双向拉伸工艺对聚氟乙烯薄膜性能的影响

在聚氟乙烯（PVF）凝胶法成膜的基础上，通过X-射线衍射及万能材料试验仪等手段，研究了在PVF薄膜双向拉伸过程中拉伸比及温度等因素与双向拉伸聚氟乙烯薄膜（BOPVF）性能的关系，讨论了结晶因素对薄膜性能的影响。实验表明，在横向拉伸比固定情况下，随着拉伸比增加，拉伸强度、拉伸模量明显增加，而断裂伸长率则逐渐降低，反之亦然。透光性能也随着拉伸比增加也有所改善。纵向拉伸温度选择：预热辊温度约140～145℃；拉伸辊温度约130～135℃。横向拉伸温度选择：横向拉伸温度比纵向温度约高20～30℃，具体温度取决于薄膜厚度和拉伸速度。在横向拉伸比固定的前提下，PVF薄膜随纵向拉伸比增加，结晶度增加，薄膜拉伸强度也随之提高，而断裂伸长率逐渐降低。     

热拉伸温度对熔体拉伸法制备聚丙烯微孔隔膜微观结构的影响

通过小角X射线散射(SAXS)、扫描电子显微镜(SEM)和调制差示扫描量热法(TMDSC)表征了熔体拉伸法制备聚丙烯微孔隔膜在105～145℃的热拉伸过程。发现随拉伸温度升高,拉伸带来的片晶破坏减少,105℃下热拉伸仍然存在片晶被破坏分离; 130和145℃下热拉伸只发生片晶堆分离。微孔隔膜的孔洞尺寸主要由拉伸倍率和热拉伸温度控制;连接分离片晶的架桥直径和长度增幅随拉伸温度的升高而增大。在热拉伸过程,架桥主要由片晶转化形成,与无定型分子链的二次结晶无关。     

双向拉伸α聚丙烯制备微孔膜的研究

通过不同的加工方式(淬火以及在80、100、120℃下等温结晶)制备出不同热历史的α聚丙烯。接着利用差示扫描量热仪和偏光显微镜研究其熔融行为和结晶形态,发现淬火样品结晶度和熔融温度最低,球晶最小;另一方面,随着等温结晶温度的升高,样品的结晶度和熔融温度逐渐升高,球晶尺寸逐渐增大。进一步对样品进行双向拉伸制备出微孔膜,扫描电子显微镜测试结果显示,淬火样品由于球晶强度较低,双拉后材料没有产生微孔;而等温结晶样品由于晶体强度较高、球晶界面较弱,双拉后产生了大量微孔,其孔径尺寸随等温结晶温度的升高逐渐增大,孔径分布均匀性优异。     

双向拉伸工艺对UHMWPE隔膜结构与性能的影响

研究了双向拉伸工艺如拉伸温度、拉伸倍数与拉伸速率对超高分子质量聚乙烯(UHMWPE)隔膜结构与性能的影响。结果表明:较低的拉伸温度与较快的拉伸速率更容易导致隔膜均匀拉伸,微孔分布变均匀;反之,较高的拉伸温度与较慢的拉伸速率会造成部分纤维束无法分离,隔膜结构均匀性变差;拉伸倍数增加,微孔结构逐渐被拉开,微孔分布变均匀,穿刺强度、横向/纵向拉伸强度增大。     

口模拉伸聚丙烯线材的性能

利用自行研制的口模拉伸装置制备聚丙烯自增强线材,通过二维广角X射线衍射仪(2D-WAXD)、差示扫描量热仪(DSC)考察自增强线材熔融、结晶行为、晶体取向度;研究了实际拉伸比与自增强线材拉伸强度的关联性;考察了拉伸温度、实际拉伸比与热收缩性的关联性。结果表明,拉伸温度、实际拉伸比越高,聚丙烯自增强线材内部形成的微纤结构越完善,结晶度越高,热收缩性越好;拉伸温度为70℃和90℃时,拉伸强度随实际拉伸比的提高先增大后减小;而拉伸温度为115、130和150℃时,拉伸强度随实际拉伸比的提高先增大后基本保持不变。     

聚四氟乙烯拉伸微孔膜的结构与性能

通过挤出、压延和拉伸等工序制备了聚四氟乙烯微孔膜，采用扫描电镜（SEM）分析了微孔膜的微观结构；采用差示扫描量热法（DSC）和广角X衍射（WXRD）表征了拉伸前后聚四氟乙烯结晶度的变化；研究了拉伸温度、拉伸倍率和拉伸速率对微孔膜力学性能的影响。结果表明：聚四氟乙烯微孔膜具有小岛状结点和与拉伸方向平行的微细纤维组成的微观结构；拉伸使PTFE的结晶度显著降低；拉伸工艺是制备微孔膜的关键因素，拉伸温度220～320℃，拉伸倍率为8倍时，微孔膜的最大拉伸强度可达8．5MPa；此外较大的拉伸速率可获得尺寸分布更均匀的微孔。     

聚乙烯薄膜拉伸过程中结构变化的原位研究

使用差示扫描量热分析(DSC)研究了其拉伸前后结晶动力学与热力学行为的区别,使用同步加速器小角X射线散射(SAXS)和广角X射线衍射(WAXD)研究了薄膜拉伸过程中晶体结构、尺寸和长周期的变化。结果表明,拉伸使薄膜结晶度提高;拉伸过程中,二维散射图案发生明显变化,片晶结构被破坏后高应力诱导下重新结晶,拉伸使薄膜晶体取向度和晶体尺寸明显增大;随拉伸进行,纵向(拉伸方向)和45°方向的长周期先增大后减小,而横向一直呈下降趋势。聚乙烯工业缠绕膜通常在拉伸应变1.5倍附近下使用,此时薄膜纵向上已经高度取向并形成了拉伸诱导结晶,从而在纵向上有较高的力学强度。而横向上片晶结构尚未完全破坏,仍保持着一定的力学性能,因此综合使用性能较好。     

拉伸热定型对PET-PA/PA6共混纤维结构与性能的影响

以聚酯-聚酰胺共聚物/聚酰胺6(PET-PA/PA6)共混物为原料,采用熔融纺丝法制备了PET-PA/PA6共混纤维,讨论了拉伸热定型工艺对PET-PA/PA6共混纤维结构与性能的影响。结果表明:随拉伸倍数的增大,PET-PA/PA6共混纤维的断裂强度、取向度、结晶度以及沸水收缩率均明显增大;拉伸温度和热定型温度对PET-PA/PA6共混纤维的断裂强度和取向度的影响相对较小;随拉伸温度的升高,PET-PA/PA6共混纤维的断裂强度、取向度和结晶度呈现先增大后减小的趋势,并在拉伸温度为85℃时出现最大值;随热定型温度的升高,PET-PA/PA6共混纤维的结晶度增大、沸水收缩率减小;较佳的工艺条件为拉伸倍数1.6,拉伸温度85℃,热定型温度150℃。     

双向拉伸聚乳酸薄膜的制备

以国产聚乳酸(PLA)和进口PLA为原料,进行双向拉伸PLA(BOPLA)薄膜的中试生产,研究了PLA干燥条件、PLA拉伸前后的性能变化,以及工艺参数对BOPLA薄膜性能的影响,并摸索BOPLA薄膜的最佳成型工艺条件。结果表明:PLA的最佳干燥条件是80℃干燥5 h;当温度升高时,经过拉伸的PLA厚片比未拉伸的PLA厚片更容易结晶。BOPLA薄膜成型的最佳工艺参数为:铸片辊温度20～25℃;纵向拉伸时,预热区温度40～75℃,拉伸区温度60～70℃,定型区温度20～30℃;横向拉伸时,预热区温度50～120℃,拉伸区温度60～130℃,定型区温度110～160℃;纵、横向拉伸比为3.0×3.0。     

双向拉伸聚氟乙烯薄膜的拉伸工艺研究

探讨了聚氟乙烯(PVF)流延膜在制备过程中常见的缺陷及产生原因,并给出了具体的加工工艺参数。结合PVF 薄膜的双向拉伸机理,通过力学及热性能测试表明:膜片的纵向拉伸温度为120～135℃,拉伸比为2.5～3.0时,薄膜不会出现细颈现象,且所需拉伸应力较小;当横向拉伸温度控制在130～150℃,拉伸比为2.5～3.5时,薄膜厚度介于23～28μm之间,且力学性能基本保持各向同性;双向拉伸的薄膜经过170～180℃热定型之后,横、纵向收缩率均小于2%,具有良好的尺寸稳定性。     

mPEG⁃PLA嵌段共聚物及其胶束的降解行为研究

采用开环聚合法制备了聚乙二醇单甲醚（mPEG）与D,L⁃丙交酯的嵌段共聚物,并以此共聚物为载体制备了紫杉醇胶束,研究了mPEG⁃聚丙交酯（PLA）与载药胶束（DMs）在不同条件下的降解特点。结果表明,在低温下（4 ℃）,mPEG⁃PLA聚合物和DMs均能长时间（24个月）保持稳定,未发生明显降解;当温度升高,mPEG⁃PLA和DMs降解速度明显增加,但降解机理有所不同,这种差异在40 ℃以上的环境中更明显;mPEG⁃PLA聚合物的高温（60 ℃）降解以链段内部无规则断裂为主,分子量显著降低;DMs在高温（60 ℃）下则更多遵循“末端降解机理”,生成更多的丙交酯和乳酸。     

双轴取向聚氯乙烯管材最佳拉伸温度和径向拉伸比的研究

以聚氯乙烯（PVC）树脂为主要原料，通过一步法挤出加工方式，采用纯净配方，在配方和轴向拉伸比不变的情况下，将拉伸温度设置为80、85、88、90 ℃，径向拉伸比设为1.8（坯料管外径63 mm、壁厚5.2 mm）和1.9（坯料管外径为60 mm、壁厚6.0 mm）制备双轴取向聚氯乙烯（PVC⁃O）管材。通过对不同工艺生产的管材进行静液压试验、落锤冲击试验、拉伸试验、环刚度试验来表征管材的力学性能。结果表明，适合此配方和轴向拉伸比的PVC⁃O管挤出成型的最佳拉伸温度为85 ℃，最佳径向拉伸比为1.9。     

Effect of processing on the crystalline orientation, morphology, and mechanical properties of polypropylene cast films and microporous membrane formation

Cast films of a high molecular weight linear polypropylene (L-PP) were prepared by extrusion followed by stretching using a chill roll. An air knife was employed to supply air to the film surface right at the exit of the die. The effects of air cooling conditions, chill roll temperature, and draw ratio on the crystalline orientation, morphology, mechanical and tear properties of the PP cast films were investigated. The crystallinity and crystal size distribution of the films were studied using differential scanning calorimetry (DSC). It was found that air blowing on the films contributed significantly to the uniformity of the lamellar structure. The orientation of crystalline and amorphous phases was measured using wide angle X-ray diffraction (WAXD) and Fourier transform infrared (FTIR). The amount of lamellae formation and long period spacing were obtained via small angle X-ray scattering (SAXS). The results showed that air cooling and the cast roll temperature have a crucial role on the orientation and amount of lamellae formation of the cast films, which was also confirmed from scanning electron microscopy (SEM) images of the films. Tensile properties and tear resistance of the cast films in machine and transverse directions (MD and TD, respectively) were evaluated. Significant increases of the Young modulus, yield stress, tensile strength, and tensile toughness along MD and drastic decreases of elongation at break along TD were observed for films subjected to air blowing. Morphological pictograms are proposed to represent the molecular structure of the films obtained without and upon applying air cooling for different chill roll temperatures. Finally, microporous membranes were prepared from annealed and stretched films to illustrate the effect of the PP cast film microstructure on the morphology and permeability of membranes. The observations of SEM surface images and water vapor transmission rate of the membranes showed higher pore density, uniform pore size, and superior permeability for the ones obtained from the precursor films prepared under controlled air cooling.     

温度对玻璃纤维增强聚合物筋与混凝土黏结性能影响试验研究

为研究不同温度及不同升温（单调升温和循环升温）、降温方式（单调升温⁃自然冷却和单调升温⁃快速冷却）对玻璃纤维增强聚合物（GFRP）筋与混凝土之间黏结性能的影响,选取2种黏结长度共90个GFRP筋⁃混凝土立方体试件在温度为20~220 ℃范围进行拉拔试验,并在同样温度条件下对54个混凝土立方体试件（单调升温、单调升温⁃自然冷却）进行抗压、抗拉强度测试。结果表明,2种升温方式下,GFRP筋与混凝土随温度升高黏结性能退化严重,温度低于120 ℃时,单调升温对黏结强度退化影响超过循环升温;温度超过120 ℃时,升温方式对黏结性能衰减程度影响减小;2种降温方式下,单调升温⁃快速冷却随温度升高黏结性能退化明显,单调升温⁃自然冷却影响轻微。     

Study of structure and properties of polypropylene microporous membrane by hot stretching

The polypropylene (PP) microporous membrane is prepared by only hot stretching of annealed PP film under different stretching rate and temperature. The structure and properties are compared with those by cold and hot stretching. The results show that apparent connecting bridges are observed on the surface of final microporous membrane only by hot stretching. With increasing stretching rate and decreasing stretching temperature, the pore size decreases and the air permeability becomes worse. The membrane only by hot stretching under 50 mm/min shows better lamellae separation, whereas under 10 mm/min the membrane gives lowest Gurley value. Compared with cold and hot stretching under the same stretching rate and whole stretching ratio, the membrane stretched only by hot stretching shows longer connecting bridges length, higher porosity and lower Gurley value. During only hot stretching, first the tie chains in the amorphous region are stretched. Then the combination of crystalline main lamellae and crystalline part formed during annealing is stretched and converted to connecting bridges. Through the control of stretching temperature and rate, PP microporous membrane with better permeability property can be obtained by only hot stretching, where room-temperature stretching is not needed. The obtained membrane can be used in Li-ion battery field as a separator, where the air permeability is an important technical parameter to characterize the Li-ion penetration ability through the separator.     

工艺条件对PBAT/PLA原位成纤共混体系结构与性能的影响

将质量比为80/20的PBAT/PLA共混物在单螺杆挤出流延成型机中通过调控工艺条件（口模温度、拉伸速度）直接熔融共混制备PBAT/PLA原位成纤共混薄膜。结果表明,在较低口模温度时,随着拉伸速度的提高,PLA微纤细化程度加大,结晶度先提高后降低,纵向拉伸强度先增加后减小,力学性能各向异性明显。在口模温度为150℃、拉伸速度为5.0 m/min时,共混体系中PLA成纤效果最明显;PBAT和PLA的结晶度最高分别为4.8%和23.7%;纵向拉伸强度达到29.8 MPa,比纯PBAT提高了41%。     

浸渍方式对纤维增强聚酰胺6复合材料真空袋压成型工艺及性能的影响

利用己内酰胺的阴离子聚合，采用真空袋压成型（VBPM）法制备了玻璃纤维（GF）增强聚酰胺6 （PA6/GF）复合材料，通过自行搭建的连续纤维增强聚酰胺6反应注射VBPM实验平台，考察了浸渍方式等参数对复合材料单体转化率、结晶度、力学性能的影响。结果表明，用等温浸渍制得的复合材料结晶度高，且内部均匀性较好；与等温浸渍相比，非等温浸渍制得的复合材料整体反应转化率和力学性能较高；非等温浸渍制得的复合材料出口的弯曲强度和剪切强度比入口分别提高了10 %~13 %和11 %~16 %，弯曲强度在150 ℃出口处达到最大值273.65 MPa，剪切强度在170 ℃出口处时达到最大值47.32 MPa。     

A study on the nonuniform deformation of PTFE membrane during its tentering transverse stretching

To understand the deformation of biaxially stretched polytetrafluoroethylene (PTFE) membrane during the tenter frame transverse stretching process, a finite element analysis (FEA) model was established to study the stress and displacement distribution during the transverse stretching. The morphology, pore size, and mechanical properties of the membrane were also characterized. It has been found from the experimental and FEA simulation results that the tentering transverse stretching of PTFE membrane is a nonuniform stretching, the stress and displacement distribution of the PTFE membrane during tentering is nonuniform because of the nonuniform deformation and the ease of yield and plastic deformation originated from the specific structure of the virgin PTFE particles. The nonuniform thickness and pore size distribution across the membrane width resulted from this nonuniform deformation was also characterized and discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

口模拉伸过程PP/CaCO3复合材料结构演变及机理

利用口模拉伸法制备了轻质、高强、高模的聚丙烯（PP）/碳酸钙（CaCO₃）复合材料，分析了口模拉伸对材料微观结构、晶体结构、热性能和密度的影响，揭示了口模拉伸过程中材料结构演变及其机理。结果表明，随着拉伸过程的进行，材料内的原始球晶向微纤状晶体转变，同时发生晶粒细化现象，结晶度增大表明存在拉伸诱导结晶现象。微孔尺寸的显著增大及材料密度的显著降低主要发生在材料离开收敛流道壁面后的自由拉伸过程中。     

A biaxial stretched β‐isotactic polypropylene microporous membrane for lithium‐ion batteries

In this article, microporous polypropylene (PP) membranes were produced with TMB‐5 as β‐crystal nucleating agent by biaxial stretching. Influences of different concentration of TMB‐5 were studied using differential scanning calorimetry and X‐ray diffraction. It was found that the highest crystallinity was reached when the nucleating agent content was 0.5 wt %. The effect of stretching temperature and stretching ratio on pore size distribution and porosity of the membranes were investigated by scanning electron microscopy and mercury porosimeter, respectively. And physical properties, such as tensile strength, permeability, and puncture resistance of the microporous membrane prepared at the optimized conditions, were evaluated. Compared with commercial PP separator membrane, the as‐prepared microporous membrane shows similar uniform pore size distribution and exhibits slightly higher porosity and ionic conductivities. When used as lithium‐ion separator, the experimental film shows more stable cycling performance than the commercial one. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45825.