环氧树脂对封端型水性聚氨酯树脂的改性研究

以聚醚多元醇、甲苯二异氰酸酯和二羟甲基丙酸为主要原料,丙烯酸单体封端,加入改性剂环氧树脂E-44,制备出稳定的水性聚氨酯分散体.红外光谱分析表明反应得到了水性聚氨酯结构;随着环氧树脂含量的增加,水性聚氨酯树脂粒径,黏度逐渐增大,乳液贮存稳定性下降,低温柔韧性变差,吸水率逐渐减小;甲基丙烷酸羟乙酯(HEMA)作为封端剂水性聚氨酯乳液高温稳定性优于季戊四醇三丙烯酸酯(PETA)封端剂乳液;环氧树脂改性增加了水性聚氨酯树脂的热稳定性.     

T型石墨烯及其衍生物的结构与电子特性

采用基于密度泛函理论的第一原理方法研究了T型石墨烯及其衍生物-n(n=1—5)的结构稳定性和电子结构性质.T型石墨烯是一种拥有四角形环的二维碳材料同素异构体,通过改变连接四角形环的碳链上的碳原子个数n,可以得到一系列的sp-sp~2杂化结构,称其为T型石墨烯衍生物-n.计算结果表明:这些材料的结构稳定性、化学键类型和电子结构性质都依存于n的奇偶性.其中T型石墨烯(n=0)的结构最稳定,并形成一个由8个碳原子构成的大环.声子谱计算的结果表明,n为偶数时的体系具有动力学稳定性,而n为奇数时的体系则是不稳定的.n为偶数时体系四角形环之间的碳链上的化学键呈单、三键交叉排列,体系显示为金属性特征,且随着n的增大,体系的金属性加强.n为奇数时体系四角形环之间的碳链上的化学键则为双键连续排列,体系呈金属性且具有磁性(n=1除外).研究表明该系列材料作为一种新的二维碳材料同素异构体,具有独特的结构和丰富的电子结构特性,很可能在纳米器件中得到广泛应用.     

nmSiO2对聚合物光纤光栅封装材料的改性研究

分析了刚性纳米粒子改性聚合物的原理，重点分析了nmSiO₂/硅氧烷（硅橡胶）复合材料的改性机理,采用120号溶剂性汽油为分散剂，通过共混法制得nmSiO₂—乙烯基硅氧烷、含氢硅氧烷硫化而成的复合材料,用AJ-Ⅲ_a型原子力显微镜分析研究了该材料的组团结构并测试了其力学性能,结果表明，硅氧烷橡胶改性后，材料的弹性模量增加了15.4%；拉伸强度增加了19.4%；扯断伸长率增加了30%,用改性后的硅氧烷聚合物材料封装光纤Bragg光栅(FBG)压力传感器，可有效改善封装材料与光纤光栅的耦联性能；通过粒子含量控制可以增韧增强硅氧烷，从而可制作变量程压力传感器，同时可以延长传感器的使用寿命,     

聚合物电光调制器的热稳定性研究

聚合物波导器件的稳定性是影响其实用化的一个关键问题。聚合物波导器件的热稳定性是由波导层(聚合物材料)的热稳定性决定的。采用侧链型和交联型聚氨酯材料分别制成波导电光调制器研究波导器件的热稳定性,热稳定性的判断依据是通过对聚合物调制器升温过程中测量器件的电光性能的变化。研究结果显示两种器件在常温时具有相同的电光性能,在器件升温过程中发现交联型聚氨酯调制器比侧链型聚氨酯调制器有优异的热稳定性。     

含氟有机硅改性多孔二氧化硅减反膜

二氧化硅减反膜的结构疏松,且胶粒表面存在大量羟基,膜层极易吸附环境中的水分和有机蒸气,透射比稳定性较低.为了改善原有减反膜的环境稳定性,以3,3,3-三氟丙基三甲氧基硅烷和3,3,3-三氟丙基甲基二乙氧基硅烷为掺杂剂,正硅酸乙酯为前躯体,采用溶胶-凝胶法制备了两个系列的SiO2减反膜.结果表明,含氟硅氧烷改性的系列膜层的疏水性能均得到显著增强.CF3-CH2-CH2-Si或CF3-CH2-CH2-Si-CH3质量分数在0.40%～1.5%的范围内时,二氧化硅膜层的减反效果较好.掺入含氟硅氧烷在一定质量分数时,膜层的抗激光损伤性能受到的影响不大.10-3Pa高真空环境的实验表明,膜层的稳定性有较大提高,含氟硅氧烷改性延长了减反膜的使用寿命.     

氢链中的Peierls机理(Ⅱ) 电子关联对Peierls不稳定性的影响

本文用相关基函数理论研究电子关联对氢链中Peierls不稳定性的影响,结果发现,电子关联使得氢链中的二聚化程度从0.37au减小为0.32au,这说明电子关联只是减弱但不会完全破坏氢链中的Peierls不稳定性,本理论表明,在电子相互作用下链状体系中的Peierls机理依然成立。     

聚倍半硅氧烷以不同方式改性纤维素绝缘纸的机理研究

本文运用分子动力学方法,建立了纯纤维素模型和一系列聚倍半硅氧烷以不同方式改性的纤维素绝缘纸模型,并对其热力学性能进行了计算、对比和讨论. 实验结果表明,各聚倍半硅氧烷纤维素改性模型的性能均优于未改性模型,并且当两条纤维素分子链作为取代基通过化学键接枝在聚倍半硅氧烷分子上(M2模型)时,改性效果最佳,其内聚能密度与溶解度参数的值相较于未改性模型提高了9%,拉伸模量、体积模量、剪切模量、柯西压的值分别提升了38.6%、29.5%、41.1%和29.5%,此外本文还计算并分析了各模型的自由体积分数和均方位移,结果显示,相较于其他模型,M2模型中的化学键在避免使纤维损失强度的同时,增加了分子链间的纠缠,使纤维素分子链占据了更多自由体积,从而使体系具有更小的自由体积分数,抑制了纤维素的链运动,进而提升了纤维素绝缘纸的热稳定性,这从微观角度解释了化学处理影响改性效果的机理.     

氢链中的Peierls机理(Ⅱ)——电子关联对Peierls不稳定性的影响

本文用相关基函数理论研究电子关联对氢链中Peierls不稳定性的影响,结果发现,电子关联使得氢链中的二聚化程度从0.37au减小为0.32au,这说明电子关联只是减弱但不会完全破坏氢链中的Peierls不稳定性,本理论表明,在电子相互作用下链状体系中的Peierls机理依然成立。 关键词：     

聚倍半硅氧烷以不同方式改性纤维素绝缘纸的机理研究（英文）

本文运用分子动力学方法,建立了纯纤维素模型和一系列聚倍半硅氧烷以不同方式改性的纤维素绝缘纸模型,并对其热力学性能进行了计算、对比和讨论.实验结果表明,各聚倍半硅氧烷纤维素改性模型的性能均优于未改性模型,并且当两条纤维素分子链作为取代基通过化学键接枝在聚倍半硅氧烷分子上(M2模型)时,改性效果最佳,其内聚能密度与溶解度参数的值相较于未改性模型提高了9%,拉伸模量、体积模量、剪切模量、柯西压的值分别提升了38.6%、29.5%、41.1%和29.5%,此外本文还计算并分析了各模型的自由体积分数和均方位移,结果显示,相较于其他模型,M2模型中的化学键在避免使纤维损失强度的同时,增加了分子链间的纠缠,使纤维素分子链占据了更多自由体积,从而使体系具有更小的自由体积分数,抑制了纤维素的链运动,进而提升了纤维素绝缘纸的热稳定性,这从微观角度解释了化学处理影响改性效果的机理.     

Nb原子链的结构稳定性和电子性质

使用基于密度泛函理论的第一性原理平面波赝势法，研究了Nb原子链的结构稳定性和电子结构性质.计算表明，Nb原子可以形成线性链，平面之字形，二聚化以及梯子形等一系列的一 维链式结构.结果也显示，其中之字形结构最为稳定，其他结构均为亚稳的.通过第一性原理 计算的电子结构和Jahn-Teller效应，讨论了这些结构的相对稳定性以及各链式结构的电子 能带、态密度和电荷密度等性质. 关键词： Nb原子链 结构稳定性 电子结构 从头计算     

Synthesis and characterization of organic soluble polyaniline prepared by one-step emulsion polymerization

Emeraldine salt of polyaniline-dodecylbenzenesulfonic acid (PANI-DBSA) in organic solvents such as toluene and xylene was obtained by a direct one-step emulsion polymerization technique. When the molar ratio of DBSA to aniline monomer was 1.5:1, solubility and electrical property showed a maximum value. The solid contents of PANI-DBSA was 8 wt.% in toluene. The casting film of PANI-DBSA was obtained on glass or plastic substrate under ambient conditions. PANI solution can also be easily blended with polyurethane and polystyrene polymers in toluene. Better electrical performance (up to 5 S/cm), good light transmittance (up to 70% at 500 nm thickness), were obtained and more homogeneous morphology was observed for the casting film of PANI-DBSA prepared by the present method as compared with that prepared by the aqueous emulsion polymerization. The partially dispersed PANI-DBSA particles of 50–400 nm sizes in organic solvents such as toluene and xylene were observed and the crystalline nature of these powder samples was confirmed from the XRD patterns.     

Chemically induced graft copolymerization of 2-hydroxyethyl methacrylate onto polyurethane surface for improving blood compatibility

To improve hydrophilicity and blood compatibility properties of polyurethane (PU) film, we chemically induced graft copolymerization of 2-hydroxyethyl methacrylate (HEMA) onto the surface of polyurethane film using benzoyl peroxide as an initiator. The effects of grafting temperature, grafting time, monomer and initiator concentrations on the grafting yields were studied. The maximum grafting yield value was obtained 0.0275 g/cm² for HEMA. Characterization of the films was carried out by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), water contact angle measurements. ATR-FTIR data showed that HEMA was successfully grafted onto the PU films surface. Water contact angle measurement demonstrated the grafted films possessed a relatively hydrophilic surface. The blood compatibility of the grafted films was preliminarily evaluated by a platelet-rich plasma adhesion test and hemolysis test. The results of platelet adhesion experiment showed that polyurethane grafted polymerization with monomer of 2-hydroxyethyl methacrylate had good blood compatibility featured by the low platelet adhesion. Hemolysis rate of the PU-g-PHEMA films was dramatically decreased than the ungrafted PU films. This kind of new biomaterials grafted with HEMA monomers might have a potential usage for biomedical applications.     

纳米银导电膜的制备及其光谱学分析

为了以温和的化学反应制备纳米银导电膜,在PET薄膜上涂布柠檬酸银乳液,并用抗坏血酸(Vc)还原,用红外光谱仪、紫外-可见光分光光度计、X射线衍射仪(XRD)、扫描电子显微镜、原子力显微镜等,研究柠檬酸银乳液及其还原涂层的微观形貌、晶体结构和导电性能。发现PVP保护的柠檬酸银乳液粒径分布在60～150 nm。银膜的UV-Vis吸收峰位于430 nm,表明其具有纳米结构。XRD分析表明,还原后的涂层形成了不完整的银晶体,水洗比乙醇处理更能促进柠檬酸银的彻底还原和银膜的晶型完善,降低银膜表面电阻。     

Novel heat-resistance UV curable waterborne polyurethane coatings modified by melamine

Novel UV curable waterborne polyurethane coatings (UVWPU) modified by melamine was prepared using isophorone diisocyanate (IPDI), polyethylene glycol (PEG), α,α-dimethylol propionic acid (DMPA), hydroxyethyl acrylate (HEA) as main materials. Copolymer structure was verified using Fourier transform infrared spectroscopy (FT-IR). Performance of the coatings was evaluated by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA), and mechanical tests such as pencil hardness and resistance to water. The results showed that the modified UVWPU film had the good thermal resistance, water resistance and mechanical properties. The optimum melamine dosage was 4.70 wt.%, the glass transition temperature (T_g) of the modified film increased by 20.4 °C and 5% weight-loss temperature (253 °C) increased by 105 °C. No change color, crinkle, desquamate, dehisce and frothy were found after the modified film dried at 130 °C for 2 h.     

Biomaterial immobilization on polyurethane films by XeCl excimer laser processing

The surface chemical modification of polyurethane (PU) films was performed by an UV laser-induced chemical reaction in a polysaccharide solution. This process may be applicable as hydrophilic packaging of implantable medical devices and in vivo sensors. When a PU film in contact with an aqueous alginic acid (AAC) solution was irradiated with a XeCl laser, the PU film turned hydrophilic. Contact angles of water on the film were reduced from 110° to 60°. Since light absorption of the AAC solution at 308 nm was negligibly small, reactive sites were generated solely on the PU surface. There, AAC could be immobilized by chemical bonds thus allowing for a nanometer-scaled grafting of this biomolecule. The mechanism was investigated by surface analyses with Fourier-transform infrared spectroscopy (FT-IR), dye staining, ultraviolet-visible (UV-VIS) spectroscopy, and scanning electron microscopy (SEM) techniques. A one-photon photochemical process could beidentified. Received: 30 June 2000 / Accepted: 4 July 2000 / Published online: 13 September 2000     

Film morphology, orientation and performance of dodecyl/carboxyl functional polysiloxane on cotton substrates

A novel polysiloxane (RCAS) bearing dodecyl and carboxyl side groups was synthesized by reaction of a dodecyl/amino functionalized polysiloxane with maleic anhydride. Film morphology, molecular orientation and performance of the synthesized polysiloxane on cotton substrates were investigated by field emission scanning electron microscope (FESEM), atomic force microscope (AFM), X-ray photoelectron microscope (XPS) and so on. Affected by the dodecyl and polar carboxyl side groups, RCAS formed a semi hydrophilic, macroscopic smooth but actually uneven siloxane film with many pillar-likes or small humps on the treated substrate surfaces. On the natural cotton surface, RCAS may take such an orientation to form its film that the Si-CH₃, Si-C₁₂H₂₅ groups projected outward into air, while the carboxyl groups pointed inward to the substrate, interacting with the hydroxyls of the cotton substrates in ester and hydrogen bonds or twisted away from the negatively charged cotton fiber surface. As a result of such a film-formation, RCAS provided the treated fabric with not only a good wettability of about 22.96 s and a whiteness of 88.44°, but also an improved softness as well as thickening handle.     

聚氨酯/聚丙烯酸酯复合乳液的紫外光谱研究

以水性聚氨酯(PU)分散液为种子,采用无皂乳液聚合技术合成出了聚氨酯／聚丙烯酸酯(PUA)复合乳液。紫外光谱研究发现,PU乳液的,n-π迁紫外吸收峰的λmax随溶液浓度增加明显红移。对于PU分散液,随着亲水性扩链剂用量增加,紫外光谱吸光度值变小;随着NCO/OH摩尔比增大,吸光度增大。对于PUA复合乳液,亲水性扩链剂用量取7．5％时,吸光度值最小;而第二阶段聚合引发剂种类对紫外光谱影响不大。紫外光谱的吸光度值反映了乳液粒子平均粒径的大小;随着NCO／OH摩尔比增大,吸光度增大。对于PUA复合浮液,亲水性扩链剂用量取7．5％时,吸光度值最小;而第二阶段聚合引发剂种类对紫外光谱影响不大。紫外光谱的吸光度值反映了乳液粒子平均粒径的大小。     

Organic-inorganic hybrid superhydrophobic surfaces using methyltriethoxysilane and tetraethoxysilane sol-gel derived materials in emulsion

By applying alkaline-catalyzed co-hydrolysis and copolycondensation reactions of tetraethoxysilane (TEOS) and methyltriethoxysilane (MTES) in organic siloxane modified polyacrylate emulsion (OSPA emulsion), we are able to demonstrate the potential for developing a sol-gel derived organic-inorganic hybrid emulsion for a superhydrophobic surface research. TEOS and MTES derived sol-gel moieties can be designed for a physical roughness and hydrophobic characteristic (Si-CH₃) of the hybrid superhydrophobic surface, while OSPA emulsion can be endowed for good film-forming property. The effect of formulation parameters on superhydrophobicity and film-forming property was analyzed. The water contact angle (WCA) on the sol-gel derived hybrid film is determined to be 156°, and the contact angle hysteresis is 5° by keeping the mole ratio of TEOS:MTES:C₂H₅OH:NH₃·H₂O:AMP-95 at 1:4:30:10:0.63 and the mass percentage of OSPA emulsion at 25%. The nanoparticle-based silica rough surface is observed as the mole ratio of MTES/TEOS at 4:1. The sol-gel derived organic-inorganic hybrid emulsion shows remarkable film-forming property when the mole ratio of MTES/TEOS reaches or exceeds 4:1. With the primer coating, the performance of superhydrophobic film achieve actual use standard. It reveals that this new procedure is an effective shortcut to obtain a superhydrophobic surface with potential applications.     

Hydrophobic Modification of Poly(Ethylene Terephthalate) with Epoxy-Modified Polysiloxane by Reactive Extrusion

Hydrophobic poly(ethylene terephthalate) (PET) was prepared by reactive blending of PET with double epoxy groups modified polysiloxane (diepsi) or multiepoxy groups modified polysiloxane (multiepsi). The structure of the modified PET was characterized by ¹H NMR and intrinsic viscosity. The grafted ratio of diepsi and multiepsi was 1.3 and 0.03 wt%, respectively. With the introduction of diepsi and multiepsi to PET, the water contact angle of modified PET increased from 73° to a maximum of 106°, showing the good hydrophobicity of the modified PET. The samples of modified PET were washed with different solvents and their water contact angles did not significantly decrease, indicating good durability of the hydrophobicity. Moreover, the films of modified PET prepared by solution casting (phenol and 1, 1, 2, 2-tetrachloroethane mixed solution) showed excellent hydrophobicity with the contact angle 151°. Scanning electron microscopy images showed the surface of the modified PET films to be rougher than those of unmodified PET because the introduction of polysiloxane to PET resulted in phase separation during the solvent evaporation process.     

脉冲激光沉积法在多孔铝衬底上生长的ZnO薄膜的结构与光学性质

ZnO是一种性质优良很有前途的紫外光电子器件材料,多孔铝是一种良好的模板型衬底,试图将二者结合起来以制备出一种全新的光电功能材料。制备了三种不同孔径多孔铝衬底,采用脉冲激光沉积法,在真空背景下,在多孔铝衬底上生长了氧化锌薄膜。利用扫描电子显微镜、X射线衍射和光致荧光对样品进行了测试和分析。研究表明:利用不同孔径的多孔铝衬底生长的氧化锌薄膜的结构和光学性质差异很大。样品A的光致发光主要是394nm的紫外发射和498nm的蓝绿光发射;样品B的光致发光主要是417nm的紫光发射和466nm蓝光发射;样品C的光致发光主要是415nm的紫光发射和495nm的蓝绿光发射。由于薄膜是富锌的,随着在空气中氧化的进行,光谱发生变化。利用固体能带理论对光谱进行了全面的分析。