Effect of Nonsolvent on the Formation of Polymer Nanomaterials in the Nanopores of Anodic Aluminum Oxide Templates

We study the effect of nonsolvent on the formation of polymer nanomaterials in the nanopores of porous templates. Water (nonsolvent) is added into a poly (methyl methacrylate) (PMMA) solution in dimethylformamide (DMF) confined in the nanopores of an anodic aluminum oxide (AAO) template. Water forms a wetting layer on the pore wall and causes the PMMA solution to be isolated in the center of the nanopore, resulting in the formation of PMMA nanospheres or nanorods after the solvent is evaporated. The formation of the polymer nanomaterials induced by nonsolvent is found to be driven by the Rayleigh‐instability‐type transformation. Without adding the nonsolvent, PMMA chains precipitate on the walls of the nanopores after the solvent is evaporated, and PMMA nanotubes are obtained.     

A simple strategy for detecting synthetic polymers on solid surfaces using liquid crystal

In this study, we developed a liquid crystal (LC)-based detection method for polymer films synthesized on solid surfaces. A dark to bright transition in the optical appearance of nematic 4-cyano-4′-pentylbiphenyl (5CB) was observed after transferring a poly(methyl methacrylate) (PMMA) film onto a glass substrate functionalized with n-octyltrichlorosilane (OTS). This phenomenon indicates an orientational transition of 5CB from a homeotropic to a planar-random state. The optical response of 5CB was then evaluated directly through polymerization reactions on the OTS-functionalized glass substrate. Polymer films of PMMA, poly(glycidyl methacrylate) (PGMA), and poly(dimethylsiloxane) (PDMS) were synthesized on OTS surfaces covered with their reaction mixtures. All polymer films displayed bright signals of 5CB, which corresponded to the planar-random orientation of LCs. However, no change in orientation was observed for the control experiments. We confirmed the formation of polymer films on the OTS surface using atomic force microscopy. Overall, our results suggest that LCs can be used to construct optical monitoring systems for the product of polymerization reactions.

Effect of nano‐size nodular structure induced by CNT‐promoted phase separation on the fabrication of superhydrophobic polyvinyl chloride films

The nonsolvent‐induced phase separation (NIPS) method was employed to fabricate the porous films based on polyvinyl chloride loaded with carbon nanotubes (CNTs). The combinational addition of CNTs and a proper nonsolvent (ethanol) resulted in a porous surface layer with the nano‐size nodular structure possessing an exact superhydrophobic behavior (water contact angle [WCA] = 157° and sliding angle [SA] <5°). The size of PVC nodules at the surface layer varies in the range of 200 to 800 nm depending on the nonsolvent concentrations, and polymer molecular weight. The effects of various nonsolvent concentrations as well as PVC molecular weight on the surface properties of the films were also investigated. Morphological and roughness analyses revealed the pronounced role of PVC molecular weight on the size of nodules, and the structural uniformity of the surface morphology based on the thermodynamic parameters such as relaxation time and dynamic of polymer chains. The concurrent use of CNTs and nonsolvent led to promote the NIPS process due to the nucleating role of CNTs, which were localized within the polymer‐rich phase leading to an ultra‐fine and packed nodular surface structure. Transmission electron microscopy results also proved the very well dispersion quality of CNTs. Glass transition temperature of PVC was also assessed, and the results were correlated to the associating ability of CNTs with polymer chains during the phase separation process. Overall, the promising potential of CNT/ethanol combination on the surface porosity and hydrophobicity of PVC nanocomposite films was revealed in this study, which could further extend its application window.     

Forming Lipid Bilayer Membrane Arrays on Micropatterned Polyelectrolyte Film Surfaces

A novel method of forming lipid bilayer membrane arrays on micropatterned polyelectrolyte film surfaces is introduced. Polyelectrolyte films were fabricated by the layer‐by‐layer technique on a silicon oxide surface modified with a 3‐aminopropyltriethoxysilane (APTES) monolayer. The surface pK_a value of the APTES monolayer was determined by cyclic voltammetry to be approximately 5.61, on the basis of which a pH value of 2.0 was chosen for layer‐by‐layer assembly. Micropatterned polyelectrolyte films were obtained by deep‐UV (254 nm) photolysis though a mask. Absorbed fluorescent latex beads were used to visualize the patterned surfaces. Lipid bilayer arrays were fabricated on the micropatterned surfaces by immersing the patterned substrates into a solution containing egg phosphatidylcholine vesicles. Fluorescence recovery after photobleaching studies yielded a lateral diffusion coefficient for probe molecules of 1.31±0.17 μm² s^?1 in the bilayer region, and migration of the lipid NBD PE in bilayer lipid membrane arrays was observed in an electric field.     

Construction of ternary phase diagrams in nonsolvent/solvent/PMMA systems

In this work, the ternary phase diagrams in three nonsolvent/solvent/PMMA systems (n-hexane/n-butyl acetate/PMMA, water/acetone/PMMA, and n-hexane/acetone/PMMA) were constructed by theoretical calculation and experimental measurement. Binodal curves were calculated by using the Flory–Huggins theory for three-component systems and measured by titrating the PMMA solution with nonsolvent until the onset of turbidity. By using concentration-dependent nonsolvent/solvent and solvent/PMMA interaction parameters and constant nonsolvent/PMMA interaction parameters, good agreement has been obtained between the calculation and the measurement. The values of nonsolvent/solvent interaction parameters were taken from the literature sources, and the values of solvent/PMMA and nonsolvent/PMMA interaction parameters were measured by vapor sorption and swelling equilibrium, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 607–615, 1998     

Nanostructure formation in polymer thin films influenced by humidity

The influence of relative humidity (RH) during the film preparation on the surface morphology and on the material distribution of the resulting technical polymer blend films consisting of poly (methyl methacrylate) (PMMA) and poly (vinyl butyral) (PVB) is investigated by atomic force microscopy. Both pure polymers and polymer blends with different compositions of PVB/PMMA dissolved in tetrahydrofuran (THF) were used. Polymer films prepared under dry conditions (RH < 20%) are compared with those that have the same polymer composition but were prepared under increased humidity conditions (RH > 80%). The films consisting of the pure polymers showed a nonporous surface morphology for low‐humidity preparation conditions, whereas high‐humidity preparation conditions lead to porous PVB and PMMA films, respectively. These pores are explained as the result of a breath figure formation. In the case of the polymer blend films containing both polymers, porous or phase‐separated surface structures were observed even at low‐humidity conditions. A superposition of the effects of phase separation and breath figure formation is observed in the case of polymer blend films prepared under high‐humidity conditions. Atomic force microscopy (AFM) images taken before and after the treatment with ethanol as a selective solvent for PVB indicate that PMMA is deposited on top of a PVB layer in the case of the low‐humidity preparation process whereas for high‐humidity conditions the silicon substrate is covered with a PMMA film. Copyright © 2006 John Wiley & Sons, Ltd.     

A novel approach to the micropatterning of proteins using dewetting of polymer bilayers

The ability to control protein and cell positioning on a microscopic scale is crucial in many biomedical and bioengineering applications, such as tissue engineering and the development of biosensors. We propose here a novel, simple, and versatile method for the micropatterning of proteins. Micropatterned substrates are produced by the dewetting of a metastable polymer film on top of another polymer film. Selective adsorption, or micropatterning, of proteins can be achieved on such substrates by choosing pairs of polymers which differ in protein affinity. In this study, patterns were produced in bilayers of poly(methylmethacrylate) (PMMA) and polystyrene (PS), and of PMMA and octadecyltrichlorosilane (OTS). Fluorescence microscopy and atomic force microscopy (AFM) provide evidence that model proteins adsorb preferentially on isolated bio-adhesive (PS and OTS) micropatches in a protein-resistant (PMMA) matrix. "Inverse" protein patterns, containing non-adhesive (PMMA) islands in a protein-adhesive (PS) matrix can also be produced. Such micropatterned substrates could potentially be used in the development of biosensors and bioassays, and in the study of cell growth and motility.     

漆酚醛胺聚合物多孔膜的制备

以漆酚醛胺聚合物(UFDP)为成膜材料,利用水辅助自组装的固体基板展开法和水面展开法制备了漆酚醛胺聚合物多孔膜.研究了在静态(即不在聚合物表面吹扫氮气)高湿度环境下聚合物溶液浓度、环境湿度和固体基板等因素对多孔膜形貌的影响.结果表明,水面展开法更有利于形成单层的多孔膜而固体基板展开法得到的是多层的多孔膜.当UFDP聚合物浓度为6.0 mg/mL,环境相对湿度为90%时,用水面展开法制得的单层多孔膜的孔径分布较均匀.     

A simple route to micropatterned polymer surfaces

Polymer surfaces with uniform microscale concave arrays were fabricated by spreading polymer solution on the nonsolvent surface, and the concave-patterned surface could further be used as a template to structure convex-patterned polymer surfaces.     

Poly(methyl methacrylate) Membrane: Dynamic Measurement of Concentrations During Water-Induced Phase Separation

The properties of membranes produced by nonsolvent-induced phase separation (NIPS) depend on the rate of mass transfer of mobile components. This paper reports the use of Fourier transform infrared-attenuated total reflectance (FTIR-ATR) using principle component regression (PCR) analysis to study the compositional change of polymer solution immersed into the water prior to the phase demixing. To correlate the compositional change with the macroscopic structure, the observation on the dynamics of NIPS is made by a low magnification optical microscope equipped with a video camera. The morphology of the films was also examined by scanning electron microscope. Acetone and N, N-dimethylformamide were chosen as solvents to present different behavior of poly (methyl methacrylate) (PMMA) solutions during the NIPS process. The ratio of solvent and nonsolvent exchange, flux ratio shows the mass transfer in the homogeneous polymer solution after immersion in a nonsolvent bath. The results show that the flux ratio ( ) is affected by solvents which probably affects the ultimate structures of the precipitated polymer.     

硅表面CS/BSA复合微图形的制备及表征

采用微加工方法在硅表面成功地制备出壳聚糖/牛血清白蛋白(CS/BSA)复合微图形. 借助光镜和荧光显微镜对复合微图形进行形貌分析. 利用大肠杆菌和白色葡萄球菌定量考察了CS/BSA复合微图形的抗菌性能, 结果表明, 硅表面沟槽交叉状CS/BSA复合微图形对两种细菌都具有较好的抗菌效果. 通过MC3T3-E成骨细胞培养考察了复合微图形的细胞相容性, 结果表明, CS/BSA复合微图形对于细胞的生长方向具有较强的诱导性, 可促进细胞在材料表面的黏附、铺展及增殖分化. 结果表明, 采用微转移模塑法制备的CS/BSA复合微图形具有较好的抗菌性和细胞相容性.     

基板界面对PS/PMMA共混物薄膜相逆转组成比的影响

近年来高分子共混体系中的界面、表面效应逐渐引起了越来越多研究者的兴趣 .人们发现 ,当共混物薄膜厚度减至一定程度时 ,聚合物共混物薄膜中的相形态、相容性及相分离动力学与本体中有较大的不同[1～ 3] .基板界面作用对共混薄膜体系的热力学、动力学行为产生很大的影响 .我们以往的研究 [4 ,5]也发现 ,PP/EVAc(70 /30 )共混体系退火过程中 ,基板界面 (如玻璃 )作用可大大加速分散相(EVAc)粒子的粗化凝聚过程 .本研究用聚甲基丙烯酸甲酯和聚苯乙烯共混物的四氢呋喃溶液在不同基板介质 (如玻璃基板 ,PP基板 )上成膜 ,用相差显微镜观测了…     

Tunable metallization by assembly of metal nanoparticles in polymer thin films by photo- or electron beam lithography

The technique of patterning of surfaces with metal-rich structures on micro- or nanoscales was developed by assembling metal nanoparticles into a thin film of polymer in a controllable way. Palladium (Pd) nanoparticles were incorporated into a thin film of poly(methyl methacrylate) (PMMA) using palladium (II) bis(acetylacetonato), Pd(acac)(2), as a precursor vaporized in a nitrogen atmosphere. Depending upon its dose, the irradiation of a PMMA film by UV light or an electron beam (EB) enhances its reducing capability against Pd(acac)(2). This dependency on dose can be used to control the formation and assembly of Pd nanoparticles. Using this technique, binary patterns consisting of metal-rich and metal-poor regions in the polymer film can be created simply by irradiating the surface of the polymer through a binary photomask. Besides the creation of binary patterns, it is also possible to create grayscale patterns where the density of Pd nanoparticles can be tuned to provide shades of gray by the use of light with continuously modulated intensity. Because the electron beam also enhances the reducing power of PMMA against Pd(acac)(2), it is thus possible to obtain highly metallized films with nanoscale pattern features. The PMMA film can be selectively removed by oxygen plasma treatment or by pyrolysis. Thus, highly metallized surfaces with binary or grayscale patterns can be obtained by selective removal of the PMMA films. The metallized regions possess relatively high resistivity against CF(4) plasma compared to the bare silicon surface; therefore, the metallized surface patterns can be transferred onto the underlying silicon substrate by CF(4) plasma treatment. Because of the nanosize effect of metal nanoparticles, the thermal treatment at 900 degrees C, which is significantly lower than the melting temperature of the bulk Pd, yields continuous metallic features by binding the assembled nanoparticles.     

Anomalous reinforcing effects in cellulose gel-based polymeric nanocomposites

Cellulose-synthetic polymer nanocomposite films were prepared by immersion of cellulose gel in polymer solutions followed by dry casting. The cellulose hydrogel was prepared from aqueous alkali-urea solution. As the synthetic polymer, polystyrene (PS) and poly(methyl methacrylate) (PMMA) were used. The polymer content could be changed between 10 and 80% by changing polymer concentration of immersing solution. While the mechanical properties of the cellulose-PMMA composite films showed a nearly linear dependence on PMMA content, those of cellulose-PS composites showed an anomalous behavior; both tensile strength and Young’s modulus showed prominent maxima at 15–30 wt% PS contents. This anomaly may have resulted from the specific interaction between the aromatic ring of PS and the hydrophobic plane of the glucopyranoside. Both PMMA and PS composite films showed significant improvements in dimensional thermal stability; up to 25 wt% synthetic polymer content, the coefficient of thermal expansion (CTE) was as low as ca. 30 ppm/K, about 1/3 of the pure polymers. This indicates that the regenerated cellulose network is effective in suppressing thermal expansion of the synthetic polymers.     

A novel quartz crystal microbalance gas sensor based on porous film coatings. A high sensitivity porous poly(methylmethacrylate) water vapor sensor

We describe a novel and generally applicable approach for creating voids in films deposited on the surface of solid substrates. Such films are advantageous when a quartz crystal microbalance (QCM) is the basis of a sensor. We show that films with large void volumes produce more sensitive sensors than with the original film. Poly(methylmethacrylate) (PMMA) was used as the polymer layer deposited on a quartz crystal microbalance (QCM) to demonstrate our technique for the model system of water vapor analysis in flowing nitrogen gas. A film of pure PMMA on a QCM is a sensor for water vapor in a gas phase. A more sensitive sensor was created by dip coating QCM crystals into solutions containing mixtures of PMMA and poly(d,l-lactide) (PDLL) and then evaporating the solution films on the QCM crystals to form mixed polymer films of varying PDLL content. The PDLL was then removed from the mixed polymer films by exposure to a NaOH solution to form pure PMMA films having various void volumes. A leached PMMA film that originally contained 50% by weight PDLL had a 3.7 times larger QCM sensitivity for water vapor than a pure PMMA film.     

Characterization of patterned poly(methyl methacrylate) brushes under various structures upon solvent immersion

In this paper we describe a graft polymerization/solvent immersion method for generating various patterns of polymer brushes. We used a very-large-scale integration (VLSI) process and oxygen plasma system to generate well-defined patterns of polymerized methyl methacrylate (MMA) on patterned Si(1 0 0) surfaces through atom transfer radical polymerization (ATRP). After immersion of wafers presenting lines of these PMMA brushes in water and tetrahydrofuran, we observed mushroom- and brush-like regimes through grafting densities and surface coverages, respectively, for the PMMA brushes with various pattern resolutions. In the mushroom-like regime, the distance between lines of PMMA brushes was smaller than that of the lines patterned lithographically on the wafer; in the brush-like regime, this distance was approximately the same. This new strategy allows polymer brushes to be prepared through graft polymerization and then have their patterns varied through solvent immersion.     

Controlling and manipulating supported phospholipid monolayers as soft resist layers for fabricating chemically micropatterned surfaces

Chemically micropatterned surfaces have broad applications in many fields. In this paper, we report a new method for preparing chemically micropatterned surfaces by controlling and manipulating supported phospholipid monolayers as soft resist layers with molecular-level precision. First, we introduce self-assembled supported phospholipid monolayers on solid surfaces and use a microcontact lift-up process to create micropatterned phospholipid monolayers (with micrometer resolution) on the surface. Next, the micropatterned phospholipid monolayers can function as "soft" resist layers to protect underlying solid substrates and create either positive or negative chemically micropatterned surfaces during subsequent treatments. Unlike traditional "hard" resist layers which can only be removed by using harsh chemical treatments, this novel soft resist layer only comprises a single layer of compact phospholipid; therefore, it can be easily removed by water rinsing after the preparation of micropatterns. This method is also versatile. It can be applied to prepare a protein microarray or silver patterns on solid substrates.     

Effect of water contact on the density distributions of thin supported polymer films investigated by an X-ray reflectivity method

The diffusion processes of water molecules into polymer films (PMMA/PS homopolymers and random copolymers) in contact with liquid water were investigated using gravimetric methods and X-ray reflectivity (XRR) analysis. Methods of water contact and XRR measurement were designed for studying the systems in the nonequilibrium state of diffusion. Gravimetric measurements confirmed the Fickian diffusion behavior of films in contact with water. Vertical density distributions in PMMA and methylmethacrylate-rich copolymer films demonstrate the existence of a water-rich layer at the interface. However, with further absorption of water into the film, the overall density increased throughout the film. The results suggest that the diffusion of water into the polymer film occurs to recover density uniformity with a high concentration of water molecules at the surface. Some XRR data for the PS- and styrene-rich copolymer films could not be fit and converted to a vertical density distribution because of their huge diffusion coefficients. However, the reflectivity curves for these films and the vertical density distribution after sufficient water contact suggested that the surfaces of these films were commonly diffused after water contact. Atomic force microscopy (AFM) analysis demonstrated that the surface roughness of these films actually increased with water content.     

Promoting organic room temperature phosphorescence through in situ polymerization

Organic room temperature phosphorescence materials (RTP) have attracted much attention for their wide application in organic light-emitting diodes, anti-counterfeiting, and sensors. In this work, a series of organic luminogens containing carbonyl and aromatics were fixed in a three-dimensional polymethyl methacrylate (PMMA) network by in situ polymerization. All organic luminogens-doped in situ PMMA (s-PMMA) columns achieved longer RTP lifetimes than those of doped commercial PMMA (c-PMMA) films, especially, the RTP lifetime of NMP2O in these PMMA matrixes increased from 1.82 ms to 156.34 ms by about 86 times. It is mainly due to the restriction of molecular motions by highly entangled polymer chains and rigid environments to efficiently inhibit the non-radiative transitions. Also, the excellent shielding effect toward oxygen by the in situ polymerization process can avoid possible quenching effects on triplet excited states, beneficial to RTP emission. Thus, it affords an efficient approach to achieving persistent RTP for three-dimensional displaying applications.     

Facile surface immobilization of ATRP initiators on colloidal polymers for grafting brushes and application to colloidal crystals

Bromo-initiators for atom transfer radical polymerization (ATRP) were successfully immobilized on the surfaces of cross-linked poly(methyl methacrylate) (PMMA) spheres by soap-free emulsion polymerization using CBr(4) as the chain transfer agent. Subsequent surface-initiated ATRP (SI-ATRP) afforded a layer of PMMA brushes covalently attached to the sphere surfaces. Colloidal crystal films of these monodisperse spheres were then studied to identify the relationship between variation in particle diameter and the optical properties. The particle diameters were controlled by varying the feed monomer proportions in soap-free emulsion polymerization and the thickness of the grafted brush layer. It was found that the particle diameter could successfully be controlled to obtain crystal films that produce a variety of brilliant colors in the visible region. The results of this study can provide useful information for facile preparation of surface-immobilized ATRP initiators on colloidal polymers and can be employed for grafting polymer brushes.