Void closure and interdiffusion processes during latex film formation from surfactant-free polystyrene particles: a fluorescence study

This study reports a steady state fluorescence (SSF) technique for studying film formation from surfactant-free polystyrene (PS) latex particles. The latex films were prepared from pyrene (P)-labeled PS particles at room temperature and annealed at elevated temperatures for 5-, 10-, 20-, and 30-min time intervals above the glass transition (T(g)) temperature of polystyrene. During the annealing processes, the transparency of the film changed considerably. Scattered light (I(sc)) and fluorescence intensity (I(0P)) from P were measured after each annealing step to monitor the stages of film formation. Evolution of transparency of latex films were monitored using photon transmission intensity, I(tr). Scanning electron microscopy (SEM) was used to detect variation in the physical structure of annealed films. Onset temperature for film formation, T(0), void closure, T(v), and healing temperatures, T(h), were determined and corresponding activation energies were measured. Void closure and interdiffusion stages were modeled and related activation energies were determined.     

Effect of Molecular Weight on Packing during Latex Film Formation

A UV-visible technique is used to study the evolution of transparency during film formation from latex particles. Latex particles with high and low molecular weight (HM and LM) polymethyl methacrylate (PMMA) are used to prepare films. Two sets of films with different latex content were prepared from HM and LM particles separately, by annealing PMMA particles above the glass transition temperature. Transmitted photon intensity, I(tr), from HM and LM films increased as the annealing temperature was increased. The increase in the transmitted photon intensity is attributed to the latex content (film thickness) for the annealed film samples. It is suggested that as the latex particles are packed (film thickness is increased) fewer voids or cracks are formed in the films. Positive and negative absorption coefficients are measured below and above 210 and 180 degrees C annealing temperatures for the HM and LM films. Packing coefficients are obtained for films in various latex contents. It is observed that LM particles are packed much easier than HM particles. Copyright 2001 Academic Press.     

Time evolution of film formation from polystyrene particles: a percolation approach

This work reports the film formation process from surfactant-free polystyrene (PS) latex particles. Steady state fluorescence and photon transmission techniques were used to study the evolution of film formation. The films were prepared from fluorescein (F)-labeled PS latex particles at room temperature and annealed in 2.5-min-time intervals above the glass transition temperature (T _g) of PS. Fluorescence intensity (I _F) from F was measured after each annealing step to monitor the stages of film formation. Evolution of transparency of latex films was monitored by using the photon transmission intensity, I _tr. Drastic increase in I _tr and I _F above the critical annealing times, t _r and t _c, respectively, were attributed to the percolation behavior of the PS material. Critical exponents, β, of percolation clusters were measured and found to be around 0.31 and 0.37 for I _tr and I _F measurement, respectively, which were attributed to the site percolation model.     

Latex film formation studied with the atomic force microscope: Influence of aging and annealing

The surface structure of latex dispersion films was examined with an atomic force microscope. All measurements were done in air on latex films having a minimum film formation temperature of 12°C and a glass transition temperature of 18°C. One aim of this study was to follow structural changes during film formation. Three minutes after spreading the film, its surface layer dried. Afterwards, the structure of the film did not change anymore. Only after 4 months could structural changes be observed: Though individual latex particles could be identified, the particles partly melted into one another.After annealing films at 50° or 60°C for 4 h, the latex particles partly melted into one another, but individual particles could still be identified. When annealing at or above 80°C, no individual latex particles were visible anymore. With increasing temperature the film roughness decreased from 3 nm without annealing to 0.8 nm at 100°C annealing temperature. In addition, islands of 2–4 nm thickness appeared on the film surface. These islands could be scraped off the film by increasing the force between tip and sample, indicating that they are composed of surfactant which was squeezed out of the film.     

Film formation from nano‐sized polystyrene latex particles

This work reports on the steady state fluorescence (SSF) technique for studying film formation from surfactant‐free, nano‐sized polystyrene (PS) latex particles prepared via emulsion polymerization. The latex films were prepared from pyrene (P)‐labeled PS particles at room temperature and annealed at elevated temperatures in 5, 10, 15, 20 and 30 min time intervals above the glass transition temperature (T_g) of PS. During the annealing processes, the transparency of the film was improved considerably. Monomer and excimer fluorescence intensities, I_P and I_E respectively, from P were measured after each annealing step to monitor the stages of film formation. Evolution of transparency of the latex films was monitored by using photon transmission intensity, I_tr. Void closure and interdiffusion stages were modeled and related activation energies were determined and found to be 10.3 and 50.3 kJ mol⁻¹. Void closure temperatures, T_v, were determined from the minima of I_tr value. Copyright © 2005 John Wiley & Sons, Ltd.     

Healing and photon diffusion during sintering of high-T latex particles

A steady-state fluorescence technique was used to examine the annealing of films formed from high-T latex particles above the glass transition temperature. The films were prepared by sintering pyrene-labeled poly(methyl methacrylate) latex particles. During the annealing processes, the transparency of the film changed considerably. Direct fluorescence emission from excited pyrene was monitored as a function of annealing temperature to detect these changes. Scanning electron microscopy in conjunction with Monte Carlo simulations of photon diffusion in latex film were used to interpret the fluorescence results. Healing temperature and time were measured at the point where the fluorescence emission intensity becomes maximum. This was associated with the longest optical path of a photon in latex film during healing of particle(SINGLEBOND)particle boundaries. Healing activation energy was measured and found to be 10 kcal/mol. © 1996 John Wiley & Sons, Inc.     

Interdiffusion of polymer chains during latex coating

The fluorescence method was used to study the interdiffusion of polymer chains during annealing of latex above its glass transition temperature (T_g). The latex film was prepared from mixture of naphthalene (N) (donor) and pyrene (P) (acceptor)-labeled poly(methyl methacrylate) (PMMA) latex particles. Heptane was used as the coalescent agent. A steady-state fluorescence technique was employed to measure the amount of direct nonradiative energy transfer from N to P during the interdiffusion of polymer chains across the particle–particle junction. Various latex films with different latex contents were used to measure the percentage critical occupation for the reliable steady-state fluorescence measurements. Diffusions activation energies in these latex films were measured and found to be around 30 kcal/mol, which was attributed to the backbone motion of PMMA chains.     

Preparations of polystyrene/aluminum hydroxide and polystyrene/alumina composite particles in an ionic liquid

Polystyrene (PS)/aluminum hydroxide (Al(OH)(3)) composite particles were successfully prepared by the sol-gel process of aluminum isopropoxide (Al(OPr(i))(3)) in a hydrophilic ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF(4)]) using ammonium hydroxide (NH(4)OH) as a catalyst in the presence of PS seed. Transmission electron microscopy observation of ultrathin cross-sections of the composite particles revealed that the composite particles had a core-shell morphology consisting of a PS core and a Al(OH)(3) shell having high crystallinity. The amount of secondary nucleated Al(OH)(3) could be reduced by dropwise addition of NH(4)OH. Moreover, PS/η-Al(2)O(3) composite particles were successfully prepared by heat treatment of PS/Al(OH)(3) at 300 °C in N(2) atmosphere, which is below the decomposition temperature of PS.     

EFFECT OF THE PHASE STRUCTURE EVOLUTION ON THE PROPERTIES OF FILMS FORMED FROM PBA/P(St-co-MMA) COMPOSITE LATEX

A group of heterogeneous latexes poly(butyl acrylate)/poly(styrene-co-methyl methacrylate)(PBA/P(St-co-MMA)) were prepared by a semi-continuous seeded emulsion polymerization process under monomer starved conditions.The glass transition temperature(T_g)and the mechanical properties of the film formed from the composite latex changed with the evolution of the particle morphology.A photon transmission method was used to monitor the phase structure evolution of films which were prepared from core-shell PBA/...     

Site percolation model for latex film formation in soft polymer matrix

The UV-visible (UVV) technique was used to monitor latex film formation in a soft polymer matrix. Various film samples were prepared by increasing the amount of poly(methyl methacrylate) (PMMA) particles in a poly(isobutylene) (PIB) matrix. These samples were then annealed above the glass transition temperature to promote latex film formation. Transmitted photon intensities, Itr, were measured for each film. It is observed that Itr decrease as the latex content is increased, which was explained by the increase in scattered light intensity, Isc. The drastic increase in Isc above a certain latex content is attributed to the site percolation of latex particles in the PIB matrix. The percolation threshold and the critical exponent were measured and found to be 0.3 and 0.4, respectively. The increase in Itr by annealing of film samples above Tg was explained with the void closure process below 0.8 occupation probability. When the film is occupied completely with the latex particles, interdiffusion of polymer chains was observed. Viscous flow and chain diffusion activation energies were determined and found to be 8 and 51 kcal/mol, respectively.     

Kinetics of latex formation of PBMA latex in the presence of alkali soluble resin using atomic force microscopy

 The effect of alkali-soluble resin (ASR), poly(ethylene-co-acrylic acid), EAA, postadded to emulsifier-free monodisperse poly(butyl methacrylate) (PBMA) latexes on the kinetics of film formation was investigated using atomic force microscopy (AFM). Corrugation height of latex particles in films was monitored at various annealing temperatures as a function of annealing time. Enhanced polymer diffusion was found in a latex film containing ASR regardless of anneal-ing temperature. With increasing annealing temperature, a much higher rate of polymer diffusion was found in latex films containing ASR. These results can be interpreted that the low molecular weight and low Tg EAA resin adsorbed at the particle surface is more susceptible to diffusion than that of the PBMA in the film formation stage, thus it enhances the mobility of PBMA polymer. Received: 30 October 1997 Accepted: 20 March 1998     

Diffusion energies of oxygen diffusing into polystyrene (PS)/poly (N‐isopropylacrylamide) composites

Diffusion coefficient of oxygen penetrating into polystyrene (PS) latex/poly (N‐isopropylacrylamide) (PNIPAM) microgel composite films were measured using Fluorescence technique. Three different (5, 15, and 40 wt%) PS content films were prepared from PS/PNIPAM mixtures. Diffusivity of PS/PNIPAM composite films were studied by diffusion measurements which were performed over the temperature range of 24–70°C. Pyrene was used as the fluorescent probe. The diffusion coefficients (D) of oxygen were determined using the Stern–Volmer fluorescence quenching method combined with Fickian transport and were computed as a function of temperature for each PS content film. The results showed that D values were strongly dependent on both temperature and PS content in the film. Diffusion energies were measured and found to be dependent on the composition of the composite films. Copyright © 2011 John Wiley & Sons, Ltd.     

Nanometer-thick surficial films in oxides as a case of prewetting

Stable, nanometer-thick films are observed to form at the {1120} facets of Bi(2)O(3)-doped ZnO in several bulk-phase stability fields. Electron microscopy shows these surficial films to exhibit some degree of partial order in quenched samples. The equilibrium film thickness, corresponding to the Gibbs excess solute, decreases monotonically with decreasing temperature until vanishing at a dewetting temperature, well below the eutectic. Assuming that perfect wetting occurs at some higher temperature above the eutectic, as is observed on polycrystal surfaces and at grain boundaries in the same system, the adsorption and wetting events in this system illustrate temperature- and composition-dependent prewetting. The observation of a second class of thicker films coexisting with nanodroplets and a numerical evaluation of thickness versus temperature elucidate the critical role of volumetric thermodynamic terms in determining film stability and thickness. Analogous temperature-dependent surface films involving adsorbed MoO(3) on Al(2)O(3) were also observed.     

ZnO及其含锌混合氧化物薄膜的充放电性能研究

从充放电性能、晶体结构等方面考察了包括粉末状的ZnO、脉冲激光沉积方法制备的ZnO薄膜和含锌混合氧化物薄膜的电化学性质.结果表明,ZnO粉末制备的电极的嵌入容量随退火温度的升高而增大,掺入其他氧化物可以明显改善ZnO薄膜的电化学性能,在Ar气氛中,基片温度为400℃时,沉积的靶子成分为Zn:B:P:Al=1:1:0.5:0.5(摩尔比)的含锌混合氧化物薄膜具有较高的可逆容量,且循环性能良好.     

Film Formation from Nanosized Copolymeric Latex Particles: A Photon Transmission Study

The photon transmission technique was used to monitor the evolution of transparency during film formation from nanosized copolymeric latex particles. The latex films were prepared from poly(methyl methacrylate-co-butyl methacrylate) (P(MMA-co-BMA)) particles which were produced by microemulsion polymerization. These films were annealed at elevated temperatures in various time intervals above the glass transition temperature (T(g)) of P(MMA-co-BMA). It is observed that the transmitted photon intensity (I(tr)) from these films increased as the annealing temperature increased. There are three different film formation stages. These stages are explained by the void closure, healing, and interdiffusion processes, respectively. The activation energies for viscous flow (DeltaH approximately 16 kcal/mol), minor chains (DeltaE(H) approximately 27 kcal/mol), and backbone motion (Delta E(b) approximately 132 kcal/mol) were obtained using various models. Void closure (tau(v), T(v)) and healing points (tau(H), T(H)) were determined. Using the time-temperature pairs, void closure and healing activation energies were measured and found to be 21 and 30 kcal/mol, respectively. Copyright 2001 Academic Press.     

宽带隙Cu(In,Al)Se2薄膜的制备及表征

以特殊脉冲电沉积方法制备CuInSe2(CIS)前驱体薄膜, 通过真空蒸镀法在CIS薄膜上沉积Al膜, 经硒化退火后在氧化铟锡(ITO)基底上制备了Cu(InAl)Se2(CIAS)薄膜. 采用扫描电子显微镜(SEM)、X射线能谱(EDS)、X射线衍射(XRD)、X射线光电子能谱(XPS)、紫外-可见吸收光谱(UV-Vis)对其形貌、结构、成分及光学吸收性质进行了表征. 结果表明, 制备的CIAS薄膜颗粒均匀, 表面平整致密, 呈黄铜矿结构. 薄膜在可见光区具有良好的吸收, 带隙约为1.65 eV.     

Polystyrene(1)/poly(butyl acrylate-methacrylic acid)(2) core-shell emulsion polymers. Part II: Thermomechanical properties of latex films

Polystyrene(1)/poly(n-butyl acrylate-methacrylic acid)(2) structured latex particles were prepared through a two-stage emulsion polymerization procedure, using a polystyrene (PS) latex seed (118 nm), and differentn-butyl acrylate (BA)/methacrylic acid (MAA) ratios. Polymerization kinetics, particle morphology, and MAA location have already been discussed in the first part of this series. In this second part the thermomechanical behavior of films cast from these latexes was studied. Differential Thermal Analysis and Dynamic Mechanical Analysis (DMA) were employed as characterization techniques for the films. Two polymer phases corresponding to polystyrene and a poly(BA-MAA) copolymer were distinguished. Comparison was made to analogous unfunctionalized PS/PBA systems, as a result of which an effect of MAA upon the phase arrangement in the film was found. Scanning Electron Microscopy of film samples and DMA showed that the evolution of the phase arrangement as a result of annealing was strongly dependent on the type of mechanical and heat treatments being applied to functionalized systems. Finally, the thermomechanical behavior of films was related to the structural features of the corresponding latexes, and computer simulation techniques wer eemployed to establish a mechanistic support for these relationships.     

Competition between dewetting and cross-linking in poly(N-vinylpyrrolidone)/polystyrene bilayer films

We investigated the dewetting of metastable poly(N-vinylpyrrolidone) (PNVP) thin films (45 nm) on top of polystyrene (PS) thin films (58 nm) as a function of annealing temperature and molecular weight of PS (96 and 6850 kg/mol). We focused on the competition between dewetting, occurring as a result of unfavorable intermolecular interactions at the PNVP/PS interface, and spontaneous cross-linking of PNVP, occurring during thermal annealing, as we recently reported (Telford, A. M.; James, M.; Meagher, L.; Neto, C. ACS Appl. Mater. Interfaces 2010, 2, 2399-2408). Using optical microscopy, we studied how the dewetting morphology and dynamics at different temperatures depended on the relative viscosity of the top PNVP film, which increased with cross-linking time, and of the bottom PS film. In the PNVP/PS96K system, cross-linking dominated over dewetting at temperatures below 180 °C, reducing drastically nucleated hole density and their maximum size, while above 180 °C the two processes reversed, with complete dewetting occurring at 200 °C. On the other hand, the PNVP/PS6850K system never achieved advanced dewetting stages as the dewetting was slower than cross-linking in the investigated temperature range. In both systems, dewetting of the PNVP films could be avoided altogether by thermally annealing the bilayers at temperatures where cross-linking dominated. The cross-linking was characterized quantitatively using neutron reflectometry, which indicated shrinkage and densification of the PNVP film, and qualitatively through selective removal of the bottom PS film. A simple model accounting for progressive cross-linking during the dewetting process predicted well the observed hole growth profiles and produced estimates of the PNVP cross-linking rate coefficients and of the activation energy of the process, in good agreement with literature values for similar systems.     

颗粒模板法制备大孔Al2O3材料

采用颗粒模板法制备了大孔氧化铝(Al2O3)材料. 扫描电子显微镜(SEM)结果显示, 大孔Al2O3结构中的大孔呈“囊泡状”且孔道的贯通性较差. Zeta电位测量表明, 共沉积条件下聚苯乙烯(PS)和Al2O3两种胶体颗粒带有相反的电荷, 在静电引力作用下先发生了吸附, 再沉积在一起. 吸附在PS微球表面的Al2O3纳米颗粒形成的吸附层是导致大孔呈“囊泡状”和孔道不贯通的主要原因. 采用聚二烯丙基二甲基氯化铵(PD)溶液对PS胶体微球带电性质进行了改性, PS微球的Zeta电位由−44.36 mV变成了+37.41 mV, 进而消除了沉积过程中二元颗粒间的吸附现象. 扫描电子显微镜显示, 大孔样品中“囊泡状”大孔消失, 同时孔道贯通性得到改善.     

A photon transmission study for film formation from poly(vinyl acetate) latex particles with different molecular weights

The photon transmission technique was used to monitor the temperature evolution of film formation from poly(vinyl acetate) (PVAc) latex particles with two different molecular weights. Two sets of latex films were prepared below the glass transition temperature (T_g) of PVAc, which are named as low (LM) and high molecular weight (HM) films. These films were annealed at elevated temperatures above the T_g of PVAc for various time intervals. It is observed that transmitted photon intensity (I_tr) from these films increased as the annealing temperature was increased. Onset temperatures (T_H) at given times (τ_H) for starting the optical clarity of LM and HM films were measured and used to calculate the healing activation energies (ΔH) for the PVAc minor chains, and found to be as 28.1 kcal/mol and 27.7 kcal/mol, respectively. The increase in the transmitted photon intensity, I_tr above T_H was attributed to the increase in the number of disappeared interfaces between the deformed latex particles. Prager–Tirrell (PT) model was employed to interpret the increase in the crossing density of chains at the junction surfaces. The interdiffusion (backbone) activation energies (ΔE) were measured and found to be 177.5 kcal/mol and 210.7 kcal/mol for a diffusing PVAc chains across the junction surface of LM and HM latex films, respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2918–2925, 2007