Kinetics of the hydroxymethylation of phenol II: values of rate parameters and results of simulation experiments

The reaction course of the sodium hydroxidecatalyzed hydroxymethylation of phenol was analyzed by use of high-performance liquid chromatography (HPLC), and the rate constants for the seven reactions taking place consecutively and competitively were evaluated by means of a computer simulation technique. Calibration was done at the quantification of the six phenolic monomers from the peak areas in the HPLC chromatogram, taking the differences in molar ultraviolet absorption intensities of the six compounds into account. The values of the energies of activation for the seven reactions obtained differed greatly from those reported by Eapen and Yeddanapalli. Simulation experiments carried out by use of the newly obtained rate parameters showed that the amounts of phenol left unreacted and 2,4,6-trihydroxymethylphenol in the final reaction product increased as the reaction temperature was increased and the alkali/phenol molar ratio decreased. These phenomena can be attributed to the differences in the energies of activation for the seven reactions and differences in the acid strengths of the six phenolic monomers.Part of this paper was presented at the 48th annual meeting of the Japan Wood Research Society, Shizuoka, April 1998 and at the 1998 annual meeting of the Forest Products Society, Merida, Mexico, June 1998     

TiO2/核桃壳炭复合材料的制备及光催化降解苯酚研究

为提高TiO2的回收性能,促进农林废弃物的资源化利用,以核桃壳为炭源,采用溶胶 凝胶法制备TiO2/核桃壳炭复合材料。通过傅里叶红外光谱、X射线衍射、比表面积和电镜扫描等手段对复合材料的化学和晶相结构、比表面积和微观形貌进行表征,并测试其对苯酚的吸附 光催化性能。物相表征结果显示,TiO2/核桃壳炭(400℃,2 h)中TiO2以锐钛矿相颗粒分散在核桃壳炭表面,炭的固载提高了TiO2的分散性能,使其晶粒尺寸由15.7 nm降低至11.6 nm,增强了可见光吸收能力。活性分析结果表明:当TiO2含量为80%,催化剂用量为2 g/L,苯酚初始质量浓度为10 mg/L,紫外光照射240 min时,TiO2/核桃壳炭(400℃,2 h)对苯酚的降解率为97.7%,化学需氧量降解率为92.36%,优于TiO2(分别为71.55%和63.34%)和商业购买的平均粒径为25 nm的锐钛矿晶和金红石晶混合相的TiO2(降解率88.56%),且几乎完全矿化,符合一级反应动力学方程。TiO2和TiO2/核桃壳炭光催化降解苯酚的主要活性中心分别为·OH和·O-2,核桃壳炭的负载提高了TiO2吸附 光催化苯酚性能和回收效率。     

热分析法研究青蒿素的纯度、热分解动力学及贮存期

利用差示扫描量热技术测得青蒿素在氮气气氛中不同升温速率下的热分析曲线,采用Van’t Hoff方程建立回归曲线求得青蒿素的纯度和熔点,使用Kissinger法、Flynn-Wall-Ozawa法和Phadnis法等3种方法同时进行动力学分析。根据热分解的表观活化能(Ea)和指前因子(A)计算推断青蒿素在室温下的贮存期。研究表明,随着升温速率的提高,青蒿素的热分解温度逐渐升高;青蒿素热分解的机理是二维扩散控制,对应的函数名称是Jander方程;经Gaussian模拟青蒿素的分子键级和原子电荷数,能够对190℃时分解产生3个化合物的机理进行验证吻合;根据青蒿素热分解的Ea和A推断,在室温25℃下,青蒿素的贮存期为3年。     

Collapsing process simulations of timber structures under dynamic loading II: simplification and quantification of the calculating method

In a previous paper we presented the efficacy of the extended distinct element method (EDEM) on the collapsing process simulation of timber-frame structures. The results obtained were qualitative, and the need for quantitative simulation was pointed out. In this report, we improved our simulating programs with the aim of establishing a quantitative simulation by EDEM. For this purpose, the parameters of the frame members (beam or column) were determined by comparing the simulated results of four-point bending tests with experimental results. Other parameters of plywood and joint members were determined by simulations of two rail shear and slip tests of joint parts, respectively. Using these parameters we made simulations of the collapsing process of an actual-size plywood-sheathed wall and at the same time carried out the experiments under similar conditions. Simulated load–displacement curves of the plywood-sheathed wall were similar to those obtained in the experiments, and the sequence of failure at nailed joints of the simulation model gave good agreement with that of the experimental collapsing processes. Using these processes, we believe that we established a basic quantitative simulation method to test the collapsing process of timber-frame structures.Part of this paper was presented at the 52nd Annual Meeting of the Japan Wood Research Society, Gifu, April 2002; and at the 7th World Conference of Timber Engineering, Malaysia, August 2002     

Collapsing process simulations of timber structures under dynamic loading I: simulations of two-story frame models

In this study we tried to develop an analysis program that can simulate the collapsing process of timber-frame structures under dynamic loading by adopting the extended distinct element method (EDEM). Using the EDEM, it is possible to trace the movement of any parts that were separated from unity after the failure of connecting elements, a property that fits our purpose well. As a preliminary study, simple two-story frame structures were modeled and examined by our program. Each model is an assembly of frame members composed of the EDEM elements. The spring elements of the joints have less rigidity than those of the frame members. Several models were analyzed under dynamic loading. The models varied in the configuration of bracing shear walls. Experiments with a one-ninth model were carried out under similar conditions, and the results were compared with the results from numerical simulations. Simulated results showed various collapsing processes corresponding to the arrangement of the bracing shear wall, and the simulated aspects gave good agreement with the results of the experiments under similar conditions.Part of this paper was presented at the 50th Annual Meeting of the Japan Wood Research Society, Kyoto, April 2000     

微晶纤维素氰乙基化及其反应动力学研究

通过微晶纤维素的氰乙基化试验,研究了反应温度和反应时间对氰乙基化产物取代度(DS)的影响,表明在50℃以下,微晶纤维素的氰乙基化取代度随反应温度的升高和反应时间的延长而增加。傅里叶红外光谱分析显示微晶纤维素氰乙基化后羟基峰明显减弱,并形成了新的碳氮三键吸收峰,证明纤维素中的部分羟基氢被氰乙基所取代。X射线衍射分析显示微晶纤维素中原有的结晶结构被破坏。X4显微熔融温度测定仪、维卡软化点测定仪等的分析表明微晶纤维素氰乙基化产物的热塑性先随取代度的升高而提高,取代度超过1.43后,产物的热塑性又随取代度的升高而下降。确定了微晶纤维素氰乙基化在不同温度(30、35、40和45℃)下的反应速率常数(分别为1.30、1.61、1.94和2.26 s-1),计算出了微晶纤维素氰乙基化反应的表观活化能为29.8 kJ/mol。     

Kinetics and FTIR characteristics of the pyrolysis process of poplar wood

The pyrolysis characteristics of residues of poplar (Populus sp.) wood were investigated using a thermogravimetric analyzer coupled with a Fourier transform infrared (TG-FTIR) spectrometer. The pyrolysis process was subdivided into four stages at a rate of 10℃·min-1 , varying from 30 to 650℃. Below 180℃, a mass loss occurred for drying and preheating the sample and the onset temperature of pyrolysis ranged between 180-260℃. A significant mass loss of 61.4 wt.% occurred between 260-380℃, followed by a slow and continuous mass change with lignin devolatilization. The analysis of kinetic reactions showed that the activation energy (78.29 kJ·mol-1 ) in the low-temperature section was much larger than that (6.40 kJ·mol-1 ) in the high-temperature section. The evolved gases formed by thermal degradation of poplar wood were simultaneously analyzed by FTIR. It was observed from the main peaks that the emissions evolved during poplar wood pyrolysis were acetic acid, carbon dioxide, carbon monoxide, methane, water, some volatile com- pounds of esters, alcohols and aldehydes. The emissions gradually increased with rising temperatures before a strong peak around 360℃ and then decreased. Most gaseous products were emitted in the 320-380℃ range, while CO2 was continuously emitted in a wide range from 140-550℃.     

Pseudodynamic tests and earthquake response analysis of timber structures I: plywood-sheathed conventional wooden walls with opening

Pseudodynamic (PSD) lateral loading tests were conducted on conventional post and beam timber frames with plywood-sheathed shear walls to validate the dynamic model of wall panels, each with an opening of a different configuration. The lateral forces were applied step by step at the top of the wooden frames by the computer-controlled actuator, and the displacement response for the next step was computed on the basis of the input accelerogram of the 1940 El Centro earthquake scaled up to 0.4g. The test results were compared with those of the lumped mass time-history earthquake response analysis using the hysteresis model with pinching. The results of the dynamic analysis with this global model consisting of the envelope curves, unloading and reloading with pinching agreed well with the experimental results of the PSD tests of this type of earthquake record. Some parametric studies may be necessary, however, to validate the model with different earthquake records. The hysteretical parameters obtained in this study showed similar values for each of the wall panels with different opening configurations. This makes it possible to use the model and parameters for the plywood-sheathed shear walls to estimate the dynamic behavior of entire structures without conducting expensive PSD tests or shaking table tests.     

银杏幼苗叶片转化酶活性及其动力学

采用波钦诺克XH法研究了田间和室内栽培的银杏幼苗叶片转化酶的活性及其动力学性质。结果表明:银杏幼苗叶片转化酶在pH值5.0、温度55℃时活性最强;该酶的米氏常数为3.7×10-2mol·L-1;室内盆栽的银杏幼苗叶片转化酶的活性显著高于田间栽培的同龄银杏幼苗叶片转化酶的活性。     

Chemical changes of kenaf core binderless boards during hot pressing (I): influence of the pressing temperature condition

Self-bonding is the main factor of the performance expression of binderless boards, and therefore its clarification is considered to be an important issue. For this purpose, a series of chemical analyses were conducted on kenaf core binderless boards and their chemical changes during the hot-pressing process are discussed in this article. First of all, binderless boards were prepared from kenaf core powder at different pressing temperatures (without steam-explosion process) and were used for chemical analyses after they were reduced into powders and extracted with methanol. To investigate their chemical changes, lignin, holocellulose, and neutral sugar contents were determined, Fourier transform infrared (FTIR) spectra were recorded, and the nitrobenzene oxidation procedure was applied. As a result, it was found that parts of lignin and hemicelullose were decomposed during the hot-pressing process; however, the contribution of the resulting fractions to selfbonding was not observed. In addition, progress of condensation reactions in lignin and the formation of chemical bonds by low molecular weight conjugated carbonyl compounds in methanol extractives were observed. Thermal softening of lignin is also suggested to play an important role in the expression of board performance.     

Dependence of reaction kinetics and physical and mechanical properties on the reaction systems of acetylation I: reaction kinetic aspects

The dependence of the reaction parameters of acetylation on the reaction mixture was compared among uncatalyzed, acetic anhydride-xylene mixed, and acetic anhydride-pyridine mixed solutions. Wood meal and blocks were used to examine the effect of sample size. A first-order rate equation was applied to the data, and a rate constant and leveling off value of weight gain (WG) were estimated. The rate-determining step was examined from the viewpoint of activation energy. The results were as follows: (1) Regarding the magnitude of the rate constant, the order was pyridine system > uncatalyzed system > xylene system. (2) The ultimate value of WG was lower in the uncatalyzed and xylene systems than the pyridine system, probably because of the swelling ability of pyridine. (3) The activation energies of acetylation estimated for wood meal were 120, 135, and 110kJ/mol for the uncatalyzed, xylene, and pyridine systems, respectively. (4) The characteristics of the diffusion-controlled reaction became marked when the acetylation was carried out in the pyridine system, at elevated temperature, and for wood blocks. Under these conditions, the supply of reagent to the reaction site might not be sufficient to fuel the reaction.Part of this report was represented at the 52nd Annual Meeting of the Japan Wood Research Society, Gifu, April 2002     

Deformation analysis of timber-framed panel dome structure I: simulation of a dome model connected by elastic springs

This study develops an analytical method that enables the simulation of the deformation of timber-framed plywood panel dome structures, of which strength is largely governed by the rigidity of joints. A hybrid truss structure model was employed to analyze this structure. In this model, we aimed to incorporate the mechanical properties of bolted and nailed joints, which were employed to build the structures, although the present investigation focused on the deformation characteristics of a dome in which the panel elements were connected mutually by elastic springs. The results of the theoretical analysis are compared with those obtained by experiments. The simulated results were found to be in good agreement with the results of the experiments under similar loading conditions.     

Contribution of lignin to the reactivity of wood in chemical modifications I: influence of delignification on acetylation

In order to examine the contribution of wood components to the acetylation of wood, we acetylated wood meal that had been partially delignified. The results were analyzed in terms of the reaction kinetics. The first-order rate equation was successfully adjusted to the weight gain data. The rate constant for acetylation initially increased with progress of lignin elimination and then turned to decrease; the apparent activation energy showed the reverse tendency and ranged from about 90 to 130 kJ/mol. These results suggest that lignin elimination brings not only separation of lignin but also drastic change of the chemical and/or physical structure in the residual lignin, and this affects the reactivity of wood meal as a whole. The ultimate weight gain estimated by the regression of the rate equation showed a minimum when lignin was moderately eliminated, which was explained in terms of enhanced reactivity of lignin and lower accessibility for holocellulose than predicted. The equilibrium moisture content had a maximum when lignin was moderately eliminated. This tendency is the opposite of that observed for the ultimate weight gain, and suggests that the sites for acetylation do not always correspond to those for moisture adsorption. Part of this report was presented at the 54th Annual Meeting of the Japan Wood Research Society, Sapporo, August 2004     

Predicting maize and soybean production in a sheltered field in the Cornbelt region of North Central USA

Shelterbelts (field windbreaks) are an important tool for farming in semi-arid areas but are not commonly used. An obstacle to the adoption of shelterbelts is the lack of site-specific information about the benefits and costs associated with establishing and maintaining them. A group of researchers has been developing a modeling system that will estimate site-specific effects, benefits, and costs for sheltered fields that produce maize or corn (Zea maize) and soybean (Glycine max) in the U.S. Corn Belt region. Akey component of the modeling system is the use of the CROPGRO-Soybean and CERES-Maize models to simulate yield response to microclimatic changes acrossa sheltered field. In this work, we tested the ability of both models to simulate yield in a sheltered field, evaluated the potential yield increase of shelterbelts based on long-term simulations, and compared the influence of shelter induced changes in temperature and windrun on yield. Both models simulated yield increases due to shelter. The soybean model was more responsive to microclimatic differences than the maize model. Long-term simulations generally showed a field level increase in yield due to shelter for maize and soybeans with an average increase of 4.1 and 3.3, respectively. Change in windrun due to shelter is more important in increasing yield than changes in temperature. The CERES-Maize model seems to be more sensitive to changes in windrun than the CROPGRO-Soybean model.     

Stem taper equation analysis for Larix kaempferi species in the Central Region of South Korea

Taper equation was developed to predict diameters at specific height for Larix kaempferi species in the Central Region of South Korea. The sampled trees that were collected through destructive sampling ranged from 0.60 to 47.90 cm DBH with total height ranging from 2.00 to 33.00 m. The dataset was randomly split into two: 80% for initial model fitting and 20% for model validation. The combined that means 100% dataset was used for final model fitting. Statistics of fit were used as criteria, including the coefficient of determination (R²), standard error of the estimate (SEE), bias (ē), the absolute mean difference (AMD), and the Akaike information criterion (AIC) values and weight (AICw), with a rank analysis being applied. Initial model fitting utilized a total of nine taper equations, with the three segmented taper equations and another three non-segmented determined for model validation and final model fitting. Kozak02 equation, which had not yet been evaluated for L. kaempferi species, indicated the best performance for the species in the Central Region of South Korea. Upon comparison, the ability of this study to predict diameters at specific height and stem volume was better than the existing taper equation for L. kaempferi in South Korea.     

大兴安岭东南部兴安落叶松胸径生长率与材积生长率的关系研究

兴安落叶松 ( L arix gmelini,以下简称落叶松 )是大兴安岭林区的主要树种 ,文章研究落叶松胸径生长率与材积生长率的关系 ,建立数学模型 ,使之通过测算胸径生长率来预测材积生长率 ,为简化材积生长量调查提供了理论依据。     

以电导法配合Logistic方程确定不同冬青抗寒性

采用人工模拟低温处理技术测定了6种(含品种)冬青树种离体叶片的相对电导率,并用Logistic方程计算它们的半致死温度(LT50)。结果表明:6种(含品种)冬青耐低温能力有显著差异,由高到低依次为克恩氏冬青>欧洲冬青>大别山冬青>‘蓝少年’冬青>杂种冬青>‘蓝少女’冬青,其半致死温度值LT50在-11～-24℃之间。     

Mechanical properties of wood in an unstable state due to temperature changes,and analysis of the relevant mechanism IV: effect of chemical components on destabilization of wood

In order to investigate the effects of chemical components and matrix structure on the destabilization of quenched wood, we examined the physical and mechanical properties of steam-treated wood, hemicellulose-extracted wood, and delignified wood, which were treated at different levels. For steam-treated and hemicellulose-extracted wood,the relative relaxation modulus of the quenched sample was lower than that of the respective control sample. For delignified wood, the relative relaxation modulus fell with weight loss and reached a minimum value at a certain weight loss, and subsequently increased significantly. The hygroscopicity of all treated samples changed slightly by steaming, whereas increased with removing the component. More-over, the average volumetric swelling per 1% MC at 100% relative humidity (RH) was less than at 75% RH and 93% RH for component-removed wood. It was clear that a void structure existed. As a result, the destabilization evaluated by the fluidity (1 - E _t/E ₀) of steam-treated wood was influenced by the amount of adsorbed water. For component-removed wood, destabilization increased temporarily at lower weight loss because of nonuniform cohesive structure. At high weight loss, destabilization will decreased because capillary-condensed water gathered in the voids and obstructed the motion of adsorbed water. However, the destabilization of all treated wood changed less than that of chemically modified wood.     

AN ANALYSIS OF AND APPROACH TO THE METHOD FOR TESTING THE PARALLELISM OF SAW GUIDE MOTION LOCUS AGAINST THE BLADE

UNDERSTANDINGoFTHESTANDARDSIntheWoodworkingBandSawing--MachineandCarriagePrecision(GBlo956-89),thetechnicaldemandsoftheparallelismofsawguidemotion1ocusagainstthebladeareasfollows:usingthetestingsteelbandandindicatortotestandmeasure,itsparallelismtoleranceiso.lommatalengthof3oomm.ltstestingmethod,referto"Theindicatorisfixedtothemotioncomponent,andmovestogetherwithitaccordingtotheregularrange,itsmeasuringheadtouchestheplanetested,andslidesalongit;themaximumdifferencevalueoftheindic-…     

计算机在家具结构设计与制图中的应用

利用计算机辅助设计中的自动参数化软件整体设计家具，只要确定产品外观尺寸，就能一次性绘出产品的结构装配图和零件图，达到提高制图效率和制图质量的目的。