Applications of rheological torque–time curves to the study of thermooxidative degradation of polypropylene powder

The torque–time curves of polypropylene (PP) powder treated under various thermooxidative degradation conditions were obtained through processing in the mixing chamber of a rheometer. Meanwhile, the Fourier transform infrared (FTIR) spectra of the corresponding samples were determined, and the quantitative analysis of the carbonyl indices of the FTIR spectra of the samples of the PP powder was carried out to provide evidence for the rheological characterization. PP granules, to which an antideteriorant was added before they were commercially supplied so good antidegradation could be achieved, was investigated for the sake of contrast. The analysis of the experimental results showed that the height of the torque–time curve of the PP powder and the corresponding value of the equilibrium torque could be used to characterize or evaluate the variations of the thermooxidative degradation of the PP powder. Under the same processing conditions, the heights of the torque–time curves of the PP powder and the corresponding values of the equilibrium torque decreased with the enhancement of the thermooxidative degradation treatment before mixing; on the contrary, the heights and areas of the characteristic bands of the carbonyl groups in the FTIR spectra of the PP powder and the corresponding values of the carbonyl index increased. The quantitative analysis of the FTIR spectra provided evidence for the conclusion that the heights of the torque–time curves of the PP powder and the corresponding values of the equilibrium torque could be used to characterize or evaluate the thermooxidative degradation of the PP powder. If the treatment under thermooxidative degradation conditions weakened or the degradation of the PP powder just began (i.e., in the viscosity range for processability), the evaluation method using the heights of the torque–time curves of the PP powder or the corresponding values of the equilibrium torque could provide more sensitivity than the method using the values of the carbonyl index. Consequently, the method using the heights of the torque–time curves to evaluate the thermooxidative degradation of the PP powder had its advantages. The application of the torque–time curves could be used to evaluate not only the variation of the thermooxidative degradation of the PP powder treated under aging conditions before mixing but also the variation of the degradation, including the mechanochemical degradation, of the PP powder during the period of mixing. The dependence of the variation of the degradation of the polymer on the processing time during mixing could be evaluated by the study of the variation of the torque–time curves. It can be concluded that the application of torque–time curves to the evaluation of degradation of PP powder has the advantages of being convenient, real‐time, in situ, online, and production‐oriented. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

考虑多因素作用下的RC梁抗力时空退化模型

为研究钢筋混凝土结构锈蚀后的力学性能和抗力退化规律,基于RC梁加速锈蚀试验结果,首先综合考虑均匀锈蚀和点蚀同时发生的影响,对钢筋截面面积的时变模型进行分析,其次探讨裂缝宽度与氯离子扩散系数及RC梁抗力的关系,随后考虑受拉主筋锈蚀不均衡的影响,对结构抗力计算模型进行讨论,最后基于材料性能和结构尺寸的空间变异性,建立RC梁抗力时空退化模型,并对桥梁服役100 a后的抗力进行预测.研究发现:当考虑各参数的空间变异性时,不考虑裂缝影响得到的抗力值比考虑裂缝影响得到的抗力值高了9.91%;考虑各参数空间变异性时的抗力值比不考虑时下降了14.68%;适当的选取波动系数和单元尺寸对考虑结构各参数的空间变异性十分重要;潮汐区和浪溅区环境下结构的剩余抗力分别为初始抗力的43.23%和36.45%,较海岸线大气区环境下的抗力值分别下降了6.73%和21.35%,因此在结构服役期间,应尽量做好防腐措施,减少氯离子侵蚀对结构耐久性的破坏.     

Fe3O4-H2O2类Fenton体系催化降解苯酚

为提出基于新型磁纳米Fe3 O4催化剂的类Fenton体系,采用化学共沉淀法制备磁纳米Fe3 O4,用四甲基氢氧化铵（ TMAH）对所制备的磁纳米Fe3 O4进行表面改性,就Fe3 O4－H2 O2类Fenton体系对苯酚废水的处理效果进行探讨,考察催化剂投量、H2 O2浓度、pH、反应时间等因素对COD和挥发酚去除率的影响．结果表明：磁纳米颗粒平均粒径为30 nm,并在20～100 nm内呈现良好的粒度分布．不同剂量TMAH包覆的3种催化剂经超声预处理后,在室温（13℃）下对50 mg／L苯酚（相当于112 mg／L COD）的降解效果基本一致．当催化剂投量为0．8 mmol／L、H2 O2浓度为2．0 mmol／L、pH为4．5、反应时间180 min时,COD去除率最高可达72％;催化剂投量为0．4 mmol／L、H2 O2浓度为2．0 mmol／L、 pH为4．5、反应时间为90 min时,挥发酚的去除率接近100％．而在重复使用方面,3＃Fe3O4－TMAH（2 mL）催化剂的回用性最好,4次反应COD的去除率分别为73％、29％、28％、26％,挥发酚去除率分别为100％、84％、67％、54％．该类Fenton体系具有不产生多余泥量的优点,且磁纳米催化剂在外磁场作用下可实现快速分离回收．     

TiO2∶Fe的制备及其在可见光下降解罗丹明B的催化性能

通过溶胶-凝胶法和水热法分别制备了锐钛矿的TiO2颗粒和TiO2纤维,并在可见光下降解罗丹明B以考察其催化性能,结果表明,TiO2颗粒的催化性能略好于TiO2纤维.通过溶胶-凝胶法原位复合一系列Fe以提高纯TiO2颗粒的催化性能,在可见光下降解罗丹明B的结果显示,添加质量分数为1％的TiO2 （TiO2∶1％ Fe）比纯TiO2的降解率提高10％.并进一步通过扫描电镜（SEM）和X射线能量色散谱分析得出TiO2：1％ Fe样品为颗粒状,并由Ti,O和Fe元素组成.     

介质阻挡放电反应器降解邻二甲苯的特性研究

采用介质阻挡放电(DBD)降解常压下流动态的邻二甲苯模拟废气,系统地考察了放电极值电压,气体的初始质量浓度、停留时间以及相对湿度等工艺参数对邻二甲苯降解的影响,并初步探讨了邻二甲苯的降解产物.实验研究结果表明:在7.0kV的放电极间电压下,邻二甲苯的初始质量浓度为1 500mg/m3,停留时间为9s,其去除率可达到80%以上.降解产物主要为CO2、H2O以及苯甲酸、苯乙酸、苯乙醛等有机物,并且经降解后产物的生物可生化性得到提高,因而为后续的等离子-生物法联合处理VOCs提供了依据.     

锈蚀混凝土梁承载力退化的试验研究

通过试验研究了锈蚀混凝土梁承载力的退化.试验中,共浇铸和试验了58个梁以调查钢筋锈蚀程度、锈蚀电流密度、水灰比和保护层厚度对梁承载力退化的影响.结果表明:当纵向裂缝宽度小于0.01mm时,梁承载力有较小程度的提高,但当纵向裂缝宽度大于0.01mm时,梁承载力随着纵向裂缝宽度的增大而减小.梁承载力退化速率随着锈蚀电流密度和保护层厚度的增大而减小,但随着水灰比的增大而增大.     

2-（4-氯苯氨基）甲基苯酚降解的动力学研究

采用高效液相色谱技术,开展了Fenton试剂对2-（4-氯苯氨基）甲基苯酚（CMP）的氧化降解动力学的研究。考察了初始双氧水摩尔浓度、亚铁离子摩尔浓度和温度等因素对CMP降解速率的影响,结果表明,当双氧水摩尔浓度、亚铁离子摩尔浓度增大和温度升高时,CMP的氧化速率明显加快。在30~45℃的温度范围内,其氧化降解符合假一级反应动力学模型,反应的表观活化能Ea为102.90kJ/mol。     

C／T iO 2复合材料的制备及光催化性能的研究

采用溶胶-凝胶法制得了C/TiO2复合光催化剂,并采用X射线衍射（XRD）﹑扫描电子显微镜（ SEM ）﹑紫外光谱等方法对复合材料进行了表征。以1-萘胺-4-偶氮对苯磺酸为模型化合物评价了C/TiO2复合材料的光催化性能,考察了降解时间、初始浓度和催化剂投加量等因素对降解率的影响。研究表明,在1-萘胺-4-偶氮对苯磺酸初始浓度为2×10-5 mol/L,催化剂投加量为1．0 g/L时,光催化反应5 h后,1-萘胺-4-偶氮对苯磺酸的降解率达到85．41％。     

Degradability and biocompatibility of bioglass/poly(amino acid) composites with different surface bioactivity as bone repair materials

Bioglass (BG) possesses excellent bioactivity and has been widely used in the manufacture of biomaterials. In this study, a composite with different surface bioactivity was fabricated via in situ melting polymerization by incorporating BG and poly(amino acid) (PAA) at a suitable ratio. The structure of the composite was characterized by Fourier transform infrared spectroscopy and XRD. The compressive strength of the BG/PAA composites was 139 MPa (BG:PAA = 30:70). The BG/PAA composites were degradable, and higher BG in composite showed higher weight loss after 4 weeks of incubation in simulated body fluid. In addition, the BG/PAA composite maintained adequate residual compressive strength during the degradation period. The SEM results showed the differences in surface bioactivities of the composites directly, and 30BG/PAA composite showed thicker apatite layer and higher Ca/p than 15BG/PAA. in vitro MG-63 cell culture experiments showed that the composite was noncytotoxic and thus allows cells to adhere, proliferate, and differentiate. This indicates that the composite has good biocompatibility. The implantations in the bone defects of rabbits for 4 and 12 weeks were studied. The composites had good biocompatibility and were capable of guiding new bone formation without causing any inflammation. The composite may be successfully used in the development of bone implants.     

Microstructural properties,thermal insulation and thermal degradation behavior of boron-containing monolithic novolac xerogels

Enhancement of thermal stability-insulation performance of hyper porous materials is the premier issue to design of novel porous thermal protection systems. Boron-containing monolithic novolac xerogels (BCNXs) were synthesized using sol–gel networking of novolac resin with hexamethylenetetramine (HMTA) and boric acid at the solvent saturated vapor atmosphere (SSVA). The aim was to elucidate the effect of higher crosslinking density and thermal stable boron containing chemical bonds on the microstructure, thermal conductivity, and thermal oxidation stability of novolac xerogels. The results of FESEM and BET analysis showed that the microstructural characteristics of xerogels are significantly depend on the HMTA and boric acid concentration. The thermogravimetric results were analyzed using characteristic kinetic temperature (CKT)-characteristic kinetic temperature range (CKTR) approximations. The effect of micromorphology of xerogels on the thermal conductivity was investigated. The effective thermal conductivity of samples were in the range of 0.031–0.048 W/m K.