Molecular orientation evolution during low‐density polyethylene blown film extrusion using real‐time Raman spectroscopy

Real‐time polarized Raman spectroscopy was used in this study to measure the molecular orientation evolution during blown film extrusion of low‐density polyethylene (LDPE). Spectra were obtained at different locations along the blown film line, starting from the molten state near the die and extending up to the solidified state near the nip rolls. The trans C C symmetrical stretching vibration of polyethylene (PE) at 1132 cm⁻¹ was analyzed for films possessing uniaxial symmetry. For the given peak, the principal axis of the Raman tensor is coincident with the c‐axis of the orthorhombic crystal, and was used to solve a set of intensity ratio equations to obtain second (〈P₂(cosθ)〉) and fourth (〈P₄(cosθ)〉) moments of the orientation distribution function. The orientation parameters (P₂, P₄) were found to increase along the axial distance in the film line even past the frost‐line height (FLH). The P₂ values also showed an increasing trend with crystalline evolution during extrusion, consistent with past observations that molecular orientation takes place even after the blown film diameter is locked into place. It was also found that the integral ratio (I₁₁₃₂/I₁₀₆₄) obtained from a single, ZZ‐back‐scattered mode can provide a reasonable estimate of molecular orientation. These results indicate the potential of real‐time Raman spectroscopy as a rapid microstructure monitoring tool for better process control during blown film extrusion. Copyright © 2008 John Wiley & Sons, Ltd.     

用光刺激放电法研究纳米粉末掺杂低密度聚乙烯中陷阱能级

通过光刺激放电(PSD)技术研究了纳米粉末掺杂低密度聚乙烯(LDPE)中的陷阱能级.利用连续扫描法得到了不同掺杂比例的Al₂O₃,MgO纳米粉末掺杂试样以及相同掺杂比例的多种纳米粉末掺杂试样的PSD电流谱,定性地得出了试样陷阱能级的深浅变化.分步扫描法定量地描述了LDPE试样在Al₂O₃纳米掺杂前后陷阱能量分布的变化.结果表明,掺杂比例大于0.2%的Al₂O₃纳米粉末掺杂、大于0.5%的MgO纳米粉末掺杂能够显著地使得LDPE陷阱能级变深.结合纳米掺杂对LDPE空间电荷注入影响的相关报道,可推测纳米掺杂对空间电荷注入的抑制与试样中陷阱能级变深存在密切的关联.     

入射电子能量对低密度聚乙烯深层充电特性的影响

高能带电粒子与航天器介质材料相互作用引起的深层带电现象, 一直是威胁航天器安全运行的重要因素之一. 考虑入射电子在介质中的电荷沉积、能量沉积分布以及介质中的非线性暗电导和辐射诱导电导, 建立了介质深层充电的单极性电荷输运物理模型. 通过求解电荷连续性方程和泊松方程, 可以得出不同能量 (0.1–0.5 MeV) 电子辐射下, 低密度聚乙烯 (厚度为1 mm) 介质中的电荷输运特性. 计算结果表明, 不同能量的电子辐射下, 介质充电达到平衡时, 最大电场随入射能量的增加而减小; 同一能量辐射下, 最大电场随束流密度的增大而增加. 入射电子能量较低时 (≤ 0.3 MeV) , 最大电场随束流密度的变化趋势基本相同. 具体表现为: 当束流密度大于3× 10^-9 A/m²时, 最大场强超过击穿阈值2×10⁷ V/m, 发生静电放电 (ESD) 的可能性较大. 随着入射电子能量的增加, 发生静电放电 (ESD) 的临界束流密度增大, 在能量为0.4 MeV时, 临界束流密度为6×10^-8 A/m². 当能量大于等于0.5 MeV时, 在束流密度为10^-9–10^-6 A/m²的范围内, 均不会发生静电放电 (ESD) . 该物理模型对于深入研究深层充放电效应、评估航天器在空间环境下 深层带电程度及防护设计具有重要的意义. 关键词： 高能电子辐射 低密度聚乙烯(LDPE) 介质深层充电 电导特性     

低密度聚乙烯热压成型过程中的空间电荷

借助开路热刺激放电(TSD)电流及原位实时电荷TSD和电荷等温衰减测量，研究了低密度聚乙烯(LDPE)在热压成型过程中所产生的空间电荷特性.结果表明具有良好室温稳定性的成型电荷被束缚在两类陷阱能级中：浅阱和深阱，其陷阱中心深度分别约为0.92eV和1.31eV.初步的分析进一步表明了它们应该分别位于试样的表层和体内，为近表面陷阱和体陷阱. 关键词： 低密度聚乙烯(LDPE) 热压成型 空间电荷 热刺激放电(TSD)     

Stretched exponential kinetics for photoinduced birefringence in azo dye doped PVA films

We fabricated azo dye (methylorange) doped poly vinyl alcohol (MO/PVA) thin films and measured the photoinduced birefringence (PIB) kinetics for several pump beam intensities and for various MO concentrations by using the pump-probe technique. A novel approach to explain the transient behaviors of the photoinduced anisotropy is presented by employing an empirical stretched exponential time response in the course of the trans-cis-trans photoisomerization of azo molecules and is compared with the experimental data, showing excellent agreement. The stretched exponent is estimated to be β = 0.34 ± 0.04, revealing amorphous nature of the MO/PVA system.     

线性低密度聚乙烯中空间电荷陷阱的能量分布与空间分布的关系

使用激光感应压力波法和热刺激放电技术,系统地研究了直流高压作用下线性低密度聚乙烯(LLDPE)半导性电极试样中空间电荷的形成和演变及电荷陷阱分布和退极化过程.在直流高压作用下试样中空间电荷的分布明显地表现为两电极同极性电荷快速对称注入的特征,半导性电极与LLDPE的界面近乎呈现欧姆接触特征.LLDPE中的电荷陷阱分布表现出体内为浅陷阱、表层为深陷阱的特征.半导性电极与LLDPE薄片间的压合条件或电极材料对LLDPE表层的掺杂显著地影响表层陷阱的能量分布,导致表层中较深陷阱的深度和密度减小、较浅陷阱的密度增大.在整个短路退极化过程中,试样中正、负电荷的中心分别向距它们较近的电极迁移,而在开路退极后期则表现为与短路时不同的行为、被表层深陷阱再俘获的电荷脱阱后向背电极迁移. 关键词： 线性低密度聚乙烯 空间电荷 陷阱分布 热刺激放电     

Effect of γ-radiation on the birefringence of stretched polyethylene films

The spectral dependences of the birefringence and of the retardance of polyethylene films of thickness 67 μm exposed to γ-radiation doses up to 500 kGy are studied in the spectral range 400–700 nm. It is shown that the characteristics of polymeric polarization elements could be controlled by irradiation processes.     

Improved measurements of thermally induced birefringence effects in a laser material using a half-wave plate

The polarization dependence of a probe beam for use in measuring thermally induced birefringence effects in a laser-diode end-pumped Nd:YAG ceramic laser has been investigated. The variation in intensity of the probe beam was found to be 10.2% for a linearly polarized probe beam, 20.6% for a circularly polarized probe beam, and 31.4% for a circularly polarized probe beam using a half-wave plate with a pump power of 12 W. The angle between the analyzer and the inclination of the major axis of the elliptical polarization with respect to the x axis was controlled using a half-wave plate. By combining a half-wave plate with a circularly polarized probe beam, the variation in intensity increased compared with conventional methods.     

体心立方多晶膜中应变能密度的各向异性分析

根据弹性理论和多晶膜的屈服强度公式，计算了附着在基体上体心立方多晶薄膜中不同取向晶粒中的应变能密度.结果表明：1）在屈服之前，对Fe和Ta两种薄膜，4个最小的应变能密度对应的晶粒取向依次为（100），（510），（410）和（511）；对Cr，Mo，Nb和V四种薄膜，4个最小的应变能密度对应的晶粒取向依次为（111），（332），（322）和（221）；对W膜，应变能密度与晶粒取向无关.2）在屈服的体心立方多晶膜中，4个最小的应变能密度对应的晶粒取向依次为（100），（111），（110）和（411）.从 关键词： 体心立方多晶薄膜 晶粒取向 应变能密度 织构     

面心立方多晶薄膜中应变能密度对晶粒取向的依赖

对附着在基体上面心立方多晶薄膜中不同取向晶粒的应变能密度进行了计算.结果表明:在屈服之前,5个最小的应变能密度对应的晶粒取向依次为(100),(510),(410),(511)和(310);在屈服膜中,5个最小的应变能密度对应的晶粒取向依次为(110),(100),(511),(411)和(211).仅考虑应变能,这些取向的晶粒将依次优先生长 关键词： 薄膜 应变能密度 晶粒生长     

低密度聚亚胺酮泡沫的制备

确定了以1,4-二氧六环为溶剂体系,经热致相分离和冷冻干燥技术制备了低密度聚亚胺酮泡沫,分析了其质量浓度对泡沫密度的影响,结果显示:泡沫实验密度与聚合物浓度有较好的线性关系,可实现对泡沫密度的有效控制。差示扫描量热法、热重法等热性能测试结果表明:聚亚胺酮泡沫材料的热分解行为与本体材料一致,但玻璃化温度较本体材料玻璃化温度高。泡沫孔结构测试结果表明:随着密度的增加,平均孔径有降低的趋势,孔径分布趋于单一化。对其力学性能进行分析可知:所制备的泡沫硬而强,具有较高的模量和抗压强度,断裂压缩随密度增加而增加。随着泡沫密度的增加,其破坏形变随之增加。     

低密度对二乙烯基苯泡沫的优化制备

针对惯性约束聚变(ICF)物理实验对具有微加工能力低密度CH泡沫材料的需求,介绍了对二乙烯基苯泡沫的高内相乳液（HIPE）法制备工艺,并讨论了引发剂含量、乳化剂含量、苯乙烯的比例和无机添加剂等对泡沫形貌结构的影响,获得了低密度对二乙烯基苯泡沫的优化制备配方。不同密度对二乙烯基苯泡沫的形貌结构、力学性能和加工性能的表征结果表明：所得泡沫由开孔状球形孔构成,球形孔的直径在1~10 μm之间,孔壁上具有直径为0.2~2.0 μm的圆形孔洞结构;在密度为50 mg/cm3时,泡沫具有5 MPa的弹性模量;通过微加工技术能够获得ICF所需柱状和片状低密度泡沫微靶样品,样品最小尺寸可达100 μm。     

低密度对二乙烯基苯泡沫的优化制备

针对惯性约束聚变(ICF)物理实验对具有微加工能力低密度CH泡沫材料的需求,介绍了对二乙烯基苯泡沫的高内相乳液(HIPE)法制备工艺,并讨论了引发剂含量、乳化剂含量、苯乙烯的比例和无机添加剂等对泡沫形貌结构的影响,获得了低密度对二乙烯基苯泡沫的优化制备配方。不同密度对二乙烯基苯泡沫的形貌结构、力学性能和加工性能的表征结果表明:所得泡沫由开孔状球形孔构成,球形孔的直径在1～10μm之间,孔壁上具有直径为0.2～2.0μm的圆形孔洞结构;在密度为50mg/cm3时,泡沫具有5MPa的弹性模量;通过微加工技术能够获得ICF所需柱状和片状低密度泡沫微靶样品,样品最小尺寸可达100μm。     

溅射条件对Ni80Fe20薄膜各向异性磁电阻的影响

研究了基片温度和溅射气压对磁控溅射方法制备的Ni80Fe20磁性薄膜各向异性磁电阻的影响.实验发现基片温度是影响Ni80Fe20薄膜各向异性磁电阻最重要的因素.在较高的基片温度下,溅射气压对Ni80Fe20薄膜各向异性磁电阻也有较大的影响.基片温度在150~180℃,溅射气压在0.3~0.5 Pa范围内制备的Ni80Fe20薄膜有较大的各向异性磁电阻(3.7%~4.3%).     

Ion tracks in ultrathin polymer films: The role of the substrate

Surface damage produced by single MeV-GeV heavy ions impacting ultrathin polymer films has been shown to be weaker than those observed under bulk (thick film) conditions. The decrease in damage efficiency has been attributed to the suppression of long-range effects arising from excited atoms lying deeply in the solid. This raises the possibility that the substrate of the films itself is relevant to the radiation effects seen at the top surface. Here, the role of the substrate on cratering induced by individual 1.1 GeV Au ions in ultrathin poly(methyl methacrylate) (PMMA) layers is investigated. Materials of different thermal and electrical properties (Si, SiO₂, and Au) are used as substrates to deposit PMMA thin films of various thicknesses from ∼1 to ∼300 nm. We show that in films thinner than ∼40 nm craters are modulated by the underlying substrate to a degree that depends on the transport properties of the medium. Crater size in ultrathin films deposited on the insulating SiO₂ is larger than in similar films deposited on the conducting Au layer. This is consistent with an inefficient coupling of the electronic excitation energy to the atomic cores in metals. On the other hand, the damage on films deposited on SiO₂ is not very different from the Si substrate with a native oxide layer, suggesting, in addition, poor energy transmission across the film/substrate interface. The experimental observations are also compared to calculations from an analytical model based on energy addition and transport from the excited ion track, which describe only partially the results.     

低密度聚亚胺酮泡沫的制备

确定了以1,4-二氧六环为溶剂体系,经热致相分离和冷冻干燥技术制备了低密度聚亚胺酮泡沫,分析了其质量浓度对泡沫密度的影响,结果显示：泡沫实验密度与聚合物浓度有较好的线性关系,可实现对泡沫密度的有效控制。差示扫描量热法、热重法等热性能测试结果表明：聚亚胺酮泡沫材料的热分解行为与本体材料一致,但玻璃化温度较本体材料玻璃化温度高。泡沫孔结构测试结果表明：随着密度的增加,平均孔径有降低的趋势,孔径分布趋于单一化。对其力学性能进行分析可知：所制备的泡沫硬而强,具有较高的模量和抗压强度,断裂压缩随密度增加而增加。随着泡沫密度的增加,其破坏形变随之增加。     

Accurate determination of polyethylene pellet density using transmission Raman spectroscopy

In this study, transmission Raman spectroscopy was explored for the direct measurement of the density of packed polyethylene (PE) pellets. A simple and direct transmission Raman measurement of packed, solid granules or pellet samples without pretreatment is greatly advantageous. Initially, the optimal packing thickness of PE pellets for transmission Raman measurement was determined by investigating the reproducibility of triplicate spectra collected by varying the thickness from 2 to 9 cm. Once determined, transmission Raman spectra were collected for 25 different grades of PE pellets and the partial least squares method was used to determine the sample density. The resulting accuracy was 0.00067 g·cm⁻³, while that obtained using backscattering measurements was 0.00083 g·cm⁻³. To investigate possible inhomogeneity within a pellet, Raman line mapping was performed over the face of a sectioned pellet and spectral variations among the mapped spectra were examined using principal component analysis. In addition, differential scanning calorimetry was performed on three samples prepared separately by cutting a pellet into left, middle, and right sections. Based on both studies, internal pellet inhomogeneity was found to be minute, but was clearly present. The correct sample representation of internally inhomogeneous PE pellets by the transmission Raman measurement eventually improved the accuracy for density determination. Finally sample‐to‐sample two‐dimensional correlation analysis was used to further examine the origin of the improved accuracy. Copyright © 2011 John Wiley & Sons, Ltd.     

Optical and magnetic properties of porous anodic alumina films embedded with Co nanowires

A simple method to tune the optical properties of porous anodic alumina （PAA） films embedded with Co nanowires （PAA@Co nanocomposite films） is reported in this paper. The films exhibit vivid structural colors and magnetic properties. The optical properties of the films can be effectively tuned by adjusting the thickness of the PAA template. The deposition of Co nanowires greatly increases the color saturation of the PAA films. The theoretical results of the changes in structural color according to the Bragg-Snell formula are consistent with the experimental results. PAA@Co films can be used in many areas, including decoration, display, and multifunctional anti-counterfeiting applications.     

基于密度泛函理论的外电场下盐交联聚乙烯分子的结构及其特性

交联聚乙烯是主要的高压电缆绝缘材料.为了研究外电场对盐交联分子结构的影响,本文对Zn原子使用def2-TZVP基组, C, H, O原子使用6-31G(d)基组,运用明尼苏达密度泛函(M06-2X)对交联聚乙烯分子进行优化得到了它的稳定结构.并研究了不同外电场(0—0.020 a.u., 1 a.u.=5.142×10~(11)V/m)作用下盐交联聚乙烯分子结构和能量变化,外电场对前线轨道的能级和成分的影响,原子之间的键级、断键和红光光谱的变化.研究结果表明:随着电场的增大,交联聚乙烯分子从空间网状结构逐渐变成线性结构,总能量降低,但势能增大,偶极矩和极化率升高,交联聚乙烯分子的稳定性随着电场的增大而降低;最高占据轨道能级持续增大,最低空轨道能级从0.011 a.u.电场开始持续降低,能隙持续降低,临界击穿场强为11.16 GV/m;沿电场方向聚乙烯链端表现出亲核反应活性,它的C—C键更容易断裂,形成甲基碳负离子,逆电场方向聚乙烯链端表现出亲电反应活性,它的C—H键更容易断裂形成H正离子;分子红外光谱高频区吸收峰明显红移,低频区吸收峰既有红移又有蓝移.     

The Rayleigh law in silicon doped hafnium oxide ferroelectric thin films

A wealth of studies have confirmed that the low‐field hysteresis behaviour of ferroelectric bulk ceramics and thin films can be described using Rayleigh relations, and irreversible domain wall motion across the array of pining defects has been commonly accepted as the underlying micro‐mechanism. Recently, HfO₂ thin films incorporated with various dopants were reported to show pronounced ferroelectricity, however, their microscopic domain structure remains unclear till now. In this work, the effects of the applied electric field amplitude, frequency and temperature on the sub‐coercive polarization reversal properties were investigated for 10 nm thick Si‐doped HfO₂ thin films. The applicability of the Rayleigh law to ultra‐thin ferroelectric films was first confirmed, indicating the existence of a multi‐domain structure. Since the grain size is about 20–30 nm, a direct observation of domain walls within the grains is rather challenging and this indirect method is a feasible approach to resolve the domain structure. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)