聚丙烯腈预氧丝皮芯结构的影响因素与防控措施

在恒温和梯度升温两种模式下,对不同纤度、横截面形状的3种聚丙烯腈原丝进行了预氧化处理,采用扫描电镜、光学显微镜、元素分析等技术研究了预氧丝的皮芯结构及氧元素的扩散。结果表明,对于恒温模式,在250℃加热1h的预氧丝已经产生了明显的皮芯结构,而对于梯度升温模式,直到275℃才开始出现皮芯结构;原丝的横截面形状不影响氧的扩散,在相同加热条件下,肾形截面预氧丝的皮层厚度与圆形截面的相同;原丝纤度越小,越容易获得均质的预氧丝。原丝的细旦化以及适当的梯度升温预氧化工艺是获得优质预氧丝的重要保证。     

PAN原丝工艺过程结晶行为的研究

结晶度是影响ＰＡＮ原丝及其碳纤维性能的重要因素之一，本文通过Ｘ－ｒａｙ衍射法研究了不同凝固条件及纺丝工艺对凝固丝条及纤维结晶度的影响规律。结果表明不同的凝固条件，不同的纺丝工艺都将对凝固丝条及纤维的结晶度产生重要影响。     

干燥致密化对通用碳纤维用PAN原丝力学性能升级的考察

为提升国产通用碳纤维用PAN原丝的力学性能,再次对原丝进行水洗及干燥致密化工艺处理。实验结果表明,水洗因使丝束增韧,与致密化起到相反的作用,不利于原丝力学性能的升级;不同温度下,随致密化时间的增加,丝束强度先增大后减小,55s时丝束强度提高最大;确定致密化时间55s时,在140～150℃温梯下丝束强度最大,约提升初始原丝的35.6%。     

盐雾环境下受荷混凝土中氯离子扩散试验

针对海洋盐雾环境,开展不同荷载水平作用下混凝土中氯离子扩散试验,测试混凝土中不同深度的氯离子含量,总结混凝土中氯离子扩散规律,拟合氯离子扩散荷载影响系数与构件应力状态之间的关系式。结果表明,拉应力作用下混凝土中氯离子含量增加,氯离子扩散系数增大;压应力作用下混凝土中氯离子含量降低,氯离子扩散系数减小;氯离子扩散系数随着时间增加逐渐减小,表面氯离子浓度随着时间的增加逐渐增大。考虑荷载影响的氯离子扩散模型可为预测实际工程受荷混凝土结构的使用寿命提供参考。     

水洗条件对PAN水洗丝条结构和力学性能的影响

研究了水洗条件对聚丙烯腈(PAN)水洗丝条结构和力学性能的影响.用万能材料测试机、XRD、SEM、压汞仪测试纤维的力学性能、晶态结构、表面形态和孔结构,得到结构对力学性能的影响规律.结果表明:随着水洗温度升高,丝束的最大应力和最大载荷降低;水洗温度从55℃增大到90℃,结晶度从64.84%降低到57.73%,晶粒大小从4.034nm变为5.007nm;水洗温度升高,丝表面出现更加明显的纵向沟槽,表面缺陷增多,丝的直径也变得不均匀,孔隙率和孔径变小,微孔逐渐增多;随着结晶度降低、晶粒尺寸变大、表面缺陷增多,丝的力学性能随之下降;相同温度,超声波使纤维的孔径和孔隙率变小,同时使表面缺陷增多,所以超声波对丝的力学性能影响不大.     

聚丙烯腈原丝离线循环水洗工艺

通过设计新型自动控制水洗机,将筒管离线循环水洗技术应用到碳纤维用聚丙烯腈原丝水洗工艺中.降低了聚丙烯晴原丝中残留的DMSO(二甲基亚砜)溶剂量,减弱了其在原丝的拉伸、预氧化处理等过程造成的碳纤维结构缺陷、强度降低等不利影响.实验证明新方法明显提高了水洗效果,能够快速有效的降低原丝中DMSO残留量,并大大节约了用水量.     

纤维聚合物复合材料的有效湿扩散系数

根据纤维聚合物复合材料的微观结构, 建立了基于复合材料单胞模型的湿扩散计算方法, 研究了不同温度和不同体积分数下纤维聚合物复合材料的湿扩散性能。假设纤维是不可渗透的, 并在聚合物基体中均匀分布, 计算了不同温度不同体积分数下复合材料的有效湿扩散系数。结果表明: 复合材料的有效湿扩散系数随温度的升高而增大, 随纤维体积分数的增大而减小; 在相同温度、 相同体积分数下, 正六边形排列的纤维复合材料的湿扩散系数比正方形的略大。计算结果及经验公式与Gueribiz曲线基本一致, 说明用单胞模型计算复合材料的湿扩散性能是非常有效的, 有助于理解纤维复合材料的湿扩散机制和性能。      

聚乙烯毛细管挂丝及区域拉伸自增强

本文通过测定塑化曲线确定聚乙烯(PE)的毛细管挂丝温度范围,测试了挤出原丝和低温区域拉伸丝的力学性能和热收缩行为。结果表明,低压下的毛细管挤出工艺对 PE 丝的力学性能影响很小,而低温区域拉伸能大幅度提高原丝的力学性能,产生自增强效应,但热收缩率明显增大。     

残余溶剂DMSO对PAN纤维结构及热性能的影响

在PAN／DMSO湿法纺丝体系中，改变水洗条件，得到含有不同DMSO含量的聚丙烯腈原丝．通过先学显微镜、X射线衍射、DSC和TG等分析测试手段，研究了残余溶剂二甲基亚砜(DMSO)对PAN纤维结构及热性能的影响。在纤维低温热处理过程中，原丝中痕量DMSO的存在，可以改变纤维的截面形状、破坏纤维的晶态结构，并使纤维的热稳定性降低。     

考虑纤维/基体界面相的复合材料湿扩散模型

通过类比复合材料湿扩散与热传导的控制方程以及边界条件,以Halpin & Tsai模型为基础,发展了一个考虑了纤维/基体界面相的三相复合材料湿扩散模型,并研究了纤维界面随机损伤对湿扩散的影响。建立了纤维周期排布、随机排布、界面相损伤随机分布3种细观有限元模型。用上述模型分析了单向复合材料横向有效湿扩散系数（TEMDUC）随纤维和界面相体积分数、湿扩散性能以及界面相损伤率变化的规律,理论预测与有限元计算结果一致。研究发现：界面相或纤维相的扩散系数存在一个临界值,当扩散系数小于该临界值时,TEMDUC随纤维体积分数的增大而减小;反之,TEMDUC随纤维体积分数的增大而增大,此临界值的大小与纤维体积含量无关。研究还发现纤维界面损伤率相同的条件下,其分布的随机性对复合材料的有效湿扩散系数影响不大。     

同步辐射小角X射线散射研究PAN原丝制备过程中孔结构的演变

采用同步辐射小角X射线散射研究了PAN原丝制备过程中纤维孔结构的演变。结果表明,在水洗工艺中,纤维孔隙较多、较大,孔径分布较宽,近似圆形;在热水牵伸工艺中,纤维孔隙仍较多、较大,孔径分布较宽,近似椭圆形,长轴约17 nm~21 nm,短轴约4 nm~11 nm;在干燥致密化工艺中,孔隙急剧减少、减小,孔径分布较窄,沿纤维轴向约7 nm~9nm,垂直纤维轴向约2 nm;经过蒸汽牵伸,孔隙又增多、增大,孔径分布变宽,孔隙沿纤维轴向被牵伸得很长,近似梭形;但是随后的松弛热定型又使孔隙减小,孔径分布变窄。     

Diffusion control of porous membrane by modifying the nanopore properties

We have investigated the diffusion of various solvents on nanoporous membranes with various pore size and surface energy. We have modified the size of pore channel and surface energy of porous membrane through grafting different sized alkyl chain on inorganic membranes. Typically, disc type zirconia membranes with pore size of 3 nm and silica ones with 1 nm pore were purchased from Inocermic Co. Ltd. (Germany), and the surface and pore channel was modified by either octyltriethoxysilane (OTS) with chain length approximately 1 nm or pentyltriethoxysilane (PTS) with chain length approximately 0.5 nm. The water contact angles of both OTS and PTS grafted membrane were larger than 100 degrees indicating the hydrophobically modified surface. Contact angles of hydrophilic and hydrophobic solvents were also examined to obtain exact surface energy (gamma(sv)) of grafted membrane, and the values were determined to be 56.3, 45.3, and 42.2 mN/m for ungrafted, PTS- and OTS-grafted membrane, respectively. The solvent diffusion patterns were evaluated by measuring the concentration gradient of small dye molecule, azobenzene. The diffusion coefficients of various solvents were measured on the basis of Fick's diffusion law. It was concluded that the diffusivity is dependent on the pore size for solvent with low surface tension and on the gamma(sv) value for solvent with high surface tension.     

金属有机骨架化合物MIL-101负载纳米Ni的制备及储氢性能

采用2-甲基咪唑代替HF酸以溶剂热法成功制备了纯度较高的金属有机骨架化合物MIL-101,利用过量浸渍法结合液相还原法成功负载了Ni,制备出Ni/MIL-101复合材料。通过XRD、SEM、TEM、BET、TG对所得MIL-101、Ni/MIL-101复合材料的结构、形貌、比表面积孔径及热稳定性进行表征,对MIL-101、Ni/MIL-101复合材料的氢扩散系数、吸氢形成焓进行测定计算,考查其储氢能力。结果表明,该方法成功制备了Ni/MIL-101复合材料,该产物是一种两类孔结构的金属骨架化合物,Ni的负载可降低Ni/MIL-101复合材料的吸氢形成焓,Ni/MIL-101复合材料的氢扩散系数达到7.6373×10^-7 cm/s,提高了MIL-101的储氢能力。     

An examination of two methods for studying diffusion kinetics in hydrated cements

Two methods of measuring, diffusion in hydrated cement are described. The first method, solvent exchange, involves measuring the rate of exchange of pore water with a miscible organic fluid by a process of counter-diffusion. Solvent exchange measurements are sensitive to the pore structure of the hydrated cement and alteration to the pore structure caused by previous drying. The second method involves measuring the rate of water diffusion during drying and rewetting tests at selected relative humidities. The results are complicated by lack of equilibrium but can reflect the importance of the degree of specimen saturation as well as the effects of pore structure.     

Preparation of nanoporous carbons via a grafting method for the application to electrochemical double layer capacitors

Nanoporous carbon materials with a controlled pore size and surface area were prepared using grafting method. The use of 3-mercaptopropyltrimethoxysilane (MPTMS) as a grafting material played an important role in producing a porous structure by linking the silica to the polymer, with the subsequent formation of a silica-polymer composite. Importantly, the use of an organic solvent, compared to an aqueous solvent, has a positive effect in forming uniform and well-developed carbon structures, due to the high degree of dispersion with well-mixing of the carbon and silica precursors. The amounts of MPTMS and carbon precursor used determined the pore size and surface area of resulting carbon materials. The optimum ratio of MPTMS and carbon precursor for achieving a high surface area in excess of 2000 m2/g was determined. The use of a large amount of carbon precursor resulted in carbons with a relatively small surface area and an increase in MPTMS content led to an increase in the microporous structures. The capacitance value of the porous carbon prepared using the optimum ratio was determined to be 150 F/g.     

水相溶胶路线制备钇掺杂ZrO2纳滤膜及其分离性能研究

以氧氯化锆为前驱体, 采用环境友好的水相溶胶路线制备出完整无缺陷的管式钇掺杂的ZrO₂(YSZ)纳滤膜。并考察了溶胶粒径, 材料晶型与孔结构的关系。结果表明: 前驱体浓度越低, 所制备的溶胶粒径越小, 经400℃煅烧得到的粉末中单斜相含量越高, 堆积孔径增大; 向ZrOC₂O₄溶胶中添加8mol%钇, 有效抑制了ZrO₂四方相向单斜相的转变, 延缓晶粒生长, 同时防止膜层开裂。经纳滤测试表明, 实验制备的YSZ纳滤膜对PEG的截留分子量为860 Da, 纯水渗透率为200 L/(m²·h·MPa)。实验还详细考察了YSZ纳滤膜在pH=6, 压力0.8 MPa的条件下对NaCl、Na₂SO₄、CaCl₂和MgCl₂ 4种溶液的截留性能, 结果显示YSZ纳滤膜对0.005 mol/L CaCl₂和MgCl₂溶液的离子截留率分别达到65%和78%。     

Research on structural compatibility of eco-porous concrete and vegetation

To investigate the structural compatibility of eco-porous concrete (EPC) and vegetation, a simulation method (sand penetration coefficient) of structure compatibility between the eco-porous concrete (EPC) and vegetation was put forward. Furthermore, the relation between sand penetration coefficient and pore characteristics were analyzed, and the technology of acquiring equivalent pore size was optimized. The results present that the new simulation method, characterized by sand penetration coefficient, can effectively assess the ability of eco-porous concrete (EPC) to allow the root system to pass through. In addition, the real pore structure shape by “rubbing technology” can be easily and quickly obtained.     

Controlling the Pore Size of Mesoporous Carbon Thin Films through Thermal and Solvent Annealing

Herein an approach to controlling the pore size of mesoporous carbon thin films from metal‐free polyacrylonitrile‐containing block copolymers is described. A high‐molecular‐weight poly(acrylonitrile‐block‐methyl methacrylate) (PAN‐b‐PMMA) is synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization. The authors systematically investigate the self‐assembly behavior of PAN‐b‐PMMA thin films during thermal and solvent annealing, as well as the pore size of mesoporous carbon thin films after pyrolysis. The as‐spin‐coated PAN‐b‐PMMA is microphase‐separated into uniformly spaced globular nanostructures, and these globular nanostructures evolve into various morphologies after thermal or solvent annealing. Surprisingly, through thermal annealing and subsequent pyrolysis of PAN‐b‐PMMA into mesoporous carbon thin films, the pore size and center‐to‐center spacing increase significantly with thermal annealing temperature, different from most block copolymers. In addition, the choice of solvent in solvent annealing strongly influences the block copolymer nanostructure and the pore size of mesoporous carbon thin films. The discoveries herein provide a simple strategy to control the pore size of mesoporous carbon thin films by tuning thermal or solvent annealing conditions, instead of synthesizing a series of block copolymers of various molecular weights and compositions.     

Influence of the usage of waste oyster shell powder on mechanical properties and durability of mortar

In order to investigate feasibility of waste oyster shell powder (WOSP) as fine aggregate to produce eco-friendly mortar, workability (slump flow and slump flow loss), mechanical properties (compressive strength and flexural strength), durability (sorptivity, volume of permeability coefficient, water permeability coefficient and chloride ion diffusion coefficient) and microstructure (pore size diffusion) were studied. The effect of replacing river sand with different WOSP proportions (0%, 10%, 20% and 30%) in flowability, strength, permeability and microstructure of mortar have been revealed. The results indicate that increasing substitution ratio of WOSP could decrease the mortar slump flow. The utilization of WOSP in mortar enhanced the compressive strength, flexural strength, resistance to water penetration and chloride diffusion. The WOSP addition exhibits a positive contribution to the pore size distribution of the mortar. Furthermore, it is founded that the utilization of WOSP as construction material is a satisfactory way to reduce waste pollution. Based on its superior mechanical property, durability, eco-efficiency and cost-efficiency in mortar, it is recommended to utilize WOSP alternative to river sand at 10–30% in construction engineering.     

Recycling of solvent used in a solvent extraction of petroleum hydrocarbons contaminated soil

The application of water washing technology for recycling an organic composite solvent consisting of hexane and pentane (4:1; TU-A solvent) was investigated for extracting total petroleum hydrocarbons (TPH) from contaminated soil. The effects of water volume, water temperature, washing time and initial concentration of solvent were evaluated using orthogonal experiments followed by single factor experiments. Our results showed that the water volume was a statistically significant factor influencing greatly the water washing efficiency. Although less important, the other three factors have all increased the efficacy of water washing treatment. Based on a treatment of 20 g of contaminated soil with a TPH concentration of 140 mg g(-1), optimal conditions were found to be at 40°C, 100 mL water, 5 min washing time and 660 mg g(-1) solvent. Semi-continuous water extraction method showed that the concentration of the composite solvent TU-A was reduced below 15 mg g(-1) d.w. soil with a recovery extraction efficiency >97%. This finding suggests that water washing is a promising technology for recycling solvent used in TPH extraction from contaminated soils.