ACQ防腐处理对马尾松木材胶合强度的影响研究

采用铜氨(胺)季铵盐(ACQ-D)防腐剂处理马尾松木材,以水性高分子异氰酸酯(API)、聚氨酯(PUR)和间苯二酚-苯酚-甲醛树脂(RPF)为胶黏剂制备防腐材胶合试样,研究胶黏剂种类和防腐剂处理浓度对马尾松胶合强度的影响。结果表明:API、PUR、RPF适用于ACQ处理马尾松的胶合,平均剪切强度和木破率均达到GB/T 26899—2011《结构用集成材》要求。胶黏剂种类对防腐材胶合强度有显著影响,表现为PUR和RPF的剪切强度优于API。与未处理材相比,ACQ处理对API胶合有负面影响,对PUR胶合有增强效应,对RPF胶合没有显著影响。在ACQ浓度为0.1%～1.0%范围内,胶合强度没有显著变化。     

新型酚醛树脂改性大豆蛋白基胶黏剂的研究

以脱脂大豆粉为原料制备大豆蛋白基胶黏剂(豆胶,S),以普通甲醛制备的酚醛树脂(PF_1)和高浓度甲醛制备的酚醛树脂(PF_2)为交联剂,使用前将两者直接混合得酚醛树脂改性豆胶(PF_1/S、PF_2/S)。利用差示扫描量热(DSC)、红外光谱(FT-IR)、动态热机械性能(DMA)和核磁共振碳谱(~(13) C NMR)分析对产品性能进行了测试与表征。结果表明:等物质的量之比条件下,高浓度甲醛较之普通甲醛制备的酚醛树脂改性豆胶胶合板干、湿剪切强度分别提高4.3%和11.6%,并且强度稳定性好;动态DSC分析表明,PF_2可以降低豆胶体系的固化温度和活化能,与豆胶的交联反应较容易;~(13) C NMR分析表明,PF_2体系羟甲基达88.73%,明显高于PF_1的80.91%;FT-IR分析证实酚醛树脂与豆胶中的氨基发生反应,并且PF_2反应效率更高;DMA分析表明,PF_2/S能够改善胶合产品的力学性能和热稳定性,降低豆胶的固化反应起始温度,提高固化反应速率。     

Physical properties and termite durability of maritime pine Pinus pinaster Ait., heat-treated under vacuum pressure

An original heat treatment performed under vacuum pressure was investigated. Maritime pine samples were treated at six different temperatures: 140, 160, 180, 200, 230 and 260°C. The physical and mechanical consequences, i.e. bending strength (MOR), modulus of elasticity (MOE), hygroscopic behaviour, equilibrium moisture contents and anti-swelling efficiency (ASE) were studied. A no-choice feeding test according to the NF EN 117 standard was achieved. Temperatures up to 200°C had no significant effect on wood properties. However, at 230 and 260°C, the decrease in MOR was severe, reaching 42.5 and 62.5%, respectively. Whatever the treatment conditions, wood samples were still highly degraded by termites, revealing no increase in their durability.     

Durability of isocyanate resin adhesives for wood IV: degradation under constant steam heating

The durability of isocyanate resins consisting of emulsion-type polymeric diphenylmethane diisocyanate (EMDI) was investigated under constant steam heating. Two kinds of resin, water only-added resin and polyol/water-added resin, were used in this study. The degradation of the resins under steam heating was observed using Fourier transform infrared spectroscopy (FT-IR), weight changes, and thermogravimetric analysis (TGA). FT-IR analysis showed that the degradation reaction of the resins scarcely proceeded for a few hours and then increased significantly. The weights of the resins decreased linearly during steam heating. The thermal stability of steam-treated resins was made clear by TGA. The bond strength reductions of the specimens bonded with the resins were also observed. The best fitting regression function for the behavior of bond strength reduction was determined statistically. The apparent activation energy of each resin was calculated from the regression function, for the half-life period. Considering the calculated values, the adhesion durability of using polyol-added resin was superior to that of using water only-added resin. It was clarified that the durability of the isocyanate resins under steam heating was markedly inferior to that under dry heating.Part of this paper was presented at the 50th Annual Meeting of the Japan Wood Research Society, Kyoto, 2000     

Modulus of elasticity in scarf-jointed wooden beams: a case study with polyvinyl acetate and isocyanate adhesives

In the present study, elastic properties of scarf-jointed oak (Quercus castaneifolia) timbers with the application of two different types of adhesives (polyvinyl acetate and isocyanate) were evaluated using free flexural vibration of free–free beam method in different flexural directions of vibration, i.e., tangential and redial directions. Samples were taken from trees of Hyrcanian forests in Iran with nominal dimensions of 20 × 20 × 360 mm³. Comparing the results of elastic properties of clear oak wood beams with scarf-jointed samples wood showed that scarf joints with the bonding angles of 70° and 75°, covered by polyvinyl acetate adhesive, did not demonstrate any significant effect on modules of elasticity. Scarf-jointed beams with smaller joint angles (60° and 65°) were considerably weaker or totally unreliable in their moduli of elasticity. It is also shown that the magnitude of effect gets worst by using isocyanate rather than polyvinyl acetate adhesive.     

Moisture and decay resistance and reaction to fire properties of self-binding fibreboard made from steam-exploded grey alder wood

A study of self-binding fibreboards pressed without synthetic adhesives is reported. The board samples of steam-exploded grey alder (Alnus incana L. Moench) particles hot-pressed under a variety of conditions including moisture content of the mat (8% and 12%), temperature (150°C, 160°C, 170°C and 180°C) and pressure (0.2–8 MPa) are tested for moisture resistance (standard EN 1087-1), decay resistance (standard ENV 12038) and reaction to fire performance (ISO 5660-1). The moisture resistance of the board samples is found to satisfy the standard EN 622-5 for load-bearing medium-density fibreboard for use in humid conditions (MDF.HLS). The tested board samples are not fully resistant to the Trametes versicolor fungus, the mass loss of specimens exceeding 3%. Reaction to fire performance of the self-binding board evaluated by the average rate of heat emission being by about 25% higher is worse compared with MDF.HLS.     

水性改性淀粉--多异氰酸酯胶粘剂的研究

对利用酯化玉米淀粉，制造水性高分子——异氰酸酯胶粘剂(API)的配方进行了系统的研究。将玉米淀粉的酯化产物处理成乳液，在一定酸碱度条件下，与无毒无公害的合成橡胶胶乳共聚制成API胶的主剂；将多异氰酸酯化合物的异氰酸酯基封闭处理后，作为API胶的固化剂，制成双组分无醛耐水的API胶。经生产性试验，用此API胶压制的三层实木复合地板、机拼细木工板、胶合板及集成材等胶合制品，其理化性能指标完全达到有关标准要求，并且制品无甲醛等有毒物质挥发。此种胶粘剂具有明显的生产可操作性，完全满足现有的工艺要求，其原料成本为同类进口胶粘剂的一半，具有明显的社会环境效益和经济效益。     

Bondability of tropical fast-growing tree species I: Indonesian wood species

To estimate the potential bonding performance of bonded wood products from tropical fast-growing tree species, a study on the bondability of Paraserianthes falcataria L. Nielsen, Pinus merkusii Jungh et. De. Vriese, and Acacia mangium Willd from Indonesia was conducted. Two-ply laminations were produced using polyvinyl acetate emulsion (PVAc), urea formaldehyde (UF), resorcinol formaldehyde (RF), and water-based polymer isocyanate (API) adhesives. In order to determine the bonding performance, the block-shear test was applied according to the Japanese Agricultural Standard for structural glued laminated timber under normal conditions and after accelerated-aging treatments. To support this study, the wettability of each wood species was also investigated through contact-angle measurement. The results showed that the bonding performance of low-density P. falcataria was better than that of medium-density P. merkusii and medium-density A. mangium, while the bonding performance of medium-density P. merkusii was better than that of medium-density A. mangium. Furthermore, compared with A. mangium, the small contact angle and good wettability in P. falcataria and P. merkusii result in better adhesion and more intimate contact between the wood surfaces and adhesive.     

秸秆板贴面用异氰酸酯胶的改性

通过对异氰酸酯(API)主剂进行改性,从而减少交联剂的用量,降低API胶黏剂的生产成本。将改性API胶黏剂用于秸秆板薄木贴面的试验表明,当主剂、交联剂、填料之比为100∶4∶30,热压温度为60~110℃时,秸秆板的贴面效果达到相关国标要求。     

Relaxation mechanism of residual stress inside logs by heat treatment: choosing the heating time and temperature

 Some methods to reduce residual stress inside logs have been reported, although the conditions for stress relaxation are not yet clarified. Our study using precise experiments revealed that residual stress relaxation occurs only when both heat and moisture exist inside the logs. We then determined the heating time and temperature required to relax the residual stress inside the logs. Short air-drying treatments did not relax residual stress even though free water in the logs was greatly reduced. The residual stress of the 33-h 80°C-heated bolts was relaxed, whereas that of the 48-h 70°C-heated bolts was not. As for the influence of treatment time, bolts heated at 100°C were relaxed after 18 h of treatment. The 13-h heated bolts did not show any relaxation. Therefore, residual stress relaxation occurred rapidly owing to the thermomechanical change of the individual wood components comprising the cell wall. The moisture content inside all the bolts was much higher than the fiber saturation point. This is because relaxation occurs only when the heating temperature is maintained above 80°C for a particular duration of treatment. Received: December 12, 2001 / Accepted: February 18, 2002 Present address: Institute for Structural and Engineering Materials, National Institute of Advanced Industrial Sciences and Technology, Independent Administrative Institution, Nagoya 463-8560, Japan Tel. +81-52-736-7320; Fax +81-52-736-7419 e-mail: m.nogi@aist.go.jp Part of this report was presented at the 50th Annual Meeting of the Japan Wood Research Society, Kyoto, April 2000 Correspondence to:M. Nogi     

油茶饼粕的苯酚液化及产物的结构表征

为了综合利用油茶饼粕,分析了油茶饼粕的基本组成,采用苯酚为液化剂,硫酸为催化剂,对油茶饼粕进行了液化实验。结果显示油茶饼粕中糖类、粗纤维和粗蛋白质的总质量分数约为75%,能够有效进行液化。研究了反应温度、苯酚与油茶饼粕的质量比(液比)、催化剂的用量及液化时间对液化反应的影响,实验得出较佳的液化工艺条件为:硫酸用量4%,液化时间1.5 h,液化温度140℃,液比值4,此时液化残渣率16.25%。利用傅里叶红外光谱(FT-IR)分析了油茶饼粕及其液化残渣和产物的结构特征,结果显示苯酚与油茶饼粕组分发生了明显酚化反应和醚化反应,形成了更多的活性官能团。油茶饼粕中蛋白质结构遭到破坏,蛋白质也发生了液化反应。     

Shear strength of furfurylated,N-methylol melamine and thermally modified wood bonded with three conventional adhesives

The shear strength of furfurylated, N-methylol melamine (NMM) and thermally modified wood bonded with emulsion polymer isocyanate, polyvinyl acetate (PVAc), and polyurethane (PU) adhesives was examined. Furfurylation and NMM modification of Scots pine had a significant negative effect on the bonding strength with all adhesives irrespective of the treatment intensity. The obtained low-shear strength values were related to the brittle nature of the wood after modifications rather to the failure of the bondline. PVAc showed a better bonding performance with both furfurylated and NMM modified wood while the combination of furfurylated wood and PU gave the highest reduction in bonding strength (47–51%). Shear strength also decreased significantly after thermal modification in both Scots pine (36–56%) and beech (34–48%) with all adhesives. With the exception of thermally modified beech samples bonded with PU, bondline was found to be the weakest link in thermally modified wood as it was revealed by the wood failure surfaces. Bondline thickness and effective penetration of adhesives did not relate to the shear strength of all modified wood materials. The lower shear strength of modified wood could be attributed to other factors, such as the reduced chemical bonding or mechanical interlocking of adhesives, and the reduced strength of brittle modified wood substrate.     

超临界水中蔗渣的液化反应及其产物的结构表征

以Na2CO3、K2CO3、NaOH为催化剂,在375~400℃的超临界水中进行蔗渣的液化反应。考察了液固比、反应时间、反应温度和催化剂对蔗渣液化的影响。在380℃、液固比18∶1(质量比)、反应时间20 min条件下,NaOH或Na2CO3催化剂用量为1%时,液化残渣率降到10%以下,而在同样条件下,KCO催化剂用量为3%时,液化反应的残渣率降到7%以下。对液化产物进行了表征。GC-MS分析表明,液体产物的主要组成是含环状结构的酮和一些含甲基、羟甲基等官能团的苯酚类化合物,气体产物主要为C1~C4烷烃和CO、CO2、H2等无机气体,且其组成因液化温度而变化。液化残渣经过FT-IR分析和扫描电镜分析,发现其主要由焦炭以及尚未完全分解的木质素组成。     

Production of hemicellulosic sugars from Pinus pinaster wood by sequential steps of aqueous extraction and acid hydrolysis

Pinus pinaster wood samples were subjected to aqueous extraction at 130°C to remove extractives and to a sequential stage of hydrothermal processing under selected operational conditions to obtain hemicelluloses-free solids and liquors containing hemicelluloses-derived products (mainly oligomeric saccharides and monosaccharides). Liquors were separated from the media, supplemented with sulfuric acid (4%), and heated to cause the posthydrolysis of oligomeric saccharides to yield hemicellulosic sugars. The effects of the major operational conditions on the yields of the target products were assessed in selected experiments. The considered process enabled the recovery of hemicellulosic sugars (mannose, glucose, xylose, and galactose) at almost quantitative yields.     

Effects of high temperature kiln drying on the practical performances of Japanese cedar wood (Cryptomeria japonica) I: changes in hygroscopicity due to heating

The effect of heating on the hygroscopicity of Japanese cedar wood was investigated as a simple evaluation of thermal degradation in large-dimension timber being kiln-dried at high temperatures (>100°C). Small wood pieces were heated at 120°C in the absence of moisture (dry heating) and steamed at 60°, 90°, and 120°C with saturated water vapor over 2 weeks, and their equilibrium moisture contents (M) at 20°C and 60% relative humidity (RH) were compared with those of unheated samples. No significant change was induced by steaming at 60°C, while heating above 90°C caused loss in weight (WL) and reduction in M of wood. The effects of steaming were greater than those of dry heating at the same heating temperature. After extraction in water, the steamed wood showed additional WL and slight increase in M because of the loss of water-soluble decomposition residue. The M of heated wood decreased with increasing WL, and such a correlation became clearer after the extraction in water. On the basis of experimental correlation, the WL of local parts in large-dimension kiln-dried timber was evaluated from their M values. The results indicated that the thermal degradation of inner parts was greater than that of outer parts.     

Durability of isocyanate resin adhesives for wood I: Thermal properties of isocyanate resin cured with water

The thermal properties of isocyanate (IC) resin cured with water were studied using dynamic mechanical analysis (DMA) and Fourier transform infrared spectroscopy. The thermal properties of cured phenol formaldehyde (PF) resin were also studied for comparison purposes. The DMA specimens were prepared using a unique technique. The relation between the mechanical and chemical changes of the resin during DMA was clarified. The cured PF resin had better thermal stability than the IC resin cured with water. The improvement of thermal stability in cured IC resin by heat treatment was considered to be less effective. The effect of the heating rate on the mechanical properties was also investigated. The apparent activation energy in the thermal degradation of cured IC resin was calculated based on the results obtained.Part of this paper was presented at the 47th Annual Meeting of the Japan Wood Research Society, Kochi, April 1997     

Effect of polyol on thermo-oxidative degradation of isocyanate resin for wood adhesives

The thermo-oxidative degradation of various polyol-added isocyanate resins for wood adhesives was studied using differential scanning calorimetry and thermogravimetry. The degradation of the resin cured with water began at 150°C. When a certain polyol was added to the resin at an NCO/OH ratio of 25 in addition to water, the cured resin began to degrade at 200°C. To clarify the cause of the good thermal stability in polyol-added resins, the effect of various polyols on the reactivity of isocyanate was investigated. It was found that the reactivity of isocyanate was enhanced by the addition of a dipropylene glycol and glycerin-type polyols. In addition, the effect of the NCO/ polyol-OH ratio was investigated using dipropylene glycoltype polyol. The reactivity of isocyanate increased with increasing polyol content. The thermal stability of the resin was improved to a certain degree by addition of a small amount of the polyol but deteriorated when a large amount of the polyol was added.Part of this paper was presented at the 48th annual meeting of the Japan Wood Research Society, Shizuoka, April 1998     

水性异氰酸酯交联剂的应用研究

采用不同链长的聚醚多元醇与多亚甲基多苯基多异氰酸酯（PAPI）反应,制备了两种不同结构的水性异氰酸酯（P-C、P-D）,联剂分别加入到氧化玉米淀粉胶黏剂和脲醛树脂胶黏剂中,以改善胶黏剂的胶接性能。通过粘接强度测试研究不同结构、不同用量的水性异氰酸酯对改性胶黏剂的胶接强度和耐水性的影响。实验结果表明：氧化玉米淀粉和脲醛树脂中加入水性异氰酸酯交联剂制备胶合板,胶接强度及耐水性均有显著提高。氧化玉米淀粉胶黏剂中加入10%的水性异氰酸酯P-D后,所制备胶合板的干态剪切强度可达2.64MPa。脲醛树脂胶黏剂中加入7.5%的P-D后,干态、湿态剪切强度分别为1.24MPa和1.23MPa,甲醛释放量为0.31mg/L,达到E0级标准。     

Effects of water soaking and outdoor exposure on nail joint properties of particleboard

Phenol-formaldehyde resin-bonded particleboard (PF board) and isocyanate resin-bonded particleboard (MDI board) were soaked in water at 40, 70 and 100 °C, and the relationships between soaking conditions and nail joint properties were analyzed. The soaking time to reach the lower limit of nail-head pull-through (NHPT) of the PF board was 2 h at 100 °C, while it took 168 h at 70 °C. The soaking time to reach the lower limit of lateral nail resistance (LNR) of the PF board was 24 h at 100 °C, but it did not take 168 h at 70 °C to reach it. The lower limits of NHPT and LNR for the MDI board were higher than those for the PF board. For the PF board, there was a high correlation between modulus of rupture, internal bond strength and nail joint properties. Based on the results of water soaking and outdoor exposure, it was shown that thickness change has a significant effect on NHPT and LNR, and that the reduction in NHPT and LNR results from the collapse of bonding points owing to swelling of the board.     

基于面料熨烫胶接的木质家具饰面翻新研究

为实现木质旧家具在居家条件下的翻新改造,采用熨烫固化胶接方法用面料对桦木板表面进行饰面翻新,通过探究胶黏剂种类、熨烫温度和熨烫时间对面料翻新木材的胶合强度及耐水性的影响,得出理想的烫熨胶接工艺并将之用于木质旧家具的饰面翻新。结果表明:使用电熨斗的熨烫固化代替热压机的热压固化可实现居家条件下对木质家具的面料饰面翻新,胶黏剂种类、熨烫温度和熨烫时间对饰面翻新木材的胶合强度及耐水性有着重要影响;适当提高熨烫温度和延长熨烫时间可促进胶黏剂的固化进而确保胶合性能;在3种胶黏剂中最适于居家饰面翻新木质家具的胶黏剂为API胶黏剂。通过手工熨烫方法可实现对旧家具的个性化翻新,在避免家居审美疲劳的同时实现旧家具的再利用。