陶瓷/VDF-TrFE 0-3型铁电复合物的三阶非线性介电系数

在自建的非线性介电测试装置上测得了PT,BT、PZT和VDF-TrFE共聚物形成的0-3型铁电复合物厚片的三阶非线性介电系数ε3.研究发现,三种复合物的ε3都随陶瓷组分含量的上升而增大.测试场强升高,测得的ε3值减小,但对高陶瓷含量(φ＞0.4)的BT/VDF-TrFE和PZT/VDF-TrFE复合物则在6MV/m场强下出现极小值.二相都被预极化的复合物小于仅陶瓷相被预极化的ε3值.PZT/VDF-TrFE复合物的温度依赖关系显示了与(-阶)介电系数类似的表观热滞后现象.高PZT含量的复合物在相变区出现较大的ε3值.     

接枝共聚法制备聚乙二醇(PEG)/聚乙烯醇(PVA)高分子固-固相变材料性能研究

用接枝共聚法将具有相变特征的聚乙二醇(PEG)接枝到具有较高熔点的聚乙烯醇(PVA)主链上,得到了系列性能稳定的PEG/PVA高分子固-固相转变材料,用DSC,WAXD和POM对其相变行为及形态结构进行了研究.结果表明,该材料呈现出可逆的固-固相转变特性;其结晶峰值温度和相变焓比纯PEG低,接枝率对相变温度和归一化相变焓影响不大;接枝率只影响结晶与熔融行为,不影响结晶结构.     

丙烯酸共聚物囊壁的正十八烷微胶囊的制备和性能表征

以二丙烯酸1,4-丁二醇酯为交联剂, 成功制备了甲基丙烯酸甲酯-甲基丙烯酸共聚物为壁材, 正十八烷为囊芯的相变材料微胶囊. 采用扫描电子显微镜(SEM)、差示扫描量热仪(DSC)和热重分析仪(TG)分别考察了单体与芯材投料比、单体浓度和交联剂的含量对微胶囊形貌、相变热性能、热稳定性能的影响. 实验结果表明: 随着单体与芯材投料比或单体浓度的增加, 微胶囊表面均变得致密, 壁厚增加; 随着交联剂含量的增加, 微胶囊的表面变得更加致密光滑, 热稳定性显著增强; 随着单体与芯材投料比的增大, 微胶囊热焓值减小, 被包裹的囊芯含量减少.     

抗冲共聚聚丙烯的结晶与相形态

用POM、DSC、WAXD、DMA、AFM对两种乙烯含量、相对分子量及其分布、橡胶相含量几乎完全相同的、韧性差异很大的抗冲共聚聚丙烯(IPC)的结晶、相形态进行了研究.实验结果表明,两者的结晶形态、结晶行为相似.相比IPC-B,IPC-A中分散相和基体的相容性较好.IPC基体、分散相的组成分析发现,分散相的外层为软的乙丙无规共聚物(EPR),内部为硬的聚乙烯(PE)晶区,构成一种复杂的包藏结构.IPC的增韧效果主要来自于相形态和分散状况的贡献.提出了IPC的相结构模型,以描述IPC多相体系的相结构及两种IPC中E-b-P的作用与差异.     

钛酸铅与偏氟乙烯-三氟乙烯共聚物形成的铁电复合物相变过程的热释电研究

研究了偏氟乙烯-三氟乙烯共聚物与钛酸铅形成的铁电复合物PT/P[VDF(70)-TrFE(30)]的热释电流行为。P[VDF(70)-TrFE(30)]室温下存在两个铁电相,即较无序的铁电相和较有序的铁电相,升温经过各自的相转变点后转变成较有序的顺电相和较无序的顺电相。热释电流谱上出现在95℃和108℃的两个电流峰,分别由两个铁电相的结构陷阱以及部分取向的偶极所贡献。采用Tc以上温度极化并冷却到不同温度的方法可明确鉴别出该试样两个顺电相降温转变过程,转变点分别为62℃和50℃。实验证实陷阱仅存在于铁电相而不存在于顺电相中。钛酸铅的引入虽不导致新电流峰出现,但可使共聚物的Tc降低、电流加大。热释电流方法可非常灵敏地跟踪铁电共聚物的相变过程。     

聚对二氧环己酮/聚乙二醇多嵌段共聚物的合成与表征

首先合成双端羟基的聚对二氧环己酮预聚物(PPDO)和双端羧基的聚乙二醇预聚物(PEG),然后以丁二酸酐/二环己基碳二亚胺(DCC)将PPDO与PEG偶联共聚,得到PPDO/PEG多嵌段共聚物.通过1H-NMR和GPC表征了聚合物的结构和分子量.采用差示扫描量热法(DSC)和热重分析(TGA)研究了共聚物的结晶性能和热稳定性.用透析法制备了共聚物纳米粒子,并用动态光散射(DLS)表征了共聚物纳米粒子的粒径及分散度,结果表明,随着共聚物亲水链段PEG含量的增加,其纳米粒子更易形成,粒子粒径随共聚物分子量增大而增大.     

多晶Ni-Mn-Ga磁性记忆合金的相变行为及稀土元素铽的作用

研究了Ni50Mn25 xGa25-x 和Ni50Mn29Ga21-xTbx 2种成分系列磁性记忆合金的相变行为. 保持Ni含量不变, 增加Mn, 降低Ga含量会使马氏体相变温度明显提高, 同时相变滞后温区减小, 居里温度基本不变. 如果添加稀土元素铽, 相变温度继续升高, 居里温度仍然不变, 材料继续保持强的铁磁性及热弹性马氏体相变的特征.     

含mPEG侧链的水溶性梳状聚合物的合成及其侧链受限结晶行为研究

采用大单体与小单体共聚的技术,通过自由基引发溶液聚合,合成了一系列水溶性梳状聚合物———聚丙烯酸接枝聚乙二醇单甲醚(PAA-g-mPEG).制备过程分两步进行,首先合成大单体聚乙二醇单甲醚丙烯酸酯,然后将大单体与丙烯酸单体共聚,合成了梳状聚合物.通过控制反应条件,获得了一系列主链和支链组成比不同的接枝共聚物.用傅立叶变换红外光谱(FT-IR)和核磁共振氢谱(1H-NMR)表征了共聚物的结构,并对其侧链的结晶行为进行了研究.采用差热扫描量热法(DSC)表征并分析了不同侧链长度的mPEG的热性能及其结晶情况.利用相差显微镜和原子力显微镜(AFM)观察薄膜的结晶形貌,表明梳状聚合物的侧链mPEG在受限条件下的薄膜结晶形貌为高度支化的晶体,初步分析了mPEG链长及其在共聚物中的重量百分含量对晶体形貌的影响.     

聚乙二醇/二醋酸纤维素相变材料的组成与储能性能间的关系

以刚性的二醋酸纤维素 (CDA)链为骨架 ,接枝上聚乙二醇 (PEG)柔性链段 ,可得到一种具有固固相变性能的网状储能材料 .利用该材料的PEG支链从结晶态到无定形态间的相转变 ,可以实现储能和释能的目的 .具体研究了PEG的百分含量及PEG的分子量对材料储能性能的影响 .研究结果表明 ,通过改变PEG的百分含量与PEG的分子量 ,可以得到不同相变焓和不同相变温度的材料     

SiO2粒子对PMMA/SAN共混体系相分离行为的影响

采用小角激光光散射(SALLS)并结合动态流变学方法,考察了气相法二氧化硅(SiO2)粒子的加入对聚甲基丙烯酸甲酯/苯乙烯-丙烯腈无规共聚物(PMMA/SAN)共混体系相行为的影响,得到了添加SiO2粒子前后的相图,发现SiO2粒子对基体相行为的影响与基体的组成有关.对PMMA/SAN(60/40)体系,加入SiO2粒子后相分离温度上升,但并未改变相分离机理,仍为亚稳单相分解过程(spinodal decomposition,SD);而对于PMMA/SAN(30/70)体系,加入SiO2粒子后却降低了体系的相分离温度.该现象可能是SiO2粒子和基体组分界面间组成与PMMA/SAN共混物基体组成的差异造成的.     

Curie transition,ferroelectric crystal structure,and ferroelectricity of a VDF/TrFE(75/25) copolymer 1. The effect of the consecutive annealing in the ferroelectric state on curie transition and ferroelectric crystal structure

We have completely deconvoluted multiple ferroelectric-to-paraelectric phase transitions of a VDF/TrFE copolymer often observed on DSC by consecutive annealing below the Curie transition temperature and obtained three clear endothermic peaks resolved well from each other. We could also increase the Curie transition temperature by using the consecutive annealing performed in the ferroelectric state. Annealing time, as well as annealing temperature, was found to affect the Curie transition behavior significantly. Each ferroelectric crystalline phase was characterized by IR, Raman scattering, x-ray diffraction, and DSC measurements. The ferroelectric phase, having higher Curie transition temperature, has been found to have more trans sequences and less gauche defects and to require larger thermal energy for the Curie transition. © 1994 John Wiley & Sons, Inc.     

聚乙二醇单甲醚(MPEG)/聚乙烯醇(PVA)高分子固-固相变材料的合成与性能

高分子固-固相转变材料是近年来新兴的课题,其主要优点是体积变化小,发生相转变时不出现液态,可以减少对容器的要求,甚至不需要容器即可把相变材料作为结构材料,可简化工艺和降低成本,我们相继合成了系列聚乙二醇／聚乙烯醇高分子固-固相变材料,由于形成交联网络结构,难溶于一般有机溶剂。     

Poling influence on the mechanical properties and molecular mobility of highly piezoelectric P(VDF‐TrFE) copolymer

The calorimetric, dielectric, and mechanical responses of highly piezoelectric 70/30 P(VDF‐TrFE) displaying homogenous d₃₃ of ?19 pC N^?1 are studied. This work aims at better understanding the influence of poling on the mechanical properties of this copolymer. To explain the one decade mechanical modulus drop observed across the Curie transition, a stiffening process of the amorphous phase due to the local electric fields in the ferroelectric crystals is proposed. In poled P(VDF‐TrFE), these fields are preferentially aligned resulting in a more stable and higher modulus below the Curie transition. This hypothesis accounts for the lower dielectric signals obtained with the poled sample. Through the Curie transition, the vanishing of these local electric fields, stemming from progressive disorientation and conversion of ferroelectric crystals to paraelectric ones, releases the constraints on the amorphous phase, leading to a storage modulus drop typical of a viscoelastic transition. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 1414–1422     

Spectroscopic studies on the effect of field strength upon the curie transition of a VDF/TrFE copolymer

Infrared spectroscopic studies of the effects of field strength upon the ferroelectric phase transition behavior of a VDF/TrFE (75/25) copolymer upon heating and cooling in an electric field have revealed new findings. The paraelectric phase in the absence of an electric field resembles the α phase of PVDF with a trace of short trans sequences distributed randomly along the chain axis. The paraelectric phase in a high electric field is very different from that in the absence of an electric field. The paraelectric phase under an electric field has much longer trans sequences. The Curie transition temperature upon heating is a first-order transition temperature (T^↑_c) and is dramatically elevated from 120 to 135°C under the field of more than 0.4 MV/cm. Upon cooling, the paraelectric phase in an electric field does not show a clear transition. The field-induced phase transition and the loss of dipole switchability observed below a cooling temperature of 120°C, and their dependence on time and filed strength when exposed to a cyclic bipolar electric field are discussed. © 1993 John Wiley & Sons, Inc.     

相容剂对PP/POE共混体系脆韧转变行为的影响

采用熔融挤出法制备了不同相容剂含量的PP/POE共混体系,测试了不同体系的脆韧转变温度、热性能和力学性能.结果表明,乙烯-丙烯多嵌段共聚物相容剂的加入降低了PP/POE共混物的脆韧转变温度,提高了共混物的韧性.AFM和STEM照片显示相容剂的加入减小了橡胶分散相的临界粒子间距,PP和POE在两相界面结合处相互扩散或渗透,实现了POE弹性体在PP树脂中合适的尺度分布以及良好的形态分散.当相容剂含量达到10％时,POE分散相尺寸细小均匀,分散相粒子粒径为0.54μm,粒子间距为0.1 μm,PP结晶链段更多地插入到弹性体内部,弹性体POE分散相形成明显的“硬核-软壳”结构.DSC曲线中结晶峰和熔融峰的变化说明适量的相容剂对于材料结晶度的提高具有一定的促进作用.力学性能测试结果可以看出相容剂的加入在提高材料韧性,降低其脆韧转变温度的同时也保持了材料的刚性性能.     

弛豫基铁电单晶0.91Pb(Zn1/3Nb2/3)O3-0.09PbTiO3的制备与 性能研究

用改进的Bridgman法,在加入助熔剂的条件下,生长出最大尺寸为φ30×25mm^3的铌锌酸铅-钛酸铅固溶体单晶[0.91Pb(Zn1/3Nb2/3)O3-0.09PbTiO3]。无宏观缺陷的晶片的典型尺寸为20×15mm^2。晶体的单晶性及其结构用X射线衍射法加以研究。所得晶体用Laue衍射法定向,取(001)晶片进行性能表征。研究了材料的介电性能,并用偏光显微镜观察了(001)晶片的电畴结构。结果表明,室温下材料的介电常数较大,为2500～5000。随着温度的升高,材料发生四方铁电相—立方顺电相的相变,相变温度为190℃左右。单晶的介电温谱呈现明显的频率色钐现象,同时,介电常数最大值的温度tm随着频率的升高而降低,观察到了电畴结构的不均匀与孪生现象。     

Synergistic effects on polyurethane/lead zirconate titanate/carbon black three-phase composites

Synergistic processes in hybrid composites have frequently been described in the literature over the past few years, opening doors to new studies and applications for this type of material. In this study, three-phase composites were obtained using polyurethane (PU) as the matrix, lead zirconate titanate (PZT) as the ferroelectric ceramic and carbon black (CB) as the conductive phase. The discussion is primarily focused on a comparison of the electrical, thermal and dielectric properties of three-phase composites with those of PU_CB and PU_PZT biphasic composites. The study describes a synergistic effect between the PU/PZT/CB phases involved in the generation of charges between the particles, implying better homogeneity of the composites as well as influence over the PU crystallization. The PU_CB conductivity profile showed a phenomenon of multi-step percolation thresholds attributed to the molecular structure and repulsive surface charge of CB particles. The surface charge phenomenon restricted the percolation curve analysis of the three-phase composites by means of classic percolation theory, shown by distortion of the critical exponents. The dielectric constant three-phase composites increased gradually as a function of CB in accordance with the percolation profile.     

Time‐resolved wide‐angle X‐ray scattering measurements during the isothermal crystallization and ferroelectric phase‐transition processes of a vinylidene fluoride/trifluoroethylene copolymer

The time‐resolved measurement of wide‐angle X‐ray scattering was performed with a synchrotron radiation source during the processes of the isothermal crystallization and ferroelectric phase transition of a vinylidene fluoride/trifluoroethylene copolymer with 73 mol % vinylidene fluoride. When the sample was cooled rapidly from the melt to the temperature region of the paraelectric high‐temperature phase, the peak position of the 200/110 reflection shifted toward the higher angle side and the half‐width became narrower. This indicated an increase in the crystallite size with a more compact chain‐packing mode. Even when the temperature jump was made from the melt into the region of the ferroelectric or low‐temperature phase, the crystallization of the high‐temperature phase was first observed before the appearance of the low‐temperature phase. This was consistent with a prediction based on the so‐called Ostwald state rule: the thermodynamically unstable but kinetically preferable high‐temperature phase can appear first even when the thermodynamically more stable low‐temperature phase should be created. The time‐dependent intensity changes were analyzed with the Avrami kinetic equation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4175–4181, 2004     

Compaction of TiO2 suspension utilizing hydrophilic/hydrophobic transition of cationic thermosensitive polymers

Compaction of TiO2 suspended particles utilizing the hydrophilic/hydrophobic transition of a cationic thermosensitive copolymer of N-isopropylacrylamide (NIPAM) and N-dimethylaminopropylacrylamide (DMAPAA) was examined. The surface of suspended TiO2 particles were sufficiently covered with the adsorbed polymer molecules at room temperature, and the suspension was subsequently heated above the transition temperature of the polymer. The thrusting motion of a plunger was used in order to provide an adequate mechanical force to compact the TiO2 suspended particles. The transition temperature was dependent on the DMAPAA content in the copolymer and the pH of the suspension. The transition temperature increased with increasing DMAPAA content and decreased with increasing pH. While suspended TiO2 particles were not compacted with poly(NIPAM), hard compacted sludge was readily obtained for cationic copolymer even if the content of DMAPAA groups was as low as 0.23 mol%. Furthermore, residual polymer molecules in the supernatant were not detected even if the polymer dosage was increased. These findings were attributed to the hydrophobic interaction of thermosensitive copolymer molecules adsorbed on TiO2 particles.