TPPS在EVAL膜表面的吸附及超分子自组装

TPPS(四-(4-磺酸基苯基)卟啉)在一定条件下可以自组装形成超分子聚集体.将TPPS超分子聚集体与膜材料结合,可制备一种超分子负载膜.本实验以EVAL(乙烯-乙烯醇共聚物)为基膜,以DMAEMA(甲基丙烯酸N,N-二甲氨基乙酯)为单体,采用紫外接枝的方法制备了EVAL-g-PDMAEMA接枝膜,利用氢键、静电作用等非共价键作用将TPPS负载于EVAL原膜及EVAL-g-PDMAEMA接枝膜上.研究了pH值、离子强度、接枝率对吸附过程的影响及等温吸附机理.结果表明,当pH=3.6时接枝膜对TPPS的吸附容量最大,pH=7时,原膜对TPPS的吸附容量最大;离子强度的增大不利于膜对TPPS的吸附;EVAL-gPDMAEMA接枝率的增大,接枝膜对TPPS的吸附容量也随之增大;Langmuir吸附等温方程可以对吸附过程进行很好的描述.改变EVAL/TPPS负载膜的pH条件,利用紫外漫反射光谱表征膜表面TPPS的聚集状态,考察不同DMAEMA接枝率的负载膜实现超分子结构的条件.实验结果显示,当pH1时,TPPS在接枝膜和原膜表面均形成超分子J-聚集体,而pH1时,TPPS仅在接枝膜表面形成H-聚集;并且DMAEMA的接枝率越高,越有利于TPPS聚集体的形成,进而有利于超分子负载膜的构筑.     

pH响应性乙烯-乙烯醇共聚物分离膜的纳滤特性

具有纳滤特性的pH响应性膜在小分子分离体系中具有广泛应用前景。文中以铸膜液浓度为25%的乙烯-乙烯醇共聚物(EVAL)超滤膜为基膜,接枝具有pH响应性的功能单体甲基丙烯酸二甲氨基乙酯,制备pH响应性EVAL膜,通过考察膜对标准物聚乙二醇(PEG)与无机盐的截留性能,研究其纳滤特性。结果表明,当pH小于pKa时,pH响应性EVAL膜对聚乙二醇(PEG)与无机盐的截留效果均明显高于未接枝膜,接枝率6%的接枝膜对PEG 800、PEG 1000及PEG 2000的截留率均达到90%以上,对二价阳离子的截留率达到80%以上,无机盐的截留顺序为:CaCl_2MgCl_2MgSO_4NaClNa2SO_4。当pH大于pKa时,PEG及无机盐截留率明显下降,膜对PEG 1000的截留率由95.6%降至62.9%,对MgCl_2截留率降至30.6%,截留率及膜水通量变化存在显著的pH响应性。     

四(4-磺酸苯基)-卟啉在聚4-乙烯基吡啶接枝的乙烯-乙烯醇膜表面的吸附和自组装行为

四(4-磺酸苯基)-卟啉(TPPS)是一种水溶性卟啉,在一定条件下可以自组装形成超分子聚集体,将这种超分子聚集体与膜材料相结合,可以形成超分子负载膜。文中以乙烯-乙烯醇共聚物(EVAL)为膜材料,4-乙烯基吡啶(4VP)为单体,采用紫外辐照表面接枝法制备了表面带有P4VP接枝链的EVAL-P4VP接枝膜,利用非共价键作用将TPPS负载于EVAL原膜及EVAL-P4VP接枝膜上,研究了p H值、离子强度、接枝率等因素对TPPS吸附过程以及TPPS在膜表面存在形态和自组装行为的影响。结果表明,TPPS溶液中自身聚集及离子强度的增加对其在膜上的吸附产生不利影响;吸附过程可用Langmuir等温吸附模型进行描述;接枝率的增加、p H值的减小和吸附量的增加有利于TPPS在接枝膜表面形成J-聚集体。     

聚全氟乙丙膜电子束引发预辐射接枝AA和SSS制备阳离子交换膜的性能

利用电子束引发预辐射接枝技术,在聚全氟乙丙烯(FEP)膜上接枝丙烯酸(AA)和对苯乙烯磺酸钠(SSS)两单体,制备出一种含羧酸基团和磺酸基团的阳离子交换膜,接枝率越高,接枝膜的吸碱性能越好。差示量热扫描及X射线衍射测试表明,接枝膜结晶度随接枝率的升高而降低。这是接枝膜中FEP组份的“结晶变形”及接枝链对晶区的“稀释作用”综合影响的结果。     

两亲性PP-g-(NVP-co-PEGMA)抗污染改性剂的制备及改性聚丙烯亲水微孔膜的表征

以乙烯基吡咯烷酮(NVP)和聚乙二醇甲基丙烯酸酯(PEGMA)为共聚单体,采用熔融接枝法制备了两亲性改性剂PP-g-(NVP-co-PEGMA);利用红外光谱、X射线光电子能谱对制得的改性剂进行表征,研究了PEGMA单体用量对熔融接枝聚合PVP接枝率的影响。利用熔融共混和拉伸成孔工艺制备了聚丙烯亲水微孔膜。利用接触角、热失重分析、扫描电镜和水通量测试对改性剂及膜性能进行表征。结果表明,亲水性支链成功接枝到PP大分子链上,少量PEGMA的加入提高了NVP的接枝率,相比NVP作为唯一单体的情况提高了5.66%;改性PP微孔膜的热稳定性能提高,亲水性也得到很大改善,起始接触角从96.0°下降到57.5°。膜的平均孔径在0.15μm左右,孔径分布相对均匀,孔隙率为32.7%。改性后的PP膜水通量随时间的延长下降缓慢,亲水性和抗污染性能得到大幅度提高。     

锂离子电池隔膜的紫外辐照接枝改性

利用紫外辐照法在聚乙烯(PE)锂离子电池隔膜表面接枝上丙烯酸甲酯(MA)以改善隔膜的润湿性,研究了引发剂浓度、单体浓度和辐照时间对接枝率的影响,通过红外光谱、SEM观察和接触角测定等手段进行了表征分析。在纯MA单体溶液中,引发剂二苯甲酮(BP)浓度为0.02g/mL,辐照90s接枝率达到68.9%,接触角从原膜的46°降低到12°。     

pH敏感型管式陶瓷复合膜的制备

采用硅烷偶联剂KH-570在乙醇溶剂中以盐酸溶液为催化剂进行水解后对管式ZrO2陶瓷膜进行表面修饰,进一步用化学接枝法将丙烯酸单体接枝到改性ZrO2陶瓷膜上,制备pH敏感型陶瓷复合膜.系统考察了不同偶联反应条件对氧化锆陶瓷膜的硅烷化改性效果的影响;研究了丙烯酸单体浓度对pH敏感膜渗透通量及pH开关系数的影响.通过扫描电镜(SEM)、X射线光电子能谱(XPS)、热重(TG)及水通量测定等对改性前后膜结构和pH敏感性能进行分析.结果表明,在以乙醇为溶剂进行硅烷化改性后,成功引入了碳-碳双键,并将丙烯酸成功接枝在陶瓷膜表面;单体浓度对pH敏感的膜通量及pH开关系数有重要的影响;所制备膜显示了良好的pH敏感性能.     

光接枝制备功能性核孔膜

采用光接枝聚合方法，可以实现多种单体在PET核孔膜上的接枝。如丙烯酸、4-乙烯基吡啶、异丙基丙烯酰胺等，得到具有环境敏感性的分离膜．接枝膜采用XPS、ATR-FTIR进行了表征，接枝膜结构及形貌采用SEM、AFM观察．PET的紫外屏蔽效应以及核孔膜的结构特征，决定了接枝只能在膜的表面进行，孔内不受影响；接枝膜具有孔封盖结构，即膜表面的接枝链可以伸入膜孔将其封堵，产生孔封盖效应，从而影响膜的通量．丙烯酸和4-乙烯吡啶接枝膜具有pH值敏感性，膜通量随外界酸性的强弱而变化；4-乙烯吡啶接枝膜具有优异的开关性能，在很低接枝程度下(Dg=0．3％，0．2μm)，即有明显的pH敏感性，通量变化达到几十倍．N-异丙基丙烯酰胺接枝膜具有温度敏感效应，可以随温度的升降而改变通量．     

马来酸酐/N-乙烯基吡咯烷酮双单体接枝聚丙烯的制备及对聚丙烯微孔膜的亲水改性EI北大核心CSCD

以马来酸酐(MAH)为功能单体,N-乙烯基吡咯烷酮(NVP)为共聚单体,采用熔融接枝法制备两亲性改性剂PP-g-(MAH-co-NVP),并通过热致相分离法制备聚丙烯(PP)亲水微孔膜。通过红外光谱仪和元素分析仪表征了PP-g-(MAHco-NVP)的化学结构和接枝率,使用差示扫描量热仪、X射线衍射仪表征了PP-g-(MAH-co-NVP)的结晶性能。利用接触角、热失重分析、扫描电子显微镜和孔隙率测试对改性前后的PP膜进行研究。结果显示,亲水支链成功接枝到PP大分子链上,相比于MAH作为唯一的接枝单体,NVP的加入使MAH的接枝率增加了270%;且NVP的加入促进了PP分子链的结晶。改性PP微孔膜的热稳定性能提高,膜孔数增多,孔隙率增加了2. 8%。并且改性PP微孔膜的亲水性也得到改善,接触角下降了28. 5%。     

马来酸酐/N-乙烯基吡咯烷酮双单体接枝聚丙烯的制备及对聚丙烯微孔膜的亲水改性

以马来酸酐(MAH)为功能单体,N-乙烯基吡咯烷酮(NVP)为共聚单体,采用熔融接枝法制备两亲性改性剂PP-g-(MAH-co-NVP),并通过热致相分离法制备聚丙烯(PP)亲水微孔膜。通过红外光谱仪和元素分析仪表征了PP-g-(MAHco-NVP)的化学结构和接枝率,使用差示扫描量热仪、X射线衍射仪表征了PP-g-(MAH-co-NVP)的结晶性能。利用接触角、热失重分析、扫描电子显微镜和孔隙率测试对改性前后的PP膜进行研究。结果显示,亲水支链成功接枝到PP大分子链上,相比于MAH作为唯一的接枝单体,NVP的加入使MAH的接枝率增加了270%;且NVP的加入促进了PP分子链的结晶。改性PP微孔膜的热稳定性能提高,膜孔数增多,孔隙率增加了2. 8%。并且改性PP微孔膜的亲水性也得到改善,接触角下降了28. 5%。     

Real gas choked flow conditions at low reduced-temperatures

Real gas choked mass flux is calculated for a frictionless stream expanding isentropically until it reaches the speed of sound and without phase changes. The other parameters associated with the choked state are the pressure, density, temperature ratios, and the speed of sound. Departure of the choked mass flux from the ideal gas model is discussed first in absolute terms and then in relative terms, using the Principle of Corresponding States, for gases with boiling points in the low temperature range. Reduced-stagnation pressures are examined up to values of 30 for hydrogen, neon, nitrogen, argon, methane, krypton, xenon, and R-14 and up to 100 for ⁴He. The corresponding reduced-stagnation temperatures go down to 1.4 and in some cases down to 1.2 for nitrogen and argon. Also discussed are the limiting values of stagnation parameters for which no phase change occurs in the choked state. Compared to the ideal gas, the mass flux may almost double and the critical pressure ratio may decrease by an order of magnitude. The relevance of results is discussed qualitatively and quantitatively for Joule-Thomson cryocooling.     

As-cast microstructures and behavior at high temperature of chromium-rich cobalt-based alloys containing hafnium carbides

Hafnium is often used to improve the high temperature oxidation resistance of superalloys but not to form carbides for strengthen them against creep. In this work hafnium was added in cobalt-based alloys for verifying that HfC can be obtained in cobalt-based alloys and for characterizing their behavior at a very temperature. Three Co–25Cr–0.25 and 0.50C alloys containing 3.7 and 7.4 Hf to promote HfC carbides, and four Co–25Cr– 0 to 1C alloys for comparison (all contents in wt.%), were cast and exposed at 1200 °C for 50 h in synthetic air. The HfC carbides formed instead chromium carbides during solidification, in eutectic with matrix and as dispersed compact particles. During the stage at 1200 °C the HfC carbides did not significantly evolve, even near the oxidation front despite oxidation early become very fast and generalized. At the same time the chromium carbides present in the Co–Cr–C alloys totally disappeared in the same conditions. Such HfC-alloys potentially bring efficient and sustainable mechanical strengthening at high temperature, but their hot oxidation resistance must be significantly improved.     

Degradation behaviour of sputtered Co–Al coatings on superalloy

Degradation behaviour of sputtered Co–Al coatings on Superni-718 substrate has been investigated. Cyclic high temperature oxidation tests were conducted on uncoated and coated samples at peak temperatures of 900 °C for up to 100 thermal cycles between the peak and room temperatures. The results showed that a dense scale formed on the coated samples during thermal cycling at the peak temperature of 900 °C. The external scale exhibited good spallation resistance during cyclic oxidation testing at both temperatures. The improvement in oxide scale spallation resistance is believed to be related to the fine-grained structure of the coating. Nanostructured Co–Al coatings on Superni-718 substrate were deposited by DC/RF magnetron sputtering. FE-SEM/EDS, AFM, and XRD were used to characterize the morphology and formation of different phases in the coatings, respectively. The Co–Al coating on superalloy substrate showed better performance of cyclic high temperature oxidation resistance due to its possession of β-CoAl phase as Al reservoir and the formation of Al₂O₃ and spinel phases such as CoCr₂O₄ and CoAl₂O₄ in scale. The oxidation results confirmed an improved oxidation resistance of the Co–Al coating on superalloy as compare to bare substrate in air at 900 °C temperature up to 100 cycles.     

Capacitance based mass metering for cryogenic fluids

This paper describes a method for measuring the mass of cryogenic fluids in on-board rocket propellant tanks or ground storage tanks. Linear approximations to the Clausius-Mossotti relationship serve as the foundation for a capacitance based mass sensor, regardless of fluid density stratification or tank shape. Sensor design considerations are presented along with the experimental results for a capacitance based mass gage tested in liquid nitrogen. This test data is shown to be consistent with theory resulting in a demonstrated mass measurement accuracy of ±0.75% and a deviation from linearity of less than ±0.30% of full scale mass. Theoretical accuracies are also shown to be ±0.73% for hydrogen and ±1.39% for oxygen for a select range of pressures and temperatures.     

Equipment using a “static-analytic” method for solubility measurements in potentially hazardous binary mixtures under cryogenic temperatures

A new apparatus designed to study, at cryogenic temperatures, thermodynamic equilibria of potentially explosive binary systems such as hydrocarbon-oxygen mixtures is described herein. This equipment has an equilibrium cell which was especially designed to minimize hazards while allowing accurate phase equilibrium measurements. Reliability of results, obtained with this equipment has been verified by working on the nitrogen-propane system, for which data are already available in literature, over a large range of compositions and at various temperatures. Four isothermal curves describing liquid phase compositions at 109.98, 113.77, 119.75 and 125.63 K have been determined. Our experimental data are represented within 2% in compositions and in pressures through the Peng-Robinson equation of state implying Mathias-Copeman alpha function and Huron-Vidal mixing rule. Comparisons to literature allow pointing out: good agreement is observed with Kremer and Knapp data (1983) while the three sets of Poon and Lu data (1974) presenting systematic positive deviation are consequently judged as suspicious.     

Thermal Stability of Amorphous Hydride Mg_(50)Ni_(50)H_(54) and Mg_(30)Ni_(70)H_(45)

The thermal stability of amorphous ternary hydrides Mg_(50)Ni_(50)H_(54) and Mg_(30)Ni_(70)H_(45) and their corre-sponding amorphous binary alloys Mg_(50)Ni_(50) and Mg_(30)Ni_(70) were studied with X-ray diffraction(XRD) and differential scanning calorimetry(DSC). Samples of the amorphous alloys were preparedby mechanical alloying and the amorphous hydrides were obtained by charging the alloys with gas-eous hydrogen at 3.0 MPa and 423 K. It was found that the amorphous hydrides released most oftheir hydrogen before the crystallization of the essentially hydrogen depleted amorphous alloy. Thecrystallization temperature of amorphous Mg_(50)Ni_(50)H_(54) elevated and that of amorphousMg_(30)Ni_(70)H_(45) did not change in relation to the original binary amorphous alloy. This is very excep-tional for amorphous hydrides. The reason for the effects of hydrogen absorption/desorption on thecrystallization of amorphous alloys was discussed.     

Percolation and the resistive transition of the critical temperature Tc of Nb3Sn

The relationship between the distribution of the critical temperature, the percolation function, and the resistive transition of the critical temperature is explored for polycrystalline Nb₃Sn. In the neighborhood of the critical temperature, Nb₃Sn is assumed to be a random mixture of superconducting and normal grains. Percolation concepts are applied to a study of the resistivity. A general analysis is made showing that the onset and shape of the resistive transition for composite conductors are determined by the percolation function and the distribution of the critical temperature. An approximate form of the percolation function is determined based on a linear FEM analysis. Example resistive transitions are calculated for an assumed normal distribution of the critical temperature. An argument is presented that relates grain orientation and strain dependence in Nb₃Sn. It is noted that a dependence of the distribution of T_c with strain, in addition to the usual shift in T_c with strain, would be the result of a strain dependence that is a function of grain orientation. The analysis shows the extent to which the slope of the resistive transition is a measure of the distribution of the critical temperature, and therefore a measure of the grain orientation strain sensitivity. Finally, a method is described to determine the percolation function experimentally.     

Liquid helium cryostat for SQUID-based MRI receivers

We describe a liquid helium cryostat, developed to cool SQUID-based receivers in low field MRI systems. The cryostat has a 4 L liquid helium capacity, a hold time of over 3 days and accommodates 10 cm diameter receiver coils. New vacuum insulation methods reduce the noise level by at least an order of magnitude compared to existing commercial designs. The minimum detectable field at 425 kHz, with a 5 cm diameter circular coil, was estimated to be 0.018 fT/Hz^1/2 from Q-factor measurements and 0.035 fT/Hz^1/2 by direct measurement with a SQUID amplifier. Further measurements indicated that most of this field noise probably originates with dielectric losses in the cryostat’s fibreglass shells.     

Development of No-Vent™ liquid hydrogen storage system for space applications

A number of technological advances required to store and maintain normal-boiling-point and densified cryogenic liquids, including liquid hydrogen, under zero boil-off conditions in-space, for long periods of time, have been developed. These technologies include (1) thermally optimized compact cryogen storage systems that reduce environmental heat leak to the lowest-temperature cryogen, which minimizes cryocooler size and input power, and (2) actively-cooled shields that surround the storage systems and intercept heat leak. The processes and tools used to develop these technologies are discussed. A zero boil-off liquid hydrogen storage system technology demonstrator for validating the actively-cooled shield technology is presented.     

长余辉材料Sr_4Al_(14)O_(25)∶Eu~(2+),Nd~(3+)的溶胶凝胶法制备及性能研究

首次研究了以Nd~(3+)离子为辅助激活剂,对Eu~(2+)掺杂的发光材料Sr_4Al_(14)O_(25):Eu~(2+)余辉性能的影响.用溶胶凝胶法合成了Eu~(2+), Nd~(3+)共掺杂的Sr_4Al_(14)O_(25):Eu~(2+),Nd~(3+)发光粉末,并用扫描电镜、X射线衍射计、荧光分光光度计、余辉亮度测试仪、热释光剂量计等手段对粉末样品进行了表征.结果表明,在1350℃得到了单一的Sr_4Al_(14)O_(25)相,粉末颗粒平均粒度在1μm左右.Eu~(2+), Nd~(3+)共掺杂的Sr_4Al_(14)O_(25):Eu~(2+),Nd~(3+)发光粉末有402和485nm两个发射峰,与Eu~(2+)单掺杂的Sr_4Al_(14)O_(25):Eu~(2+)相比,发射峰位置没有变化,但适量的掺杂可以大大提高余辉时间和余辉亮度,余辉时间可达18h以上.最后通过对热释光谱的分析解释了双掺杂发光粉余辉性能增强的原因,适宜深度的陷阱可以有效存储光能,增强余辉的时间和强度.