母料制备纳米CaCO3/PP复合材料的结晶性能

本文用溶液法制备的不同单体改性PP包覆纳米CaCO3母料制备纳米CaCO3/PP复合材料,用DSC和POM研究了复合材料中PP的结晶与熔融行为及结晶形态.研究结果表明改性复合材料中PP的结晶温度与单体类型和用量有关.单体的极性增加,异相成核作用越强.除马来酸酐外,反应单体改性对PP熔融温度影响不大,但峰形不同.丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸甲酯、马来酸酐和苯乙烯改性更有利于形成β晶,β晶熔融峰的强度与单体类型有关;但丙烯酸改性无β晶形成.改性复合材料的球晶明显变小.     

大分子相容剂改性纳米CaCO3 / PP复合材料的非等温结晶行为

熔融混炼制备了4 种大分子相容剂改性的纳米CaCO₃ / PP 复合材料, 用DSC 和WXRD 研究了复合材料中PP 的结晶与熔融行为。结果表明, 纳米CaCO₃对PP 结晶存在异相成核作用, 并诱导PP 形成β晶。相容剂丙烯酸接枝聚丙烯( PP-g-AA) 和马来酸酐接枝聚丙烯( PP-g-MA) 也存在异相成核作用, 提高PP 结晶温度。PP-g-AA、PP-g-MA 和马来酸酐接枝乙烯2辛烯共聚物(POE-g-MA) 与纳米CaCO₃存在异相成核协同作用, 进一步提高PP 的结晶和熔融温度, PP-g-MA 和POE-g-MA 还促使纳米CaCO₃诱导PP 生成β晶。但马来酸酐接枝乙烯2醋酸乙烯酯共聚物( EVA-g-MA) 则阻碍纳米CaCO₃对PP 的异相成核作用。实验结果表明纳米CaCO₃ / PP 复合材料中PP 结晶的异相成核作用与纳米CaCO₃ / PP 界面的相互作用有关, 而纳米CaCO₃ / PP 界面的相互作用与相容剂的结构有关。      

PP/POE共混物的热行为与晶态结构

采用双螺杆挤出机熔融共混制备了不同组成的聚丙烯(PP)/乙烯-辛烯弹性体(POE)共混物,利用差示扫描量热仪、偏光显微镜和广角X射线衍射系统研究了共混物的热行为与晶态结构。结果表明PP与POE之间具有一定的相容性,POE的异相成核作用提高了共混物中PP的结晶温度和结晶速率,有效地诱导β晶型PP的形成,增大了共混物中α晶型和β晶型PP的晶面表观厚度。另一方面,由于POE与PP之间存在较强的相互作用,POE大分子链使PP分子链的扩散和堆积受阻,从而导致PP/POE共混物总结晶度的降低。     

苯乙烯与丙烯酸改性PP/PS共混物的相形态与动态力学性能

制备了反应性单体(S t、AA)改性PP/PS共混物,用TEM、SEM、POM和DM A研究了改性对PP/PS共混物的相结构与动态力学性能的影响。结果表明,反应单体存在异相成核作用与增容作用,并促进PS在PP中的分散,分散相粒子尺寸和PP球晶尺寸明显变小,AA的异相成核作用比S t的大。反应性单体改性提高共混物的储存和损耗模量,AA单体改性共混物的储存模量(E′)和损耗能量(E″)比S t改性的高。     

从β-聚丙烯到β-聚丙烯共混物

相对于聚丙烯(PP)共混物,β-PP共混物研究很少。文中对本实验室近几年开展的β-成核PP与聚苯乙烯(PS)、丙烯腈-苯乙烯共聚物(AS)、丙烯腈-丁二烯-苯乙烯共聚物(ABS)、尼龙(PA)、对苯二甲酸乙二醇酯(PET)共混物的制备、结构与性能进行了总结。重点讨论了不同第二组分及其用量、结晶度与极性,增容和制备方法等对PP共混物的β-成核作用的影响。观察到PS、AS和ABS对β-成核作用影响很小,可获得高β-晶含量的PP共混物。β-成核PP与PA、PET共混物的β-成核作用取决于制备方法,降低PET结晶度的方法和加入相容剂有利于共混物β-晶的形成。第二组分极性并不是影响共混物β-成核作用的主要因素。     

聚丙烯接枝马来酸酐改性纳米ZnO/聚丙烯复合材料的成核结晶行为及力学性能

采用熔融共混法制备了nano-ZnO/聚丙烯(PP)复合材料,研究了相容剂聚丙烯接枝马来酸酐(PP-gMAH)的加入对nano-ZnO/PP复合材料的成核结晶行为、晶体结构、结晶形态以及力学性能的影响。结果表明,低添加量(质量分数小于5%)的nano-ZnO对PP有较好的β晶成核效应,而当其质量分数大于5%时,nano-ZnO对PP结晶有明显的异相成核作用,使PP结晶温度大幅度提高,PP结晶在(040)晶面呈现生长择优性;PP-gMAH的加入增强了nano-ZnO粒子与PP基体之间的界面相互作用,改善了纳米粒子的分散性,促进了PP基体的异相成核,提高了nano-ZnO/PP复合材料的拉伸强度和冲击强度,但却抑制了nano-ZnO诱导PP生成β晶。nano-ZnO/PP复合材料体系中因界面相互作用改善所致的韧性提高明显强于nano-ZnO诱导PP形成β晶的增韧效应。     

马来酸酐混合单体改性PP/PS共混物的结晶与动态力学性能

用熔融法制备了马来酸酐（MAH）及其与苯乙烯（St）混合单体改性PP／PS共混物,以及MAH、St改性聚丙烯（原住形成PP／PS共混物）。用DSC、DMA和FT—IR研究了改性共混物的结晶与熔融行为、动态力学性能和接枝产物。结果表明,MAH加入对PP／PS共混物中PP的结晶温度影响不大,但其与St混合单体对共混物中PP的结晶温度影响明显,原位生成PP／PS的结晶温度也有较大提高。改性对共混物中PP的熔融温度影响不大,但熔融峰形变化明显。改性PP／PS共混物具有高的E′和E″强度。     

液晶聚合物β成核剂/等规聚丙烯的等温结晶动力学和熔融行为

将主链型液晶聚酯(PBDPS)大分子β成核剂与等规聚丙烯(i PP)熔融共混,得到不同添加量的i PP/PBDPS样品。利用差示扫描量热分析、X射线衍射、偏光显微镜等研究了i PP和PBDPS共混物的等温结晶动力学、结晶熔融行为、晶型结构和结晶形态。结果表明,i PP和i PP/PBDPS共混物的等温结晶动力学适用于Avrami方程,Avrami指数(n)从2. 62～2. 81变为2. 60～3. 25,晶体的生长方式为二维生长与三维生长并存。PBDPS起到异相成核作用,i PP结晶速率常数(K)随着PBDPS的添加而增大,半结晶时间(t1/2)随之缩短。使用Arrhenius方程计算了等温结晶活化能,并通过HoffmanWeeks外推法得到了i PP/PBDPS中α、β晶的平衡熔点。液晶高分子PBDPS能有效诱导i PP形成β晶型,β晶含量随着PBDPS添加量与结晶温度的提升而增大,当PBDPS质量分数为4%,结晶温度为130℃时,β晶含量高达92. 5%。     

纳米CaCO3/PP的等温结晶动力学

熔融制备了纳米CaCO3／PP复合材料,用DSC研究了纳米CaCO3用量、制备方法、粒径和结晶温度对PP等温结晶行为的影响。并用Avrami方程分析了CaCO3／PP复合材料的结晶动力学。结果表明,纳米CaCO3时PP有异相成核作用,随纳米CaCO3用量增加,结晶加快。随结晶温度提高,结晶时间延长。Avrami指数n在2．0～2．6．纳米CaCO3加入对PP的成核与生长机理影响不大。     

PP/PC的结晶行为和物理性能

研究了PP／PC不同共混比对PP结晶行为、共混物物理性能的影响．探讨了以PP-g-MAH为增容剂、PF为增容助剂对共混物的增容效果。对比了单双螺杆挤出两种共混方式对共混物物理性能和相结构的影响。结果表明,PC的加入使PP球晶细化、结晶度降低、结晶不完善．共混物强度提高．韧性下降。加入PP—g—MAH可同时提高强度和韧性,再加入PF可使强度进一步提高．但韧性变差。PP／PP—g—MAH／PC的Tg与Tm差值比PP／PC的差值缩小了2．9℃,说明PP—g—MAH的确起到增容作用。运用双螺杆挤出机共混效果较好。     

Structural and optical properties of AlxOy/Pt/AlxOy multilayer absorber

We report on the microstructure and optical properties of Al_xO_y–Pt–Al_xO_y interference-type multilayer films, deposited by electron beam (e-beam) deposition onto corning 1737 glass, silicon (1 1 1) and copper substrates. The structural properties were investigated by Rutherford backscattering spectrometry, X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy and atomic force microscopy. The optical properties were extracted from specular reflection/transmission, diffuse reflectance and emissometer measurements. The stratification of the coatings consists of a semi-transparent middle Pt layer sandwiched between two layers of Al_xO_y. The top and bottom Al_xO_y layers were non-stoichiometric with no crystalline phases present. The Pt layer is in the fcc crystalline phase with a broad size distribution and spheroidal shape in and between the rims of Al_xO_y. The surface roughness of the stack was found to be comparable to the inter-particle distance. The optical calculations confirm a high solar absorptance of ∼0.94 and a low thermal emittance of ∼0.06 for the multilayer stack, which is attributed not only to the optimized nature of the multilayer interference stacks, but also to the specific surface morphology and texture of the coatings. These optical characteristics validate the spectral selectivity of the Al_xO_y–Pt–Al_xO_y interference-type multilayer stack for use in high temperature solar-thermal applications.     

Optimization of AlxOy/Pt/AlxOy multilayer spectrally selective coatings for solar-thermal applications

Spectrally selective Al_xO_y/Pt/Al_xO_y multilayer absorber coatings were deposited onto corning 1737 glass, Si (111) and copper substrates using electron beam (e-beam) vacuum evaporator at room temperature. The employment of ellipsometric measurements and optical simulation was proposed as an effective method to optimize and deposit multilayer solar absorber coatings. The optical constants (n and k) measured using spectroscopic ellipsometry, showed that both Al_xO_y layers, which used in the coatings, were dielectric in nature and the Pt layer was semi-transparent. The optimized multilayer coatings exhibited high solar absorptance α ∼ 0.94 ± 0.01 and low thermal emittance ? ∼ 0.06 ± 0.01 at 82 °C. The Rutherford backscattering spectroscopy (RBS) data of Al_xO_y/Pt/Al_xO_y multilayer absorber indicated the Al_xO_y layers present in the coating were nearly stoichiometry. The scanning electron microscope analysis (SEM) result indicated that the average diameter and inter-particles distance of Pt grains were statistically about 146 ± 0.17 nm and 6-10 ± 0.2 nm respectively.     

Interfacial microstructure of NiSix/HfO2/SiOx/Si gate stacks

Integration of NiSi_x based fully silicided metal gates with HfO₂ high-k gate dielectrics offers promise for further scaling of complementary metal-oxide- semiconductor devices. A combination of high resolution transmission electron microscopy and small probe electron energy loss spectroscopy (EELS) and energy dispersive X-ray analysis has been applied to study interfacial reactions in the undoped gate stack. NiSi was found to be polycrystalline with the grain size decreasing from top to bottom of NiSi_x film. Ni content varies near the NiSi/HfO_x interface whereby both Ni-rich and monosilicide phases were observed. Spatially non-uniform distribution of oxygen along NiSi_x/HfO₂ interface was observed by dark field Scanning Transmission Electron Microscopy and EELS. Interfacial roughness of NiSi_x/HfO_x was found higher than that of poly-Si/HfO₂, likely due to compositional non-uniformity of NiSi_x. No intermixing between Hf, Ni and Si beyond interfacial roughness was observed.     

Tc trend in high-Tc superconductors

In our previous works, we have shown that most existing ceramic superconductors can be considered to be built of superconductor-semiconductor composite and we have estimated the change in phonon spectrum of the intrinsic superconductor unit if a semiconductor unit is attached to it. Moreover, the proximity effect under the size quantization condition has been examined in the superconductor-semiconductor composite. Each of the stated effects by itself could causeT _c enhancement in general as more semiconductor blocks are added to the system. We extend our study in this paper to analyze the combined actions of phonon spectral change and proximity effect without size quantization condition onT _c variation in members of the Tl₁ series of high-T _c superconductors. Our results indicate that an optimumT _c is obtained if the stated effects are included in the idealized unit cells of the superconductors made up of a superconductor-semiconductor array.     

Anomalous Hall Effect in Sn1?x?yMnxEuyTe and Sn1?x?yMnxEryTe Mixed Crystals

The Anomalous Hall Effect (AHE) was investigated in IV–VI ferromagnetic semimagnetic semiconductors of Sn_1–x Mn _x Te codoped with either Eu or Er. The analysis of experimental data is as follows. Hall resistivity and magnetization showed that AHE coefficient R _s depends on temperature and its value decreases with thetemperature increase. We observe that above ferromagnet–paramagnet transition temperature R _s changes sign. We discuss the possible physical mechanisms responsible for observed temperature dependence of R _s , particularly change of the sign.     

Synthesis of a new perovskite Pb(Li14Nb34)O3

A high-pressure technique was adopted to obtain perovskite-type $\text{Pb(Li}{}_{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}\text{Nb}{}_{\mathrm{<mtext>3</mtext><mtext>4</mtext>}}\text{)}\text{O}{}_3$. A new perovskite $\text{Pb(Li}{}_{\mathrm{<mtext>1</mtext><mtext>4</mtext>}}\text{Nb}{}_{\mathrm{<mtext>3</mtext><mtext>4</mtext>}}\text{)}\text{O}{}_3$ was characterized to have a cubic symmetry with $\text{a}{}_{\mathrm{<mtext>o</mtext>}}\text{= 4.069}\text{A}\text{?}$; Li and Nb ions in the B-site of perovskite lattice may be in a random arrangement.     

Bulk crystalline BaPb34Bi14O3: A ceramic superconductor

The preparation conditions of the high T_C ceramic superconductor Ba(Pb,Bi)O₃ is correlated with the superconducting transition. Transition onsets of all materials are similar, but transition widths and transition completeness is strongly dependent on firing temperature. Only materials prepared over a narrow temperature range, resulting in a nearly ideal weight loss, have a complete and narrow transition.     

Electrostriction in Pb (Zn13Nb23)O3

The electrostriction in $\text{Pb (Zn}{}_{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}\text{Nb}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}\text{)}\text{O}{}_3$ crystals has been investigated using a strain gauge method. In the ferroelectric phase below 140 C, the strain vs the electric field shows a hysteresis, which is ascribed to the effect of ferroelectric domains. A quadratic relation holds between the strain x and the electric polarization P as x = QP² above about 170 C in the paraelectric phase. Values of the electrostrictive Q coefficients are determined from the measurements near 190 C, as Q₁₁ = 1.6·10^?2m⁴/C², Q₁₂ = ?0.86·10^?2m⁴/C², and Q₄₄ = 0.85·10^?2m⁴/C².     

Effect of pressure onTc in La2-xBaxCuO4 withx=0.125

The superconducting transition temperature,T _c , of La_2–x Ba _x CuO₄ has been measured under high pressure up to 8 GPa.T _c is found to change drastically at the pressure where the structural phase transition takes place. This finding clearly indicates that there exists an intimate relation between the crystal structure and superconductivity.