有机无机杂化膜材料的制备技术

有机无机杂化膜兼有机膜韧性和无机膜耐高温性能,具有优良的气体渗透选择性,成为高分子化学和材料科学等领域的研究热点.本文综述了近年来有机无机杂化膜材料的制备技术进展,着重探讨了溶胶-凝胶法制备聚酰亚胺类杂化膜材料的研究状况,并作了简要述评。     

Mo Back Contact for Flexible Polyimide Substrate Cu（In,Ga）Se2 Thin-Film Solar Cells

A dc magnetic sputtering process is applied to growth of a Mo back. contact layer onto the flexible polyimide （PI） and rigid soda-lime glass （SLC） substrates. The structural and electrical properties of the Mo layer coated on the two kinds of substrates are investigated by x-ray diffraction （XRD） and Hall effect measurements. The results show that the Mo layer on SLG indicate more better crystal quality and lower resistivity than that on the PI sheets. In contrast to the SLG substrate, the resistivity of the Mo layer on PI is increased by the vacuum annealing process at the substrate temperature of 450℃ under Se atmosphere, which is attributed to the cracked Mo layer induced by the mismatch of the coefficient of thermal expansion between PI and Mo material. The Cu（In,Ga）Se2 （CIGS） solar cells based on the PI and SLO substrates show the best conversion efficiencies of 8.16% and 10.98% （active area, 0.2cm^2）, respectively. The cell efficiency of flexible CIGS solar cells on PI is limited by its relatively lower fill factor caused by the Mo back contact.     

含硫醚结构均苯型聚酰亚胺的合成及表征

以4,4′-二氨基二苯硫醚(SDA)和均苯四酸酐(PMDA)为原料,通过溶液缩聚法-热酰亚胺/化学酰亚胺化的方法制备了一种含硫醚结构均苯型聚酰亚胺.利用高级旋转流变仪建立了在线跟踪反应进程的方法,采用热失重分析仪研究反应条件对热酰亚胺化及化学酰亚胺化法的影响,这些方法的建立为进一步制备高性能的聚酰亚胺提供有效的实验手段.采用小角激光光散射法、红外光谱、元素分析、接触角仪、DSC等方法对聚合物的结构与性能进行表征.结果显示,硫醚结构的引入,可有效改善聚合物薄膜的表面性能,其与铜箔之间的粘附功明显大于传统聚酰亚胺,在无胶挠性线路板应用方面显示出较好的应用前景.所获聚合物的Mw为(6.7±1.6)×104,分解温度均高于560℃;DSC的结果显示所制备的两种酰亚胺化聚合物均具有较高的玻璃化转变温度,相比之下,化学酰亚胺化更有利于获得高酰亚胺化程度的聚合物,产物的玻璃化转变温度也更高.     

反相非水乳液法制备聚酰亚胺微球

在N,N-二甲基甲酰胺(DMF)/Pluronic-F127、十二烷基苯磺酸钠(SDBS)/液体石蜡(LP)反相非水乳液体系中,以均苯四甲酸二酐(PMDA)和4,4′-二氨基二苯醚(ODA)为单体合成聚酰胺酸(PAA),采用吡啶/乙酸酐脱水剂,对PAA化学酰亚胺化,并进一步热酰亚胺化,制得PI耐热微球.产物通过红外、热重、扫描电镜表征.结果表明,较高的固含量和良好的乳液分散性有利于PI微球的形成;反相非水乳液体系稳定的配比条件是,VDMF∶VLP为1∶4,MF127∶MSDBS为3:2,乳化剂用量为9 wt%;在此配比条件下,当固含量为20%,热酰亚胺化温度不高于330℃时,可制得分散良好、球形规整、高热稳定性的PI微球,其粒径约为10μm.     

苯胺分散聚合中稳定剂PVP-K90的稳定机理

通过分散聚合,在聚酰亚胺(PI)薄膜表面原位沉积聚苯胺(PANI)制备聚苯胺-聚酰亚胺-聚苯胺(PANI-PI-PANI)复合膜。考察了苯胺分散聚合中,不同空间稳定剂的稳定效果(不同分子量的大分子稳定剂PVP及小分子稳定剂CTAB、Tween-20),初步探讨了大分子稳定剂PVP-K90的稳定机理。实验表明,高分子量PVP-K90可稳定PANI良好成膜,且紫外和红外光谱分析证实PANI膜为掺杂态PANI,膜中不含有稳定剂PVP-K90。低分子量的PVP-K30和两亲性小分子稳定剂不能良好地稳定PANI成膜,稳定作用较差。PVP-K90的稳定作用不仅依据亲水-疏水相互作用和表面能的减少,还可能与高分子量PVP的长链分子结构及与水和苯胺的特殊相互作用有关,可用齐聚物沉淀成核机理解释。     

激光诱民聚酰亚胺纳米微结构中分子链取向排列的研究

通过Ｎｄ：ＹＡＧ偏振脉冲激光辐射聚酰亚胺薄膜,在其表面制得大面积纳米级周藏一微线条,线条的周期性为２００ｎｍ,线条方向始终平行于偏振激束电场方向,线条横截面为圆形或椭的柱状稔胍射红外光谱分别在平行与垂直纳米线条的方向上测试聚合物表面ＩＲＫ结果发现,１７２２和１２３１ｃｍ＾－１处的吸收有明显的二向色性,表明二线条内聚合物分子链部分呈现取排列,且聚酰亚胺分子我边方向与微线条方向垂直。     

无加热氧碘化学激光器超音速喷管

针对氧碘化学激光器的金属喷管在使用过程中需加热保温且存在结构复杂、故障率高等问题,初步选择了几种可用于加工无加热喷管的非金属材料,并以kW级氧碘化学激光器为原型,以聚酰亚胺为例,对激光器运行条件下的喷管温度场进行数值模拟,以验证此种非金属无加热喷管的可行性。结果表明:与金属喷管相比,非金属喷管在不加热保温的情况下能够有效阻止热量传递,防止碘蒸气冷却凝结,满足激光器喷管的使用要求。     

Charge Transport and Magnetotransport Properties of Polyimide Irradiated by 80keV Co Ions

Charge transport properties of polyimide films implanted with 80 keV Co ions at two different fluences （series I： 1.25 × 10^17 ions/cm^2, series Ⅱ： 1.75 × 10^17 ions/cm^2） are studied in detail. For series I, the temperature dependence of surface resistivity fits Mott＇s equation very well. It is on the insulating side of the insulator-metal transition （IMT）. However, for series Ⅱ, the temperature dependence of surface resistivity is not in agreement with Mott＇s equation. It is on the metallic side of lMT. The magnetotransport properties of these two series are also studied. No significant magnetoresistive effect is observed for series I at both 5 K and 300 K. For series Ⅱ, an obvious magnetoresistive effect is observed at 5 K, while there is no magnetoresistive effect at 300 K. Rutherford backscattering spectrometry （RBS） is applied to confirm the actual fluence for these two series.     

Structure Characterization of Modified Polyimide Films Irradiated by 2MeV Si Ions

Structures of polyimide （6051） films modified by irradiation of 2.0 MeV Si ions with different fluences are studied in detail. Variations of the functional groups in polyimide are investigated by attenuated total reflection Fourier transform infrared spectroscopy （ATR-FTIR） and Raman spectroscopy. The results indicate that the functional groups can be destroyed gradually with the increasing ion fluenee. The variations of structure and element contents are characterized by x-ray diffraction （XRD）, Rutherford backscattering spectrometry （RBS） and x- ray photoelectron spectroscopy （XPS）. The results indicate that the contents of N and O decrease significantly compared with the original samples, some graphite-like and carbon-rich phases are formed in the process of irradiation.     

利用数字散斑相关法测定聚酰亚胺/SiO2合成薄膜的力学性能

聚酰亚胺 /SiO2 合成薄膜是一种具有优良力热光电性能的薄膜材料,在MEMS工艺中具有广阔的应用前景,其力学性能测量的研究具有非常重要的意义。本文将数字散斑相关技术和微拉伸试验相结合,对厚度为 37μm的聚酰亚胺(polyimide) /二氧化硅(SiO2 )合成薄膜进行了力学性能测量,获得了比较满意的结果。文章给出了测得的弹性模量和泊松比。为了解决数字散斑相关法不能直接测量较大变形的缺陷,本文提出了多级相关算法,并利用亚像素搜索和双线性插值进行了数据处理。