Effect of surface tension and coefficient of thermal expansion in 30 nm scale nanoimprinting with two flexible polymer molds

We report on nanoimprinting of polymer thin films at 30?nm scale resolution using two types of ultraviolet (UV)-curable, flexible polymer molds: perfluoropolyether (PFPE) and polyurethane acrylate (PUA). It was found that the quality of nanopatterning at the 30?nm scale is largely determined by the combined effects of surface tension and the coefficient of thermal expansion of the polymer mold. In particular, the polar component of surface tension may play a critical role in clean release of the mold, as evidenced by much reduced delamination or broken structures for the less polarized PFPE mold when patterning a relatively hydrophilic PMMA film. In contrast, such problems were not notably observed with a relatively hydrophobic PS film for both polymer molds. In addition, the demolding characteristic was also influenced by the coefficient of thermal expansion so that no delamination or uniformity problems were observed when patterning a UV-curable polymer film at room temperature. These results suggest that a proper polymeric mold material needs to be chosen for patterning polymer films under different surface properties and processing conditions, providing insights into how a clean demolding characteristic can be obtained at 30?nm scale nanopatterning.     

Flame retardancy and thermal properties of epoxy acrylate resin/alpha-zirconium phosphate nanocomposites used for UV-curing flame retardant films

This paper reported the UV-curing flame retardant film, which consisted of epoxy acrylate resin (EA) used as an oligomer, tri(acryloyloxyethyl) phosphate (TAEP) and triglycidyl isocyanurate acrylate (TGICA) used as flame retardant (FR). The flame retardancy and thermal properties of films were reinforced by using alpha-zirconium phosphate (α-Zr (HPO₄)₂H₂O, α-ZrP). The morphology of nanocomposite film was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results showed that the organophilic α-ZrP (OZrP) layers were dispersed well in epoxy acrylate resin. Microscale Combustion Calorimeter (MCC), thermogravimetric analysis (TGA) and thermogravimetric analysis/infrared spectrometry (TGA-IR) were used to characterize the flame retardant property and thermal stability. It was found that the incorporation of TAEP and TGICA can reduce the flammability of EA. Moreover, further reductions were observed due to the addition of OZrP. The char residue for systems with or without OZrP was also explored by scanning electron microscopy (SEM).     

水性聚氨酯丙烯酸酯乳液的制备及性能

目的制备丙烯酸酯改性水性聚氨酯乳液,研究内交联剂对其性能的影响。方法以聚氨酯为种子乳液,以三羟甲基丙烷单烯丙基醚(TMPME)为扩链剂和内交联剂,以甲基丙烯酸甲酯(MMA)及丙烯酸酯丁酯(BA)为丙烯酸酯单体,制备丙烯酸酯改性的水性聚氨酯(WPUA),研究TMPME用量对WPUA及其胶膜性能的影响。结果当TMPME质量分数为3%时,乳胶膜的吸水率可降至7%;对乳胶膜进行热处理可进一步提高膜的耐水性;当TMPME质量分数为2%时,乳胶膜的拉伸强度可提高至8.7MPa,断裂伸长率升高至620%,综合性能最佳。结论引入一定量的TMPME,可以提高WPUA中分子的交联度和膜的致密性,从而显著改善乳胶膜的耐水性和力学性能。     

乙二胺化氧化石墨烯改性超支化聚氨酯-含丙烯酸酯复合乳液的制备与表征

采用乙二胺与丙烯酸丁酯依次对氧化石墨烯(GO)进行改性引入乙烯基(MGO),然后与丙烯酸酯类(含羟基)单体聚合获得含-OH的MGO/PA;同时在超支化聚氨酯核外围接枝线性聚氨酯获得含-NCO的超支化聚氨酯预聚体,两者混合后缩聚并交联,经乳化获得乙二胺化GO改性超支化聚氨酯-含丙烯酸酯复合乳液。通过红外光谱、X射线衍射、X射线光电子能谱、透射电镜、原子力显微镜、扫描电镜、热重分析等对材料进行表征,并探讨了不同含量MGO对乳液力学稳定性、胶膜耐水性、热性能以及力学性能的影响。结果表明,乙二胺对GO改性成功,剥离更完全且分散性很好。当引入聚丙烯酸酯(PA)固定含量为16%,随着MGO含量的增加,胶膜的水接触角、拉伸强度、吸水率均呈现先增加后降低的趋势,当MGO质量分数为0.46%时,与HBPU基体有较好的相容性,复合材料的综合性能最佳,其热分解温度提高了29℃,胶膜表面水接触角为99.7°,24 h吸水率为5.21%,拉伸强度为15.37 MPa,断裂伸长率为445.3%。     

自由基引发活性聚碳硅烷交联及其在制备SiC纤维中的应用

在基于先驱体聚碳硅烷转化制备SiC陶瓷纤维过程中,交联过程是保持纤维形貌和提高陶瓷产率的必要条件。本研究以含丙烯酸酯基的聚碳硅烷(A-PCS)为原料,通过引入自由基热引发剂在热解升温过程中实现原料的交联成型。采用红外光谱仪(FT-IR)和差示扫描量热仪(DSC)研究了引发剂含量对A-PCS交联程度、交联速率以及热降解速率的影响规律;采用热失重(TG)、元素分析仪和X射线衍射仪(XRD)分析了陶瓷产率、陶瓷产物组成以及无定形态随温度的变化。研究结果表明:加入自由基热引发剂可提高A-PCS中的丙烯酸酯基的交联速率,减少交联阶段的热失重;将质量百分比为1%自由基热引发剂的A-PCS以5℃/min升至250℃时,丙烯酸酯基反应完全,1500℃的陶瓷产率为69.5%;通过静电纺丝加工工艺可获得直径介于2～5μm的A-PCS原丝,并通过后续升温热解转化为SiC纤维;所得SiC纤维形貌规整、无熔并现象,且随着热解温度的升高从无定形态向结晶形态转变。     

铕杂EVA透明光转换膜的制备及交联动力学

将乙烯-乙酸乙烯酯共聚物（EVA）和乙酸乙烯酯-丙烯酸铕共聚物（VAA-Eu）的共混物（EVA/VAA-Eu）制成掺杂铕交联型透明光转换膜材料。紫外-可见吸收光谱和荧光光谱分析,表明此材料能将紫外线转换成蓝紫光和红光,作为农膜,可促进绿色植物的光合作用,提高阳光的利用效率。以硫化仪研究EVA/VAA-Eu的交联行为和动...     

单体组成对苯丙乳液及纸塑复膜胶性能的影响

以丙烯酸丁酯、苯乙烯等为主要单体,采用乳液聚合法制备了苯丙乳液纸塑复膜胶.主要研究了单体组成对乳液及胶粘剂性能的影响.结果表明,当软硬单体质量比在1.5～2.5范围内,甲基丙烯酸甲酯、2-乙基丙烯酸己酯、甲基丙烯酸含量分别为10%(质量分量,后同)、8%、2%～5%时,合成的乳液性能最佳.在最佳条件下合成的乳液配制成的胶粘剂对纸-聚酯(聚丙烯)膜表现出良好的粘接力,180°剥离强度可达7.75N/2.5cm(聚酯膜-白卡纸).     

多孔硅基热敏薄膜的制备与性能

对MEMS用具有绝热性能的多孔硅基底上沉积的热敏感薄膜进行了研究．首先用电化学方法制备多孔硅,分别在多孔硅基底和硅基底上通过溅射镀膜方法沉积氧化钒、Cu、Au热敏薄膜,测试多孔硅基底和硅基底上的氧化钒及金属薄膜电阻的热敏特性．结果表明,在多孔硅基底表面沉积的热敏薄膜具有与硅基表面热敏薄膜同样的热敏特性且表现出更高的灵敏度;此外,对沉积在不同制备条件得到的多孔硅上的氧化钒薄膜电阻热敏特性进行比较,发现随着孔隙率和厚度的增加,多孔硅的绝热性能提高,其上沉积的氧化钒薄膜电阻热敏特性增强．     

超临界CO2中聚丙烯酸丁酯/Fe3O4复合物的制备及应用

通过超临界二氧化碳(scCO2)沉淀聚合法制备了磁性聚丙烯酸丁酯(PBA/Fe3O4)复合物。首先经共沉淀法制备油酸(OA)改性的纳米Fe3O4颗粒,然后以丙烯酸丁酯(BA)为反应单体,偶氮二异丁腈(AIBN)为引发剂,二甲基丙烯酸乙二醇酯(EGDMA)为交联剂,正己烷为助溶剂,在scCO2中制备了PBA/Fe3O4复合物。对复合物进行了红外光谱、透射电镜、热重分析、X射线衍射表征和磁性能测试,结果显示OA-Fe3O4与PBA复合。对磁性复合物进行吸油性能测试,当反应压力为17MPa,改性纳米Fe3O4用量为6.7%时,反应生成的PBA/Fe3O4复合物对柴油的吸附量达7g/g,利用磁铁可对吸油复合物进行回收,经CO2再生后可重复使用10次,复合物对柴油的吸附量仍维持在5g/g以上。     

含氟丙烯酸酯聚合物研究进展

含氟聚丙烯酸酯除具备丙烯酸酯聚合物本身的成膜性好、网络结构疏松特点外,还表现出了氟聚合物的特点,有较低的表面能,疏水、疏油、耐腐蚀、耐热、抗氧化性等性能。文中介绍了近年来含氟丙烯酸酯聚合物的研究进展及与防水防油作用机理相应的结构特点,同时概括介绍了含氟丙烯酸酯中的碳原子对其性能的影响,并对常用的性能表征方法及应用研究作了简要总结和展望。     

Preparation of conductive transparent adhesive films from carbon nanomaterials and polar acrylate

Electrically conductive optically clear adhesives (ECOCAs) were prepared using a nanostructured carbon material (CMK-3(150)) as a conductive filler. The mesoporous carbon material, CMK-3(150), was synthesized using an ordered mesoporous silica template to produce inverse replica ordered mesoporous carbon material with an approximately 10 nm pore diameter. An adhesive solution of acrylic monomers containing polar acrylate, CMK-3(150), and thermal initiator was reacted at 80 degrees C to prepare the ECOCA composite which had appropriate viscosity for further processing. The adhesive composite was adhered to various surfaces including ITO films upon thermal processing at 60 degrees C to afford a highly transparent and adhesive film. Tensile strength of the ECOCA films was increased with the contents of conductive filler up to 4 wt%. The percolation concentration of the CMK-3(150) in the composite was approximately 7 wt%, which is much less than those of typical conductive fillers. The optimum content of CMK-3(150) to assure optical clarity, tensile strength, and high conductivity was 2-3 wt%.     

Measurement technique for thermal conductivity of thin polymer films

We present a modified steady-state heat flow technique, which allows measuring the thermal conductivity of films applied on a substrate. The measurement technique with the here presented setup provides an accuracy (overestimation) of 5-10% for film thickness up to 100 μm. For thicker films a correction factor based on finite-element simulations has to be used or the geometry has to be adapted. The technique is validated with thin glass plates of known thermal conductivity. To demonstrate the application of the technique the thermal conductivity of a thin polymer film of fluorinated acrylate is determined as 0.19 ± 0.02 W/mK.     

Thin film temperature sensor for cryogenic region with small magnetoresistance

Chromium nitride (CrN) thin films were fabricated onto Si wafers by RF magnetron sputtering equipment in pure N₂ gas. By adjusting the fabrication conditions, the film had negative temperature coefficient of resistance (TCR) below 300 K. It showed reasonable sensitivity between 300 and 1.8 K. The temperature resolution in the cryogenic temperature region was better than 1 mK. A good thermal cycle stability was observed. After 27 thermal cycles between 4 and 300 K, the coefficient of variation (CV) value was as small as 0.098% at 4 K, which corresponds to a 2.1 mK temperature shift. In addition, the thermometer was nearly insensitive to the magnetic field. The temperature shift due to magnetoresistance in a magnetic field of 9 T was less than 5 mK at 4 and 2 K. Therefore CrN can be an excellent choice of material for cryogenic temperature sensors under magnetic fields.     

Controlled preparation of macroporous TiO2 films by photo polymerization-induced phase separation method and their photocatalytic performance

TiO₂ films with controlled macroporous structures have been prepared from the precursor solution containing photo monomer pentaerythritol tetraacrylate by a photo polymerization-induced phase separation method (PIPS) in the absence of any surfactant and colloidal templates. The gel TiO₂ film deposited from the precursor solution by dip-coating was irradiated with ultraviolet light for some time. During the irradiation process, the polymerization of the photo monomer was induced, which resulted in the phase separation in the film system. After the reaction, two phases existed in the film, one was the emerging polymer rich phase, another was the residual monomer-TiO₂ oligomer rich phase. After heat-treatment at 600 °C, the entire polymer decomposed and a well-defined interconnected macroporous TiO₂ films could be obtained. X-ray diffraction, scanning electron microscopy, atomic force microscopy, thermogravimetric and differential thermal analysis were used to characterize the macroporous TiO₂ films. The results showed that the macroporous texture could be tuned by changing the composition of the precursor solution. The solvent evaporation was controlled by the addition of polyvinylpyrrolidone. Highly macroporous TiO₂ films prepared by the PIPS method exhibited much higher photocatalytic activity for the decomposition of methylene blue dye than the dense TiO₂ film.     

PBS/氧化石墨烯复合薄膜的制备与性能

目的利用氧化石墨烯(GO)为填料制备聚丁二酸丁二醇酯(PBS)的增强复合薄膜材料。方法以生物可降解材料PBS为基体,以GO为纳米增强相,首先用双十二烷基二甲基溴化胺(DDAB)对GO进行修饰,进而通过溶液复合法制备PBS/GO复合薄膜,并对其力学性能、结晶熔融行为和热稳定性进行表征。结果力学性能测试表明,在GO质量分数为0.1%时,复合薄膜的拉伸强度和断裂伸长率较纯PBS分别提高了37%和25%,但是随着GO含量的继续增加,其拉伸强度和断裂伸长率都呈现出下降趋势;热行为分析表明,GO的加入使PBS的熔融温度和结晶温度均有所提高,结晶度有所下降,但GO对PBS的热稳定性并无明显影响。结论适量GO的加入有利于改善PBS生物降解材料的力学性能和结晶熔融行为。     

Thermal conductivity of graded composites: Numerical simulations and an effective medium approximation

We describe two methods for modeling the thermal conductivity and temperature profile in a graded composite film. The film consists of a random binary composite, whose concentration varies in the direction perpendicular to the film surface, and a fixed temperature difference is applied across the film. In the first method, the temperature profile is modeled directly, using a finite element technique in which the film is represented as a discrete network of thermal conductances, randomly distributed according to the assumed composition profile. The temperature at each node, and the effective thermal conductance, is then obtained by a transfer matrix technique. In the second approach, the film is treated by an effective-medium approximation, suitably generalized to account for the composition gradient. The methods are in rough agreement with each other, and suggest that thermophysical properties of the film can be treated reasonably well by approaches generalized from those which succeed in conventional composites.     

含氟丙烯酸酯复合乳液的制备及性能

含氟丙烯酸酯性能优异,目前以丙烯酸六氟丁酯(HFBM)单体合成水性含氟丙烯酸酯乳液的报道较少。以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)、丙烯酸(AA)为主要单体,HFBM为功能单体,采用预乳化工艺合成了含氟丙烯酸酯复合乳液,优化了乳液合成条件(复合乳化剂配比、引发剂用量、含氟单体用量),并用红外光谱和热重分析研究了优化条件合成乳液的结构和其所成乳胶膜的热稳定性。结果表明:复合乳化剂中m(十二烷基硫酸钠)∶m(曲拉通X-100)=3∶2,引发剂(过硫酸钾)用量为1.0%,含氟单体用量为9%时,合成的含氟丙烯酸酯复合乳液性能最好,具有较大的单体转化率和较小的凝胶率,乳胶膜有较大的拉伸强度;HFBM被成功地引入聚合物链段结构中,并使聚合物的热稳定性大幅提高。     

Amorphous thin film active elements in switching devices

The history of amorphous switches in the field of solid state electronic devices is quite unusual. Switching was first demonstrated before there was any understanding of the mechanism involved and it triggered off wide research activity and speculations as to whether it would revolutionize microelectronics. After a few years of intense research the enthusiasm in amorphous active devices began to decrease as the basic switching mechanism was found to be associated with electrothermal instabilities. Although electronic switching models were suggested, at the same time the generality of the thermal explanation became evident because it could be based on measurable electrical and thermal characteristics of the device and was therefore not influenced by the actual current transport mechanism. The high temperatures connected with switching gave little promise of marked improvements in the maintenance characteristics of amorphous thin film switches. The many studies of amorphous semiconducting materials have significantly increased the understanding of basic material properties, thus forming an improved basis for future evaluations of possible applications.     

Measurement and modelling of heat transfer in paper coating structures

Thermal conductivity of paper coatings is increasingly important in the performance of many printing processes, including traditional heatset web offset and thermal papers, as well as digital processes, such as electrophotography. This work studies the extension of a Modified Lumped Parameter Model, previously used successfully to describe talc coatings, to model the thermal conductivity–coating structure relationships of calcium carbonate (gcc: 60 wt% < 2 μm) coatings. A series of compact tablets were used to provide experimental values of thermal diffusivity and conductivity. The samples studied covered a range of latex binder addition levels, namely 0–25 parts, based on 100 parts pigment, of 0.2 μm styrene acrylate latex. Combining the observed thermal properties with knowledge of the pore structure changes induced by the latex addition, it is possible to establish initial correlation with the model, in which the connectivity of the structure is increased at low latex dose illustrating the initial increase in effective thermal conductivity. The practically hard sphere properties of the latex used, combined with the broad size distribution of the gcc, produce a disruptive packing effect as the dose level increases, such that the conductivity reflects a competition between the increasing connectivity provided by the latex versus the increasing relative pore size in the network structure. It is recognized that the fixed pigment volume in the model unit cell diverts from a true representation of the residual porosity. At the highest latex dose levels, the intrinsically less conducting properties of the latex begin to dominate.

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A directly patternable click-active polymer film via initiated chemical vapor deposition (iCVD)

A new “click chemistry” active functional polymer film was directly obtained from a commercially available monomer of propargyl acrylate (PA) via easy, one-step process of initiated chemical vapor deposition (iCVD). Fourier transform infrared (FTIR) spectra confirmed that significant amount of the click-active acetylene functional group was retained after the iCVD process. The degree of crosslinking could be controlled by intentionally adding crosslinker, such as ethylene glycol diacrylate (EGDA) that was polymerized with PA to form click-active, completely insoluble copolymer. The formed iCVD polymers could also be grafted on various inorganic substrates with silane coupling agents. These crosslinking and grafting techniques give iCVD polymers chemical and mechanical stability, which allows iCVD polymers applicable to various click chemistry without any modification of reaction conditions. Pre-patterned iCVD polymer could be obtained via photolithography and an azido-functionalized dye molecule was also successfully attached on iCVD polymer via click chemistry. Moreover, pPA film demonstrated sensitivity to e-beam irradiation, which enabled clickable substrates having nanometer scale patterns without requiring the use of an additional e-beam resist. Direct e-beam exposure of this multifunctional iCVD layer, a 200 nm pattern, and QD particles were selectively conjugated on the substrates via click chemistry. Thus, iCVD pPA has shown dual functionality as of “clickable” e-beam sensitive material.