低共熔离子液体改性木质素-酚醛树脂的热解和热解动力学研究

采用氯化锌/乙酰胺低共熔离子液(DES)处理2种木质素,加水作为反相溶剂得到再生木质素。研究用其替代部分苯酚制备木质素改性酚醛树脂(LPF)的基本性能变化,结合热重分析法(TGA)分析树脂的热解特性,引入Flynn-WallOzawa模型量化了树脂的表观活化能。结果表明,经该DES处理前后的磨木木质素和酶解木质素均可在保持树脂基本性能稳定的前提下替代20%苯酚制备LPF。升温速率β影响树脂的热分解过程,4种LPF的初始分解温度、热解过程所需的活化能均高于未改性酚醛树脂(PF),特别是经氯化锌/L酰胺DES处理后的再生磨木木质素改性酚醛树脂(RMLPF),其热降解温度更高,残炭率更多,热解过程所需的活化能比PF高出2~4倍,热稳定性明显提高。     

氯化胆碱/丙三醇低共熔离子液改性木质素酚醛树脂

研究氯化胆碱和丙三醇在不同物质的量比、不同温度条件下合成氯化胆碱/丙三醇低共熔离子液体(Ch Cl/Glycerol DES)的最佳合成工艺,并用其处理木质素(Dealkaline CAS9005-53-2)。通过傅里叶红外光谱(FTIR)、离子化差示光谱、热重(TG)、核磁共振氢谱(1H-NMR)等分析手段对氯化胆碱/丙三醇低共熔离子液体处理前后木质素的分子结构及热稳定性变化进行表征。研究结果表明:反应温度为100℃,氯化胆碱和丙三醇物质的量比为1∶2时,体系的反应效率最高,所制备的离子液体黏度适中、稳定性好。木质素经Ch Cl/Glycerol DES改性处理后酚羟基总含量明显增加,反应活性明显提高,其中,木质素中紫丁香基结构(S)被降解,说明Ch Cl/Glycerol DES处理木质素可显著提高其反应活性。经Ch Cl/Glycerol DES处理后的木质素按10%,20%,30%和40%的替代量替代苯酚,制备的木质素-酚醛树脂胶黏剂的胶合强度均可达到国标GB/T 8942.3—2004中Ⅰ类胶合板标准要求。     

酶解木质素改性酚醛树脂胶黏剂的研究

利用秸秆发酵制备能源酒精的残渣中提取的酶解木质素(EHL),部分代替苯酚合成改性酚醛树脂胶,并热压制得胶合板.测定了胶合板的胶合强度,改性树脂胶的黏度、固含量、水混合比、可被溴化物、游离酚、游离醛等性能指标.结果表明:木质素替代量达20%时,各项性能仍能基本达到国家标准Ⅰ类板的要求,特别是耐水性十分良好,水煮两次后胶合强度仍远大于国家标准Ⅰ类板≥0.7MPa的要求.     

用湿地松树皮提取物制备改性酚醛树脂胶的工艺

采用湿地松树皮提取物对酚醛树脂胶改性,以研制人造板胶粘剂.选用L9(34)方案进行正交试验,找出最佳改性酚醛树脂胶制备的工艺条件.结果表明:制备改性酚醛树脂胶最佳工艺条件为反应温度90℃、反应时间25 min、催化剂加入量(催化剂与总酚量摩尔比)0.06∶1、湿地松树皮提取物替代苯酚量40%.所制成的胶粘剂用于压制胶合板,其质量符合类胶合板国家标准.     

酚化木质素改性酚醛树脂胶黏剂的制备及性能表征

在碱性条件下,酸性木质素先经苯酚处理,再用于对酚醛树脂进行改性,制备得到木质素改性酚醛树脂(LPF)胶黏剂,考察了木质素用量、苯酚处理时间及温度、苯酚处理木质素时氢氧化钠水溶液用量(第一批次氢氧化钠)、酚醛物质的量比对LPF胶黏剂性能的影响。研究结果表明:在木质素用量25%、苯酚处理时间2 h、苯酚处理温度80℃、第一批次氢氧化钠水溶液用量8%、苯酚与甲醛的物质的量比1.0∶2.0时,LPF胶黏剂的胶合强度为1.57 MPa,较未经改性的酚醛树脂(PF)胶黏剂的1.35 MPa提高了16.3%,游离苯酚为0.58%,比PF的0.72%降低了19.4%,游离甲醛0.16%、固体质量分数51.2%、pH值11.4、黏度80 mPa·s、贮存期为60天。FT-IR分析表明:LPF在2893和1213 cm~(-1)处吸收峰明显减弱,表明木质素分子中甲氧基部分脱落;在1505、1320、1114和875 cm~(-1)处吸收峰消失,表明合成酚醛树脂过程中,木质素中的磺酸基消失;在1018 cm~(-1)处的吸收峰明显增强,表明有新的醚键生成。     

新型酶解木质素酚醛泡沫的制备及性能研究

利用酶解木质素部分替代苯酚,以十二胺为增韧剂,成功制备了含有柔性侧链的酶解木质素酚醛树脂,并利用其制备改性酶解木质素酚醛泡沫。系统研究了该树脂的发泡工艺,结果表明:当十二胺添加量为苯酚质量的8%,固化剂用量为12%(树脂的质量分数,下同),发泡剂用量为7%,表面活性剂用量为6%时,该泡沫的综合性能较佳。同时使用核磁共振(1H NMR)对树脂结构分析,使用热重分析(TG)与扫描电镜(SEM)对泡沫进行了分析,结果表明:改性木质素酚醛泡沫孔和孔壁厚度均匀,具有规则和致密的网络结构。改性后泡沫残碳率为49.0%。研究结论为今后利用脂肪单胺体系长链结构改性木质素酚醛树脂刚性结构提供了理论基础。     

纤维素乙醇木质素改性酚醛树脂胶黏剂的初步研究

以纤维素乙醇木质素、苯酚、甲醛为原料,氢氧化钠为催化剂,制备了纤维素乙醇木质素改性酚醛树脂胶黏剂,研究了木质素替代苯酚的工艺以及对胶黏剂性能的影响。研究发现:当木质素替代率为30%时,纤维素乙醇木质素改性酚醛树脂胶黏剂胶合强度达到国家Ⅰ类板要求,甲醛释放量达到Eo级,且成本低、胶合强度好、低毒环保,可广泛用于制备室外级人造板。     

木质纤维素及其组分转化木材胶粘剂的发展趋势

木质素是造纸工业废液中的主要成分。其具有和酚醛树脂相似的结构, 因此可以部分替代苯酚用于酚醛树脂的生产。但是由于木质素化学结构复杂, 具有化学反应活性的位点少、反应官能团所收到的空间位阻大, 一般添加量不超过10%~20%。有机溶剂法制浆分离的木质素分子量大, 纯度高, 酚醛树脂允许的添加量可达20%~30%, 但是要求提高固化温度、延长固化时间来克服木质素反应活性低的限制。对木质素进行化学改性如羟甲基化、酚解、醇解、还原等, 可以降低分子量, 增加活性基团如酚羟基的含量、并使苯环上更多的活性位点暴露出来, 从而提高木质素的化学反应活性。酚醛树脂经过改性木质素的允许的添加量可达30%~40%。部分木质素含量高的木质纤维素类原料如核桃壳粉等, 经过研磨和化学活化处理后可以直接添加到酚醛树脂中, 部分替代苯酚而不对胶接性能产生影响。环碳酸酯类和多元醇混合物被用来作为全新的液化剂来把木质纤维素快速液化为有用的化学原料。所得到的液化产物具有较高的反应活性, 是今后利用木质纤维素开发绿色木材胶粘剂的一条可资利用的途径。     

木质素基酚醛树脂泡沫的制备及性能研究

在碱性条件下,先利用木质素部分替代苯酚与甲醛反应合成酚醛树脂,然后利用酚醛树脂经发泡工艺制备木质素基酚醛树脂泡沫,当木质素替代量为0%、10%、20%和30%时,分别记为LPF-0%、LPF-10%、LPF-20%和LPF-30%。对泡沫的性能研究结果表明:木质素可部分替代苯酚,与甲醛发生缩合反应生成酚醛树脂;当木质素替代量为20%(LPF-20%)时,泡沫热解具有最大的残炭率54.60%,其热稳定性优于其它酚醛树脂泡沫;随着木质素替代量的增加,木质素基酚醛树脂泡沫的颜色由黄色渐变为褐色,其表观密度由0.05 g/cm~3增加至0.11 g/cm~3,压缩强度从0.26 MPa增加为0.56 MPa,表面粉化程度由13.73%降低至3.48%,吸水率由3.73%降低至1.92%;木质素基酚醛树脂泡沫具有良好的阻燃性,LPF-30%的氧指数最大为33.67%。     

高替代率木质素酚醛树脂在胶合板中的应用性能比较

以云杉硫酸盐法制浆黑液中的碱木质素(UL)为原料,在改性得到脱甲基化木质素(DUL)和羟甲基化木质素(HUL)的基础上,合成了高替代率(≥70%)的木质素酚醛树脂(LPF),并探讨了3种木质素羟基含量对LPF胶黏剂胶合强度和游离甲醛含量的影响。木质素的结构分析结果表明：相比原料UL,DUL和HUL的羟基比例分别提高了26.41%、 72.35%。将UL、DUL和HUL替代苯酚制备LPF并将其用于杨木单板胶合实验中,实验结果显示：UL经脱甲基化改性后进一步提高了其耐热水胶合强度(σ_HWT),在30%木质素替代率下,DUL的σ_HWT最大,达1.09 MPa,比PF(0.78 MPa)提高了39.39%。木质素替代率从30%(HUL)提高至70%(DUL),同时胶合板中游离甲醛的质量浓度从0.33 mg/L(UL)降低至0.29 mg/L(DUL),仍小于国标GB 9846.2—2004要求(<0.5 mg/L);UL经羟甲基化改性后,HUL制备LPF的胶合强度大幅提高,在30%木质素替代率下,干胶合强度(σ_dry)为2...     

Browsing Damage on Pine (Pinus sylvestris and P. contorta) by a migrating moose (Alces alces) Population in Winter: Relation to Habitat Composition and Road Barriers

In Scandinavia, moose (Alces alces L.) sometimes cause severe browsing damage to economically-important pine. Moose-vehicle accidents have spurred construction of fences along roads, and these may interfere with moose migration between summer and winter ranges, or the road alone may be a barrier. If this happens and moose build up along roads, landowners may suffer economically. Therefore, this study investigated whether roads, fences or other factors influence the use of young pine stands by moose. Eighty stands along roads in northern Sweden were evaluated in which individually-browsed branches were counted on 9972 pines. Moose browsing was not significantly related to birch (Betula pendula Roth, B. pubescens Ehrh.) density, nor did it differ between pines (Pinus contorta Douglas or P. sylvestris L.). However, increased pine density, site productivity and proximity to a highway were associated with increased browsing. Further large-scale studies are needed to understand moose habitat selection and the effects of roads.     

Effects of Root Freezing on the Physiology and Growth of Picea glauca,Picea mariana and Pinus banksiana Seedlings Under Different Soil Moisture Regimes

The root systems of 2-yr-old Picea glauca, Picea mariana and Pinus banksiana seedlings were submitted to various frost temperatures during an artificial frost to induce different levels of root damage. Frost-damaged and control seedlings were placed in a greenhouse under high and low soil moisture regimes. Seedling growth and physiology were evaluated periodically. Seedling survival was reduced when root damage reached levels of 60-80%. Root systems of all three species showed partial to total recovery by the end of the experiment. In general, root freezing damage caused reductions in seedling growth, with these reductions becoming less significant over time. Root damage had little to no effect on black spruce and jack pine seedling physiology, while white spruce CO 2 uptake decreased with increasing root damage. Shoot nitrogen content of all three species decreased slightly with increasing root damage.     

Decomposition and nutrient loss from prunings of different contour hedgerow species in tea plantations in the sloping highlands of Sri Lanka

Contour hedgerows of multipurpose tree species in the sloping tea lands of Sri Lanka are expected to reduce soil erosion and also add significant amounts of plant nutrients to the soil via periodic prunings. The objective of this experiment was to characterize the biomass decomposition pattern and quantify the amount of nutrients added through prunings of six tree species (Calliandra calothyrsus, Senna spectabilis, Euphatorium innulifolium, Flemingia congesta, Gliricidia sepium and Tithonia diversifolia) currently being used in hedgerows associated with tea. Withered leaf and stem prunings (50 g) were enclosed in 2-mm litter bags, placed at 5-cm depth and retrieved after one, three, six, nine and 12 weeks. Loss of initial dry weight, N, P and K was measured. Single exponential decay function adequately described both dry weight and nutrient loss. Tree species differed significantly in their rate of breakdown with decomposition constants (k) varying from 0.0299 to 0.2006 week⁻¹ for leaves and from 0.0225 to 0.0633 week⁻¹ for stems. Gliricidia showed the highest k for leaves with the rest in the following descending order: Senna > Tithonia ≥ Euphatorium > Calliandra > Flemingia. A similar pattern was observed for loss of all nutrients with Calliandra and Flemingia always having lower k values than the rest. Although N immobilization was not observed, immobilization of P and K was observed during the first week of incubation in some species, particularly in stem prunings. Annual biomass of prunings differed significantly between tree species in the following descending order: Calliandra > Senna > Flemingia > Tithonia > Gliricidia > Euphatorium. Calliandra added the greatest amount of nutrients annually to the soil with Euphatorium adding the least. Calliandra prunings provided the annual total K requirement and 49% of the N requirement of mature tea. However, none of the species provided more than 5% of the P requirement. It is concluded that among the tree species tested, Calliandra and Flemingia are the most suitable for contour hedgerows in tea plantations of this agroclimatic region because of their higher soil nutrient enrichment capacity and slower decomposition rates which would minimize leaching losses. This revised version was published online in June 2006 with corrections to the Cover Date.     

Effects of Seed Weight and Seed Type on Early Seedling Growth of Pinus sylvestris under Harsh and Optimal Conditions

The effects of seed weight and seed type on seedling growth of Pinus sylvestris (L.) were studied by seeding individually weighed orchard and stand seed in different mixtures under harsh (direct seeding in field) and optimal (seeding in nursery) conditions. In the nursery experiment an increase in the seed weight from 3 to 7 mg increased the seedling height by 10-27% and total weight by 27-113%, and decreased the height/diameter ratio by 5-6% after 2 yrs. With elimination of seed weight effects, orchard seedlings were 2% taller than stand seedlings in year 2. Without elimination of seed weight effects, orchard seedlings were 7-13% taller. In the field experiment an increase in the seed weight from 3 to 7 mg increased seedling height by 18-65%, stem volume by 81-274% and the number of top-buds by 23-34% in year 5. After elimination of seed weight effects, orchard seedlings were 7-13% taller than stand seedlings and without elimination of seed weight effects 20-21% taller after 5 yrs. Even after elimination of both seed weight and genetic effects orchard seedlings were 3-9% larger than stand seedlings in the field experiment. In conclusion, the influence of seed weight and seed type on growth traits and slenderness is highly significant and the influence seems to be greater in harsh conditions.     

Modelling of adequate pretwist for obtaining straight timber

Abstract

Wood in general and wooden studs in particular are often distorted owing to uneven shrinkage during the drying process in the sawmill. Twist is often the most detrimental of all types of distortion, and it is caused by spiral grain in combination with variations in moisture content. For sawmills, the objective is to produce dried, straight boards, and one method of dealing with boards with excessive spiral grain is to sort them out and then dry them in a pretwisted position to obtain straight boards after drying. A model using the finite element (FE) method for the simulation of drying twist distortions was first calibrated against laboratory experiments in which boards were dried with and without restraints and pretwists. After the calibration, the FE results were compared with industrial test results for boards that were dried without restraints or with restraints with zero pretwist, i.e. straight restraints. The FE model used an elastic–ideally plastic material model to obtain permanent deformations. The calibration was to set the yield stresses so that there was a good match between FE results and results from the laboratory experiments. The comparison between the industrial test results and the FE results showed that the FE model is capable of realistic simulations of drying boards with and without restraints and presumably also pretwists.     

Potential to harness superior nutritional qualities of exotic baobabs if local adaptation can be conferred through grafting

Baobab leaves form an important part of the local diet in Sahel countries and elsewhere in Africa. Existing leaf nutritional data and agroforestry performance information are based solely on Adansonia digitata L., the baobab of continental Africa. The introduction potential of Adansonia species from the center of diversity in Madagascar and from Australia remains untapped. To assess this potential, the mineral contents and B₁ and B₂ vitamin levels of dried baobab leaves were determined for five-year old trees of A. digitata, A. gibbosa (A. Cunn.) Guymer ex D. Baum, A. rubrostipa Jum. & H. Perrier (syn. A. fony Baill.), A. perrieri Capuron and A. za Baill. grown in an introduction trial in Mali. Nutritional data were evaluated against survival and vigor to identify promising germplasm. Leaf vitamin and crude protein contents were highest in the Madagascar species, especially A. rubrostipa (B₁ 88 mg 100 g⁻¹, B₂ 187 mg 100 g⁻¹, protein 20.7% dry weight). However, the local species far outperformed the introductions in survival, tree height, basal diameter and resistance to termites. We suggest grafting as a way of harnessing the vigor of well-adapted local baobab varieties to the superior nutritional profiles of A. rubrostipa and others. Cross-species grafting tests in Adansonia were successful, thus creating new agroforestry possibilities with different scion/rootstock combinations.     

Growth of Phlebiopsis gigantea in wood of seven conifer species

Heterobasidion parviporum and Heterobasidion annosum are widely distributed root‐rot fungi that infect conifers throughout Europe. Infection of conifer stumps by spores of these pathogens can be controlled by treating fresh stumps with a competing non‐pathogenic fungus, Phlebiopsis gigantea. In this study, growth of three Latvian strains of P. gigantea and the biological control agent ‘Rotstop’ strain was evaluated in stem pieces of Norway spruce, Scots pine, lodgepole pine, Douglas‐fir, Weymouth pine, Siberian larch and Sitka spruce. The growth rates of one H. parviporum and one H. annosum isolate were also measured in the same stem pieces. The growth rate of P. gigantea varied greatly in wood of different conifer species. It was higher in the three pine species, lower in Norway spruce and lowest in Sitka spruce and Siberian larch, and in Douglas‐fir, this fungus did not grow. The largest area of wood occupied by P. gigantea was in lodgepole pine. Growth of Latvian isolates of P. gigantea in the wood of Pinus and Picea species was comparable to that of the Rotstop isolate. Consequently, stump treatment with local P. gigantea isolates should be recommended. However, our results suggest that Douglas‐fir stump treatment against Heterobasidion by P. gigantea may be ineffective and other stump treatment methods should be considered.     

Stand Structure in Pine,Spruce and Deciduous Forests: A Comparison Between Finnish and Russian Karelia

This study investigated the stand structure in pine, spruce and deciduous forests in the border district of Finland and Russia. A total of 46 mature forest stands was selected as pairs, the members of each pair being as similar as possible with respect to their forest site type, age, moisture and topography. The stands were then compared between the two countries by means of basal areas and number of stems. The proportions of dominating tree species were 2-12% lower, and correspondingly the proportions of secondary tree species higher, in Russian forests. The density of the forest stock was also higher in each forest type in Russia. The forests in the two countries differed most radically in terms of the abundance of dead trees. The amount was two to four times higher in Russian deciduous and spruce forests, and in pine forests the difference was 10-fold. The stand structures indicated that Russian coniferous stands, in particular, were more heterogeneous than intensively managed pine and spruce stands in Finland.     

Growth and Terminal Bud Formation in Picea abies Seedlings Grown with Alternating Diurnal Temperature and Different Light Qualities

The root collar diameter and the height:diameter ratio are of particular importance in container-grown seedlings where a high density in the containers may produce spindly seedlings. Temperature regimes and light quality are known to affect plant growth. The aim of this study was to identify responses in Picea abies (L.) Karst. seedlings grown with light providing different red:far-red ratios and under temperature regimes with alternating day (DT) and night temperature (NT) from negative (DT < NT) to positive (DT > NT) difference (DIF) between DT and NT. Experiments were conducted in controlled environment chambers and in a daylight phytotron. Only limited thermoperiodic responses appeared in P . abies seedlings with respect to seedling height and dry weight accumulation. The formation of terminal buds, however, was clearly delayed in seedlings grown at negative DIF. The results indicate a requirement for day extension light that is high in far-red, to prevent terminal bud formation under natural short-day conditions. An extended study should be conducted to clarify the minimum level of light intensity and the optimal light quality needed to prevent terminal bud formation under natural short-day conditions.     

CAD与建筑设计的关系

本文分析了CAD在设计中引起的正面和负面影响,并进行了系统的阐述,从而使设计者在应用中能够保持客观的态度。