Film formation from PS/AL2O3 nanocomposites prepared by dip‐drawing method

In this study, steady state fluorescence (SSF) and UV–vis (UVV) techniques were used to examine film formation from pyrene (P) labeled polystyrene (PS) latex/Al₂O₃ (PS/Al₂O₃) composites prepared by the dip‐drawing method. The effects of dip‐drawing rates and dipping time in Al₂O₃ sol on film formation behavior and the morphology of PS/Al₂O₃ films were investigated. Films were prepared first by casting PS dispersion on clean glass substrates which creates a close‐packed array of PS sphere (203 nm) templates. These templates were then covered with Al₂O₃ utilizing the dip‐drawing method for various dip‐drawing rates and dipping times in Al₂O₃ sol. The film formation of these composites was studied by annealing them at a temperature range of 100°C to 270°C and monitoring the scattered light (I_sc), fluorescence (I_P), and transmitted light (I_tr) intensities after each annealing step. The structural properties of the composite films were analyzed with a scanning electron microscope (SEM). The results demonstrated that the film formation behavior and morphology of composites depended mainly on dipping time, and no dependence on the dip‐drawing rate was observed. The optical results indicated that PS/Al₂O₃ films undergo complete film formation independent of the dip‐drawing rate and dipping time. Additionally, the film formation stages were modeled and the corresponding activation energies were determined. After completion of film formation, PS polymers were extracted to obtain porous Al₂O₃ thin films. Highly ordered porous structures were observed for long dipping time in Al₂O₃ sol but no change was observed for different dip‐drawing rates, confirming the optical data. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Study of film formation from PS latex/TiO2 nanocomposites; Effect of latex size and TiO2 content

In this work, we investigated the film formation from polystyrene (PS) latex/TiO₂ nanocomposites using the steady state fluorescence (SSF) and UV–vis (UVV) techniques depending on PS particle size and TiO₂ content. The structural properties of films were characterized by scanning electron microscope (SEM). The films were prepared from pyrene (P)‐labeled PS particles (SmPS:203 nm; LgPS:382 nm) by covering them with different layers of TiO₂ by dip‐coating method and then annealed at elevated temperatures. Two film series (SmPS/TiO₂ and LgPS/TiO₂) were prepared and seven different films were studied in various TiO₂ contents for each series. Scattered (I_sc), fluorescence (I_P), and transmitted (I_tr) light intensities were measured after each annealing step to monitor the stages of film formation. Results showed that, SmPS/TiO₂ films undergo complete film formation independent of TiO₂ content. However, no film formation occurs above a certain TiO₂ content in LgPS/TiO₂ films. SEM images showed that SmPS/TiO₂ films have highly well‐ordered microporous structures with increasing TiO₂ content after extraction of PS polymer whereas LgPS/TiO2 composites show no porous structure for high TiO₂ content. Our experiments also showed that porous TiO₂ films with different sizes could be successfully prepared using this technique. POLYM. COMPOS., 35:2376–2389, 2014. © 2014 Society of Plastics Engineers     

Fluorescence study on Al2O3‐polystyrene latex composite film formation

This work reports a steady state fluorescence (SSF) technique for studying film formation from mixture of Al₂O₃ and polystyrene (PS) latex particles. The composite films were prepared from dispersion of pyrene (P)‐labeled PS particles in Al₂O₃ solution at room temperature and annealed at elevated temperatures in 10‐min time interval above glass transition (T_g) temperature of polystyrene. Nine different composites film were studied in various latex contents. Fluorescence intensities (I_P) from P were measured after each annealing step to monitor the stages of film formation. No variations in I_P were detected for the films prepared with higher than 33 wt% Al₂O₃ content. However films prepared below 33 wt% Al₂O₃ content show considerable increase in I_P above the certain onset temperature called minimum film forming temperature, T₀. Healing temperatures T_h, were determined from the maxima of I_P. Void closure and interdiffusion stages were modeled and related activation energies were determined and found to be 20 and 97 kJ.mol^–1, respectively. POLYM. COMPOS., 26:352–360, 2005. © 2005 Society of Plastics Engineers     

Energy‐transfer method to study vapor‐induced latex film formation

Nonradiative energy transfer method was used to study latex film formation induced by organic solvent vapor. Seven different films with the same latex content were prepared separately from poly(methyl methacrylate) (PMMA) particles and exposed to ethyl benzene, toluene, chloroform, dichloromethane, tetrahydrofuran, and acetone vapor in seven different experiments. Energy‐transfer experiments were carried out between PMMA‐bound naphthalene (N) and pyrene (P) during vapor‐induced film formation. Latex films were prepared from equal amounts of N‐ and P‐labeled latex particles, and steady state spectra of N and P were monitored during film formation. It was observed that the P to N intensity ratio, I_P/I_N, increased as the vapor exposure time increased. The Prager–Tirrell (PT) model was employed to obtain back‐and‐forth frequencies, ν, of the reptating PMMA chains during latex film formation induced by solvent vapor. ν values were obtained and found to be correlated with the solubility parameter, δ. Polymer interdiffusion obeyed the t^1/2 law during film formation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 632–645, 2002; DOI 10.1002/app.10346     

Nano‐sized TiO2‐reinforced natural rubber composites prepared by latex compounding method

This paper addresses nano‐sized titanium dioxide (TiO₂) reinforced natural rubber composites. Micro‐sized TiO₂ is simultaneously prepared to make a comparison with the composites containing nano‐sized TiO₂. To improve the dispersion of TiO₂, this study also suggests a new method of incorporating TiO₂. Aqueous dispersions of micro‐ and nano‐sized TiO₂ at the loadings of 0, 2, 4, 6, and 8 parts by weight per hundred parts of resin were dispersed in natural rubber latex, and then the resulting compounds were dried prior to mixing it with other ingredients on a two‐roll mill. By applying this technique, the homogeneity of the compound is significantly improved. This can be clearly seen from the enhancement of tensile properties and morphological characteristics where the optimum loading was found at 6 parts by weight per hundred parts of resin of micro‐ and nano‐sized TiO₂. Adding TiO₂ results in delayed scorch times and curing times wherein the curing process of filled compounds is shorter than the unfilled compound. J. VINYL ADDIT. TECHNOL., 23:200–209, 2017. © 2015 Society of Plastics Engineers     

Molecular dynamics study of TiO2/poly(acrylic acid‐co‐methyl methacrylate) and Fe3O4/polystyrene composite latex particles prepared by heterocoagulation

All‐atom molecular dynamics simulations were used to study the morphology of polymer/inorganic composite particles prepared by heterocoagulation. The results were also compared to those of our previous study of the preparation of TiO₂/poly(acrylic acid‐co‐methyl methacrylate) and Fe₃O₄/polystyrene composite particles. In the simulation system, polymer or inorganic particles were simulated by surface‐charge‐modified C₆₀ or Na atoms. Through a combination of analysis of the radial distribution functions of charged atoms and snapshots of the equilibrated structure, three kinds of particle distributions were observed under different conditions. When the polymer and inorganic particles had opposite surface charges and their sizes were very different, the composite morphology showed a core–shell structure with small particles adsorbed onto the surfaces of large particles. Furthermore, when the polymer and inorganic particles had opposite surface charges but comparable sizes, the polymer and inorganic particles aggregated domain by domain. Finally, when the polymer and inorganic particles were endowed with the same surface charge, the distribution of these two types of particles was homogeneous, regardless of their size difference. The simulation results were in agreement with the experimental results. The electrostatic interaction and the size of the particles dominated the final morphology of the composite particles when the heterocoagulation method was used. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Characteristics of polystyrene/polyethylene/clay nanocomposites prepared by ultrasound‐assisted mixing process

In this study, polymer‐clay nanocomposites of various concentrations were prepared by ultrasonically assisted polymerization and melt‐mixing processes. A sonication process using power ultrasonic waves was employed to enhance nano‐scale dispersion during melt‐mixing of polymer blends and organically modified clay. We expected enhanced breakup of layered silicate bundles and further reduction in the size of the dispersed phase, with better homogeneity compared to the different immiscible blend pairs. X‐ray diffraction (XRD) and Transmission Electron Microscopy (TEM) were used to characterize the structures of the nanocomposites. The rheological behaviors of the obtained nanocomposites were measured with parallel plate rheometry. It was found that the ultrasound‐assisted process successfully generated exfoliated nanocomposites and promoted in‐situ compatibilization of the matrix comprising an immiscible pair of polymers in a blend. The resulting nanocomposite exhibited superior thermal stability and elastic modulus compared to the base polymer. Polym. Eng. Sci. 44:1198–1204, 2004. © 2004 Society of Plastics Engineers.     

The effect of clay particles on film formation from polystyrene latex

Film formation from surfactant‐free polystyrene (PS) latex was performed in the presence of 5% Na‐montmorillonite (NaMMT). The composite films were prepared from pyrene (P)‐labeled PS particles at room temperature and annealed at elevated temperatures above the glass‐transition (T_g) temperature of polystyrene. Scattered light (I_s) and fluorescence intensity (I_P) from P were measured after each annealing step to monitor the stages of composite film formation. Minimum film formation temperature, T₀, and healing temperatures, T_h, were determined. Void closure and interdiffusion stages were modeled and related activation energies were measured. From these results, it was found that the presence of NaMMT in the PS latex film only affects the minimum film formation, but does not affect the void closure and backbone motion activities. POLYM. COMPOS., 27:299–308, 2006. © 2006 Society of Plastics Engineers     

反相微乳液法制备TiO2/ZrO2复合陶瓷膜

研究了采用反相微乳液法制备TiO₂/ ZrO₂复合微乳液,并以其作为前体制得TiO₂/ ZrO₂复合膜。通过对复合微乳液的透射电镜测试,结果表明TiO₂/ ZrO₂复合微粒在油相包裹的“水池”中生成。由扫描电子显微镜观察到TiO₂/ ZrO₂复合膜表面微粒以棒状形式分布,而且复合膜对大肠杆菌的灭菌率达98 %～99 %。     

Alumina‐filled polystyrene micro‐ and nanocomposites prepared by melt mixing with and without latex precompounding: Structure and properties

Alumina fillers were incorporated in polystyrene (PS) in 4.5 wt % by melt blending with and without latex precompounding. Latex precompounding was used for the latex‐mediated predispersion of the alumina particles. The related masterbatch was produced by mixing PS latex with water dispersible boehmite alumina in various particle sizes followed by drying. The dispersion of the alumina in the PS was studied by transmission and scanning electron microscopy (TEM and SEM, respectively). The mechanical and thermomechanical properties of the PS composites were determined in uniaxial tensile, dynamic‐mechanical thermal analysis (DMTA), and short‐time creep tests performed at various temperatures. In addition, the melt flow of the composites was characterized in a plate/plate rheometer. It was found that direct melt mixing of the alumina with PS resulted in micro‐, whereas the masterbatch technique in nanocomposites. The stiffness and resistance to creep (summarized in master curves) of the nanocomposites were improved compared to those of the microcomposites. The properties of the composites were upgraded by decreasing nominal size of the water dispersible alumina. The preparation technique and the size of the alumina particles affected the tensile strength, melt viscosity, and heat distortion temperature in lesser extent than the stiffness and thus compliance data. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Film formation from nano‐sized polystrene latex covered with various TiO2 layers

Steady‐state fluorescence technique was used for studying film formation from TiO₂ covered nano‐sized polystyrene latex particles. The composite films were prepared from pyrene (P)‐labeled PS particles by covering them with various layers of TiO₂ at room temperature. These films then annealed at elevated temperatures in 10 min time interval above glass transition (T_g) temperature of polystyrene. Five different composite films were studied in various TiO₂ layer contents. Fluorescence emission intensity, I_P from P was measured after each annealing step to monitor the stages of film formation. Films present significant increase in I_P above the certain onset temperature called minimum film forming temperature, T₀. However, at higher annealing temperatures, I_P showed a decrease. Increase and decrease in I_P were modeled by void closure and interdiffusion processes and related activation energies were determined, respectively. Dissolution of annealed PS film, with high TiO₂ content presented a nice, ordered nano‐sized ceramic structure, which may predict the construction of nano‐layer photonic crystals. POLYM. COMPOS., 27:651–659, 2006. © 2006 Society of Plastics Engineers     

Photochemical diodes of a TiO2 film prepared by a sol-gel method

Photochemical diodes were prepared using a thin film of TiO₂ made from titanium isopropoxide by a sol-gel method. A half part of a conductive SnO₂ film plated on a quartz plate was coated with the TiO₂ film, and the other parts of the SnO₂ substrate were coated with a thin Pt film. The photochemical diode thus prepared shows photocatalytic activity for hydrogen evolution from aqueous ethanol solutions containing NaOH or HClO₄. No other products are detected in the gas phase. Hydrogen evolution from the Pt part is definitely observed, indicating electron transfer from the TiO₂ film to the Pt film through the SnO₂ film. Another type of photochemical diode, the TiO₂ film coated on a Pt plate, is found to show higher activity than the TiO₂/SnO₂/Pt device for the hydrogen photo-evolution without any support electrolyte. Hydrogen evolution on this device, however, occurs on the TiO₂ side but not on the Pt side. These results are discussed in terms of a photo-electrochemical mechanism at semiconductor surfaces.     

Elastic properties of natural rubber tubes produced by dip‐coating

The mechanical properties of rubber tubes produced by dip‐coating technique and the influence of the fabrication process on their structural properties were evaluated. Cyclic tension versus deformation tests were performed to investigate the elastic properties of the samples and to understand the changes in rubber tubes behavior under repetitive stress. The effect of the wall thickness on the elastic response of the tubes was also studied. The mechanical properties of opened tubes were also investigated for transversal and longitudinal directions to evaluate the influence of the fabrication process on the alignment of the polymer chains. This investigation indicated that the fabricated tubes are resistant and extremely elastic. They can be elongated up to 800% of its initial length before rupture, and thicker tubes are a bit more resistant to elongation than the thinner ones. In addition, the fabricated tubes have an anisotropic structure due to the fabrication process. Finally, natural rubber tubes may have a great potential to be used as vascular prosthesis, or in other applications that require a large range of resistance and elasticity. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 702–707, 2006     

Rheology and dispersion behavior of high‐impact polystyrene/ethylene–vinyl acetate copolymer/TiO2 nanocomposites

TiO₂ nanoparticles were introduced into high‐impact polystyrene (HIPS) in the form of a master batch in which TiO₂ was predispersed in composites of HIPS and ethylene–vinyl acetate copolymer (EVA) by melt compounding. The resulting materials were analyzed with a Rosand Precision rheometer, transmission electron microscopy, atomic force microscopy, and ultraviolet–visible light spectrophotometry. The results showed that the introduction of TiO₂ nanoparticles into HIPS influenced the apparent viscosity of the composites to a rather small extent. The addition of EVA could regulate the rheological behavior of the HIPS/TiO₂ master batch greatly. EVA helped the dispersions of the agglomerates of TiO₂ nanoparticles in the flow; this was featured by the distinct yielding in the flow after the introduction of EVA, as well as the large change in the non‐Newtonian indices. The dispersions of the HIPS/TiO₂ master batch in the HIPS matrix were improved greatly by the addition of EVA. TiO₂ nanoparticles were dispersed randomly in HIPS/EVA/TiO₂ nanocomposites. The dispersion improvement of the HIPS/EVA/TiO₂ master batch was also proved by atomic force microscopy and ultraviolet–visible spectroscopy investigations. The mechanical properties of HIPS/EVA/TiO₂ nanocomposites with low TiO₂ contents were slightly higher than those of pure HIPS. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4434–4438, 2006     

Preparation and performance of high‐impact polystyrene (HIPS)/nano‐TiO2 nanocomposites

High‐impact polystyrene (HIPS)/nano‐TiO₂ nanocomposites were prepared by surface pretreatment of nano‐TiO₂ with special structure dispersing agent (TAS) and master batch manufacturing technology. The results show that when the nano‐TiO₂ content is 2%, the notched impact strength, tensile strength, and elastic modulus of HIPS/nano‐TiO₂ nanocomposites increased to a maximum. This result indicates that nano‐TiO₂ has both toughening and reinforcing effects on HIPS. The heat‐deflection temperature and flame‐retardance of HIPS/nano‐TiO₂ nanocomposites are also obviously improved as the nano‐TiO₂ content is increased. The nanocomposites manufactured by the two‐step method have better mechanical properties than that made by a one‐step method. HIPS/nano‐TiO₂ nanocomposites are also non‐Newtonian and pseudoplastic fluids. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 381–385, 2003     

胶乳插层法制备的NR/HMMT纳米复合材料的性能研究

通过天然胶乳和有机蒙脱土（HMMT）在乳液中进行反应性插层，制得了NR／HMMT插层纳米复合材料。该得合材料中蒙脱土片层间距从1.2nm扩大到4.2nm，同时其硫化胶还表现出显著的补强效果，以及比NR显著降低的tanδ值。     

Thermal properties of PMMA/TiO2 nanocomposites prepared by in-situ bulk polymerization

The surface of anatase TiO₂ nanoparticles, obtained by the controlled hydrolysis of titanium tetrachloride, was modified by 6-palmitate ascorbic acid. The surface modified TiO₂ nanoparticles were dispersed in methyl methacrylate and mixed with a appropriate amount of poly(methyl methacrylate) to obtain a syrup. The nanocomposite sheets were made by bulk polymerization of the syrup in a glass sandwich cell using 2,2′-azobisisobutyronitrile as initiator. The molar masses and molar mass distributions of synthesized poly(methyl methacrylate) samples were determined by gel permeation chromatography. The content of unreacted double bonds in synthesized samples was determined by ¹H NMR spectroscopy. The influence of TiO₂ nanoparticles on the thermal stability of the poly(methyl methacrylate) matrix was investigated using thermogravimetric analysis and differential scanning calorimetry. The synthesized samples of poly(methyl methacrylate) have different molar mass and polydispersity depending on the content of the surface modified TiO₂ nanoparticles. The values of glass transition temperature of so prepared nanocomposite samples were lower than for pure poly(methyl methacrylate), while the glass transition temperature of samples preheated in inert atmosphere was very similar to the glass transition temperature of pure poly(methyl methacrylate). The thermal stability of nanocomposite samples in nitrogen and air was different from thermal stability of pure poly(methyl methacrylate). POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

用乳液插层法制备丙烯酸丁酯/有机蒙脱土纳米复合材料

用乳液插层法制备了丙烯酸丁酯/有机蒙脱土纳米复合材料。先将钠基蒙脱土有机化,然后用乳液聚合法反应制得纳米复合材料。X射线衍射分析表明,蒙脱土有机化后层间距增大,季铵盐插层进入蒙脱土层间,乳液聚合后层间距进一步增大,聚丙烯酸丁酯插层到蒙脱土层间,得到丙烯酸丁酯/有机蒙脱土纳米复合材料。动态力学分析表明,复合材料的储能模量大大提高,损耗因子几乎不变。     

Organic interfacial tailoring of styrene butadiene rubber–clay nanocomposites prepared by latex compounding method

The styrene butadiene rubber (SBR)–clay nanocompounds were prepared by the latex compounding method, and then hexadecyl trimethyl ammonium bromide (C16) and 3‐aminopropyl triethoxy silane (KH550) were added into these nanocompounds on a two‐roll mill to prepare nanocomposites with strong interfacial interaction. The structure and properties of SBR–clay nanocomposites were carefully studied by X‐ray diffraction (XRD) studies, transmission electron microscopy (TEM), Rubber Process Analyzer (RPA), and mechanical testing. Compared with unmodified nanocomposites, the dispersion structure of modified SBR–clay nanocomposites is better with part rubber‐intercalated or part modifier‐intercalated structure. The tensile strength and the modulus at 300% elongation of modified SBR–clay nanocomposites are higher than three times of those of unmodified nanocomposites, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1826–1833, 2007     

Fluorescence study of film formation from PS/Al2O3 nanocomposites

Steady state fluorescence (SSF) and UV–vis (UVV) techniques were used to study the film formation behavior of pyrene (P) labeled polystyrene (PS) latex and Al₂O₃ (PS/Al₂O₃) composites depending on PS particles size and Al₂O₃ content. The close-packed arrays of PS spheres (SmPS: 203 nm; LgPS: 382 nm) templates on clean glass substrates were covered with various layers of Al₂O₃ by dip-coating method. Two different film series (SmPS/Al₂O₃ and LgPS/Al₂O₃) were prepared in various Al₂O₃ layer content. The film formation behavior of these composites were studied by annealing them at a temperature range of 100–250 °C and monitoring the scattered light intensity (I_sc), fluorescence intensity (I_P) from P and transmitted light intensity (I_tr) through the films after each annealing step. Optical results indicate that classical latex film formation was occurred for all Al₂O₃ content films and film formation process was unaffected by the Al₂O₃ content for both film series. Extraction of PS template produced highly ordered porous structures for high Al₂O₃ content in both film series. SEM images showed that the pore size and porosity could be easily tailored by varying the PS particle size and the Al₂O₃ content.