Cover Picture: Toward Large‐Scale Alignment of Electrohydrodynamic Patterning of Thin Polymer Films (Adv. Funct. Mater. 15/2006)

By integrating lithography and self‐assembly via electrohydrodynamic instabilities, Russel and co‐workers are able to guide initially flat polymer films to evolve into periodic arrays of pillars over regions much greater in extent than their natural domain sizes, as detailed on p. 1992. Novel structures that involve a combination of linear ridges and pillars are also produced, mainly as as result of the dynamic merging among preformed pillars. To pattern thin polymer films via electrohydrodynamic instabilities, we design and utilize two different kinds of mask patterns to guide pillars into alignment over regions much greater in extent than their natural domain sizes. First, narrow protruding ridges that intersect to form regular patterns on the mask trigger the growth of pillars beneath. Later, square and triangular packings of pillars develop in the regions enclosed by those ridges, preserving the registry from one domain to the next over a much larger area than within individual domains in unpatterned portions of the mask. Second, small square protrusions that are prealigned into a large regular array on the mask guide the formation of square packings of pillars in domains that conform to the mask, forming a large array of pillars. Novel structures involving a combination of linear ridges and pillars are also produced mainly due to the dynamic merging among preformed pillars. Finally, we find vertex symmetry of the mask pattern is necessary for generating and preserving ordered patterns on the polymer film.     

PMMA‐modified divinylester/styrene resins: Phase diagrams and morphologies

Binary and ternary experimental cloud‐point curves (CPCs) for systems formulated with a low molar mass synthesized divinylester (DVE) resin, styrene (St), and poly(methyl methacrylate) (PMMA) were determined. The CPCs results were analyzed with the Flory–Huggins (F‐H) thermodynamic model taking into account the polydispersity of the DVE and PMMA components, to calculate the different binary interaction parameters and their temperature dependences. The St‐DVE system is miscible in all the composition range and down to the crystallization temperature of the St; therefore, the interaction parameter expression reported for a higher molar mass DVE was adapted. The interaction parameters obtained were used to calculate the phase diagrams of the St‐PMMA and the DVE‐PMMA binary systems and that of the St‐DVE‐PMMA ternary system at three different temperatures. Quasiternary phase diagrams show liquid–liquid partial miscibility of the St‐PMMA and DVE‐PMMA pairs. At room temperature, the St‐DVE‐PMMA system is miscible at all compositions. Final morphologies of PMMA‐modified cured St‐DVE materials were generated by polymerization‐induced phase separation (PIPS) mechanism from initial homogeneous mixtures. SEM and TEM micrographs were obtained to analyze the generated final morphologies, which showed a direct correlation with the initial miscibility of the system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4539–4549, 2006     

Fabrication and characterization of planar and channel polymer waveguides. III. Compositional distribution and solute loss in polymer thin films

For many microelectronic and optoelectronic applications, polymer thin films require the addition of small molecules. However, the thin‐film geometry and associated processing techniques will influence the final morphology and compositional distribution of the constituents. It is therefore important that these be examined directly rather than inferred from bulk measurements. As an example system, the concentration and distribution of Disperse Red 1 (DR1) molecules in poly(methyl methacrylate) thin films were examined. Ultraviolet visibility spectroscopy and dynamic secondary ion mass spectrometry indicate that the composition of the molecules decreased dramatically with thermal treatment of the film. The sublimation of the chromophore was observed to occur at temperatures well below the melting point of the small molecule and the glass transition of the pure polymer; this solute loss manifested itself in changes in the glass transition temperature of the film. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2021–2024, 2002     

有机玻璃的增韧研究

研究了不同聚合方法制备的聚丙烯酸丁酯（PBA）对浇铸型有机玻璃（PMMA）的增韧改性，研究结果表明，当PBA以纳米粒子簇分散在PMMA基体中时，对PMMA有较好的增韧改性效果。当PMMA中无皂乳液聚合PBA（e-PBA)的质量分数为0.5%时。改性PMMA的冲击强度比基体提高38%。SEM观察表明，本体聚合PBA（b-PBA)橡胶粒子以独特的纳米簇状结构均匀分布在PMMA基体中，大量的微裂纹以b-PBA粒子为中心呈放射状向外辐射，这些微裂纹在试样破坏的过程中吸收了大量的冲击能，使改性PMMA韧性得以提高。     

A modified model predictions and experimental results of weld-line strength in injection molded PS/PMMA blends

In this paper, the model based on melt diffusion and Flory-Huggins free energy theory for predicting the weld-line strength of injection molded amorphous polymers and polymer blends parts were modified by considering the diffusion thickness in the interface as a function of contact time. The modified model for weld-line strength prediction of homopolymers and polymer blends were, respectively, used to evaluate the weld-line strength of Polystyrene (PS) and Poly(methylmethacrylate) (PMMA), and that of PS/PMMA blends. The model predictions show that the theoretic predictions as a function of temperature and contact time for PS, PMMA and PS/PMMA (80/20, 70/30) are in good agreements with corresponding experimental results. However, the model predictions for PS/PMMA (20/80, 30/70) blends are much higher than experimental results. The morphology in weld-line regions for PS/PMMA (20/80, 30/70) shows lack of dispersed PS phase. Near the weld-line regions, dispersed PS phase is highly oriented along the weld-line. In theoretic prediction for polymer blends, three kinds of diffusion: Polymer A-Polymer A and Polymer B-Polymer B self-diffusions and Polymer A-Polymer B mutual diffusion were considered. This is why model predictions for PS/PMMA (20/80, 30/70) blends are higher than experimental results.     

Investigation on the early and late stage phase-separation dynamics of poly(methyl methacrylate)/poly(α-methyl styrene-co-acrylonitrile) blends through rheological and scattering functions

The phase-separation behavior of poly(methyl methacrylate)/poly(α-methyl styrene-co-acrylonitrile) (PMMA/α-MSAN) blends with two different compositions was studied by time-resolved small angle light scattering (SALS) in the spinodal decomposition (SD) regime from 160 to 210 °C. The rheological function (WLF-like equation) was introduced into the processing of light scattering data. It was found that the WLF-like equation was applicable to describe the temperature dependence of apparent diffusion coefficient D_app and the relaxation time τ of normalized scattering intensity (I(t)−I(0))/(I_m−I(0)) at the early stage of SD, as well as the relaxation time τ of maximum scattering intensity I_m and characteristic scattering vector q_m with I_m at the late stage of SD for PMMA/α-MSAN blends with two different compositions. This is in consistence with the phase-separation behavior of PMMA/SAN reported in our previous paper.     

Preparation of rechargeable lithium batteries with poly(methyl methacrylate) based gel polymer electrolyte by <Emphasis Type="Italic">in situ</Emphasis>γ-ray irradiation-induced polymerization

An admixture of commercial liquid electrolyte (LB302, 1 M solution of LiPF₆ in 1:1 EC/DEC) and methyl methacrylate (MMA) was enclosed in CR2032 cells. The assembled cells were then -ray-irradiated using configurations of half cells and full cells. Through this in situ irradiation polymerization process, we obtained rechargeable lithium ion cells with poly(methyl methacrylate) (PMMA) based gel polymer electrolytes (GPE). Galvanostatic cycling, AC impedance spectroscopy, and cyclic voltammetry were employed to investigate the electrochemical properties of the cells and the gel polymer electrolyte. This PMMA-based gel polymer electrolyte was found to exhibit a high ionic conductivity (at least 10^–3 S cm^–1) at room temperature. Due to a significant increase in the charge transfer resistance between the GPE and the cathode, the cell impedance of a PMMA-based lithium ion cell is greater than that of a liquid-electrolyte-based cell. The discharge capacity of a LiNi_0.8Co_0.2O₂/GPE/graphite is approximately 145 mAh g^–1 for the first cycle and decreases to123 mAh g^–1 after 20 cycles. In addition, a large initial cell impedance (LICI) was observed in the irradiated positive half cell. In this paper, we propose a possible mechanism related to the detachment of the PMMA layer from the lithium electrode. This detachment of the PMMA layer from the lithium electrode has not been explicitly discussed previously.     

定向MWNTs/PMMA的原位聚合制备及耐磨损性

采用原位聚合方法制备了定向碳纳米管/聚甲基丙烯酸甲酯复合材料,并且研究了该复合物的耐磨损性.对定向碳纳米管及其复合物进行了傅立叶红外吸收光谱分析、扫描电镜及光学显微镜观察.采用砝码质量法评价了复合物的耐磨损性.分析结果表明,混酸处理后定向碳纳米管附带了-OH、-COOH基等极性基团.混酸处理后定向碳纳米管束状结构被破坏,定向碳纳米管可以单管形态分散于基体中,碳纳米管表面包覆着PMMA.砝码质量法耐磨损性测试结果表明,定向碳纳米管的加入可提高PMMA复合物的耐磨损性和耐划痕性,当定向碳纳米管用量为0.7%时,复合物的耐磨损性能提升了54%.     

Thermal degradation of foamed polymethyl methacrylate in the expendable pattern casting process

The thermal degradation of foamed polymethyl methacrylate (PMMA) patterns in the expendable pat-tern casting process has been studied. Various physical transitions that may occur during the degradation of PMMA have been determined using scanning electron microscopy, differential scanning calorimetry, and thermogravimetric analysis, and the effects of polymer density on the degradation characteristics have been investigated. The results indicate that, when exposed to elevated temperatures, the polymer beads collapse at about 140 to 200 °. The collapsed beads melt at 260 ° and begin to volatilize. Peak volatilization temperatures are on the order of 370 °. The end temperature for volatilization is between 420 and 430 °. The initial density of the polymer does not have a significant effect on the transition tem-peratures associated with degradation.