PVC-溶剂-非溶剂相混合参数表征

<正>聚合物-溶剂-非溶剂(沉淀剂)三元相混合参数是影响浸没沉淀相转化法成膜的一个关键因素,溶剂/非溶剂的选择影响成膜机理:瞬时液-液分相和延时液-液分相。顺时液-液分相是指铸膜液浸入凝胶浴后迅速分相,有利于形成大孔结构;延时液-液分相是指铸膜液浸入凝胶浴后一定时间后才开始分相成膜倾向于形成海绵状结构[1]。这是由于当在铸     

不同聚合物浓度对聚醚砜微滤膜性能的影响

研究了不同聚合物浓度对浸没沉淀相转化法制备聚醚砜(PES)微滤膜的形态结构、成膜厚度、孔隙率、过滤性能、亲水性的影响。实验结果表明:随聚合物浓度的增加,铸膜液黏度增大,导致铸膜液分相固化时间较短,表面孔隙率逐渐减少,且成膜孔隙率、纯水通量及膜亲水性均在聚合物浓度为14%时呈现最佳值。     

聚酰胺酸对环氧树脂胶膜固化反应的影响及其机理

以液体环氧树脂与固体环氧树脂混配,4,4′-二氨基二苯砜(DDS)为固化剂,加入聚酰胺酸(PAA)对固液混配环氧树脂进行改性,采用刮膜法制备环氧树脂胶膜.通过DSC分析、平板拉丝法和傅里叶转换红外光谱法,研究了环氧树脂固液比、PAA用量等对环氧树脂胶膜成膜性、同化温度和同化速率的影响,并探索了PAA对环氧树脂/DDS体系固化反应的作用机理.结果表明,PAA可提高环氧树脂胶膜韧性,可降低固化温度,加快固化速度.对于环氧树脂(固/液质量比为50/50)/DDS/PAA体系,当PAA质量分数5%时,同化起始温度由未加PAA时的175.9℃下降到138.8℃,140℃时的固化凝胶时间由162 min下降到46 min,体系由高温固化变为近中温固化.     

以水性环氧树脂为凝胶体系的氧化铝空心球浆料的流变性能

以水性环氧树脂为凝胶体系,研究了氧化铝空心球陶瓷浆料的流变性能,考察了水性环氧树脂溶液含量、固化温度对水性环氧树脂溶液和不同固相含量氧化铝空心球陶瓷浆料凝胶过程的影响。结果表明:在同一温度下,随水性环氧树脂溶液质量分数的增加,凝胶时间缩短,当水性环氧树脂含量从15.4%(质量分数)增加到28.8%时,溶液凝胶时间从99.3min缩短至38.2min;固化温度升高后,溶液凝胶时间明显缩短,从20℃时的125.3min下降到50℃时的5.8min。以水性环氧树脂为凝胶体系的氧化铝空心球浆料也存在上述规律,随浆料固相含量增加,凝胶时间缩短。以水性环氧树脂为凝胶体系成功制备出氧化铝空心球多孔陶瓷。     

HPAM/Cr3+微凝胶体系在剪切状态下的交联

对HPAM/Cr3 微凝胶体系在静态和剪切状态下成胶过程进行了对比,并且考察了剪切速率、聚合物浓度、温度及聚合物溶液熟化时间对微凝胶成胶的影响。实验表明:与静态相比,凝胶体系在低剪切状态下成胶较快,成胶后的粘度也较低;剪切速率、温度、聚合物浓度及聚合物溶液熟化时间对剪切状态下微凝胶的成胶时间和成胶粘度都有很大影响。     

碱渣-粉煤灰基新型注浆材料固化机理试验研究

为了得到碱渣-粉煤灰-硅酸钠溶液体系新型注浆材料各组分的作用和固化机理,考虑不同固体质量配比和养护条件,通过温度变化、固化收缩、抗压强度和傅里叶变换红外光谱试验对比研究不同体系的差别.结果表明:碱渣中Ca(OH)2和粉煤灰中的CaO遇到硅酸钠溶液时发生放热反应;浆液早期抗压强度由碱渣中CaCl2、Ca(OH)2和CaSO4与硅酸钠溶液反应生成水化硅酸钙凝胶决定,由于粉煤灰受碱激发生成了硅铝酸盐聚合物凝胶使得注浆液7~50 d抗压强度有大幅增长;FTIR试验证实了水化硅酸钙凝胶(C-S-H)和硅铝酸盐凝胶(N-A-S-H)的存在;原材料组分保证了浆液收缩程度小、流动性好、不易离析、结石率大等优点.     

丙烯酸聚氨酯涂料成膜过程(Ⅰ)溶剂扩散系数的估算

采用傅里叶变换红外光谱（FTIR）测定了不同时间下丙烯酸聚氨酯涂料体系成膜聚合物的固化度及固化反应速率常数,并将该体系按二元聚合物-溶剂体系进行简化处理,在Vrentas-Duda自由体积理论模型的基础上,利用Di-Benedetto方程关联了溶剂的扩散系数与涂膜的固化度,建立了涂膜中溶剂扩散系数的预测模型.结果表明,本涂膜体系中溶剂扩散系数是溶剂浓度、干燥时间的函数.     

液-液-液三相体系的相分散与分相特性

以包含双油相和单水相的液-液-液三相体系为对象,利用编程控制的CCD照相系统,考察了搅拌槽内不同操作条件下液-液-液三相体系的相分散及分相情况. 实验结果表明,桨型对三相体系的分散情况有较大影响,径流桨的分散效果优于轴流桨,下推式轴流桨优于上推式轴流桨;各相体积比的改变会导致不同的相分散形式;不同相分散形式的分相过程也不相同,实验中体系的分相过程可以分为凝并界面水平型与无规则型两种典型情况,分别对应两种不同的相分散形式;采用分相数学模型,可成功预测凝并界面水平型分相过程中各界面的高度随时间的变化.     

含氟硅聚苯并噁嗪材料的制备及其表面性能

本文合成了含氟硅氧烷苯并噁嗪单体,在采用光学显微镜等考察水解沉积条件对单体在羟基化基片表面化学成膜的影响的基础上,考察了温度、时间等对聚苯并噁嗪成膜后表面能的影响,并对聚苯并噁嗪材料在不同热处理温度（100℃-350℃）下表面能的热稳定性能进行了研究。结果表明用pH=2的盐酸溶液调节沉积液所得单体膜最均一完整,聚合物的表面能随着固化时间的增加先降低后升高,固化温度越高,达到完全固化所需要的固化时间越短,在160℃,190℃,220℃,240℃下固化所得聚合物最低表面能分别是15.6 mJ?m-2 (4 h),15.0 mJ?m-2 (1 h),15.3 mJ?m-2 (15 min),15.5 mJ?m-2 (5 min),均低于Teflon的表面能（22.0 mJ?m-2）。聚合物膜表面能在低于200℃的温度下处理其表面能可基本保持不变,可以作为抗粘材料应用于纳米压印技术中。     

聚合物膜的研制

以聚丙烯腈(PAN)／聚乙烯醇(PVA)合金为膜材料，用液-固相转化法成膜制备PAN/PVA体系的非对称型合金微滤膜。研究了铸膜液浓度、聚合物共混配比、铸膜液温度溶剂蒸发时间、凝胶浴温度对膜结构和膜性能的影响。结果表明：采用了液-固相转化法成膜，可制成孔径为0．5～5．0μm的非对称性PAN/PVA合金微滤膜。     

非对称膜的凝胶速度及膜结构的影响因素

本文研究了凝胶介质为醇／水溶液的情况下，在相转换法制备非对称尼龙６，６膜过程中，若干因素对凝胶速度及膜结构的影响。结果表明，醇中主链上碳原子数、醇的羟基数、醇的浓度、共溶剂的组成、聚合物的浓度、铸膜液及凝胶介质的粘度、以及凝胶介质的表面张力等因素对凝胶速度及膜结构都有显著影响。     

Phase separation phenomena in solutions of polysulfone in mixtures of a solvent and a nonsolvent: relationship with membrane formation

The phase separation phenomena in ternary solutions of polysulfone (PSf) in mixtures of a solvent and a nonsolvent (N,N-dimethylacetamide (DMAc) and water, in most cases) are investigated. The liquid-liquid demixing gap is determined and it is shown that its location in the ternary phase diagram is mainly determined by the PSf-nonsolvent interaction parameter. The critical point in the PSf/DMAc/water system lies at a high polymer concentration of about 8% by weight. Calorimetric measurements with very concentrated PSf/DMAc/water solutions (prepared through liquid-liquid demixing, polymer concentration of the polymer-rich phase up to 60%) showed no heat effects in the temperature range of ?20°C to 50°C. It is suggested that gelation in PSf systems is completely amorphous. The results are incorporated into a discussion of the formation of polysulfone membranes.     

The kinetic study for asymmetric membrane formation via phase-inversion process

The kinetics of membrane formation by phase inversion was studied emphasizing the rate of solvent diffusion from a polymer solution during the phase separation. Diffusional behavior of the solvent can be considered Fickian. Membrane morphologies were shown to be strongly dependent on the rate of solvent diffusion, indicating that mass-transfer rates of solvent and nonsolvent during phase separation are crucial for determining the final membrane structure for the following system: polysulfone (polymer), dimethyl acetamide (solvent), and ethanol (gelation medium). Specific reference to the mechanism of macrovoid formation was explored. Macrovoid formation was found to be proportional to the square root of time, suggesting that it is governed by a diffusion process. In addition, latex particles of coagulated polymer formed by the nucleation and growth of a concentrated polymer phase was observed inside the macrovoids. Such a result implies that the macrovoids grow by a diffusive flow which results from the growth of the polymer lean phase during binodal decomposition. © 1996 John Wiley & Sons, Inc.     

TRANSPORT PHENOMENA ASPECTS OF THE FREE-RADICAL RETROGRADE-PRECIPITATION POLYMERIZATION (FRRPP) PROCESS

We have been studying free-radical polymerization that is accompanied by phase separation above the lower critical solution temperature. In the past, we have experimentally shown evidence of hot regions in the reactive system. We have also shown in the past that eventually the system exerts control over the rate of propagation as well as termination. In this work, we invoke a concept in polymer physics (the coil-to-globule transition) to help explain the mechanism of thermal trapping within the polymerization zones. The diffusivities of polymer chains at different stages in the reaction are calculated using appropriate methods. From the diffusivities, the propagation and termination rate coefficients are calculated using the Achilias-Kiparissides gel effect model. With experimental kinetic data, we then estimate rates of monomer consumption within polymer-rich particles. Using a pseudo-steady-state heat transfer model, we are able to show that interior temperatures of polymer-rich particle domains greater than about 1 mm can reach spinodal temperature values at the early stage of polymerization. Polymer-rich particle sizes are obtained from the same reactor system whereby a small amount of crosslinker is added to preserve particle morphology. This experiment indicates that even under turbulent flow conditions, relatively large particles can exist in the reactor fluid. This agrees with the physical implications of the coil-to-globule transition. However, since these particles were obtained during the period of slow conversion rate, our heat transfer calculations indicate that interior particle temperatures would be almost the same as surface temperatures. This points to an unknown radical-trapping mechanism at this stage of the polymerization process.     

水溶性环氧树脂体系的氧化锆凝胶浇注成型

研究了氧化锆凝胶浇注成型工艺中,水溶性环氧树脂凝胶剂对浆料的流变性和固化过程的影响.结果表明:环氧树脂的加入增加了浆料的黏度,但可制备固体含量为53.7%(体积分数),黏度为0.60Pa·s(剪切速率为100 s-1),适合浇注的浆料;为得到较高弹性模量的凝胶,固化剂(二丙三胺)最佳加入量为3.4%(质量分数);环氧树脂溶液的聚合过程和氧化锆浆料的固化过程对温度都具有较大的依赖性,利用这些依赖性可控制浆料的制备、浇注和固化过程.30℃时,浆料中环氧树脂的聚合反应在8min后开始,20min后浆料失去流动性,1 h后浆料完全固化,湿坯弹性模量达到1.96MPa.固化温度越高,浆料固化越快,固化后湿坯的弹性模量就越高.     

Transport phenomena aspects of the free-radical retrograde-precipitation polymerization (FRRPP) process

We have been studying free-radical polymerization that is accompanied by phase separation above the lower critical solution temperature. In the past, we have experimentally shown evidence of hot regions in the reactive system. We have also shown in the past that eventually the system exerts control over the rate of propagation as well as termination. In this work, we invoke a concept in polymer physics (the coil-to-globule transition) to help explain the mechanism of thermal trapping within the polymerization zones. The diffusivities of polymer chains at different stages in the reaction are calculated using appropriate methods. From the diffusivities, the propagation and termination rate coefficients are calculated using the Achilias-Kiparissides gel effect model. With experimental kinetic data, we then estimate rates of monomer consumption within polymer-rich particles. Using a pseudo-steady-state heat transfer model, we are able to show that interior temperatures of polymer-rich particle domains greater than about 1 mm can reach spinodal temperature values at the early stage of polymerization. Polymer-rich particle sizes are obtained from the same reactor system whereby a small amount of crosslinker is added to preserve particle morphology. This experiment indicates that even under turbulent flow conditions, relatively large particles can exist in the reactor fluid. This agrees with the physical implications of the coil-to-globule transition. However, since these particles were obtained during the period of slow conversion rate, our heat transfer calculations indicate that interior particle temperatures would be almost the same as surface temperatures. This points to an unknown radical-trapping mechanism at this stage of the polymerization process.     

相转化法制备聚砜膜研究进展

系统概述了相转化法制备聚矾膜时聚矾含量、添加剂、凝固浴及铸膜液在空气中的蒸发时间对其结构和性能的影响。随着聚矾含量的增加,膜结构从疏松向致密转变;在铸膜液中添加适合的添加剂可制备适当结构和渗透性能的聚矾膜;在凝固浴中添加适量的溶剂,可有效抑制膜内大孔结构的形成;空气中蒸发时间的增大时,膜表面趋于疏松,当增加到一定程度后基本趋于稳定。还综述了相转化法制备聚矾膜时聚矾含量、添加剂、凝固浴及铸膜液在空气中的蒸发时间对其结构和性能的影响。     

Investigation of Three-liquid-phase Extraction Systems for Simultaneous Separation of Emodin and Rhein

Several three-liquid-phase extraction systems comprised of organic extractant,polymer and salt aqueous solution were applied to isolate and purify simulated herbal extract containing emodin and rhein.Some influential factors on the partitioning behaviors were studied.The results revealed that extractant type and solution pH value were crucial factors for improving the separation performance.The optimal separation results were obtained at pH 8.00 with methyl isobutyl ketone as the extractant,10%（ω） polyethylene glycol with the molecular weight 4000 Da,and 10%（ω） ammonium sulphate.Under the optimized conditions,95%emodin and 97%rhein were simultaneously extracted into the organic phase and polymer-rich phase from simulated herbal solution with the initial concentration of 100×l0^-6（ω）,respectively,and their separation factor of over 10000 was achieved.By adjusting pH value,back extraction rate of both emodin and rhein could be up to about 99%.With the assistance of molecular simulation program XLOGP3 and molecular orbital package,the possible mechanism of extraction was analyzed,and hydrophobic interaction and hydrogen-bonding interaction might be the major driving forces affecting the partitioning behaviors of emodin and rhein.     

Performance control of asymmetric poly(phthalazinone ether sulfone ketone) ultrafiltration membrane using gelation

We studied the influence of the gelation conditions on the formation kinetics of the polyphthalazine ether sulfone ketone (PPESK) membrane via wet phase inversion process experimentally and theoretically. Membrane formation and its morphology were first observed with an online optical microscope - CCD camera system. The resulting membranes prepared under various gelation conditions were then characterized by the gelation parameter, optical microscope, and SEM. Lastly, the relationship between the final membrane structure/permeation properties and the gelation parameter was discussed extensively. The results showed that both the gelation rate and the membrane flux increased dramatically as the gelation temperature increased. Moreover, the membrane structures became loose, and the porosity of membrane increased. Different non-solvent could change the solubility parameter between the polymer and the non-solvent, and thus the gelation rate greatly. With the increasing number of carbons in non-solvent, the gelation rate became slow, and the membrane gradually changed from a finger structure into a sponge structure. Adding NMP into the non-solvent changed the difference in the chemical potential and the solubility parameter between the polymer solution and the non-solvent, which in turn changed the gelation rate of polymer solution greatly. With the increasing concentration of NMP in non-solvent, the gelation rate became very slow and sponge structures formed with the non-solvent system of 80% NMP. A novel conclusion could be made that we could control the flux and reject of membrane just by changing the mean diffusion coefficient of skin, D, and the diffusion coefficient of skin, D1, in the process of membrane formation. This work was presented at 13 ^th YABEC symposium held at Seoul, Korea, October 20–22, 2007.     

Viscometric and transmitted light investigation of agarose and agarose-guar water systems

Summary Agarose water solutions of different concentrations and agarose-guar water solutions of 1% (w/w) total concentration and varied compositions were submitted to viscometric and turbidimetric measurements as function of the temperature. Phase diagrams for both systems are compared. For agarose solutions, phase separation occurs prior to gelation within a certain concentration range, and network formation seems to take place by the connectivity of the polymer-rich domains. For the mixed agarose-guar system, the homogeneous solutions gel directly.