超高分子量聚乙烯熔体流动性改性研究进展

介绍了超高分子量聚乙烯(PE–UHMW)的性能及成型方法,针对PE–UHMW熔体流动性差的缺点,综述了近年来PE–UHMW熔体流动改性所取得的新进展,分析了改性的原理,并指出了今后的发展方向。     

模压成型工艺对PE–UHMW结晶度和耐磨性能的影响

在3.6 MPa的初始模压压力下,分别改变模压温度、模压时间和冷却方式对超高分子量聚乙烯(PE–UHMW)进行了模压成型,研究了PE–UHMW模压成型工艺对其结晶度和耐磨性能的影响。结果表明,在不同的模压温度或模压时间下,PE–UHMW结晶度与耐磨性能的变化没有理想的对应关系;但从整体结果可以得出,较高模压温度或较长的模压时间会导致PE–UHMW结晶度降低,耐磨性能变差。模压温度为230℃、模压时间为30 min时,PE–UHMW的耐磨性能最好。不同冷却方式对PE–UHMW结晶度的影响较小,对耐磨性能的影响较大。采用较低的冷却速率并在PE–UHMW结晶温度下保温30 min,可以得到耐磨性能优异的PE–UHMW。     

尼龙6改性超高分子量聚乙烯

采用挤出成型工艺制备了尼龙6(PA6)改性超高分子量聚乙烯(PE–UHMW)共混材料。研究了PA6含量对PE–UHMW/PA6共混材料热性能及力学性能的影响。研究表明,PA6质量分数为30%时维卡软化温度达到145.9℃,较纯PE-UHMW提高了14℃,邵氏硬度达到69,较纯PE-UHMW提高了15%;共混材料的缺口冲击强度随PA6质量分数的增加而降低,在PA6含量不变的条件下,添加适量的增容剂能够改善共混材料的缺口冲击强度。同时结合DSC测试共混材料中PE–UHMW的结晶度与对共混材料的微观形貌扫描观察,进行了PE–UHMW与PA6的作用机理分析。     

PE–UHMW抗弹复合材料及其在防护领域中的应用

根据超高分子量聚乙烯(PE–UHMW)抗弹复合材料中PE–UHMW增强体宏观结构形式的不同,概述了以纤维织物、纤维UD材料、高度取向薄膜材料为主体结构的3种PE–UHMW抗弹复合材料研究与应用现状,展望了其国内外发展趋势。     

超临界CO_2微孔发泡PE–LLD/PE–UHMW共混物

研究了线型低密度聚乙烯(PE–LLD)/超高分子量聚乙烯(PE–UHMW)共混物的超临界CO2微孔发泡行为,探讨了PE–UHMW含量、发泡温度和饱和压力对泡孔形貌的影响。采用差示扫描量热仪和旋转流变仪对PE–LLD及其共混物的热性质和流变性质进行了测试和表征,并通过扫描电子显微镜表征和分析了发泡样品的泡孔形貌。结果表明,少量PE–UHMW的加入可以显著降低PE–LLD发泡样品的孔径,增加孔密度。随着发泡温度的升高,PE–LLD样品的泡孔结构会发生塌陷现象,而加入少量PE–UHMW可以提高基体的黏度,起到支撑孔壁防止塌陷的作用,并最终得到均匀的开孔结构。另一方面,当温度一定时,饱和压力升高可以降低孔径并且得到开孔形貌的泡孔结构。     

超高分子量聚乙烯膜的制备及研究进展

介绍了超高分子量聚乙烯(PE–UHMW)膜材料的国内外发展现状,总结了PE–UHMW膜材料的制备方法及其研究进展,简述了其应用领域,并指出了今后的发展方向。     

纳米抗静电无卤阻燃PE–UHMW复合材料的研制

利用偶联接枝对纳米炭黑粒子表面处理,通过反应型增容载体载附纳米炭黑,将处理后的纳米炭黑及纳米复配阻燃剂用于改性超高分子量聚乙烯(PE–UHMW),制备出纳米抗静电无卤阻燃PE–UHMW复合材料。通过体积电阻率测试、燃烧性能测试、热重分析及扫描电子显微镜分析对该材料的导电性能、阻燃性能、热性能等进行了研究。结果表明,纳米炭黑分布在PE–UHMW球晶间缝隙处和球晶内微纤间缝隙处的非晶区内,形成了纳米级双导电网络,这种立体穿插纳米尺度均匀分布,在低炭黑含量情况下就形成稳定的导电通路,起到了抗静电作用;制备的纳米抗静电无卤阻燃PE–UHMW复合材料,其燃烧时形成高效、致密、厚实的炭层,可有效地隔绝空气,起到阻燃作用。     

高抗冲高模量聚碳酸酯复合材料的制备

以α–磷酸锆(α–Zr P)为刚性研磨介质,超高分子量聚乙烯(PE–UHMW)为抗冲改性剂,聚碳酸酯(PC)作为基体材料,通过母粒法(两步熔融共混法)制备了高抗冲高模量复合材料。研究了PE–UHMW添加量及几种无机填料对复合材料力学性能及微观结构的影响。结果表明,当PE–UHMW含量为8份、α–Zr P含量为2份时,复合材料的冲击强度、弯曲弹性模量达到最大值。α–Zr P的加入还使复合材料的其它力学性能得到了一定程度改善。经扫描电子显微镜分析表明,α–Zr P的加入起到了助分散的作用,促进了PE–UHMW在基体树脂中的均匀分散,所以冲击性能得到进一步提高。     

PE-UHMW分子量及其分布表征技术进展

针对常规分子量表征手段很难用于超高分子量聚乙烯(PE–UHMW)的分子量测试现状,综述了PE–UHMW分子量分布及其大小测试方法。PE–UHMW分子量分布可以通过以下方式实现:利用不同温度时溶解性不同实现分离,利用凝胶色谱柱实现分离,利用运动速度与分子量之间的关系实现分离。PE–UHMW分子量测试目前主要有黏度法、凝胶色谱连用技术、流变仪法等,其中黏度法在实际生产中得到了广泛应用,但这种方法重复性差,其可靠性和准确性还不稳定。     

结晶条件对超高分子量聚乙烯熔融再结晶行为的影响

应用常压差示扫描量热(DSC)仪和高压DSC仪研究了熔融温度、熔融时间、冷却速率以及压力对不同分子量的超高分子量聚乙烯(PE–UHMW)熔融再结晶行为的影响。常压DSC的研究表明,随着熔融温度、熔融时间以及冷却速率的增加,PE–UHMW的结晶峰值温度(Tc)逐渐下降。在相同的熔融温度和熔融时间下,PE–UHMW的Tc随分子量的增加而逐渐增加,但在所研究的冷却速率范围内(2.5～40℃／min),在相同的冷却速率下,Tc随分子量的增加变化不大。高压DSC的研究结果表明,结晶过程中增加压力导致PE–UHMW的Tc有所下降,并且结晶峰半峰宽变大。     

Improvement of the mechanical properties of an ultrahigh molecular weight polyethylene fiber/epoxy composite by corona‐discharge treatment

The interfacial shear strength of an ultrahigh molecular weight (UHMW) polyethylene (PE) fiber/epoxy‐resin system was greatly improved by the corona‐discharge treatment of the fiber. The UHMW PE‐fiber/epoxy‐resin composite was prepared with corona‐discharge‐treated UHMW PE fiber. The mechanical properties of the composite sheet were determined by tensile testing. The tensile strength of the composite was also very much improved. However, the tensile strength of the composite was about one‐half of the theoretical strength. This result was due to the molecular degradation of the PE‐fiber surface caused by surface modification. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1162–1168, 2001     

Effect of high-energy radiation on the uniaxial tensile creep behaviour of ultra-high molecular weight linear polyethylene

The tensile creep (and other tensile) properties of ultra-high molecular weight polyethylene (UHMW PE) have been determined before and after electron beam irradiation and compared with similar results on normal molecular weight high-density polyethylene (NMW PE). In both polymers, irradiation increases the tensile modulus and the yield stress whilst reducing creep. The major effects occur over the first 20 MRad irradiation dose, though creep strain continues to diminish with dose in UHMW PE up to 64 MRad. Most of the effects can be attributed to crosslinking in the amorphous phase, though the rise in yield stress seems to require crosslinking in the crystalline phase, and the initial rise in modulus in UHMW PE seems to reflect a rise in crystallinity. Comparison with other polymers shows that the creep behaviour of UHMW PE remains relatively poor, even after irradiation. The improvements obtained may, however, be significant in applications where creep resistance is of secondary importance compared with, say, impact and wear resistance, in which UHMW PE excels.     

干法工艺制备PE–UHMW纤维

采用干法纺丝工艺,以超高分子量聚乙烯(PE–UHMW)纤维专用树脂为原料,制备高性能PE–UHMW纤维,通过电子拉力机、扫描电子显微镜、差示扫描量热仪对不同后拉伸倍率的纤维进行力学性能和微观结构分析。结果表明,随着拉伸倍率的增加,纤维初生丝结晶度由49.57%逐渐提高至72.17%,拉伸倍率50倍以后,结晶度逐渐趋于平稳;随着拉伸倍率的增加,纤维的力学性能逐渐增强,在拉伸倍率达到83.3倍时,纤维的力学性能达到最佳,纤维断裂强度为31.53 c N/dtex,断裂伸长率为2.69%,断裂模量为1 054.78 c N/dtex;纤维微观表面结构也发生有规律的变化。     

Mechanical properties of polyethylene mixtures crystallized under high pressure

The mechanical properties of a medium molecular weight polyethylene (MMW‐PE) and an ultrahigh molecular weight PE (UHMW‐PE) binary mixture with different weight fractions crystallized from the melt at 0.1 and 450 MPa were studied. The tensile modulus, yield stress, and strain were obtained as a function of the weight fractions in the PE mixtures at 25 and 85°C. The tensile modulus in the sample crystallized at 0.1 MPa decreased from 1.5 GPa of pure MMW‐PE to about 0.4 GPa of pure UHMW‐PE with the UHMW‐PE content but it did not decrease with the UHMW‐PE in the sample crystallized at 450 MPa in testing at 25°C. A decreasing rate of the storage modulus E′ of UHMW‐PE in a dynamic measurement for the sample crystallized at 0.1 MPa with the temperature is larger than that of the sample crystallized at 450 MPa. These experimental facts are interpreted in relation to the molecular motion and crystallinity of the sample. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1962–1968, 2003     

Elongational viscosity for miscible and immiscible polymer blends. II. Blends with a small amount of UHMW polymer

The effect of miscibility on elongational viscosity of polymer blends was investigated in homogeneous, miscible, and immiscible states by the blend of 1.5 wt % of ultrahigh‐molecular‐weight (UHMW) polymer. The matrix polymer was either poly(methyl methacrylate) (PMMA), or poly(acrylonitrile‐co‐styrene) (AS) that has a comparable elongational viscosity value. The homogeneous blend consisted of 98.5 wt % of PMMA and 1.5 wt % of UHMW–PMMA. The miscible blend was composed of AS and UHMW–PMMA at the same ratio. The immiscible blend was a combination of AS and UHMW–polystyrene (PS) at the same ratio. The strain‐hardening behavior of the different blends were compared with that of pure PMMA. It was demonstrated that 1.5 wt % of UHMW induces a strong strain‐hardening property in the homogeneous and miscible blends but was hardly changed in the immiscible blend. The optical microscope observation of the immiscible blend suggested that the UHMW domains were stretched, but that the degree of domain deformation was less than a given elongational strain. It was concluded that the strain‐hardening property is strongly affected by the miscibility of UHMW chain and matrix. The strong strain‐hardening property is caused by the deformation of the UHMW polymer. UHMW chains are stretched when they are entangled with surrounding polymers. However, UHMW chains in an immiscible state are not so deformed because of viscosity difference and no entanglements between domain and matrix. A smaller degree of UHMW chain deformation in immiscible state results in weaker strain‐hardening property. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 961–969, 1999     

Disentangled State in Polymer Melts; a Route to Ultimate Physical and Mechanical Properties

The role of entanglements in obtaining a homogeneous product of ultra high molecular weight polyethylene (UHMW‐PE) has been explored. Studies performed in this report show that a disentangled state before melting is a prerequisite to obtain homogeneous products of an intractable polymer like UHMW‐PE. The disentangled state is obtained directly from the reactor by controlling the polymerisation conditions or in the solid state when there is enhanced chain mobility along the c‐axis of a unit cell. The disentangled state is maintained in the melt over a period of time, invoking implications in polymer rheology. This approach is applicable to polymers in general. The homogeneous fully sintered UHMW‐PE, obtained for the first time, shows a considerable decrease in oxygen permeability, and increase in toughness and fatigue resistance. Such homogeneous products of UHMW‐PE are of beneficial in highly demanding applications, especially in knee‐prosthesis, where the polymer is used as an inlay between the human bone and a metal or ceramic part, which slides against the polyethylene component during normal gait.

Phase diagram for the extended chain crystals.     

UHMW PE/PP共混改性体系研究(Ⅱ)

制备了UHMW PE/PP合金材料,研究了UHMW PE/PP共混体系的流动性和力学性能及相容剂对共混体系的增容作用,研究表明:PP能有效地改善UHMW PE流动性,但与UHMW PE为不相容体系,相容剂D能够有效提高UHMW PE/PP体系的相容性,提高了材料的拉伸强度和冲击强度,达到一定的增强和增韧效果。     

超倍热拉伸PE–UHMW干法纤维的结构与性能

以黏均分子量为600万的超高分子量聚乙烯(PE–UHMW)树脂为原料,通过干法路线纺丝制备出了具有较高拉伸性能的PE–UHMW纤维。测试研究了纤维在热拉伸过程中的力学性能变化,发现纤维在拉伸40倍时断裂强力出现最大值。利用动态扫描量热、X射线衍射、扫描电子显微镜表征了PE–UHMW纤维在拉伸过程中结构变化,分析了结构变化对力学性能的影响,发现过高的拉伸倍数反而会破坏纤维的结晶结构从而导致断裂强力的下降。最后对热拉伸中纤维微观结构变化机理进行了推导。