chinese fir and poplar were liquefied in phenol at 150℃ and atmospheric pressure. The liquefied wood were reacted with formaldehyde to synthesize the liquefied wood-based resin. The factors affecting the resi...Wood of Chinese fir and poplar were liquefied in phenol at 150℃ and atmospheric pressure. The liquefied wood were reacted with formaldehyde to synthesize the liquefied wood-based resin. The factors affecting the resinification and the properties of new resin were investigated. The results show that the formaldehyde/liquefied wood molar ratio, reaction temperature, reaction time and sodium hydroxide/liquefied wood molar ratio have important influence on the resin characteristics. With the increase of formaldehyde/liquefied wood molar ratio, the yield of resin increases, and the flee phenol content of resins decreases, showing that the resinification of liquefied wood is more complete at higher formaldehyde/liquefied wood molar ratios. The reaction temperature on the viscosity of the liquefied resin has considerable effect; the viscosity of resin increased with increasing reaction temperature, and the amount of liquefied poplar resin increased more quickly than that of liquefied Chinese fir resin. The resinification time also has obvious influence on the viscosity of resin; the viscosity of liquefied poplar resin is more sensitive to resinification time compared with that of liquefied Chinese fir. The amount of sodium hydroxide can improve the water miscibility of liquefied wood resin. The optimum sodium hydroxide/liquefied wood molar ratio for preparation of liquefied wood-based resins exceeds 0.4.展开更多
The nano intercalation compounding of wood and MMT has important implications for the modification of wood and for the development of new materials. With water-soluble phenol formaldehyde resin as an intermediary, the...The nano intercalation compounding of wood and MMT has important implications for the modification of wood and for the development of new materials. With water-soluble phenol formaldehyde resin as an intermediary, the nanocomposites of Chinese fir （Cunningharnia lanceolata） wood and montmorillonite （MMT） were prepared via three impregnation methods, i.e. normal pressure, once and twice vacuum methods. Based on the weight percent gain （WPG） of impregnated wood, the effects of compounding wood and MMT in terms of concentration, impregnating temperature and time, wood moisture content and wood extraction treatments, on sapwood and heartwood are discussed. Results show that： 1） the optimum MMT concentration in the impregnation solution is 3% for sapwood and 5% for heartwood; 2） room temperature is suitable in practice; 3） treatment pressure should be set at a high enough value in order to ensure sufficient permeation; 4） the effects of different impregnation methods on sapwood and heartwood are different, the heartwood extractives affect WPG significantly; cell wall permeability of sapwood is better than that of heartwood; 5） the cold water, hot water and benzene-ethanol solution extractions can all greatly improve the permeability of heartwood, hot water can dissolve some hemicellulose of low aggregation and hot water extraction improves wood cell wall permeability; 6） with an increase in wood moisture content, the permeable space in wood is reduced, but with a certain amount of water, instantaneous spaces are created and the permeation dynamic increases. This effect is especially apparent for difficult impregnating situations in heartwood and impregnation under normal pressure.展开更多
With montmorillonite （MMT） organically modified as organophilic MMT （OMMT） and water-soluble phenol formaldehyde resin （PF） as intermediate, Chinese fir （Cunningharnia lanceolata） wood/MMT nanocomposites （WMN...With montmorillonite （MMT） organically modified as organophilic MMT （OMMT） and water-soluble phenol formaldehyde resin （PF） as intermediate, Chinese fir （Cunningharnia lanceolata） wood/MMT nanocomposites （WMNC） were prepared via nano intercalation compounding and characterized by XRD, SEM and FTIR. Results show that： 1） the preparation of OMMT is very successful; 2） the self-made PF can effectively intercalate into MMT to increase markably its gallery distance and even exfoliate its nano silicate laminae; 3） the XRD analysis indicates that some exfoliated MMT enters the non-crystallized region of microfibrils in wood cell walls and the crystallinity degree of wood in WMNC decreases; 4） the SEM graphs show that multiform MMT exists in WMNC. Some grains block in wood cell lumen, some layers adhere to the wood surface of the inner cell wall and some exfoliated nanolaminae even insert into wood cell walls; and 5） the FTIR analysis suggests that MMT and wood in WMNC perhaps interact via certain chemical bonding.展开更多
In order to clarify the effect of drying on structural changes of DMSO swell treated and DEA-SO2-DMSO decrystallization treated Chinese fir （Cunninghamia lanceolate） wood, the stress relaxation of treated oven-dry s...In order to clarify the effect of drying on structural changes of DMSO swell treated and DEA-SO2-DMSO decrystallization treated Chinese fir （Cunninghamia lanceolate） wood, the stress relaxation of treated oven-dry specimens during the processes of temperature elevation and reduction and that of treated wet specimens at constant temperature were determined. A stress decrease process and a stress increase process were observed in all stress ratio curves of wood during the processes of decreasing temperature. Untreated wood, during the process of temperature reduction under higher initial temperature conditions and during the process of temperature elevation, has a larger stress decrease than treated woods. In a wet state this trend is reversed. It indicated that the drying set made treated woods have a smaller increase in fluidity of wood constituents with increasing temperature. Some bonding between decrystallization reagents and wood molecules may occur.展开更多
In order to enlarge the utilization field of wood and decrease the costs of carbon fibers, carbon fiber precursors from liquefied wood were prepared by soaking liquefied wood in a solution containing hydrochloric acid...In order to enlarge the utilization field of wood and decrease the costs of carbon fibers, carbon fiber precursors from liquefied wood were prepared by soaking liquefied wood in a solution containing hydrochloric acid and formaldehyde, after melt-spinning by adding hexamethylenetetramine. The microstructure evolution of the precursor during carbonization was studied by FTIR, X-ray analysis and Raman spectroscopy. The results show that precursors from liquefied wood above 400℃had diffraction peaks corresponding to the （100） crystal plane. When the carbonization temperature reached 500℃, Raman spectroscopy showed the D peak at wave number of 1360 cm^-1 and the G peak at 1595 cm^-1. By increasing the carbonization temperature, the microstructure of the precursors became more ordered. Although the structure of the precursor changed at 500 and 800℃, the peaks at 1632 and 1454 cm^-1 corresponding to the characteristic vibrations of aromatic rings, remained during carbonization. This implies that the precursor from liquefied wood cannot be easily formed into graphite.展开更多
基金Supported by the Key Research Program Foundation, Ministry of Educational of China (Grant No.02021)the National Natural Science Foundation of China (Grant No. 30471351)
文摘To clarify liquefaction ratios and their construction variations of the main chemical compositions of wood in phenol using phosphoric acid as a catalyst, the chemical ingredients of wood such as holocellulose, cellulose and lignin, were measured and extracted according to GB methods. With Fourier transform infrared （FTIR）, the product identification of reactant before and after liquefaction in phenol was investigated. The molecular weights and their distributions of the liquefaction results （acetone soluble parts） were studied by gel permeation chromatography （GPC）. Results show that the molecular weights and their distributions of poplar and Chinese fir are almost the same. In poplar, the distribution of cellulose is the largest, and that ofholocellulose the smallest after liquefaction. For Chinese fir, the distribution of holocellulose is the largest, and that of cellulose the smallest. After liquefaction of poplar cellulose, the change bands of FTIR spectrum observed below 1 600 cm^-1, can be attributed to new substitute groups. The same is true for poplar lignin. For Chinese fir, the spectra of liquefaction results of all chemical compositions differ from that of wood meal. This reveals the more activity groups were produced because of the reactions between Chinese fir and phenol. The research shows that the liquefaction ratios of poplar decrease in the following order： holocellulose 〉 lignin 〉 cellulose, and those of Chinese fir in the order： lignin 〉 cellulose 〉 holocellulose.
基金This study was financially supported by the National Natural Science Foundation of China （Grant No. 30471351）.
文摘To investigate value in use of liquefied wood-based resin applications in molding material, Chinese fir （Cunninghamia lanceolata） and poplar （Populus tomentosa） wood meal were liquefied in phenol. The reactant was co-condensed with formaldehyde to obtain liquefied wood-based resin. For this paper, we investigated the characterization of the resin and its application in molding material. The result shows that the basic properties of liquefied wood-based resin were satisfactory; the bonding strength of plywood prepared with liquefied Chinese fir and liquefied poplar resin can reach 1.54 and 1.00 MPa, respectively. The compression strengths of the molding material prepared with two kinds of liquefied wood resin were 73.01 and 73.58 MPa, almost the same as that of PF resin molding material. The limiting volume swelling of molding material made with liquefied Chinese resin and liquefied poplar resin were 8.5% and 8.3%, thickness swelling rates of water absorption were 3.3% and 4.2%, and the maximum weight ratios of water absorption were 25.9% and 26.2%, respectively. The soil burial test result shows that the weight loss rate of the molding materials made with liquefied Chinese resin and liquefied poplar resin were 8.3% and 9.1% and that of the PF resin molding material was 7.9%. After the soil internment test, the reduction ratio of compression strength of the two kinds of molding material achieved 16.9% and 17.7%, while that of the PF resin molding material was 15.4%. The test results of wood fungi inoculation on the three surfaces of the molding material indicate the breeding rate of molding material prepared with liquefied Chinese resin and liquefied poplar resin were at level 4 and that of PF resin molding material was at level 1 of the ISO standard.
基金supported by the Forestry Public Special Scientific Research (No. 201004057)
文摘The increase in the residue content resulting from polycondensation would be adverse to the utilization of lignocellulose and to the quality of products obtained from liquefied lignocellulosic material.The yield of the residue formed from liquefaction and the mechanism of polycondensation were reported mainly by Lin,Yamada and Kobayashi.The major products of cellulosic liquefaction are levulinic acid and hydroxymethylfurfural（HMF） derivatives under polyhydric alcohols and phenolated compounds under phenols.The cleavage of the β-O-4 bonds is the major reaction pathway of lignin liquefaction under various liquefying reagents regardless of whether they contain acid catalysts or not.The break up compounds by decomposition are polymerized to substances with high molecular weight by polycondensation in lignocellulosic liquefaction.The molecular weight of condensed residues increases almost linearly as a function of liquefaction time at the later stage of lignocellulosic liquefaction.The longer the time required,the greater the content of new residue generated by polycondensation during the entire process of liquefaction.We conclude that the condensed residues may stem from the interaction of degraded lignin and cellulose components in wood or from the products of two major components reacting with liquefying reagents.
文摘In order to investigate the shrinking and swelling behavior of wood at a non-equilibrium state, the moisture sorptlon processes of wood under constant and changing conditions were studied. For the static sorption experiment, Chinese fir （Cunninghamia lanceolata） specimens were subjected to the adsorption processes at 25℃, 10 different relative humidity environments and the moisture contents were measured at distinct time intervals of adsorption processes. For the dynamic sorption experiment, the specimens were exposed to periodically and linearly varying relative humidity between 45% and 75% at 25℃. Moisture content as well as radial and tangential dimensional changes in response to the changing relative humidity were measured. The main results from the experiments indicated that： the moisture sorption isotherms of Chinese fir at equilibrium state and different stages of adsorption processes could be characterized by S-shape curves. From the non-equilibrium state to the equilibrium state, the sigmoid moisture sorption isotherms changed from smooth, gradually increasing values to a steep rise at 100% humidity. Furthermore, under dynamic conditions with a constant temperature and a linearly and periodically varying relative humidity, the moisture content as well as radial and tangential dimensional changes of the specimens generally waved but lagged behind the relative humidity change.
基金Supported by the Key Research Program Foundation, Ministry of Education of China (Grant No. 02021)and the National Science Foundation of China (Grant No. 30471351)
文摘Wood of Chinese fir and poplar were liquefied in phenol at 150℃ and atmospheric pressure. The liquefied wood were reacted with formaldehyde to synthesize the liquefied wood-based resin. The factors affecting the resinification and the properties of new resin were investigated. The results show that the formaldehyde/liquefied wood molar ratio, reaction temperature, reaction time and sodium hydroxide/liquefied wood molar ratio have important influence on the resin characteristics. With the increase of formaldehyde/liquefied wood molar ratio, the yield of resin increases, and the flee phenol content of resins decreases, showing that the resinification of liquefied wood is more complete at higher formaldehyde/liquefied wood molar ratios. The reaction temperature on the viscosity of the liquefied resin has considerable effect; the viscosity of resin increased with increasing reaction temperature, and the amount of liquefied poplar resin increased more quickly than that of liquefied Chinese fir resin. The resinification time also has obvious influence on the viscosity of resin; the viscosity of liquefied poplar resin is more sensitive to resinification time compared with that of liquefied Chinese fir. The amount of sodium hydroxide can improve the water miscibility of liquefied wood resin. The optimum sodium hydroxide/liquefied wood molar ratio for preparation of liquefied wood-based resins exceeds 0.4.
基金This study was financially supported by the National Natural Science Foundation of China （Grant No. 30271055）.
文摘The nano intercalation compounding of wood and MMT has important implications for the modification of wood and for the development of new materials. With water-soluble phenol formaldehyde resin as an intermediary, the nanocomposites of Chinese fir （Cunningharnia lanceolata） wood and montmorillonite （MMT） were prepared via three impregnation methods, i.e. normal pressure, once and twice vacuum methods. Based on the weight percent gain （WPG） of impregnated wood, the effects of compounding wood and MMT in terms of concentration, impregnating temperature and time, wood moisture content and wood extraction treatments, on sapwood and heartwood are discussed. Results show that： 1） the optimum MMT concentration in the impregnation solution is 3% for sapwood and 5% for heartwood; 2） room temperature is suitable in practice; 3） treatment pressure should be set at a high enough value in order to ensure sufficient permeation; 4） the effects of different impregnation methods on sapwood and heartwood are different, the heartwood extractives affect WPG significantly; cell wall permeability of sapwood is better than that of heartwood; 5） the cold water, hot water and benzene-ethanol solution extractions can all greatly improve the permeability of heartwood, hot water can dissolve some hemicellulose of low aggregation and hot water extraction improves wood cell wall permeability; 6） with an increase in wood moisture content, the permeable space in wood is reduced, but with a certain amount of water, instantaneous spaces are created and the permeation dynamic increases. This effect is especially apparent for difficult impregnating situations in heartwood and impregnation under normal pressure.
文摘With montmorillonite （MMT） organically modified as organophilic MMT （OMMT） and water-soluble phenol formaldehyde resin （PF） as intermediate, Chinese fir （Cunningharnia lanceolata） wood/MMT nanocomposites （WMNC） were prepared via nano intercalation compounding and characterized by XRD, SEM and FTIR. Results show that： 1） the preparation of OMMT is very successful; 2） the self-made PF can effectively intercalate into MMT to increase markably its gallery distance and even exfoliate its nano silicate laminae; 3） the XRD analysis indicates that some exfoliated MMT enters the non-crystallized region of microfibrils in wood cell walls and the crystallinity degree of wood in WMNC decreases; 4） the SEM graphs show that multiform MMT exists in WMNC. Some grains block in wood cell lumen, some layers adhere to the wood surface of the inner cell wall and some exfoliated nanolaminae even insert into wood cell walls; and 5） the FTIR analysis suggests that MMT and wood in WMNC perhaps interact via certain chemical bonding.
基金Supported by the National Natural Science Foundation of China (Grant No. 30070606)Graduate Cultivation Foundation of Beijing Forestry University(Grant No. 304)
文摘In order to clarify the effect of drying on structural changes of DMSO swell treated and DEA-SO2-DMSO decrystallization treated Chinese fir （Cunninghamia lanceolate） wood, the stress relaxation of treated oven-dry specimens during the processes of temperature elevation and reduction and that of treated wet specimens at constant temperature were determined. A stress decrease process and a stress increase process were observed in all stress ratio curves of wood during the processes of decreasing temperature. Untreated wood, during the process of temperature reduction under higher initial temperature conditions and during the process of temperature elevation, has a larger stress decrease than treated woods. In a wet state this trend is reversed. It indicated that the drying set made treated woods have a smaller increase in fluidity of wood constituents with increasing temperature. Some bonding between decrystallization reagents and wood molecules may occur.
基金supported by the Na-tional Natural Science Foundation of China (Grant No. 30901133)
文摘In order to enlarge the utilization field of wood and decrease the costs of carbon fibers, carbon fiber precursors from liquefied wood were prepared by soaking liquefied wood in a solution containing hydrochloric acid and formaldehyde, after melt-spinning by adding hexamethylenetetramine. The microstructure evolution of the precursor during carbonization was studied by FTIR, X-ray analysis and Raman spectroscopy. The results show that precursors from liquefied wood above 400℃had diffraction peaks corresponding to the （100） crystal plane. When the carbonization temperature reached 500℃, Raman spectroscopy showed the D peak at wave number of 1360 cm^-1 and the G peak at 1595 cm^-1. By increasing the carbonization temperature, the microstructure of the precursors became more ordered. Although the structure of the precursor changed at 500 and 800℃, the peaks at 1632 and 1454 cm^-1 corresponding to the characteristic vibrations of aromatic rings, remained during carbonization. This implies that the precursor from liquefied wood cannot be easily formed into graphite.
