DSC法测定PS玻璃化温度的再研究

对Fevotte提出的由DSC曲线构建玻璃化温度谱图的方法进行了改进,将橡胶态含量为0.5时的温度定义为聚合物的Tghr.采用改进Fevotte方法重新研究了PS的玻璃-橡胶态转变,PS的Tghr值比半比热外推法结果Tghc高约4K,当考察热处理时间和降温速率对聚合物玻璃-橡胶态转变的影响规律时,改进方法得到的结果与理论分析更为一致.聚合物的Tghr受热历史影响,随热处理条件改变,通过对不同降温速率冷却后样品滞后焓数据的拟合,推测PS样品的Tghr在377.5～390.9K范围内变化.     

聚丙烯DSC测试影响因素探究

以聚丙烯注塑成型样品为例,分别以不同温度对样品进行状态调节、不同升温速率消除样品热历史和不同降温速率冷却对样品进行DSC实验,分析其对测试结果的影响.结果表明:以不同温度对样品进行状态调节后进行实验,其第一次升温熔融峰温受状态调节温度影响出现先增大后减小,最大偏差2℃,对随后的降温过程和第二次升温过程无影响;以5℃/m...     

升温速率对聚酰胺酸/聚丙烯腈基碳纤维结构的影响

采用聚酰胺酸/聚丙烯腈(PAA/PAN)为原材料制备共混前驱体,经热处理完成PAA的亚胺化和PAN的预氧化,再以一定的升温速率升温至1200℃,得到新型共混基碳纤维,采用SEM、Raman、XRD、EA等方法研究了不同的升温速率对PAA/PAN基碳纤维碳化结构的影响.结果表明,碳纤维表面沿纤维轴方向有少量的沟槽,这是湿法纺丝工艺造成的.1200℃的高温处理使碳元素富集,最终制得碳含量高于92%的碳纤维.随着碳化升温速率的增大,碳收率也在增大,最大碳收率达52.36%.碳纤维的石墨化程度和微晶尺寸随着碳化升温速率的提高均呈现先增大后减小的趋势,当升温速率为8 K/min时,所得纤维的碳化结构最为理想,微晶堆叠厚度达到1.445 nm,g(A_G/A_D)值达到0.52,此条件下,纤维的碳元素含量也达到了94.13%,电阻率最小.     

基于锥形量热仪试验的聚合物材料火灾危险评价研究

简述了锥形量热仪的试验原理,以聚合物材料锥形量热仪试验数据为基础,导出了火势增长指数（FGI）、放热指数（THRI6min）、发烟指数（TSPI6min）和毒性气体生成速率指数（ToxGI）4个评价聚合物材料火灾危险的参数,并利用这四个参数对ABS、PS、PVC、PA 4类16种商用塑料样品的火灾危险性逐项进行了分析评价.在此基础上,采用层次分析法的原理对样品的火灾危险进行了综合评价,结果表明,ABS、PS、PVC、PA四类样品的火灾综合危险依次减小.     

可交联的PMMA型和PS型高热稳定性二阶非线性光学材料的合成与表征

采用封管反应的方法,以较高产率(80%以上)合成了一系列含环氧基团的可交联PMMA型和PS型极化聚合物材料,该材料具有很好的成膜性.用DSC和T_gA等方法研究了聚合物固化前后的热性能,结果表明,由于聚合物在极化后期经热固化使引入的环氧基团开环交联,聚合物的玻璃化转变温度(T_g)较固化前明显提高30～50K.同时,固化后的聚合物具有较高的热分解温度(T_d>543K).对聚合物的二阶非线性光学性质的测试结果表明,在室温下放置100h后,聚合物的电光系数r₃₃值均保持在初始值的75%以上.这是由于环氧基团的开环使固化后的聚合物本身产生一定程度的交联,导致取向后的发色团被聚合物的交联网禁锢而不易弛豫,从而使这类PMMA型和PS型二阶非线性聚合物材料的热稳定性能得以提高.     

反相浓乳液方法制备聚苯乙烯/二乙烯基苯结构型泡孔聚合物

通过反相浓乳液聚合方法制备了系列聚苯乙烯/二乙烯基苯(PS/DVB)泡孔聚合物.水作为分散相,其分散相体积分数可达90%;苯乙烯单体作为连续相,聚合后构成PS/DVB泡孔聚合物的结构骨架.用扫描电镜系统研究了乳化剂的浓度、分散相体积分数、添加不同沸点的溶剂等对泡孔聚合物断面形态的影响,并考察了泡孔聚合物对水和柴油的吸附情况.结果表明,不同工艺条件下可以制备出不同孔径的泡孔聚合物,加入不同沸点溶剂使得泡孔壁也形成了多孔结构.     

Cu-SAPO-18催化剂氨选择性催化还原NOx钾中毒机理的研究

研究了不同水热老化温度对钾(K)中毒0.4K-Cu-SAPO-18样品的结构及其NH₃-SCR(NH₃作为还原剂的选择性还原技术)催化活性的影响. 结果表明, K中毒对样品结构影响较小, 但明显降低了其NH₃-SCR性能, 在350 ℃ 时, K中毒样品0.4K-Cu-SAPO-18的NO转化率为65.88%, 明显低于未中毒Cu-SAPO-18样品的90.85%. 水热老化温度明显影响催化剂的结构, 减少了活性位点, 降低了表面酸性. 随着水热老化温度升高, 催化剂的AEI结构被破坏, 活性物种数量降低, 催化活性明显下降. 氢气程序升温还原 (H₂-TPR)结果表明, 孤立的Cu²⁺和Cu⁺的总量分别从未中毒Cu-SAPO-18样品的66.61和1.32 μmol/g变化到K中毒0.4K-Cu-SAPO-18样品的39.52和101.96 μmol/g, 表明K中毒样品中孤立Cu²⁺ 容易转化为Cu₂O. K中毒后, 样品的弱酸、 中强酸、 强酸性位点的数量降低, 分别从未中毒Cu-SAPO-18样品的0.201, 0.103和0.302 mmol/g降低到中毒0.4K-Cu-SAPO-18样品的0.102, 0.086和0.071 mmol/g. 氨气程序升温脱附(NH₃-TPD)和原位红外结果表明, K竞争性地取代了催化剂中孤立的Cu²⁺和H⁺, 使K中毒0.4K-Cu-SAPO-18样品的活性位和酸性位减少, 导致催化活性下降. 在低温 NH₃-SCR反应中, K中毒和未中毒样品均以Eley-Rideal(E-R)和Langmuir-Hinshelwood(L-H)机理进行, 而L-H机理占主导地位, 但K中毒样品的反应速率明显降低.     

二氧化碳气体制备层状聚苯乙烯发泡材料

将珠状和粒状聚苯乙烯(PS)样品模压后在高压CO₂条件下饱和, 采取快速升温法制备了结构新颖的层状发泡材料. 通过扫描电子显微镜(SEM)以及不同饱和条件下CO₂在PS中溶解度的分析, 初步研究了区域性弱链段缠结力对气体成核、泡孔形态、泡孔尺寸和分布的影响. 结果表明珠状PS在压制成型过程中其珠粒界面链段相互作用力较弱. 由于基体中界面区域链段的缠结能力不同, 在不同区域CO₂气体的成核和增长也不同, 通过控制发泡的过程参数, 可以得到独特的PS层状泡孔形态.     

利用Flash DSC探究湿法隔膜快速降温过程结晶行为

研究了湿法隔膜超高分子量聚乙烯(UHMWPE)与白油混合体系在挤出流延过程中快速、非等温结晶行为。通过Flash DSC和常规DSC技术表征了不同固含量体系在不同冷却速率条件下微观晶体结构特性。结果表明：当冷却速率低于10⁴ K/min时,起始结晶温度随冷却速率增大而缓慢降低,得到的晶体片晶熔融温度和厚度随冷却速率增大而减小;当冷却速率高于10⁴ K/min时,起始结晶温度随冷却速率增大而迅速降低,而片晶厚度则变化不大;高的流延辊温得到的铸片晶体熔融温度高,片晶厚度大,且UHMWPE固含量越高,高、低温流延辊得到的铸片晶体熔融温度与片晶厚度差别越大。     

银离子固相萃取-程序升温大体积进样-气相色谱法定量分析市售巧克力中的饱和烷烃矿物油

建立了银渍硅胶固相萃取柱离线(Ag-SPE)净化,程序升温进样-气相色谱-氢火焰离子化检测器(PTV-GC-FID)定量分析巧克力中饱和烷烃矿物油(MOSH)的方法.以正己烷浸泡提取巧克力中的MOSH,离心后取1 mL上清液,过0.3％ Ag渍硅胶SPE柱净化,氮吹浓缩,定容至0.2 mL,注入GC分析; GC的进样口程序升温过程:初始温度45℃,保持1 min(分流比200∶1),以250℃/min升温至360℃(分流阀关闭2 min),并保持27 min(分流比100∶1); 进样量40 μL; 柱温箱升温程序为:35℃保持3 min,以25℃/min升温至350℃,以5℃/min升温至370℃,保持10 min,载气为高纯氮气,流速1.3 mL/min(压力60 kPa); FID温度为380℃.结果表明,本方法的MOSH定量限为0.5 mg/kg,加标回收率为84.9％～108.6％,相对标准偏差(RSD)为0.2％～1.5％.运用本方法对25个市售巧克力样品中的MOSH含量进行了测定,3个样品未检出,其余22个样品中MOSH含量为1.09～8.15 mg/kg(其中C16～C35 的含量为0.56～4.43 mg/kg),有3个样品含量高于5.00 mg/kg,为严重污染样品.本方法操作简便,检出限低,适用于巧克力中MOSH的定量测定.     

Large-volume methacrylate monolith for plasmid purification. Process engineering approach to synthesis and application

The extent of exothermicity associated with the construction of large-volume methacrylate monolithic columns has somewhat obstructed the realisation of large-scale rapid biomolecule purification especially for plasmid-based products which have proven to herald future trends in biotechnology. A novel synthesis technique via a heat expulsion mechanism was employed to prepare a 40 mL methacrylate monolith with a homogeneous radial pore structure along its thickness. Radial temperature gradient was recorded to be only 1.8 degrees C. Maximum radial temperature recorded at the centre of the monolith was 62.3 degrees C, which was only 2.3 degrees C higher than the actual polymerisation temperature. Pore characterisation of the monolithic polymer showed unimodal pore size distributions at different radial positions with an identical modal pore size of 400 nm. Chromatographic characterisation of the polymer after functionalisation with amino groups displayed a persistent dynamic binding capacity of 15.5 mg of plasmid DNA/mL. The maximum pressure drop recorded was only 0.12 MPa at a flow rate of 10 mL/min. The polymer demonstrated rapid separation ability by fractionating Escherichia coli DH5alpha-pUC19 clarified lysate in only 3 min after loading. The plasmid sample collected after the fast purification process was tested to be a homogeneous supercoiled plasmid with DNA electrophoresis and restriction analysis.     

Measurement of thermal diffusivity and specific heat capacity of polymers by laser flash method

We measured thermal diffusivity and heat capacity of polymers by laser flash method, and the effects of measurement condition and sample size on the accuracy of the measurement are discussed. Thermal diffusivities of PTFE films with thickness 200–500 μm were the same as those data that have been reported. But, the data for film thickness less than 200 μm have to be corrected by an equation to cancel thermal resistance between sample film and graphite layers for receiving light and detecting temperature. Thermal diffusivity was almost unaffected by the size of area vertical to the direction of laser pulse, because heat flow for the direction could be negligible. Specific heat capacity of polymer film was exactly measured at room temperature, provided that low absorbed energy (< 0.3 J) and enough sample mass (> 25 mg) were satisfied as measuring conditions. Thermal diffusivity curve of PS or PC versus temperature had a terrace around T_g, whereas that of PE decreased monotonously with increasing in temperature until T_m. Further, we estimated relative specific heat capacity (RC_p) by calculating ratios of heat capacities at various temperatures to the one at 299 K. RC_p for PS obtained by laser flash method was larger than that obtained by DSC method, whereas the RC_ps for PE obtained by the both methods agreed with one another until T_m (305 K). RC_p for PS decreased linearly, with increase in temperature after it increased linearly until T_g (389 K), showing similarity to temperature dependency of thermal conductivity. RC_p for PE also decreased until T_m, similar to thermal conductivity. ©1995 John Wiley & Sons, Inc.     

酶凝干酪素物理凝胶化过程的有限元模拟

以酶凝干酪素的凝胶化过程为对象,利用有限元方法数值分析了在凝胶化过程中温度场的空间分布和时间演变规律.在此基础上,基于一阶的凝胶化动力学方程,数值模拟了凝胶体系的复剪切模量场,进而分析了材料配方、体系尺寸与冷却方案对复剪切模量场的影响规律.模拟结果表明,由于热阻的差异,体系表面的冷却速率大于内部,表面首先发生凝胶化;而由于预凝胶化阶段的平均冷却速率决定了无穷复剪切模量的值,最终体系内部的复剪切模量超过表面的.     

An experimental method for studying nonisothermal crystallization of polymers at very high cooling rates

A new technique based on light depolarizing microscopy was developed for studying non-isothermal crystallization of polymers at average cooling rates up to about 5000°C/min. The polymer is cooled down by a gaseous cooling medium supplied at a constant temperature. The temperature of polymer is measured by a thermocouple imbedded directly in the sample. A heat transfer analysis was used to establish appropriate sample geometry to assure that, under the applied cooling condition, the temperature distribution along the sample thickness can be neglected. A light-scattering effect, which occurs when crystallization is carried out under high cooling rates, was observed. This required the development of a method to correct the depolarized light intensity for the effect of light scattering. An appropriate correction method was developed based on both a theoretical and an experimental analysis of the light intensity measurement. This provided a means to measure the overall crystallization kinetics. Examples of such measurements for iPP, HDPE, and LDPE are presented. In addition to the overall crystallization kinetics, the developed technique includes a video camera and VCR system used for measurements of spherulite growth rates during crystallization under high cooling rates. Constant spherulite growth rates were observed for isotactic polypropylene crystallized under very non-isothermal conditions. © 1996 John Wiley & Sons, Inc.     

Evaluation method for heat transfer coefficient of a contact interface across a microscale thin liquid polymer film

The research presented here evaluates the heat transfer coefficient of the contact interface of a thin liquid polymer film between a pair of columnar aluminum bodies with an initial temperature difference of approximately 160 K. We measured the unsteady temperature changes inside the columns. The heat transfer test was performed with three types of liquid polymers: squalane, oleic acid, and silicone oil. The heat transfer coefficient of the polymer films as a fitting parameter was obtained by ensuring the numerically computed time evolution of the columns’ temperature corresponded with the experimentally measured data. The interfacial heat transfer coefficients of the thin polymer films (mean thickness: 60 μm) for all three polymers used were 1.75 kW/m²·K, 2.75 kW/m²·K, and 4.10 kW/m²·K. The present estimating method for determining interfacial heat transfer coefficients was suitable for a material-polymer film-material contact model. The time evolution of the temperature at the contact surfaces was also effectively evaluated using the numerical simulation.     

核级碳化硼试样分解方法的研究

在对核级碳化硼试样的多种分解方法进行简要介绍和分析之后,提出了以碳酸钙作熔剂在高温下分解试样,以盐酸浸取的方法,此方法应用于核级碳化硼中总硼、铁、铝等的测定获得了满意的结果。     

Effects of the thermal heterogeneity of the column on chromatographic results

The influence of the thermal heterogeneity of HPLC columns on retention data was investigated. The retention factor of the retained compound phenol was measured at 24 increasing values of the flow rate, from 0.025 to 4.9 mL/min, on six different packing materials prepared with the same batch of silica particles (5 microm diameter, 90 A pore size). One column was packed with the neat silica particles, another with the silica endcapped with trimethylchlorosilane (TMS)(C(1), 3.92 micromol/m(2)), and the other four with silica first derivatized with octadecyl-dimethyl-chlorosilane (C(18), 0.42, 1.01, 2.03, and 3.15 micromol/m(2)), and second endcapped with TMS. Four different sources of heat contributing to raise the column temperature were considered: (1) the heat supplied by the hot high-pressure pump chamber to the solvent; (2) the adiabatic (dS=0) compression of the solvent in the high-pressure pump; (3) the isenthalpic (dH=0) decompression of the solvent during its migration along the porous chromatographic bed; and (4) the heat released by the friction of the solvent percolating through the column bed. The main contributions appear to be the heat supplied to the solvent by the HP pump and the friction heat. The average column temperature (ACT) was indirectly derived from the measurements of the first moment, mu(1), of phenol peak, of the column pressure drop, DeltaP, and of the retention factors of the phenol peak apices as a function of the flow rate applied. If the column is placed in a still-air bath at 298 K (and its temperature is not externally controlled), a longitudinal temperature gradient is established along the column and the average column temperature is about 6 K higher when this column is operated at 4.9 mL/min than when the flow rate is only 0.025 mL/min. If the column is placed in a heated air bath (temperature controlled at 316 or 338 K), the ACT changes by less than 3 K over the whole flow rate range applied.     

Experimental Study of Oil Deposition Through a Flow Loop

In this article, the effect of temperature, pressure, and flow rate on deposition rate has been investigated by using chemical analysis method for calculating the deposit thickness and comparing to heat transfer and pressure drop methods. To do so, an experimental high pressure flow loop setup was designed and constructed to conduct various experiments. Caliper readings at the end of each test showed the chemical analysis method in comparison to the heat transfer and pressure drop methods is superior for deposit thickness calculation.     

甲烷在MIL-101上的吸附平衡分析及充放气特性

为研制吸附储存天然气(ANG)用的金属有机框架物(MOFs),选择MIL-101(Cr)试样进行甲烷的吸附平衡与充放气实验。试样由溶剂热法合成,经测试77.15 K氮吸附数据作表征结构后,在温度293-313 K、压力0-100 k Pa和0-7 MPa条件下测试甲烷吸附平衡数据,运用亨利定律标绘和Toth方程确定甲烷在试样上的极限吸附热和绝对吸附量,比较了ClausiusClapeyron(C-C)方程和Toth势函数计算的等量吸附热。最后,在工程应用对应的流率10-30 L/min,对装填940 g试样、容积为3.2 L的适型储罐吸附床进行甲烷充放气实验。结果表明,甲烷在试样上的平均极限吸附热为23.89 k J/mol,测试范围内Toth方程预测的平均相对误差为1.06%,由C-C方程和Toth势函数确定的平均等量吸附热分别为15.51和13.56 k J/mol;在有效充放气时间内,储罐在10和30 L/min流率时的总充/放气量分别为347 L/338 L和341 L/318 L,放气率为98.3%和94.1%。工程应用应选用C-C方程确定的等量吸附热,并采取慢充/放以增大充/放气量和提高吸附床脱气率。