Property of nano-SiO2/urea formaldehyde resin

In this paper, we discuss the effects of a nanometer silicon dioxide (nano-SiO₂) coupling agent, dispersal methods and the amount of nano-SiO₂/urea formaldehyde resin. The results of our study indicate that when nano-SiO₂, using KH-550 silane as a coupling agent, was added to UF resin by discontinuous ultrasonic vibration, its properties improved effectively. When the content of nano-SiO₂ was below 1.5%, the amount of free formaldehyde decreased, and the viscosity and bonding strength of resin increased with an increase in the added nano-SiO₂, which did not prolong the curing time. The performance indices of plywood, particleboard and medium density fiberboard (MDF), hot-pressed by nano-SiO2 (1%)/UF resin (F/U molar ratio=1.2), exceeded the requirements of the National Standard. Their free formaldehyde emission reached E1 grade. Finally, we analyzed the mechanism of the strengthening effects of nano-SiO₂ on UF resin by means of infrared spectrum analysis and X-ray photoelectronic spectrum (XPS). __________ Translated from Scientia Silvae Sinicae, 2005, 41(2) [译自: 林业科学, 2005, 41(2)]     

芳香型纤维板制造工艺

为实现中密度纤维板的芳香功能,开展了将香精加入至胶黏剂中与木材纤维共混压制中密度纤维板的试验。试验结果表明,无论是檀香香精还是茉莉香精,加入脲醛树脂后,虽对胶黏剂的pH值、黏度及固化时间略有影响,但在纤维板的热压过程中,可作为固化剂使用,对中密度纤维板的物理力学性能并无明显影响,而芳香型纤维板所具有的芳香性能广泛受到好评。     

Urea-formaldehyde microspheres as a potential additive to wood adhesive

Urea formaldehyde (UF) resins are important for wood industry due to their attractive properties at reasonable price. Particulate fillers added to UF are of interest with regard to improving the functionality of UF and also in terms of reduced UF consumption. To study their potential as filler, solid UF microspheres were synthesized and characterised respecting its morphology, chemical curing and thermal stability. Marigold flower structured spheres with diameters between 5 and 20 µm are presented and application trials demonstrated that high amounts of UF may be replaced by solid microspheres without impairing adhesive bond strength of solid wood bond lines. Fluorescence microscopy showed that microspheres greatly reduce adhesive penetration into the wood substrate, retaining the modified adhesive in the bondline. UF microspheres may thus be considered as viable filler for UF adhesives, particularly with regard to the possibility of endowing them with added functionality like self-healing properties.     

固体核磁共振法对低甲醛释放脲醛树脂化学结构的研究

在采用液体核磁对3种低甲醛释放脲醛树脂化学构造进行分析的基础上,利用13CCP/MASNMR对脲醛树脂固化产物的化学结构进行了研究.结果表明,不同固化体系下,3种低甲醛释放脲醛树脂胶黏剂的固化历程不同,固化后树脂的结构有所差别.不添加固化剂时,脲醛树脂的固化交联反应程度低,固化产物中羟甲基含量高,甲醛释放量也随之增加.加入固化剂后,促进了羟甲基的固化交联反应,脲醛树脂固化产物中羟甲基含量普遍降低.3种固化体系下,UF-3羟甲基含量最高;在氯化铵为固化剂的条件下,UF-2羟甲基含量最低,为0.0582;不添加固化剂和复合固化体系条件下,UF-1羟甲基含量最低,分别为0.0784和0.0713.不同固化体系对不同种类脲醛树脂的固化效果不同,固化后树脂的结构不同,其力学性能和甲醛释放能力也不同.     

Penetration of urea–formaldehyde resins with different formaldehyde/urea mole ratios into softwood tissues

In order to understand the impact of formaldehyde/urea (F/U) mole ratio on penetration characteristics of urea–formaldehyde (UF) resin into softwood tissues, a quantitative measurement of UF resin penetration into radiata pine (Pinus radiata) tissues from the bond-line was undertaken. Four different F/U mole ratios (1.6, 1.4, 1.2, and 1.0) of UF resins with different viscosities and two levels of hardener (NH₄Cl) for two extreme F/U mole ratios (1.6 and 1.0) were studied. Firstly, field emission scanning electron microscope and confocal laser scanning microscopy were used to localize UF resins in the bond-line for the qualitative evaluation of resin penetration. Then light microscopy was employed to quantitatively measure the resin penetration and bond-line thickness. A decrease in the F/U mole ratio of UF resin that proportionately decreased the resin viscosity resulted in an increase in the average resin penetration and a decrease in the bond-line thickness. Higher hardener level provided a greater resin penetration with all F/U mole ratio UF resins. These results demonstrated that F/U mole ratio had an impact on the penetration and bond-line thickness of UF resins, owing to differences in the reactivity of resins, with higher F/U mole ratio resins being more reactive.     

Liquefaction of bamboo, preparation of liquefied bamboo adhesives, and properties of the adhesives

This study investigated the liquefaction of bamboo in phenol, which involved the effects of weight ratios of phenol to bamboo, amount of catalyst, temperature, etc. The study showed that liquefaction could be accomplished with a phenol to bamboo weight ratio of 2–1: 1, a 5% catalyst of HCl or BF₃, and a temperature of 115°C. Liquefied bamboo formaldehyde (BLF) resin adhesive for exterior use could be obtained with a phenol to formaldehyde molar ratio of 1:1.6–2.0. The curing behavior of BLF resin adhesive, studied by TG-DSC and IR analyses, showed that BLF resin adhesives had a lower curing temperature than PF adhesives but had the same characteristic trough in IR spectra as PF adhesives. __________ Translated from Chemistry and Industry of Forest Products, 2004, 24(3) [译自: 林产化学与工业, 2004, 24(3)]     

低甲醛释放脲醛树脂胶粘剂研究进展

对脲醛树脂的合成、固化以及甲醛释放机理的研究进展进行了概述，并简要综述了国内外近几十年来对于树脂改性所做的工作，重点从合成过程中和树脂固化后如何降低甲醛量这两方面介绍其改性机理的研究进展。     

微波等离子处理对脲醛胶性能的影响

脲醛树脂胶粘剂是木材加工领域应用最广泛的胶粘剂,在保障其胶合性能的前提下降低脲醛胶的甲醛释放量是社会关注的焦点和难点。通过试验,研究不同的微波等离子处理方法对脲醛树脂胶粘剂的固化时间、适用期、胶合强度、游离甲醛含量的影响。试验结果表明:等离子处理对脲醛树脂胶粘剂的固化时间和适用期的影响不明显;合适的等离子处理条件可以改善脲醛胶的胶合性能;与未经等离子处理脲醛胶相比,等离子处理后脲醛胶的游离甲醛含量显著降低。     

Preparation and properties of waste tea leaves particleboard

Urea-formaldehyde (UF) adhesive is the main source of formaldehyde emission from UF-bonded boards. The components in waste tea leaves can react with formaldehyde to serve as a raw material in the production of low formaldehyde emission boards. In our study, waste tea leaves and UF adhesive were employed in the preparation of waste tea leaves particleboard (WTLB). An orthogonal experimental method was applied to investigate the effects of process parameters on formaldehyde emission and mechanical properties of WTLB. The results indicated that: 1) waste tea leaves had the ability to abate formaldehyde emission from boards; and 2) density of the WTLB was a significant factor affecting its modulus of rupture (MOR), modulus of elasticity (MOE) and internal bonding (IB).     

利用动态热机械分析仪对低毒脲醛树脂性能的研究

利用动态热机械分析(DMA)对不同固化体系下3种低毒UF树脂固化物的力学性能进行了研究。试验结果表明:不同固化体系下3种低毒UF树脂固化物的力学性能不同。对于UF-1,使用氯化铵为固化剂,树脂交联固化程度要高于其他两种固化体系,固化物储存模量最高。对于UF-2来说,在3种固化体系下,固化物的储存模量之间相差不是很大。对于UF-3,在第2种固化体系条件下,固化物的储存模量最大,损耗角正切最小。因此在实际应用过程中,针对不同的低毒UF树脂胶黏剂需要选择与之相匹配的固化体系,才能达到最佳的固化效果和胶接强度。     

复合工艺对竹/塑复合刨花板性能的影响

利用聚乙烯(PE)粉末取代部分脲醛树脂(UF)胶黏剂,与竹刨花制备三层结构竹/塑复合刨花板。通过正交试验探讨PE添加量、UF施胶量、热压温度及热压时间对竹/塑复合刨花板主要物理力学性能的影响。结果表明:较优工艺组合为PE添加量6%、UF施胶量2%、热压温度205℃、热压时间12s/mm,竹/塑复合刨花板达到LY/T1842—2009《竹材刨花板》A类理化性能指标要求;2h吸水厚度膨胀率和甲醛释放量分别为2.6%和2.4mg/100g,与普通竹材刨花板对比,分别减少了54.4%和54.7%;静曲强度达到19.6MPa,提高了14.0%。采用PE粉末替代部分UF胶黏剂生产竹/塑复合刨花板可行,且具有广泛的应用前景。     

Bondability of tropical fast-growing tree species III: curing behavior of resorcinol formaldehyde resin adhesive at room temperature and effects of extractives of <Emphasis Type="Italic">Acacia mangium</Emphasis> wood on bonding

The effects of curing time at room temperature and methanol extracts from Acacia mangium on the curing behavior of resorcinol formaldehyde (RF) adhesive were examined by using the thermomechanical analysis spring method. For a specimen that was cured for 3 months at room temperature, the relative elasticity (E _r) curve did not change to a hard glass state from room temperature to 200°C and the adhesive had cured completely. The initial temperature of the reactive zone for chemical and mechanical changes was 15° and 25°C higher than that for the control when 10 and 15 parts by weight methanol extract was added to the liquid adhesive, respectively. It appears that the extractives of A. mangium in RF adhesive interferes with the chemical cure of the adhesive. It is suggested that a combination of curing time and sweeping by methanol on the laminae surface can improve the bonding performance of A. mangium laminates bonded with RF at room temperature.     

Technologies of liquefaction of bamboo and preparation of adhesive

The technology of liquefying processed-waste bamboo with phenol is investigated by single factor trials and an orthogonal design. We studied the preparation technology and properties of adhesives from this phenol-liquefied bamboo with formaldehyde (BPF). The results show that temperature has a significant effect on liquefaction. The effect of the mass ratio of phenol to bamboo comes second and the catalyst dosage within the range of 2%–4% is the least effective. The optimum conditions of liquefaction are as follows: a mass ratio of phenol to bamboo 3.5, a catalyst dosage of 4%, liquefying temperature 145°C and liquefying time 60 min. The liquefaction rate of bamboo reached 99.1%. For the preparation of the adhesive, a mass ratio of liquefied bamboo products to formaldehyde (37%) is 100 to 164.8–199.5, while the ratio 100 to 108.2 is the best. This adhesive has a lower curing temperature than that of normal PF resin. At a hot-press temperature of 130 or 140°C, this new adhesive provides excellent bonding strength of plywood. The most favorable temperature for hot-pressing is 140°C. __________ Translated from Chemistry and Industry of Forest Products, 2007, 27(6): 65–70 [译自: 林产化学与工业]     

Soil NH4 +/NO3 − nitrogen characteristics in primary forests and the adaptability of some coniferous species

In terrestrial ecosystems, soil nutrient regimes at a plant’s living site generally represent the plant’s “nutrition habitat”. Plant species frequently well adapt to their original “nutrition habitat” during a long process of evolution, and the apparent preference for ammonium or nitrate nitrogen source (NH₄ ⁺ or NO₃ ⁻) might be an important aspect of the adaptation. Plants typically favor the nitrogen form most abundant in their natural habitats. Nitrate has been recognized as the dominant mineral nitrogen form in most agricultural soils and the main nitrogen source for crops, but it is not usually the case in forest ecosystems. A large number of studies show that the “nutrition habitats” associated with primary forest soils are typically dominated by NH₄ ⁺ rather than NO₃ ⁻, generally with NO₃ ⁻ content much lower than NH₄ ⁺. Low levels of NO₃ ⁻ in these forest soils generally correspond to low net rates of nitrification. The probable reasons for this phenomenon include: 1) nitrification limitations and/or inhibitions caused by lower pH, lower NH₄ ⁺ availability (autotrophic nitrifiers cannot successfully compete for NH₄ ⁺ with heterotrophic organisms and plants), or allelopathic inhibitors (tannins or higher-molecular-weight proanthocyanidins) in the soil; or 2) substantial microbial acquisition of nitrate in the soils, which makes net nitrification rates substantially less than gross nitrification rates even though the latter are relatively high. Many coniferous species (especially such late successional tree species as Tsuga heterophylla, Pinus banksiana, Picea glauca, Pseudotsuga meziesii, Picea abies, etc.) fully adapt to their original NH₄ ⁺-dominated “nutrition habitats” so that their capacities of absorbing and using non-reduced forms of nitrogen (e.g., NO₃ ⁻) substantially decrease. These conifers typically show distinct preference to NH₄ ⁺ and reduced growth due to nitrogen-metabolism disorder when NO₃ ⁻ is the main nitrogen source. The physiological and biochemical mechanisms that account for the adaptation to NH₄ ⁺-dominated systems (or limited ability to use NO₃ ⁻) for the coniferous species include: i) distribution and activity of enzymes for catalyzing nitrogen reduction and assimilation, generally characterized by lower nitrate reductase (NR); ii) greater tolerance to NH₄ ⁺ or rapid detoxification of ammonium nitrogen in the roots; iii) lower capacity of absorption to NO₃ ⁻ by roots that might be controlled by feedback regulations of certain N-transport compounds, such as glutamine; iv) relations and balance between nitrogen and other elements (such as Ca²⁺, Mg²⁺, and Zn²⁺ etc.). Some NH₄ ⁺-preferred conifers might be more adapted (tolerant) to lower base cation conditions; v) NO₃ ⁻ nutrition, rather than NH₄ ⁺, that may lead to the loss of considerable quantities of organic and inorganic carbon to the surrounding media and mycorrhizal symbiont and probably contribute to slower growth; and vi) the metabolic cost of reducing NO₃ ⁻ to NH₄ ⁺ that may make shade-tolerant conifers favor the uptake of reduced nitrogen (NH₄ ⁺). The adaptation of late successional conifers to NH₄ ⁺-dominated habitats has profound ecological implications. First, it might be an important prerequisite for the climax forest communities dominated by these conifers to maintain long-term stability. Second, primary coniferous or coniferous-broadleaved forests have been widely perturbed because of commercial exploitation, where the soil ammonium nitrogen pool tends to be largely transformed to nitrate after disturbance. In such a situation, the coniferous species that were dominant in undisturbed ecosystems may become poor competitors for nitrogen, and the site will be occupied by early successional (pioneer) plants better adapted to nitrate utilization. In other words, the implicit adaptation of many conifers dominant in undisturbed communities to ammonium nitrogen will cause difficulties in their regeneration on disturbed sites, which must be taken into account in the practical restoration of degraded temperate forest ecosystems. __________ Translated from Acta Ecologica Sinica, 2005, 25(11): 3,082–3,092 [译自: 生态学报]     

Variations of root hydraulic conductance of Fraxinus mandshurica seedlings in different concentrations of NH4NO3 solution

Absorbing water from soil by roots in vascular plants is an important physiological function and plays an essential role on their water balance. The root hydraulic conductance (L _P) determined by radical water transport inside the root is a major influence on the shoot water status, plant growth, and development. However, a few studies have focused on the effect of different substances on L _P of roots, and the role of radical water transport was poorly understood. Based on the pressure-flux approach, this study used the roots of Fraxinus mandshurica seedlings with different treatments, i.e., distilled water, NH₄NO₃ solution, and HgCl₂ to determine the effect of various substances on L _P of roots. The objectives are: 1) to evaluate the difference in L _P occurred between distilled water and NH₄NO₃ solution with various concentrations; and 2) to examine the changes of L _P under distilled water and NH₄NO₃ solution with various concentrations after HgCl₂ treatment. The results showed that L _P of roots were 18.85×10⁻⁸ m/(s·MPa) in distilled water, 31.25–34.15×10⁻⁸ m/(s·MPa) in four NH₄NO₃ solutions (2, 4, 8 and 16 mmol/L), 14.69×10⁻⁸ m/(s·MPa) in distilled water after HgCl₂-treated, and 9.63–13.57×10⁻⁸ m/(s·MPa) in four NH₄NO₃ solutions after HgCl₂-treated, respectively. Aquaporins play an important role in regulating water uptake and transport in roots. NH₄ ⁺ and NO₃ ⁻ could stimulate activity of aquaporins, and L _P of roots in NH₄NO₃ solution was distinctly 77% higher than in distilled water. Nevertheless, Hg²⁺ can inhibit activity of aquaporins, and and L _P of roots decreased 22% in distilled water and 68% in NH₄NO₃ solution after treatment by HgCl₂ respectively. These evidences suggested that both Hg²⁺-sensitive aquaporins and ion channels existing in the protoplasm and vacuole membranes could regulate root water uptake, transport, and integral plant water balance. __________ Translated from Acta Phytoecologica Sinica, 2005, 29(5): 706–712 [译自: 植物生态学报, 2005, 29(5): 706–712]     

Improvement of wood properties by urea-formaldehyde resin and nano-SiO2

In order to improve wood properties of triploid clones of Populus tomentosa, urea-formaldehyde (UF) resin was compounded with nano-SiO₂, coupling agents and flame retardants in different ways to prepare five kinds of modifiers. The poplar wood samples were impregnated with the modifiers and heated to prepare UF-SiO₂-wood composites. The antiswelling efficiency, resistance of water absorption, oxygen index and hardness of the composites were measured. Results show that all of the modifiers reduced water absorption of poplar wood and enhanced flame resistance and hardness. Nano-SiO₂ showed a marked effect in improving the hardness of wood. In addition, all of the modifiers, except UF-C-SiO₂-polymer, improved the dimensional stability of poplar wood. The UF resin and nano-SiO₂ compound improved general properties of poplar wood. __________ Translated from Journal of Beijing Forestry University, 2006, 28(2): 123–128 [译自: 北京林业大学学报]     

Development of a novel polyvinyl acetate type emulsion curing agent for urea formaldehyde resin

High formaldehyde emission and poor water resistance are two main disadvantages of urea formaldehyde (UF) resin. For that reason, a novel polyvinyl acetate (PVAc) type emulsion curing agent was developed in this paper. PVAc type emulsions, including PVAc, the co-polymer of PVAc and N-hydroxymethyl acrylamide (PVAc–NMA), and the ternary co-polymer of PVAc, NMA, and urea (PVAc–NMA–urea), were the main components. Water, aluminum chloride, ammonium dihydrogen phosphate, polypropylene glycol, silicone oil, and urea were the other components. Under heating, aluminum chloride and ammonium dihydrogen phosphate often underwent thermal decomposition and hydrolysis in solution, produce free acid to cure UF resin, so the curing agent could enhance the curing rate, and then shorten the curing time. In this curing agent, ammonium dihydrogen phosphate and urea worked as formaldehyde removers and reacted with free formaldehyde in UF resin, thus the formaldehyde emission exuded from the plywood could be effectively limited and reduced. The bonding strength of plywood was not improved very much, especially the dry bonding strength, but the wet bonding strength was little enhanced for the active hydroxymethyl group contained in PVAc–NMA and PVAc–NMA–urea underwent a self-cross-linking reaction to improve the bonding strength and adhesion force to the bonded substrate. More importantly, the results from the industrial production experiments were shown to be very good.     

Shear strength development of the phenol–formaldehyde adhesive bond during cure

The development of the shear strength of the phenol–formaldehyde (PF) adhesive bond during curing was investigated. Five different PF adhesive mixtures and 1.1 mm thick peeled beech (Fagus sylvatica L.) veneer were used to produce lap-shear specimens, which were cured at a pressing temperature of 160°C. Dielectric analysis (DEA) and modified ABES (automated bonding evaluation system) were used to evaluate the physical–chemical and mechanical aspects of PF adhesive cure in a miniature hot-press. The degree of cure, which was calculated from conductivity data, was dependent on pressing time and the composition of the PF adhesive. An addition of rye flour to the PF adhesive significantly postponed the curing process as determined by DEA. It was found that the adhesive bond started to develop in the last stage of the curing (vitrification), by which time most of the physical–chemical conversion of the adhesive had been completed.     

轻质豆秸刨花板工艺的研究

从UF胶制造轻质豆秸刨花板的初步研究,分析了板的密度、施胶量、热压时间等工艺因子对板性能的影响。试验结果表明,利用豆秸制造轻质刨花板是完全可行的,其产品主要物理力学性能为:密度0.483 g/cm 3、吸水厚度膨胀率11.2 % 、内结合强度0.303 MPa、静曲强度8.98 MPa,均达到日本JISA 5908 的技术指标。     

改性脲醛树脂胶低密度稻壳-木材复合材料制造工艺的研究

采用异氰酸酯(ISO)改性的脲醛树脂胶制造低密度稻壳-木材复合材料。稻壳与木质刨花的混合比例为1:1,施胶量为7%,试验结果表明,异氰酸酯改性的脲醛树脂胶黏剂适用于低密度稻壳-木材复合材料,其物理力学性能明显优于使用传统的脲醛树脂胶黏剂。低密度稻壳-木材复合材料的物理力学性能随着改性剂异氰酸酯用量的增加而提高。密度是稻壳-木材复合材料物理力学性能的重要影响因素,低密度稻壳-木材复合材料的物理力学性能随着密度的增加而提高。在设定密度为0.45g/m~3和0.5g/cm~3的条件下,3:4的ISO/UF的稻壳-木材复合材料的物理力学性能均达到日本刨花板工业标准(JIS A5908)的要求。