稻草中密度纤维板用改性脲醛树脂的研究

对比三聚氰胺、二甲基硅油、硅树脂和偶联剂KH-550四种改性剂改性的脲醛(UF)树脂性能的差别及其对稻草中密度纤维板性能的影响,并进行经济评价,最终确定适用于稻草纤维板的改性UF树脂的工艺条件,同时借助于红外光谱(FT-IR)和差热扫描分析(DSC)研究最佳改性UF树脂的结构和固化特性.结果表明,三聚氰胺改性脲醛(MUF)树脂不论是对树脂性能、板性能改善还是从成本分析方面均为稻草纤维板最佳的胶黏剂,FT-IR显示出与未加三聚氰胺相比,加入三聚氰胺后树脂的羟甲基含量降低了10 %,DSC分析则表明其峰值温度有较大幅度的提高,但放出的热量较少.加入三聚氰胺改性的UF树脂其表面张力变小.     

Lignin distribution in wood from a progeny trial of genetically selected Pinus radiata D. Don

Summary Cell wall lignin distribution was assessed in Pinus radiata wood using quantitative interference microscopy. Three groups of trees were examined. Five trees, offspring of NZ clone 850-55, and five trees of NZ 850-55 crossed with several parents of the Guadelupe provenance, were compared with five trees of unselected P. radiata. Lignin concentration in the cell corner middle lamella region was significantly lower in both offspring groups of NZ 850-55 when compared with the unselected control trees. No difference in S2 lignin concentration was observed among the three groups. This result represents the first indication that variations in lignin distribution are genetically controlled in pines.The author gratefully acknowledges the assistance of Dr. C. J. A. Shelbourne, Mr. G. D. Young, FRI, and Mr. R. S. Foster, Papro (NZ), during the course of this work     

The validity of the use of SEM/EDAX as a tool for the detection of UF resin penetration into wood cell walls in particleboard

Summary The interpretation of data from scanning electron microscopy (SEM) combined with energy dispersive analysis of X-rays (EDAX) is dependent on the size of the excitation volume, the magnitude of which for organic materials such as wood has been little studied. From the analysis of a model system comprised of a thin layer of gold sandwiched between two layers of an epoxy plastic, it was shown that about 90% of all excitations arise from a volume about 6 m wide and 4 m deep. However, these dimensions vary with the orientation of the gold relative to the specimen surface, and the specimen tilt. Theoretical predictions based on these data support, but not conclusively, the previously published SEM/EDAX evidence of the penetration of urea formaldehyde resins into the wood cell wall in particleboard manufacture.This paper was written while A. J. Bolton was Heritage Visiting Scientist at the Forest Products Laboratory, U.S. Department of Agriculture, and Visiting Professor at the Department of Forestry, University of Wisconsin, both at Madison, Wisconsin, U.S.A. This support is gratefully acknowledged. The authors would also like to acknowledge the assistance of E. Edwards in machining the SEM specimens     

我国脲醛树脂制备技术研究概述

介绍了我国近年来脲醛树脂制备技术和实际应用概况,总结了生产实践中较为实用的树脂制备和改性方法,探讨了脲醛树脂目前存在问题,并指出发展方向。     

An immersion technique for studying wood wettability

Summary The wetting properties of wood were studied by a modification of the Wilhelmy technique. This method involved continuously monitoring the force exerted on a wood specimen as it was immersed at a controlled rate into a liquid. Wettability was expressed in terms of the area under the force-immersion curve and was referred to in this study as wettability index. The applicability of the technique was demonstrated for padauk and white spruce wood specimens heated for various time periods. The wettability of these woods in both distilled water and sodium hydroxide solutions decreased with increasing heating time. Sodium hydroxide solution yielded higher wettability index values, indicating that it was a better wetting agent than distilled water. The pH of the sodium hydroxide solution had a strong influence on magnitude of the wettability index. The possibility of using the technique for examining wood surface inactivation in relation to bonding with different adhesives is discussed.The authors gratefully acknowledge the assistance of Dr. W. G. Warren and his staff for the statistical analyses and curve fitting. Dr. Casilla also expresses his gratitude to the National Research Council of Canada and to the Canadian Forestry Service, Department of the Environment, for a postdoctoral fellowship     

Stress model of a wood fibre in relation to collapse

A wood fibre cell from a Tasmanian Eucalypt is typically cylindrical in shape with a length to diameter ratio of approximately 501. Early in the process of seasoning for solid timber, when the fibre lumens are still saturated, internal tension within a fibre can rise to a value high enough to cause it to physically flatten, or collapse. A stress model of a fibre cell has been developed which predicts the stress and strain distributions within the fibre wall as a function of temperature, moisture content, and fibre wall strength properties and size in the early stages of drying. This model will be used together with measurement of the behaviour of collapse prone timbers to determine conditions which will avoid collapse during seasoning.The author is pleased to acknowledge the assistance of Emeritus Professor A. R. Oliver, Associate Professor P. E. Doe, University of Tasmania, and the Australian Furniture Research and Development Institute     

On the fine structure of bamboo fibres

Summary The thick-walled bamboo fibres exhibit a polylamellate structure with alternating broad and narrow lamellae. Characteristically the cellulose fibrils in the broad lamellae are oriented almost parallel to the longitudinal axis of the fibre (2–20°), whereby there is a gradual but only slight increase in the angle from middle lamella to lumen. The narrow lamellae consist of fibrils oriented almost perpendicular to the cell axis (85–90°); this angle remains constant in all the successive narrow lamellae. The concentration of lignin is higher in the narrow lamellae than in the broad ones. Xylan seems to occur in a higher concentration in the narrow lamellae. The pits between the fibres are bordered. The results are discussed in relation to earlier data on wall structure and development. A model for the thick-walled bamboo fibre is presented with a new terminology for the various lamellae.We are thankful to Mrs. R. Schultze and Miss B. Schröder for their technical assistance. Grateful acknowledgement is also due to Dr. D. Keyser and Mrs. K. Hoffmann for the SEM facilities and to Prof. Dr. J. Bauch and Mrs. R. Endeward for the UV-microspectrophotometry. Prof. T. E. Timell (Syracuse) and Dr. O. Faix were helpful with the preparation of hydrofluoric acid concentrations.     

基于UFC和葡萄糖改性脲醛树脂的合成与性能

在碱性条件下用尿素和甲醛合成脲醛预缩液(UFC),然后用UFC与尿素制备脲醛树脂(UFC/U),并添加葡萄糖对UFC/U改性得到G/UFC/U树脂,采用DSC和FT-IR等对树脂进行分析。结果表明:与普通脲醛树脂(UF)相比,UFC/U树脂胶合强度提高5.83%,游离甲醛含量降低3.70%,G/UFC/U树脂贮存期大于30 d,综合性能较好,G_1-25/UFC/U树脂游离甲醛含量降低44.44%,胶合板湿胶合强度为1.11 MPa,优于国家II类胶合板标准;DSC结果表明:UFC/U、G_1-25/UFC/U比UF树脂的固化特征温度高;FT-IR分析表明:G_1-25/UFC/U和UF树脂相比,羟基及亚甲基醚键的峰强度增强,改性树脂的羟甲基优先和葡萄糖分子C(6)的羟基发生反应生成亚甲基醚键。     

纳米结晶纤维素改善脲醛树脂胶黏剂游离甲醛的研究

为了降低脲醛树脂胶黏剂的游离甲醛释放量,以俄罗斯落叶松浆粕为原料,利用酸水解,硅烷偶联剂改性等制备获得表面改性纳米结晶纤维素(M-NCC),并将M-NCC作为吸附材料用于脲醛树脂基材制备胶合板,研究M-NCC对脲醛树脂胶黏剂游离甲醛的吸附效果和机理。结果表明:透射电镜(TEM)检测可知,制备的NCC颗粒长度约为100~200 nm、直径约为20~30 nm,结晶度为57.3%,相比原始纤维素提高了41.1%;硅烷偶联剂3-(2-氨乙基)-氨丙基甲基二甲氧基硅烷(MCPS)使NCC的浸润性显著增强,当MCPS用量为8%时M-NCC接枝率达到27.2%,M-NCC对脲醛树脂的接触角为65.7°,下降32.7%;由扫描电镜(SEM)照片可观测到,表面改性显著改善了低浓度NCC颗粒在脲醛树脂基材中的分散状态,当M-NCC质量分数2%时,纳米颗粒的分散性能明显下降;M-NCC可有效吸附脲醛树脂基材中的游离甲醛,当M-NCC质量分数1.5%时可致游离甲醛比对照组(0.51 mg/L)下降50.9%。     

Kraft lignin utilization in adhesives

Summary The utilization of lignin from Pinus radiata black liquor, as a copolymer in ligninphenol-formaldehyde resin binders was studied. Methylolation, demethylation and ultrafiltration separation of high molecular-weight fractions were carried out in order to increase lignin reactivity. The different modified lignins were tested in preparation of lignin-phenolformaldehyde resin binders. Mechanical properties and water resistance were evaluated through testing particleboard panels manufactured with the resins obtained. The best resin was composed of 18,8% ultrafiltrated high molecular weight lignin, 22,9% phenol and 58,3% formaldehyde and had comparable properties with typical commercial resins prepared only with phenol and formaldehyde. An economic analysis was made in order to compare possible benefits obtained through the replacement of phenol by lignin products. The ultrafiltrated lignin copolymer was significantly less costly than a phenol-formaldehyde resin and had comparable physical and chemical properties.The authors acknowledge financial support from the Office of Research, Catholic University of Chile (DIUC) and the National Science Foundation of Chile (CONICYT)     

利用响应曲面法优化脲醛树脂合成工艺

使用响应曲面法研究尿素添加次数和尿素添加时间间隔对脲醛树脂性能和其板材性能的影响,使用傅里叶红外光谱仪定性分析尿素添加次数和尿素添加时间间隔对脲醛树脂主要基团的影响。结果表明:尿素添加次数和尿素添加时间间隔对脲醛树脂的固体含量及固化时间影响不大,而对黏度、树脂中羟甲基含量、游离甲醛含量、各主要基团含量和板材的性能有很大影响。树脂合成工艺中2次添加尿素,间隔时间20min时,树脂和板材性能比较好。     

无机硅化物接枝脲醛树脂木材胶粘剂

介绍了一种新型无机硅化物接枝脲醛树脂胶粘剂制备方法及性能,并与普通脲醛树脂进行了对比实验。该接枝脲醛树脂游离甲醛含量较低,胶合强度优良,耐水性、耐热性、耐燃性良好,适用于人造板的制造。     

Comparative studies on lignin distribution by UV microscopy and bromination combined with EDXA

Summary In order to elucidate a previously reported discrepancy in the ratio of the lignin concentration in the middle lamella to that in the secondary wall as determined by ultraviolet (UV) microscopy and bromination combined with EDXA, the ultraviolet absorptivity of the lignin and the lignin reactivity towards bromination were compared for black spruce wood (Picea mariana Mill.). In addition, UV microscopy and EDXA techniques were applied to the determination of lignin distribution in the tracheids in order to establish the relationship between the two techniques. The results indicated that, although the ultraviolet absorptivity in different morphological regions is essentially the same, the secondary wall lignin was 1.70 times more reactive towards bromination than the middle lamella lignin. By applying the value of 1.70 as a correction to the EDXA results, the estimated lignin distribution by EDXA was in fairly good agreement with that from UV microscopy.The authors would like to thank Dr. J.-F. Revol and Dr. M. Tsuji for their assistance during this study     

有机/无机复合浸渍液对杨木的改性处理

利用脲醛树脂／丙烯酸酯乳液／硅溶胶三元复合浸渍液制备复合木材,并与杨木素材为对照。采用红外光谱研究复合木材的组成变化,热分析研究其热稳定性的变化,并研究了复合木材的力学性能。结果表明,杨木中的功能基团与复合浸渍液中的脲醛树脂可发生键合作用,使改性木材的热稳定性及力学性能均有所提高。     

Variation of tensile strength along the length of lumber

Summary A model has been developed for the within member variation of tensile strengths parallel to grain in nominal 38 × 89 mm No. 2 Spruce-Pine-Fir lumber. Tensile strength data from two modulus of elasticity matched groups were considered. Model parameters obtained from data group 1 were used to generate tensile strength profiles of lumber 6.10 m long. Within member tensile strength cumulative probability distributions of the simulated data were evaluated by window analyses. The spatial correlation of the simulated data were evaluated by semivariogram and regression analyses. Good agreement was obtained between model predictions and test results of both groups.The authors gratefully acknowledge the support of the Canadian Forest Service and the technical assistance of Mr. H. Sue, Mr. B. Deacon and Dr. J. Cook for this study. The research was performed while the principal author was working at Forintek Canada Corp.     

三聚氰胺脲醛树脂改性酚醛树脂胶粘剂的研究

采用常规合成的脲醛(UF)或酚醛(PF)树脂胶对多层胶合板贴面时，很容易出现开胶或透胶现象。本研究采用三聚氰胺脲醛(MUF)树脂对PF树脂进行改性，生产浅色改性PF胶粘剂，探讨了MUF与PF树脂摩尔比、混合比、热压条件等对胶液的粘度、缩合度、稳定性、胶层颜色及胶合质量的影响。结果表明，改性后的浅色酚醛树脂胶粘剂筘存性好、固化后胶层近似木材本色、高强耐水、耐候，用来压制的多层实木复合地板可达到GB9846．1～12-88Ⅰ类胶合板要求。     

Relationship between fracture toughness and acoustic emission during cleavage failure in adhesive joints

Summary Fracture toughness in mode I was determined for wood bonded with various adhesive systems. Tapered double-cantilever beam (TDCB) specimens were used, with attached transducer connected to instrumentation for monitoring acoustic emission. Adhesives used fro bonding the TDCB specimens included urea-formaldehyde resin, phenol-resorcinol resin, and emulsion polymer isocyanate, among others. Test parameters measured included critical load for cleavage fracture and number of events (stress waves) emitted, from which fracture toughness and cumulative count of acoustic emission were computed. It was found that there was a well defined, linear relation between fracture toughness and cumulative counts of acoustic emission per fracture area. The fracture toughness values of systems containing polyvinyl acetate and of epoxy resin were larger than those of thermosetting resins such as urea-or phenol formaldehyde. The high fracture toughness imparted by polyvinyl acetate was attributed to viscous movement of linear molecular chain segments, as compared with the more brittle behavior of the crosslinked molecular structure of such resins as ureaformaldehyde.     

基于纳米压痕技术的木材胶合界面力学行为

【目的】研究木材胶合界面的静态和动态力学行为,探讨树脂渗透对木材管胞壁层力学性能的影响,为木质复合材料制造工艺优化和增强改性提供理论依据。【方法】采用纳米压痕静态和动态力学测试技术(Nano-DMA),对针叶材火炬松与酚醛树脂(PF)、脲醛树脂(UF)胶黏剂所形成胶合界面区域各相材料的静态弹性模量、硬度、蠕变性能以及储能模量和损耗模量等力学行为进行分析。【结果】静态力学行为方面,在界面区域,PF和UF渗透进入管胞壁层后,木材管胞壁的弹性模量( E r)和硬度( H )提高;经PF渗透后,木材管胞壁的 E r和 H 分别增加7%和26%;Burgers蠕变力学模型可有效描述胶合界面区域管胞壁的纳米压痕蠕变特性,经树脂渗透后,木材管胞壁的瞬时弹性模量增加,黏弹性模量和黏性系数减小;在保载初期,PF界面区域木材管胞壁的蠕变柔量约下降60%,UF界面区域木材管胞壁的蠕变柔量约下降58%。动态力学行为方面,随着加载频率增加,界面材料的储能模量( E ′ r)逐渐增大,而损耗模量( E ″ r)和损耗因子(tan δ)呈减小趋势;当加载频率为10 Hz时,PF和UF树脂渗透使得管胞壁层的储能模量分别增加16%和29%。【结论】胶合界面区域胶黏剂进入管胞壁层,对木材管胞的静态力学性能具有增强作用,同时胶黏剂可提高管胞壁的短期抗蠕变能力;木材管胞壁具有较高的储能模量和损耗模量,而树脂的储能模量和损耗模量较低,经树脂渗透后,木材管胞壁的储能模量增加,但损耗模量和损耗因子呈下降趋势,可能对界面传递和分散应力产生不利影响。     

苯酚-尿素-甲醛共缩聚树脂结构形成比较

用13C NMR 定量分析跟踪研究了两种不同合成路线中苯酚-尿素-甲醛共缩聚树脂(PUF)结构形成过程,比较了3种PUF树脂的结构构成.研究发现树脂制备过程中的酸性环境导致脲醛树脂初聚物含量增加以及尿素与苯酚之间的共缩聚增加;合成反应初期的介质环境对羟甲基酚的形成有着决定性的影响;合成过程中酸性环境所处阶段不同,最终树脂结构出现差异.     

木材工业用脲醛树脂的研究进展

对脲醛树脂的理论研究及其在木材工业中的实际应用进行了较全面的概括和评述。在将核磁共振应用于脲醛树脂的结构研究之后,区分了结构上的细微差别。讨论了脲醛树脂的合成过程,特别是酸性缩聚阶段的工艺条件对树脂甲醛释放量的影响。列举了脲醛树脂常用的各种改性物质及它们对脲醛树脂各种性能的改性效果。