用CONE法研究木材阻燃剂FRW的阻燃性能

利用锥形量热仪 (CONE)系统地测定了新型木材阻燃剂FRW的阻燃性能 ,讨论了FRW对阻燃木材在燃烧时的热释放、质量变化及耐点燃性的影响 ,并与Dricon阻燃剂进行了对比。结果表明 ,在 5 0kW·m2 的热辐射功率下 ,FRW阻燃处理木材的热释放速率 (RHR)和总热释放量 (THR)随FRW载药率的升高而降低 ,至载药率达到 10 %左右时 ,RHR及THR降低为未处理木材的 5 0 %左右 ,并且降低的趋势明显变缓 ;FRW与Dri con阻燃木材的有效燃烧热 (EHC)曲线基本重合 ,说明二者的阻燃机理类似 ;FRW阻燃木材的质量损失速率(MLR)曲线与RHR曲线相似 ,失重和热释放主要发生在有焰燃烧阶段 ;FRW阻燃处理能显著提高木材燃烧时的成炭率 ,但对木材的点燃时间影响不大 ;FRW与Dricon的阻燃效力相当 ,属高效木材阻燃剂。     

PN型木材阻燃防腐复合剂的研制

ＰＮ型木材用阻燃防腐复合剂是一种含有磷氮及防腐剂成分的浅绿色或无色透明液体，经该复合剂处理的木材试件，氧指数＞５０％。木垛法测定的结果是，当木材的复合剂吸收量达７０ｋｇ／ｍ３以上时，燃烧失重趋于稳定，失重率保持在２５％以下。４５°斜面燃烧法测定，复合剂处理材达难燃级水平。复合剂中含有２％的防腐剂时，真菌腐蚀后的试材重量损失率小于３％，能防止木材腐朽变质。复合剂处理材的部分力学性能、胶合、抗吸湿性稍有降低，但对油漆、金属腐蚀无影响。该复合剂适用于车辆木结构材及其他室内木材的处理。     

磷酸铵盐处理人工林木材的燃烧性能

利用锥形量热仪对磷酸铵盐处理的人工林杉木、杨木和马尾松木材的燃烧性能进行研究。结果表明 :磷酸铵盐阻燃处理木材的引燃时间与阻燃剂量有关 ,对 3种木材而言 ,阻燃剂量超过 10 0kg·m- 3,木材才不会被点燃 ;磷酸铵盐对降低木材的释热性能效果明显 ,释热速度降低 ,释热总量减少 ,气相燃烧放热降低 ,而且随着阻燃剂量的增加 ,降低程度更加明显 ;经磷酸铵盐阻燃处理 ,木材失重降低 ,这对保证结构外形的稳定性具有重要作用 ;磷酸铵盐阻燃剂的抑烟作用不理想 ,虽然降低了最强发烟过程的强度 ,但是也提高了最弱发烟过程的强度 ,而且随着阻燃剂量的增加 ,发烟量呈增加的趋势 ;在阻燃研究中 ,阻燃剂在木材内分布状态是一个不可忽视的影响因素 ,特别是木材这种非均质性材料 ,阻燃剂分布的不均匀性将会影响材料整体的耐火性能     

阻燃剂浸渍处理木材方法研究

本研究以ZR-M-301型木材阻燃剂为浸渍药液,樟子松和水曲柳为木材试样,选择常压浸渍、压力浸渍、微波处理后常压浸渍、超声波加压浸渍和微波处理后超声波加压浸渍五种木材阻燃处理方法,经过试验,探索在生产阻燃木材的浸渍方法中引入微波和超声波技术的可行性,找到效果好的木材阻燃处理方法.本研究的创新点是将微波处理与超声波辐射技术应用于木材阻燃处理中,利用微波加热处理改善木材构造的渗透性能,利用超声波的空化作用强化阻燃剂浸入性能,并提出了新的技术路线.     

用CONE法研究木材阻燃剂FRW的阻燃机理

采用锥形量热仪(CONE)法对复合木材阻燃剂FRW处理紫椴木材(FZ)、FRW的组分磷酸脒基脲(GUP)处理紫椴木材(GZ)、硼酸处理紫椴木材(BZ)和未处理的紫椴木材(UZ)的燃烧性进行了系统的测定，通过对上述试样在燃烧时的热释放、质量变化、烟气产生以及尾气成分等实验数据的综合对比分析，讨论了阻燃剂的作用机理。结果表明：1)FRW阻燃剂显著降低了木材的热释放速率(RHR)、总热释放量(1FHR)、有效燃烧热(EHC)、质量损失速率(MLR)、烟比率(SR)、比消光面积(SEA)、CO2的浓度及产率(Yco2)；2)GUP与硼酸之间存在显著的阻燃协同效应；3)FRW阻燃木材的MLR曲线与RHR曲线相似，失重和热释放主要发生在有焰燃烧阶段；4)FRW阻燃处理能显著提高木材燃烧时的成炭率，说明催化成炭是FRW阻燃机理的主要方面。     

三乙醇胺对木材阻燃剂的阻燃效果和吸湿性的影响

考察了三乙醇胺(TEM)对3种木材阻燃剂(F1、F2、DPB)处理试件的载药率、阻燃效果、吸湿性的影响。试验结果表明:随三乙醇胺加入量的增加,阻燃试件的载药率增加,氧指数增加,阻燃效果得到改善;三乙醇胺加入量大于3.5%时,处理液的黏度增加,载药率增加不明显;加入2.5%～3.5%的三乙醇胺时,处理试件的吸湿率最小。同时实验还显示了在3种木材阻燃剂中加入三乙醇胺后,只有F2与三乙醇胺有协同效应,其它两种阻燃剂协同效应不明显。     

Effect of Triethanolamine on the Retardant Effectiveness and Hygroscopicity of Wood Fire-retardant

考察了三乙醇胺(TEM)对3种木材阻燃剂(F1、F2、DPB)处理试件的载药率、阻燃效果、吸湿性的影响.试验结果表明:随三乙醇胺加入量的增加,阻燃试件的载药率增加,氧指数增加,阻燃效果得到改善;三乙醇胺加入量大于3.5％时,处理液的黏度增加,载药率增加不明显;加入2.5％～3.5％的三乙醇胺时,处理试件的吸湿率最小.同时实验还显示了在3种木材阻燃剂中加入三乙醇胺后,只有F2与三乙醇胺有协同效应,其它两种阻燃剂协同效应不明显.     

美国阻燃处理木材的现状

总结美国阻燃处理木材的规范与标准,介绍美国主要阻燃处理木材生产商的阻燃木材产品,分析主要阻燃剂的配方及合成工艺、处理木材的工艺与技术特点,为国内阻燃处理木材行业的技术发展提出建议.     

硼化物处理人工林木材的燃烧性能

利用锥形量热仪对硼化物处理的人工木材的燃烧性能进行评价研究.结果表明,硼化物对抑制木材点燃、释热、减少失重等效果不理想.虽然随着吸收量的增加木材引燃时间有延长的趋势,但还未达到抑制着火的程度.随着吸药量的增加,释热降低,但仍保持有两个强释热过程;木材平均失重率呈下降的趋势,但不甚明显.阻燃处理后,发烟总量随着吸收量的增加有增加趋势,但均未超过未处理木材.     

FRW阻燃刨切薄竹的阻燃特性

采用FRW阻燃剂对刨切薄竹进行阻燃处理,用锥形量热仪(CONE)测定不同载药率下处理材与未处理材的阻燃性能。结果表明:在25kW·m-2的热辐射功率下,刨切薄竹经FRW阻燃处理后,热释放速率、总热释放量和总烟释放量随着载药率的增大而减小,处理材在燃烧过程中不会出现较高火焰的燃烧过程;处理材与未处理材相比,点燃时间延长,残余物质量增加;FRW阻燃处理刨切薄竹的阻燃和抑烟效果明显。     

Silicic acid: boric acid complexes as wood preservatives

Wood was treated with a low molecular-weight silicic acid: boric acid agent and examined for increased resistance to termites and combustion. Wood treated with silicic acid only exhibited increased termite resistance, but not to the marked extent observed after treatment with a mixture of silicic and boric acids. Increasing the quantity of boric acid also increased the termite mortality rate and shortened the time to death. Oral-toxicity tests using dyed silicic acid: boric acid suggested that the boric acid in the agent acted as a stomach poison. Field tests on stakes over three years showed that even if stakes were placed near the termite exit, those treated with silicic acid and high levels of boric acid had no attack by termites and maintained their original form. Though these specimens were installed in the field during three rainy seasons (about six months in total) in three years, the termite resistance ability of these chemicals was maintained. It became clear that this silicic acid: boric acid agent has a high water resistance ability worthy of application in the outdoors. Combustion tests showed that flame and glowing combustion times were shortened at high levels of boric acid. When a boric acid: methanol solution was added at of rate of not less than 25 ml for 100 g of colloidal silicic acid solution (CSAS), flaming and glowing combustion were not observed. Although the charring length of the wood specimen which was treated with a low molecular weight silicic acid: boric acid agent decreased to 2/3 of that of the control wood, the charring lengths were not influenced by the level of boric acid. However, the volume of smoke decreased relative to the amount of boric acid that had been added.     

阻燃处理米槠热分解的热动力学分析

将硼酸、硼砂混和制成均匀的阻燃剂,并以脲醛预缩液为载体,用于处理试材,并采用TG和DTA方法来分析经处理与未经处理的米槠热解时的热动力学特性,结果表明该阻燃体系能使米槠的热解温度降低,平均热解失重率降低、失重过程变缓,产炭量增加、在炭化阶段的失重变小。     

Fire-retarding properties of nano-silver in solid woods

Fire-retarding properties of 200?ppm nano-silver solution, with a size ranging from 20 to 80?nm, on five woody species were studied and compared with Borax and Celcune ^? . Blocks of 150?×?130?×?9?mm3 were prepared and divided into four groups of control samples, nano-silver-, Borax-, and Celcune-impregnated specimens. A special apparatus was designed, and six fire-retarding properties of each specimen were measured, namely ignition, glowing, back-darkening and back-holing times, as well as length and width of burning. Results showed that all three kinds of treatments had improving effects on the fire-retarding properties. Celcune showed the best improvement on glowing time. Cluster analysis showed direct relation between density and fire-retardant properties; also, fire-retarding behaviors of the four hardwoods were quite different to those of the one softwood. Furthermore, there are improvements in some fire-retarding properties of nano-silver-impregnated specimens that are in connection with its heat-transfer property.     

PEI/APP改性脲醛树脂制备阻燃胶合板及性能

以聚乙烯亚胺(PEI)为改性剂处理聚磷酸铵(APP)制备得到APP@PEI阻燃体系,并将其加入到脲醛树脂(UF)中,制备阻燃胶合板。研究了APP@PEI对UF胶黏剂理化性能的影响,并进一步探讨其对胶合性能及阻燃性能的影响。结果表明:APP、PEI和APP@PEI对UF的黏度、pH和固化时间均有影响。当APP添加量为10%时,UF的黏度由3.843 Pa·s上升至8.270 Pa·s,pH降至5.67,固化时间由91 s降至87 s;当PEI添加量为0.91%时,由于UF体系中支化和交联程度增加,黏度上升至41.433 Pa·s,pH和固化时间分别提升至9.91和116.3 s;而APP@PEI能降低对UF各项性能的影响,添加10%APP@PEI时UF的黏度、pH和固化时间分别为5.966 Pa·s、6.33和94.3 s。添加APP后,胶合板的胶合强度均低于Ⅱ类胶合板强度标准(0.7 MPa);添加PEI后,胶合板的胶合强度能够提升18%以上;APP@PEI添加量为10%时,胶合板的胶合强度达0.85 MPa,高于Ⅱ类胶合板强度标准要求。添加APP、PEI和APP@PEI对胶合板的阻燃性能有不同影响,单独添加PEI无法改善胶合板的阻燃性能,当APP和APP@PEI添加量为10%,15%和20%时,胶合板的极限氧指数(LOI)分别比未添加阻燃剂时提高0.8%,2.0%,2.5%和1.2%,2.2%,3.1%。     

Fire-retardant and smoke-suppressant performance of an intumescent waterborne amino-resin fire-retardant coating for wood

An intumescent waterborne amino-resin fire-retardant coating for wood (C) was synthesized and its fire-retardant and smoke-suppressant properties were investigated. The main film-builder of C was urea-formaldehyde resin blended with polyvinyl acetate resin. The intumescent fire-retardant system of C consisted of guanylurea phosphate (GUP), ammonium polyphosphate (APP), pentaerythritol (PER) and melamine (MEL). Specimens of plywood painted, respectively, with a commercial intumescent fire-retardant coating (A), a synthesized coating (C), and the main film-builder of coating C (B), as well as an unpainted plywood (S-JHB), were analyzed by cone calorimetry (CONE). The results show a marked decrease in the heat release rate (HRR) and the total heat release (THR), an increased mass of residual char (Mass), a marked postponement in time to ignition (TTI) and a reduced carbon monoxide production rate (P _CO). The smoke production rate (SPR) and total smoke production (TSP) of the plywood painted with coating C were observed with the CONE test. The overall fire-retardant and smoke-suppressant performance of the synthesized coating C was much better than that of the commercial coating A. The thermo-gravimetric analysis (TGA) results of coating C and its film-builder B indicated that the thermal degradation process of B was slowed down by the addition of the intumescent fire-retardant system; the increase in the amount of charring of coating C was considerable. __________ Translated from Scientia Silvae Sinicae, 2007, 43(12): 117–121 [译自: 林业科学]     

Screening of properties of modified chitosan-treated wood

Chitosan is a biopolymer derived from chitin in crustacean shells. Over the past decade it has been studied as an environmentally benign wood-protecting agent. It is assumed to act as a fungi-stat against a wide range of fungi and even as a fungicide at higher concentrations. This study investigated the properties of wood treated with modified chitosan of different molecular weights. Scots pine (Pinus sylvestris L.) and beech (Fagus sylvatica L.) samples were impregnated with two chitosan solutions differing in their average molecular weights. The chitosan solutions were depolymerized by nitrous acid to one solution of high molecular weight and one solution of low molecular weight with a concentration of 5% (w/v). The results show changes in sorption properties, antifungal properties, fire-retardant properties and mechanical properties of modified chitosan-treated wood. Heat-modified, chitosan-treated wood showed similar properties to chitosan-treated wood, except for brownish coloration, enhanced hydrophobation, and slightly reduced antifungal and fire-retardant properties. The modulus of rupture and hardness showed little or no change. The modulus of elasticity of the heat-modified, chitosan-treated wood increased by 27% compared with untreated wood.     

Pyrolytic characteristics of burning residue of fire-retardant wood

In order to investigate the pyrolytic characteristics of the burning residue of fire-retardant wood, a multifunctional fire-resistance test oven aimed at simulating the course of a fire was used to burn fire-retardant wood and untreated wood. Samples at different distances from the combustion surface were obtained and a thermogravimetric analysis (TG) was applied to test the prrolytic process of the burning residue in an atmosphere of nitrogen. The results showed that: 1) there was little difference between fire-retardant wood and its residue in the initial temperature of thermal degradation. The initial temperature of thermal degradation of the combustion layer in untreated wood was higher than that in the no burning wood sample; 2) the temperature of the flame retardant in fire-retardant wood was 200°C in the differential thermogravimetry (DTG). The peak belonging to the flame retardant tended to dissipate during the time of burning; 3) for the burning residue of fire-retardant wood, the peak belonging to hemicellulose near 230°C in the DTG disappeared and there was a gentle shoulder from 210 to 240°C; 4) the temperature of the main peaks of the fire-retardant wood and its burning residue in DTG was 100°C lower than that of the untreated wood and its burning residue. The rate of weight loss also decreased sharply; 5) the residual weight of fire-retardant wood at 600°C clearly increased compared with that of untreated wood. Residual weight of the burning residue increased markedly as the heating temperature increased when burning; 6) there was a considerable difference with respect to the thermal degradation temperature of the no burning sample and the burning residue between fire-retardant wood and untreated wood. __________ Translated from Journal of Beijing Forestry University, 2006, 28(3): 133–138 [译自: 北京林业大学学报]     

Screening of properties of modified chitosan-treated wood

Abstract

Chitosan is a biopolymer derived from chitin in crustacean shells. Over the past decade it has been studied as an environmentally benign wood-protecting agent. It is assumed to act as a fungi-stat against a wide range of fungi and even as a fungicide at higher concentrations. This study investigated the properties of wood treated with modified chitosan of different molecular weights. Scots pine (Pinus sylvestris L.) and beech (Fagus sylvatica L.) samples were impregnated with two chitosan solutions differing in their average molecular weights. The chitosan solutions were depolymerized by nitrous acid to one solution of high molecular weight and one solution of low molecular weight with a concentration of 5% (w/v). The results show changes in sorption properties, antifungal properties, fire-retardant properties and mechanical properties of modified chitosan-treated wood. Heat-modified, chitosan-treated wood showed similar properties to chitosan-treated wood, except for brownish coloration, enhanced hydrophobation, and slightly reduced antifungal and fire-retardant properties. The modulus of rupture and hardness showed little or no change. The modulus of elasticity of the heat-modified, chitosan-treated wood increased by 27% compared with untreated wood.     

高支化聚脲对脲醛树脂胶黏剂耐水性能和甲醛释放量的影响

引入高分子量、高支化度以及端基为尿素的高支化聚脲(HBPU)用于低摩尔比脲醛树脂(UF)改性,利用HBPU与游离甲醛的反应以及与UF组分的共缩聚反应实现树脂耐水性能的提升和人造板甲醛释放量的降低,有效平衡胶合性能和甲醛释放量之间的矛盾。在无溶剂、无催化剂条件下,通过尿素(U)与三(2-氨基乙基)胺(TAEA)的脱氨缩合反应,一步合成了具有尿素端基的HBPU,并对HBPU的分子量分布和结构进行了表征。使用HBPU水溶液,采用UF合成反应后期加入和共混2种方法对UF进行改性,通过胶合板性能测试以及甲醛释放量测定,考察了HBPU添加量和添加方式的影响。凝胶渗透色谱和碳-13核磁共振分析表明,通过本研究的合成方法可以获得具有高分子量、高支化度、尿素为端基且水溶性良好的HBPU,并且随着U与TAEA摩尔比的提高,更多尿素封端产物形成。电喷雾电离质谱对改性树脂的分析结果表明,HBPU不仅与UF中的一部分游离甲醛发生羟甲基化反应,同时与UF组分反应生成了部分共缩聚产物。胶合板性能测试结果表明,共混以及反应后期加入HBPU两种方式得到的改性树脂耐水性能均显著提升。同时,使用添加5%HBPU改性树脂制备的胶合板甲醛释放量较未改性树脂制备胶合板降低41%。HBPU改性同步实现胶合性能的提升和甲醛释放量降低的主要原因在于HBPU在提高树脂支化程度的同时,还起到捕捉游离甲醛的作用。解决UF胶合性能和人造板甲醛释放量之间矛盾的关键在于提升树脂的支化程度,同时降低树脂中游离甲醛的含量,而引入高分子量、高支化度、具有类似尿素反应活性的聚合物是同步实现胶合性能提升和甲醛释放量降低的有效途径。