无规剥离结构环氧树脂/粘土纳米复合材料的制备及剥离机理

用质子化的2,4,6-三(二甲氨基甲基)苯酚(DMP-30)通过阳离子交换反应对原始粘土进行修饰,采用一种与新的制备方法——"湿粘土加入法"合成了环氧树脂/粘土纳米复合材料。透射电镜(TEM)观察显示,粘土片层以3-5片为聚集单元均匀、无规地分布在整个环氧树脂的基体中,呈现高度、无规剥离形态。利用X射线衍射(XRD)跟踪了粘土片层在复合材料制备过程各阶段的分散状况,初步阐明了粘土片层在环氧树脂中的剥离机理:粘土片层在固化反应之前已经实现了在环氧预聚体中的剥离。有机改性剂带有的亲水基团及能与环氧树脂反应的叔胺基对形成剥离结构纳米复合材料有决定性作用。     

反应型有机修饰剂对环氧树脂/粘土纳米复合材料热/机械性能的影响

使带有环氧基团的三缩水甘油基对氨基苯酚(TGPAP)分别与溴代正丁烷(BB)、2-溴乙醇(BE)反应,合成了反应型粘土有机修饰剂溴化(正定烷基)双环氧基(4-环氧醚基)铵(TGPAPB)和溴化(2-羟乙基)双环氧基(4-环氧醚基)铵(TGPAPE)。用这两种修饰剂改性粘土,分别制备出具有相同反应官能团但与环氧树脂的相容性略有不同的两种有机化粘土(B-Clay和E-Clay)。再用“粘土淤浆复合法”制备出两种环氧树脂/粘土纳米复合材料,研究了两种反应型有机修饰剂对纳米复合材料的结构和性能的影响。结果表明：带有羟基的E-Clay以高度无规剥离形式均匀分布在环氧树脂基体中;而B-Clay则形成了无规剥离/插层混合结构。两种粘土均参与固化反应在环氧树脂基体和粘土片层间产生了较强的界面作用力,从而显著提高了纳米复合材料的拉伸强度。粘土质量分数为3%的两种纳米复合材料,其拉伸强度分别达到32.4 MPa(E-Clay)和28.0 MPa(B-Clay),比对应的纯环氧树脂聚合物分别提高了76.47%和52.51%。同时,这两种纳米复合材料的玻璃化转变温度(T_g)也略有提高。     

界面强度对柔性环氧树脂/粘土纳米复合材料热/力学性能的影响

先合成反应型BBDMP30-clay有机化粘土和非反应型CPDMP30-clay有机化粘土,然后以其为纳米增强体分别制备了两种界面强度不同的环氧树脂/粘土纳米复合材料。用透射电子显微镜(TEM)、拉伸实验表征这两种环氧树脂/粘土纳米复合材料并进行动态力学分析(DMA),研究了界面强度对其力学性能的影响。结果表明：这两种纳米复合材料具有几乎相同的无规剥离结构,反应型BBDMP30-clay比非反应型CPDMP30-clay能更有效地提高材料的热/机械性能。粘土质量分数为3.5%时BBDMP30-clay可使纳米复合材料的拉伸强度提高250%,而CPDMP30-clay只能使材料的拉伸强度提高190%。BBDMP30-clay使纳米复合材料的玻璃化转变温度(Tg)提高了6.5℃,而CPDMP30-clay只能使材料的Tg提高2.5℃。这些不同都可归因于这两种纳米复合材料界面强度的差异。     

有机修饰剂对环氧树脂/粘土纳米复合材料结构的影响

分别用质子化的2,4,6-三(二甲氨基甲基)苯酚(HDMP30)、质子化的十八胺(HODA)及氯化胆碱(CC)作为有机修饰剂对原始粘土进行改性,通过"粘土淤浆复合法"合成了环氧树脂/粘土纳米复合材料。采用透射电镜及X射线衍射研究了"粘土淤浆复合法"工艺中有机修饰剂的种类对环氧树脂/粘土纳米复合材料微观结构的影响。结果表明,憎水性的HODA改性粘土所制备的纳米复合材料只能形成插层结构;带有亲水基团羟基的CC改性粘土为剥离与插层混合型结构;而既带有亲水基团又与环氧预聚体有良好相容性的HDMP30改性的粘土则可形成高度无规剥离结构。阐明了3种不同类型有机修饰剂改性粘土所导致的不同微观结构形成的机理。     

有机修饰剂对环氧树脂/粘土纳米复合材料结构的影响EI北大核心CSCD

分别用质子化的2,4,6-三(二甲氨基甲基)苯酚(HDMP30)、质子化的十八胺(HODA)及氯化胆碱(CC)作为有机修饰剂对原始粘土进行改性,通过"粘土淤浆复合法"合成了环氧树脂/粘土纳米复合材料。采用透射电镜及X射线衍射研究了"粘土淤浆复合法"工艺中有机修饰剂的种类对环氧树脂/粘土纳米复合材料微观结构的影响。结果表明,憎水性的HODA改性粘土所制备的纳米复合材料只能形成插层结构;带有亲水基团羟基的CC改性粘土为剥离与插层混合型结构;而既带有亲水基团又与环氧预聚体有良好相容性的HDMP30改性的粘土则可形成高度无规剥离结构。阐明了3种不同类型有机修饰剂改性粘土所导致的不同微观结构形成的机理。     

氧化石墨烯纳米片/环氧树脂复合材料的制备与性能

氧化石墨烯(GO)是石墨烯重要的衍生物之一,通过氧化和超声波分散制备了GO纳米片/环氧树脂复合材料。采用XRD、拉曼光谱、FTIR和TEM表征了GO纳米片的结构与形貌,研究了GO纳米片用量对GO纳米片/环氧树脂复合材料热稳定性、力学性能及介电性能的影响。结果表明:GO纳米片的加入提高了GO纳米片/环氧树脂复合材料失热稳定性;随着GO纳米片填充量的增加,GO纳米片/环氧树脂复合材料的冲击强度和抗弯性能先提高后降低,其介电常数和介电损耗则先减小后增加。GO纳米片填充量为0.3wt%的GO纳米片/环氧树脂复合材料的失重5%时的热分解温度由纯环氧树脂的400.2℃提高到424.5℃,而冲击强度和弯曲强度分别在GO纳米片填充量为0.2wt%和0.3wt%时达到最大,冲击强度由纯环氧树脂的10.5kJ/m2提高到19.7kJ/m2,弯曲强度由80.5 MPa提高到104.0 MPa。     

有机粘土/聚醚砜/环氧树脂杂化纳米复合材料的制备和性能

分别用溶剂法和熔融法成功制备了有机粘土/聚醚砜/环氧树脂杂化纳米复合材料,对其拉伸性能、断裂韧性、热性能和微观结构进行了研究。结果表明:两种杂化纳米复合材料的拉伸强度可达75 MPa以上,模量可达3.0 GPa以上,断裂韧性可达1.1 MPam1/2以上。观察到了聚醚砜和有机粘土对环氧树脂的协同增韧现象。聚醚砜/环氧树脂基体具有半互穿网络结构,有机粘土片层呈有序剥离形态。用溶剂法制备的杂化纳米复合材料样本的玻璃化转变温度(Tg)在170℃以上,用熔融法制备的样本的Tg在180℃以上。     

胺类固化剂-插层剂体系对粘土在环氧树脂中剥离的影响

在对胺类固化剂-插层剂体系分析的基础上,选定叔胺类固化剂(BDMA)-Bronsted酸类插层剂(CH3(CH2)11NH3Cl)体系,制得了环氧树脂/粘土纳米复合材料,复合材料的XRD分析表明粘土在环氧树脂中已经剥离.结合有关研究成果,得出以下结论:在其他条件合适的情况下,只要插层剂为Bronsted酸类或者固化剂为叔胺类,就能得到剥离型的环氧树脂/粘土纳米复合材料.     

尼龙6/POE/粘土纳米复合材料的形态、结构及性能研究

采用熔融方法制备了PA 6/POE/粘土纳米复合材料.PA 6/POE/粘土纳米复合材料具有良好的力学性能,其缺口冲击强度比PA 6有显著提高.研究结果表明,有机粘土剥离于PA 6基体中,POE相以岛状结构均匀分散于PA 6基体中;PA 6/POE/粘土纳米复合材料的储能模量比PA 6的低,并且随着有机粘土含量的增加而降低.PA 6/POE/粘土纳米复合材料的玻璃化转变温度(Tg)随着粘土含量的增加而升高,具有良好的热稳定性.     

纳米粘土/环氧树脂复合材料的制备及力学性能研究

借助超声分散,采用固化处理制备了不同纳米粘土掺量(0,1%,3%,5%和7%(质量分数))的纳米粘土/环氧树脂复合材料,研究了纳米粘土掺量对复合材料性能的影响。通过X射线衍射(XRD)、力学性能测试、扫描电镜(SEM)等对复合材料进行了表征。结果表明,不同掺杂比例的纳米粘土和环氧树脂都均匀结合,纳米粘土掺量为7%(质量分数)的复合材料衍射峰强度最高,其结晶性能最佳;随着纳米粘土掺量的增加,复合材料的拉伸模量、极限抗压强度和断裂韧性KIC值整体均高于纯环氧树脂,而复合材料的破坏应变低于纯环氧树脂;当纳米粘土掺量为1%(质量分数)时,复合材料的极限抗拉强度略有提高,但随着纳米粘土掺量的继续增加,复合材料的极限抗拉强度逐渐降低;当纳米粘土掺量为5%(质量分数)时,复合材料的拉伸模量达到3 513 MPa,相比纯环氧树脂的3 300 MPa,增加了6.5%;当纳米粘土掺量为7%(质量分数)时,复合材料的断裂韧性KIC值达到1.97 MPa·m~(1/2),相比纯环氧树脂的1.60 MPa·m~(1/2),增加了23.1%;纯环氧树脂的断裂表面光滑无褶皱,断裂时裂纹没有产生无偏离的扩展,而复合材料的断裂表面随纳米粘土掺量的增加均趋于粗糙,裂纹在扩展过程中发生了偏移。     

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.