Effect of ionic liquid on chain segment motion and charge detrapping in poly(l-lactide)/ionic liquid composites

The effect of ionic liquid on the chain segment motion and charge detrapping in poly(l-lactide) (PLA)/ionic liquid (IL) composites has been investigated by means of thermally stimulated depolarization current (TSDC), scanning electron microscopy, and differential scanning calorimetry. There are four current peaks (namely, α, ρ₁, ρ₂, and ρ₃ peaks, respectively) in TSDC spectra of PLA and PLA/IL composites. The α peak corresponds to the glass transition, the ρ₁ peak is attributed to space charge trapped in the amorphous phase, the ρ₂ peak is originated from space charge trapped in the interphase that includes PLA/IL interface and crystalline/amorphous interface of PLA, and the ρ₃ peak is originated from space charge trapped in the crystalline phase. With the increase of IL content from 0 to 5phr, ρ₂ and ρ₃ peaks gradually merge into one single peak. By analyzing the characteristic parameters of these peaks, it is found that IL can accelerate the mobility of chain segments and increase structural defects in PLA/IL composites. In addition, IL decreases the stability of trapped charge in both amorphous and crystalline phases, but not affecting the stability of trapped charge in interphase.     

The Chain Segment Motion and Traps in γ‐Irradiation Crystalline Nylon 1010

The chain segment motion, charge trapping and detrapping in γ‐irradiated nylon 1010 films (doses in the range 0–2,000 kGy were used) have been investigated by means of thermally stimulated depolarization current (TSDC). There are three current peaks (named α, ρ₁ and ρ₂, respectively) in the TSDC spectra, corrected by spontaneous current, above room temperature. By analyzing the characteristic parameters of the three peaks, it is found that the chain segment motion in the amorphous regions becomes more difficult at low irradiation dose (<100 kGy) and then becomes easier with further increasing irradiation dose. The stability of the traps at the crystalline‐amorphous interfaces increases at low irradiation dose (<500 kGy) and then decreases with further increasing irradiation dose; the irradiation promotes the creation of traps and the stability of traps in the crystalline regions.     

Effect of Polarization Temperature on the Chain Segment Motion and Space Charge Detrapping in Polyamide 610 Film Electrets

The effect of polarization temperature on the chain segment motion and charge trapping and detrapping in polyamide 610 films has been investigated by means of thermally stimulated depolarization current (TSDC) and wide-angle X-ray diffraction (WAXD). A small part of the amorphous phase of quenched polyamide 610 changes into the crystalline state with increasing polarization temperature. There are three current peaks (named α, ρ₁, and ρ₂ peak, respectively) in the TSDC spectra. The α peak corresponds to the glass transition, the ρ ₁ peak is attributed to space charge trapped in the amorphous phase, and interphase between crystalline and amorphous phases, and the ρ ₂ peak originates from space charge trapped in the crystalline phase. By analyzing the characteristic parameters of these peaks, it was found that the increase of polarization temperature induced a decrease of the chain segment mobility and promoted the creation of structural traps in polyamide 610. The decrease of the chain segment mobility in the amorphous phase made the intensity of the α peak weak and the activation energy increased. The higher the polarization temperature, the higher the degree of crystallinity and the more charge carriers trapped in the crystalline phase. So, the increase of polarization temperature made the intensity of the ρ ₂ peak strong and increased the stability of trapped charge in the crystalline phase. The increase of polarization temperature also made the intensity of the ρ ₁ peak strong and decreased the stability of trapped charge in the amorphous phase and interphase.     

Effect of heating treatment on trap level distribution in polyamide 66 film electrets

The effect of heating treatment on the trap level distribution in polyamide 66 film electret is studied by thermally stimulated depolarization current （TSDC） technique. For annealed polyamide 66, there are three trap levels that respectively originate from space charge trapped in amorphous phase, interphase and crystalline phase. There is one peak that originates from space charge trapped in amorphous phase for quenched one. Using multi-point method to fit the experimental curves, the detrapping current peaks can be separated and the trap depth is obtained. The shallower trap levels trapped in amorphous phase and interphase are obviously close to the deeper trap level trapped in crystalline phase for annealed polyamide 66 as the polarization temperature increases, while the trap level distribution remains unaffected by polarization temperature for quenched one.     

退火与极化温度对尼龙11薄膜驻极体内陷阱能级分布的影响

用热释电技术研究了尼龙11薄膜驻极体制备过程中热处理与极化温度对驻极体陷阱能级分布的影响.结果显示，淬火驻极体的热释电流谱上存在四个空间电荷退陷阱电流峰，而在退火处理后则显示两个退陷阱电流峰.采用多点法对热释电流谱进行理论拟合可以将各个退陷阱电流峰分离并得到它们的陷阱深度参数.这些参数进一步表明，淬火尼龙11薄膜驻极体内存在四个空间电荷的陷阱能级，极化温度升高对它们的分布情况影响不大；退火处理后，陷阱能级减少为两个，且随着极化温度的升高，较浅的陷阱能级有明显向较深陷阱能级接近的趋势. 关键词： 尼龙11 薄膜驻极体 热释电 热处理     

Investigation of Pendant Group and Chain Segment Motions in P(MMA/BA) Copolymers by Thermally Stimulated Depolarization Current

Poly(methyl methacrylate/butyl acrylate) [P(MMA/BA)] copolymers (M_η ～2×10⁵) with different mass percentages of MMA were synthesized by the method of solution polymerization. Thermally stimulated depolarization current (TSDC) technique was used to investigate the effect of copolymerization on pendant group and chain segment motions. Three TSDC peaks were observed over the temperature range from 310 to 400 K. The highest temperature, ρ peak originates from the detrapping of trapped charge carriers. The lower temperature, α peak corresponds to the glass transition. The activation energy of the α relaxation decreases from 1.2 eV for PMMA to 0.98 eV for MMA(75)/BA(25). In the fitting process, another peak, β′, is separated on the low temperature side. The apparent energy barrier of the β′ for PMMA is 0.80 eV. The β′ relaxation is thought to correspond to the motion of pendant groups including intra‐ and inter‐molecular interactions. All three peaks move to lower temperatures with an increase in BA component, and the activation energy for the α and β′ relaxations also decreases with the increase of BA component in copolymers, indicating that the flexible side groups of BA have an effect of plasticization on the glass transition and motion of pendent groups. The temperatures of the α and β′ peaks of P(MMA/BA) copolymers follow the Fox equation. Fitting results gives the α peak at 238 K and β′ peak at 225 K for polybutyl acrylate (PBA).     

Investigation of MWS Relaxation in Nylon 1010 using Dielectric Relaxation Spectroscopy

Maxwell–Wagner–Sillars (MWS) relaxation in nylon 1010, arising from charge carriers accumulated at the interphase between amorphous and crystalline regions, has been investigated by means of dielectric relaxation spectra. In the frequency spectra of nylon 1010, dielectric permittivity showed high values at low frequencies originating from charge carrier movement. For the MWS relaxation, the dielectric strength was independent of temperature. The results revealed that there is a transition temperature, located between 110 and 120°C, resulting in the separation of two different charge carrier movement mechanisms. Below and above this transition temperature, the temperature dependence of the MWS relaxation time follows the Vogel–Tammann–Fulcher type, showing that the charge carrier transport is governed by the motion of the polymer chains. The change of charge carrier movement mechanisms is due to the onset of polymer chain motion in the interphase.     

Heat treatment effects on dielectric and physico-chemical properties of an epoxy polymer

Infrared (IR) spectroscopy, dielectric spectroscopy (DS), and thermally stimulated depolarization current (TSDC) have been used to study heat treatment effects on an epoxy-based polymer. Variations in physico-chemical and dielectric properties were examined for annealing temperatures between 55 and 170 °C. IR results have shown that heating causes both chain scission and thermal oxidation of the polymer, increasing thus the amount of trapped charges. The complex dielectric permittivity and the dielectric modulus have been analyzed, by means of DS, to highlight and separate charge relaxation phenomena from conduction contributions. Results indicate structural rearrangements, leading to a decrease of dipolar relaxation frequency (from 16 to 13.5 kHz) and an increase of the relaxation strength (around 20%). TSDC measurements have shown a current peak shift towards higher temperatures, and a significant intensity decrease, which is proportional to the quantity of released charges.     

Thermally stimulated depolarization currents and ionic conductivity of cubic lead fluoride containing small rare earth ions

Abstract

This work is concerned with thermally stimulated depolarization current (TSDC) and ionic conductivity studies in lead fluoride containing the small rare earths Dy, Ho, Er and Yb. The TSDC scans from 80 to 300 K show two peaks. For Pb_1?xEr_xF_2+x one is located at 106 K, and another, which is much stronger, occurs at about 160 K. The former is associated with a dipolar defect containing at least two rare earths and the latter is attributed to the development of F^? space charge during polarization of the sample. The activation energies obtained from both the high temperature TSDC peak and the ionic conductivity are the same, which corroborates the latter assignment. In addition, the ionic conductivity is shown to be independent of concentration. Those results can be understood of rare earth clustering, which is either absent or is unobservable dielectrically for large rare earths such as lanthanum, occurs extensively even at very low concentrations of the small rare earths. The explanation is that the majority of fluorine charge compensators are trapped by clusters.     

Luminescence excitation and its relation to the structures of natural crystalline diamond and diamond-like films

The luminescence excitation spectra (LES) of natural crystalline diamond and amorphous diamond-like films are measured at energies from 4 to 20 eV at the LOCUS station for luminescence and optical studies of the Kurchatov Institute synchrotron radiation source. Two sharp peaks at 5.5 and 10.5 eV are observed in the LES of diamond, while the LES of the film demonstrate only one peak at 10.5 eV. For crystalline diamond, the peaks can be explained within the framework of the diamond band structure and the processes of inelastic scattering of photoexcited holes. Dark-field electron microscope images of the diamond-like film show that, in spite of its amorphous structure, this film contains regions of coherent electron scattering whose dimensions are on the order of 2–5 nm, which is sufficient to describe the film LES using a model for crystalline diamond. The absence of the first peak in the film LES is related to the fact that the absorption coefficient of diamond is very small at 5.5 eV and radiation is only slightly absorbed by the thin film.     

A method for correlating charge traps of polypropylene to its morphology

A method for differentiating charge traps in amorphous parts from those in crystalline parts of crystalline polymers was proposed and applied it to polypropylene (PP) charge traps. The proposed method is combined use of two techniques: organic solvent vapor-induced charge decay (OSVICD) and partial neutralization (PN), slight recharging with the counter corona charges. From thermally stimulated current (TSC) spectra of OSVICD- and PN-treated PP, the shallow and deep charge traps were correlated to the trap sites existing in the amorphous and crystalline regions of PP, respectively. From TSC spectra of PN-treated PP, it was found that in the surface region the ratio of charges existed in the deep traps to those in the shallow ones was about 87% while in the bulk region it was 48%. This fact is consistent with crystalline-rich surface nature of the sample films, which was revealed by the usual transmission and ATR infrared spectroscopic analyses.     

聚合物材料空间电荷陷阱模型及参数

采用电声脉冲测量技术研究了直流电场下低密度聚乙烯材料的电荷入陷和脱陷特征. 发现在不同电场周期下样品的电荷衰减呈现不同的特征, 为此提出了一个简单的基于两陷阱水平的入陷和脱陷模型, 并计算了相应的参数, 如陷阱能级和密度. 确定了不含任何添加剂的低密度聚乙烯样品中存在的两种水平的陷阱能级分别为: 较浅陷阱能级0.77–0.81 eV 对应的浅陷阱电荷密度为(1.168–1.553)× 10¹⁹ m^-3; 较深陷阱能级0.96–1.01 eV 对应的深陷阱电荷密度为(1.194–4.615)× 10¹⁸ m^-3. 最后初步验证了材料的深陷阱能级和对应的深陷阱电荷密度随老化而增加, 可考虑将模型中的两能级陷阱参数作为老化诊断特征参量. 关键词： 聚合物 空间电荷 陷阱 老化     

Liquid–Liquid Transition and Detrapping of Trapped Carriers of P(MMA/BA) Copolymers by Thermally Stimulated Depolarization Current

Poly (methyl methacrylate/butyl acrylate) [P(MMA/BA)] copolymers (M _η～2×10⁵) with different mass percentages of PMMA (100/0, 90/10, 81/19, and 75/25), were synthesized by the method of solution polymerization. In addition to the normal α and ρ peak, a third τ peak is observed in thermally stimulated depolarization current (TSDC) spectra of the copolymers in the high temperature region. The α peak‐corresponds to the glass transition, the ρ peak originates from the detrapping of trapped carriers in the bulk amorphous structure related with flexible side groups, and the τ peak can be attributed to the charge detrapping related to the liquid–liquid transition of the copolymers. The three peaks all move to lower temperature with an increase of the BA component, indicating that the flexible side groups of butyl acrylate not only have an effect of plasticization on the glass transition and liquid–liquid transition, but also make the trap depth shallower and the detrapping process easier for the ρ and τ peaks. The experimental results confirm that TSDC analysis is very sensitive for investigating the liquid–liquid transition of polymers. The liquid–liquid transition temperature (T _LL) of the copolymers follows a type of the Fox equation. Fitting the results gives a T _LL of 102°C for polybutyl acrylate.     

The effect of electric field stress on pure poly(vinyl chloride), poly(methyl methacrylate) and their polyblend samples

The TSDC and transient currents measurement have been carried out on pure poly(vinyl chloride), poly(methyl methacrylate) and polyblends of various weight ratios as a function of electric fields at constant poling temperature. For PVC and different blend samples single peak in the temperature range 100–170 °C has been observed in TSDC thermograms, however, for PMMA samples two peaks were observed at around 90 and 165 °C. The various TSDC parameters i.e. activation energy, charge released and relaxation times have been calculated. Results suggest that dipolar and space charge mechanism are dominant for observed current.     

Dielectric relaxation investigations of 100 MeV Ag-ion-irradiated polyetherimide using thermally stimulated discharge current techniques

The thermally stimulated discharge current technique (TSDC) has been used to elucidate various dielectric relaxation processes in 100 MeV Ag-ion-irradiated polyetherimide (PEI). The irradiated PEI samples (85 μm thickness, area 0.12 cm²) were polarized at different temperatures ranging from 50–200 °C under various biasing fields (50–300 kV/cm). TSDC spectra, in general, consist of four current maxima namely γ, β, α and ρ in ascending order of temperature, appearing around 40, 110, 200 and 230 °C, respectively. The origin of γ - and β -peaks has been attributed to the dipolar nature of ether linkages and carbonyl groups, respectively, whereas α- and ρ-maxima have been attributed to the space charge polarization process. The absence of γ-peak in irradiated samples is attributed to the significant loss in ether linkages due to irradiation. The free radical formation, demerization of carbonyl groups and cross-linking of imide groups due to ion irradiation in PEI have been held to be responsible for the behavior of these relaxation processes. In the vicinity of the β-relaxation, a new relaxation process, termed δ-relaxation, is also observed.     

以能带理论诠释直流聚乙烯绝缘中空间电荷的形成和抑制机理

高压直流塑料交联聚乙烯电缆的研发难点是消除其中的空间电荷效应. 目前, 国内外学者普遍通过添加纳米粒子在聚乙烯体内形成深陷阱捕获电荷的机理来抑制电荷积聚, 但此抑制机理违背了电场的基本理论. 以能带理论全面阐述聚合物介质中空间电荷的形成和抑制机理, 从一级陷阱模型出发, 应用电荷入陷和脱陷动力方程, 推导了聚合物介质中空间电荷的形成过程. 在聚合物介质中引入深陷阱后, 介质Fermi能级位移, 电极与介质之间界面接触由Ohm接触转变为阻塞接触. 考虑到无定形相中大量的陷阱密度, 电荷耗尽区宽度小于100 Å, 电极与介质之间的界面对电子变得透明, 形成中性接触, 在电压作用下, 这种聚乙烯介质中不再可能形成空间电荷. 最后, 在纯聚乙烯和纳米改性后含有深陷阱的聚乙烯两种试样上, 分别测量了电导与电场强度的关系和空间电荷分布曲线, 实验结果符合理论推导. 关键词： 直流绝缘 能带理论 空间电荷 抑制机理     

Thermally Stimulated Depolarization Current and Thermal Analysis Studies of Gamma Irradiated Lithium‐Salt/Polymer Electrolyte Blends

Thermally stimulated depolarization current (TSDC) and thermal analysis studies of gamma irradiated LiOH/PVA blends were done. To study the mechanisms of conduction and TSDC in poly(vinyl alcohol) (PVA) and LiOH/PVA blends, short circuit TSDC at a polarizing temperature 353 K with a polarizing field of 3 kV cm^?1 have been analyzed in the temperature range 300–410 K. Two peaks are evident from the global TSDC measurements on the pure PVA homopolymer. Meanwhile, in all blended samples; there is only one broad peak with a shoulder on the high temperature side due to the relaxation of the poly‐blend system. The temperature dependence, 300–408 K, of the current density (J) for pure PVA and its blended samples has been studied. It was observed that J values increase dramatically with increasing temperature (in the low temperature region from 300–340 K) owing to the formation of local ordered regions in the otherwise disordered amorphous matrix of PVA. Further increase in the temperature caused a marginal increase in J values. The temperature dependence of the specific heat for all samples was measured. A linear increase of C _p was observed with an increase in temperature, which is ascribed to the increase in lattice vibration of linear macromolecules and consequently, increases in the number of internal degree of freedom of phonons.     

聚丙烯孔洞铁电驻极体膜的电极化及其电荷动态特性

根据栅控恒压电晕充电组合反极性电晕补偿充电法的实验结果计算出铁电驻极体的极化强度.结果说明，伴随着薄膜内孔洞气体的Paschen击穿，该铁电体的极化强度随栅压增加而显著上升.利用上述充电方法和热刺激放电(TSD)谱的分析讨论了这类空间电荷型宏观电偶极子，及与其补偿的空间电荷热退极化的电荷动态特性；阐明了这两类俘获电荷的能阱分布，即构成宏观电偶极子的位于孔洞上下介质层内的等值异号空间电荷分别被俘获在深、浅两种能值陷阱内，而位于薄膜表面层的注入空间电荷则被俘获在中等能值陷阱中. 关键词： 反极性电晕补偿充电法 铁电驻极体 充电电流 热刺激放电     

A facile synthesis about amorphous CoS<Subscript>2</Subscript> combined with first principle analysis for supercapacitor materials

The structure and electrochemical properties of amorphous CoS₂ and crystalline CoS₂ have been studied with both experimental characterization and theoretical calculations. In the field of experimental characterization, a facile chemical precipitation method is used to synthesize amorphous and crystalline CoS₂ samples with calcining temperatures of 200 and 280 °C, respectively. Comparing with crystalline CoS₂, amorphous structure of CoS₂ manifests great electron conductivity, effective porous structure, and exhibit a high specific capacitance of 996.16 F g^?1 at current density of 0.5 A g^?1, excellent rate capability of 89.8% retention with the current density ranging from 0.5 to 5 A g^?1, and a great cycling stability of 97.6% retention after 10,000 cycles at 2 A g^?1 in 6 mol L^?1 KOH aqueous electrolyte. In the area of theoretical calculation, we used the first principle and obtained the band structure with band gap of 0.00369 eV and DOSs with high locality of D-orbital from 69.88689 electrons/eV main peak, in the CoS₂ amorphous. The result confirms that amorphous CoS₂ have higher conductivity than crystalline CoS₂ in theory. In addition, the as-assembled asymmetric supercapacitor of Co-S-200//AC also exhibits the maximum specific capacitance of 104 F g^?1 within a cell voltage from 0 to 1.5 V at current density of 0.5 A g^?1 and indicates a great cycling stability of 95.68% and excellent capacitance behavior. All results demonstrate a great potential of amorphous CoS₂ active material for supercapacitors.     

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)