过氧化苯甲酰氧化废胶粉在橡胶沥青中的应用

采用过氧化苯甲酰对废胶粉表面进行氧化改性,并于实验室制备胶粉改性沥青。通过设计3因素3水平正交试验,研究氧化温度、氧化时间及氧化剂用量对改性沥青基本性能指标(针入度、软化点和延度)的影响。对试验结果的极差分析与方差分析表明,氧化温度是影响胶粉改性沥青性能的主要因素,建议氧化改性胶粉的最优反应条件为:氧化温度40℃,氧化时间3.0h,氧化剂用量25g。氧化胶粉改性沥青能使软化点提高到68.2℃,显著改善改性沥青的高温性能。XPS试验结果表明过氧化苯甲酰氧化能使胶粉表面的C—C键和C—H键打开,形成较多的羟基(C—O)和羰基(C=O)等活性基团,显著增加胶粉的表面活性。     

弹性体高黏改性沥青制备及性能影响研究

设计利用弹性体聚合物改性沥青料,大幅提升沥青黏韧性,并分析改性组分(如改性剂、相容剂、稳定剂等)、以及改性工艺(如发育温度、发育时间)对改性沥青性能的影响机理,进而对针入度、软化点、老化前后延度、60℃动力粘度、(135℃、175℃)运动黏度、离析等指标进行系统分析,对高黏改性沥青性能进行优化设计,并利用荧光显微观察聚...     

废旧橡胶改性沥青的老化研究现状

废旧橡胶改性沥青可显著延长路面寿命。本文综述了国内外废旧橡胶改性沥青的热氧老化、紫外老化和水老化行为,使用宏观性能和微观结构变化分析了橡胶改性沥青老化特点。橡胶改性沥青在热、氧、紫外、水的作用下发生老化,软化点升高,针入度降低,羰基含量增加。特别是光、氧老化对经过水老化后的橡胶改性沥青老化作用尤为明显,水溶解了部分老化产物促进了沥青的老化。目前对于橡胶改性沥青老化过程中胶粉、沥青的结构性能变化和其环境耦合因素对橡胶改性沥青的老化研究及分析手段还很少,在今后的研究中须引起重视。     

废橡胶粉的表面改性及其表征

研究了二氯异氰尿酸钠对废橡胶粉表面的改性,得到的活化改性胶粉可作为复合材料添加剂用于制备新型复合材料.用扫描电镜(SEM )、接触角方法、X射线光电子能谱(XPS)对改性胶粉进行表征,并且研究了反应时间、反应温度和改性剂用量因素对改性反应的影响.结果表明,反应的最佳条件为反应时间1.5 h、反应温度40℃、改性剂质量分...     

超临界水中煤焦油沥青轻质化的实验研究

采用间歇超临界水（supercritical water, SCW）反应器,考察了反应温度（400℃~480℃）、停留时间(1 min~80 min)和反应压力（25 MPa~40 MPa）对煤焦油沥青轻质化的影响。与常压N2热解相比,煤焦油沥青在SCW中反应后产物中的轻油质量分数高,残焦质量分数低,表明SCW可以促进煤焦油沥青的轻质化反应进行并抑制缩合反应。沥青质是煤焦油沥青在SCW中发生反应的主要组分。在440 ℃和34 MPa时反应20 min,产物中轻油的质量分数可达原料的两倍,说明煤焦油沥青在SCW中可以发生明显轻质化反应。与温度相比,压力和停留时间的影响相对较小。     

钨酸钠/冰乙酸/过氧化氢作用下聚丁二烯橡胶环氧化及降解行为研究

本文研究了在钨酸钠/冰乙酸/过氧化氢催化体系作用下聚丁二烯橡胶环氧化及降解行为.采用红外(FT-IR)、核磁(1H-NMR)和气相凝胶渗透色谱(GPC)对降解产物进行了表征,结果表明60℃反应24h,聚丁二烯橡胶环氧度为21.27％,而其分子量没有明显降低.     

肠杆菌Enterobacter sp. S8共代谢生物降解邻苯二甲酸二丁酯的特性研究

邻苯二甲酸二丁酯(DBP)是目前应用最为广泛的邻苯二甲酸酯之一,属于难降解有机污染物,具有较强的内分泌干扰性。本文以分离得到的DBP降解菌Enterobacter sp.S8为研究对象,系统考察了共代谢基质类型和共代谢反应条件对S8共代谢生物降解DBP的影响,同时对其反应动力学及酶的稳定性进行了研究。结果表明,在无共基质添加的条件下,S8对DBP的降解率仅为30.2%,而在温度为30℃、pH为7、甲醇投加量为20mg/L以及DBP初始浓度为300mg/L的优化共代谢降解条件下降解率达到最大,为75.6%;其中DBP初始浓度对共代谢降解效果影响最大。本文的结果为采用生物共代谢方式进行DBP污染环境的治理提供了依据。     

大庆减压渣油热转化前后镍分布的研究

大庆减压渣油在高压釜中 4 0 5℃、1h条件下进行热转化反应 ,对原料及热转化后尾油 (>5 0 0℃ )用正戊烷沉淀沥青质 ,再用含水 5 % (质量分数 )的氧化铝为吸附剂的色谱法将大庆减压渣油分离为六个组分 ,然后用硅胶色谱法对每个组分中的镍卟啉进行富集 ,并根据可见光谱加以测定。用原子吸收法测定了原料减压渣油、尾油及各组分的镍含量。研究结果表明 ,大庆减压渣油经过热转化后有近 5 0 %的渣油转化为气体和馏分油 ,并有少量的焦炭生成。大庆减压渣油无戊烷沥青质 ,其中的Ni主要集中在中胶、重胶及n C5沥青质中。在热转化尾油中 ,大部分的镍集中在中胶、重胶及戊烷沥青质中 ,卟啉镍主要集中在多环芳烃和轻胶质中 ,非卟啉镍主要集中在中胶、重胶和戊烷沥青质中。热转化对镍起到了脱除作用     

煤焦油及其组分在超临界水中的反应特性研究

采用间歇超临界水（supercritical water, SCW）反应器,考察了三种煤焦油及其组分在SCW中的反应性。实验结果表明,沥青质裂解活性高的煤焦油在SCW中反应,轻质产物多,轻质化效果好。沥青质是轻质化反应的主要组分,它发生两极分化反应生成轻油和残焦。与常压N2热解相比,SCW可以促进沥青质转化为轻油并抑制缩合成焦的反应。由沥青质组分反应产物推断,煤焦油沥青质的芳香核主要是由1~4环的芳香族化合物构成。轻油组分在SCW中较为稳定,不足10%的轻油转化为沥青质和残焦。残焦组分在SCW中不发生反应。基于各组分的反应,探讨了煤焦油组分在SCW中的反应路径。     

煤基重质产物对滨州90#沥青的改性作用

对照优质道路沥青改性剂TLA,考察了六种煤基重质产物对滨州90#沥青的改性作用及作用原理。实验结果表明,六种改性剂对滨州90#沥青均表现出一定的改性作用。依据美国ASTM D5710-95以及英国BSI BS3690对TLA改性沥青的标准,六种改性沥青中,四种符合标准要求,其余两种不符合延度指标要求。FT-IR谱图分析表明,煤液化或煤油共处理重质产物的添加,没有生成新官能团,但使官能团的分布发生了变化,从而改善了基质沥青的路用性能,添加TLA,可增加C=O和S=O极性官能团,可增加沥青与石料的作用;煤焦油沥青过高的芳香结构,妨碍了其与基质沥青的混合作用。结合四组分分析结果,基于沥青胶体化学理论分析,发现不符合要求的改性沥青具有较高的饱和分含量,导致了较小的CI值(胶体指数),不利于沥青胶体结构的稳定。按线性加和法计算得到的改性沥青CI值与实测值的差距表明,改性过程包含有一定程度的化学反应。     

Waste Cooking Oil-Modified Epoxy Asphalt Rubber Binders with Improved Compatibility and Extended Allowable Construction Time

The application of crumb rubber from end-of-life tires and waste cooking oil (WCO) in road pavements is of significant importance from an economic and environmental viewpoint. However, the incorporation of crumb rubber greatly shortens the allowable construction time of epoxy asphalt binders due to the high viscosity of the epoxy asphalt rubber (EAR) binder and poor compatibility between crumb rubber and asphalt binder. To lower the viscosity of asphalt rubber, extend the allowable construction time and improve the compatibility of EAR binder, waste cooking oil (WCO) was introduced. The effect of WCO on the viscosity–time behavior, thermal stability, dynamic modulus, glass transitions, crosslink density, damping ability, compatibility, mechanical properties and phase separation of WCO-modified EAR binders was investigated by using the Brookfield viscometer, thermogravimetric analysis, dynamic mechanical analysis, universal testing machine and laser confocal microscopy. The test results demonstrated that the incorporation of WCO declined the viscosity and extended the allowable construction time of the unmodified EAR binder. The inclusion of WCO improved the compatibility between asphalt and crumb rubber and the damping ability and elongation at the break of the unmodified EAR binder. The presence of WCO had a marginal effect on the thermal stability of the unmodified EAR binder. Confocal microscopy observation revealed that asphalt rubber particles aggregated in the epoxy phase of the unmodified EAR binder. With the inclusion of WCO, co-continuous asphalt rubber particles became more spherical.     

Comparison of changes of basic parameters of asphalt caused by various additives

This work presents a study on asphalt mixtures prepared with different kinds of additives: poly(styrene-co-butadiene-co-styrene), poly(ethylene-co-vinyl acetate), crumb rubber, fibers, zeolites and clays. The aim of this study was to determine the influence of inorganic dirt and fibers present in crumb rubber on the qualitative parameters of asphalt mixtures. The experiments showed that dynamic viscosity is the best criterion for assessing the effectiveness of the additives in asphalt mixtures. It was also found that fibers and inorganic impurities present in crumb rubber at low concentrations have a negligible effect on the characteristics of asphalt mixtures. This investigation is important in terms of determining the degree of crumb rubber devulcanization in crumb rubber-asphalt mixtures as higher crumb rubber devulcanization could bring the properties of such a mixture closer to those of asphalts modified by poly(styrene-co-butadiene-co-styrene) copolymers.     

Thermal decomposition behaviour of cobalt(II)-picolyl-terminated poly(dimethylsiloxane)

Thermal, chemical and rheological properties of ultraviolet aged asphalt binder were characterized by differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) and dynamic shear rheometer (DSR), respectively. Asphalt binder samples were made with different film thickness (50, 100, 200 and 500 μm) and suffered different ageing time (0, 48, 96 and 144 h), at a certain UV radiant intensity of 20 w m^–2 in a self-made accelerated ageing oven. The results indicate that the UV light ageing would lead to the improvement of thermal behavior and the growth of the glass transition temperature of asphalt binder. This type of ageing can be also reflected from the FTIR spectra in terms of the characteristic peaks of the carbonyl groups and sulphoxides. The UV light ageing can change some rheological parameters of asphalt binder, such as complex modulus and phase angle. The ageing degrees of asphalt binder by this type of ageing test are mainly related to the ageing time and film thickness of the sample.     

原油空气氧化前后多环芳烃组分的气相色谱-质谱分析

采用柱层析法对空气氧化前后的原油进行族组分分离,利用气相色谱-质谱(GC-MS)分离测定其芳香烃组分,分析多环芳烃组分的变化.结果表明,随着氧化过程的进行,烷基化多环芳烃占多环芳烃的含量从氧化前的71.5%增加到92.0%(175℃)和90.2%(225℃).轻质组分萘和菲的优势逐渐被重质组分艹屈取代.侧链少的多环芳烃比侧链多的更易氧化.氧化后,其他稠环化合物蒽、萤蒽、芘、苯并蒽含量降低,苯并萤蒽含量增加;苯并芘在175℃氧化后含量降低,而在225℃氧化后含量增加.与此同时,175℃氧化后生成了原油所不含有的三芳甾烃、联苯和苯并呋喃.     

Surface oxidation of rubber crumb with ozone

Rubber crumb derived from the grinding of used truck tread and tyres is used as a low cost filler in rubber compounds based on diene rubber. In order to expand its application to other fields, the surface modification of the rubber crumb could be an interesting and feasible solution. In fact, the surface modification of rubber crumb may be used as a tool to expand its use in applications to compounds with polar rubber matrices or where hydrophilic surface of the rubber crumb could be desirable, for example in water-based dispersion or as filler for asphalt. In the present work, ozone has been used as the active agent to cause surface oxidation and functionalisation of rubber crumb in a fluidized bed reaction. The rubber crumb reacts swiftly with ozone producing CO₂ in the initial stages of reaction and then leading to the desired surface oxidized product. The rate constant of the reaction between ozone and rubber crumb has been determined by FT-IR spectroscopy, monitoring the consumption of ozone in the gas phase in the presence of the crumb. A rate constant value of 5.03 × 10⁻³ s⁻¹  g⁻¹ of rubber crumb was determined. The degree of the surface oxidation of the rubber crumb can be determined by FT-IR spectroscopy using as reference the intensity of the ketone band at about 1710 cm⁻¹. Additionally the nominal ratio between the amount of ozone (in mg) reacted with rubber crumb (in g) can be used as a parameter for the degree of the surface oxidation. The surface oxidized rubber crumb shows surface acidity and hydrophilicity. Thermogravimetric analysis, differential thermal analysis and pyrolysis-GC clearly demonstrate that the ozonization of the rubber crumb is directed exclusively to the surface of the crumb and does not affect the bulk properties at all.     

Aging Process Effects on the Characteristics of Vacuum Residue Oxidation Products with the Addition of Crumb Rubber

This paper considers the effect of aging processes on viscoelastic characteristics of vacuum residue oxidation products modified with crumb rubber. Viscoelastic properties were compared to original bitumen raw material-vacuum residue and vacuum residue oxidation products during short-term and long-term aging. The complex shear modulus of the vacuum residue and its oxidation products decreased with an increase in temperature. Short-term aging resulted in increased shear modulus for all samples.The vacuum residue oxidation product modified with crumb rubber had the maximum values of the rutting parameter and fatigue parameter. There was an expansion of the temperature range of plasticity: for the vacuum residue oxidation product with crumb rubber, its value was 67.2 °C. The curves of the black diagram of the modified vacuum residue oxidation product are shifted towards smaller phase angles with the increase in the shear modulus, which indicates the increase in the stiffness and elasticity of the rubber bitumen binders. The vacuum residue oxidation product modified with crumb rubber corresponded to the rubber bitumen binder of the grade RBB 60/90, according to its physical and mechanical indicators.     

Glass transition measurements of asphalts by DSC

The glass transition temperature (T_g), measured by Modulated Differential Scanning Calorimetry (MDSC), is related to the flow characteristics of asphalt at low temperatures as is the rate of change of the creep stiffnessm. This study compared the glass transition temperature of different asphalts (neat, chemically modified, and crumb rubber modified asphalts) with the creep stiffness, the rate of change of creep stiffness, and the low specification temperature of the continuous PG grading of those asphalts.From the rheological data (BBR) and the thermal data (MDSC) for the virgin and the modified asphalts, the modified products had the same variations of values ofm, S, and T_g at lower temperatures as those of their corresponding virgin asphalts. A correlation between the T_g andm value was observed for both the modified and unmodified asphalts. Since DSC measurements for asphalt low temperature properties use less operator time, less sample, and have less measurement and operator error than rheological methods, T_g has promise to be considered as a fast and easy laboratory method to obtain the low temperature useful range of asphalts in pavements.The authors would like to acknowledge Susan P. Needham for her work in conducting rheological testing for the modified and unmodified asphalts.     

改性沥青中橡胶含量的高效液相色谱测定法

用高效液相色谱法测定了改性沥青中橡胶的含量。柱温30℃,检测波长222 nm,流动相为同等比例的正己烷、四氢呋喃和乙腈的混合液,UV检测器。该方法的相对标准偏差RSD≤1.5%,线性方程:y=800.94x+579.03,线性相关系数r=0.999 8。     

NBR/CuSO4混合物的非液相配位交联反应

采用示差扫描量热法(DSC),变温傅立叶转变红外光谱(FT-IR)和X射线光电子能谱(XPS)研究了丁腈橡胶/硫酸铜(NBR/CuSO4)混合物的非液相(聚合物熔融态)配位交联反应.DSC曲线上出现了多个放热峰,并随升温速率提高,峰值一致向高温方向移动;结合XPS和FT-IR的分析表明DSC曲线上的第一个放热峰对应于混合物中发生的铜离子与腈基的非液相配位反应;同时采用非等温法(Kissinger法)及Crane方程计算了NBR/CuSO4混合物非液相配位交联反应的表观活化能和反应级数.     

纳米碳酸钙/庚二酸复合成核剂对热致相分离法制备聚丙烯微孔膜的影响

以大豆油/邻苯二甲酸二丁酯(DBP)为混合稀释剂,采用热致相分离法(TIPS)制备聚丙烯(PP)微孔膜.研究了纳米碳酸钙成核剂、纳米碳酸钙/庚二酸复合成核剂对PP/大豆油/DBP(30/42/28,质量比)混合体系中PP结晶、熔融性能和PP微孔膜微观结构的影响.结果表明,单一纳米碳酸钙成核剂加入量为PP的0%~4%(质量百分率)时,PP/DBP/大豆油体系中PP熔融曲线上对应的峰值温度(Tpm)降到150.7~151.3℃,而纯PP的熔融峰值温度为165℃;DSC实验结果还显示加入1%~4%纳米碳酸钙和0.5%庚二酸后,导致PP的熔融曲线上出现了熔融双峰,说明纳米碳酸钙/庚二酸复合成核剂与单一成核剂相比有明显地促进β晶生成的作用,宽角X射线衍射(WAXD)实验进一步证实了β晶的存在.单一纳米碳酸钙成核剂对PP微孔膜的球晶结构和微观孔结构影响不大;加入纳米碳酸钙/庚二酸复合成核剂明显影响PP微孔膜的球晶结构和微观孔结构,其中0.5%庚二酸和1%纳米碳酸钙组成的复合成核剂制得的PP微孔膜的球晶结构明显,微孔膜孔径小且分布均匀;进一步增加纳米碳酸钙用量,PP微孔膜生成了许多细小的边界模糊的不规则结晶,微孔膜孔径不规则且尺寸较大,这与此时PP形成β晶结构有关.