Surface and interface morphology of polystyrene/poly(methyl methacrylate) thin-film blends and bilayers

The surface and interface morphologies of polystyrene (PS)/poly(methyl methacrylate) (PMMA) thin-film blends and bilayers were investigated by means of atomic force microscopy (AFM) and X-ray photoelectron spectroscopy. Spin-coating a drop of a PS solution directly onto a PMMA bottom layer from a common solvent for both polymers yielded lateral domains that exhibited a well-defined topographical structure. Two common solvents were used in this study. The structure of the films changed progressively as the concentration of the PS solution was varied. The formation of the blend morphology could be explained by the difference in the solubility of the two polymers in the solvent and the dewetting of PS-rich domains from the PMMA-rich phase. Films of the PS/PMMA blend and bilayer were annealed at temperatures above their glass-transition temperatures for up to 70 h. All samples investigated with AFM were covered with PS droplets of various size distributions. Moreover, we investigated the evolution of the annealed PS/PMMA thin-film blend and bilayer and gave a proper explanation for the formation of a relatively complicated interface inside a larger PS droplet.

Nonisothermal crystallization behavior of the poly(ethylene glycol) block in poly(L-lactide)-poly(ethylene glycol) diblock copolymers: Effect of the poly(L-lactide) block length

The confined crystallization behavior, melting behavior, and nonisothermal crystallization kinetics of the poly(ethylene glycol) block (PEG) in poly(L-lactide)poly(ethylene glycol) (PLLA-PEG) diblock copolymers were investigated with wideangle X-ray diffraction and differential scanning calorimetry. The analysis showed that the nonisothermal crystallization behavior changed from fitting the Ozawa equation and the Avrami equation modified by Jeziorny to deviating from them with the molecular weight of the poly(L-lactide) (PLLA) block increasing. This resulted from the gradual strengthening of the confined effect, which was imposed by the crystallization of the PLLA block. The nucleation mechanism of the PEG block of PLLA15000-PEG5000 at a larger degree of supercooling was different from that of PLLA2500-PEG5000, PLLA5000-PEG5000, and PEG5000 (the numbers after PEG and PLLA denote the molecular weights of the PEG and PLLA blocks, respectively). They were homogeneous nucleation and heterogeneous nucleation, respectively.

Solvent and polymer concentration effects on the surface morphology evolution of immiscible polystyrene/poly(methyl methacrylate) blends

The effects of solvent nature on the surface topographies of polystyrene (PS)/poly(methyl methacrylate) (PMMA) blend films spin-coated onto the silicon wafer were investigated. Four different solvents, such as ethylbenzene, toluene, tetrahydrofuran and dichloromethane, were chosen. They are better solvents for PS than that for PMMA. When dichloromethane, tetrahydrofuran and toluene were used, PMMA-rich phase domains protruded from the background of PS. When ethylbenzene was used, PS-rich phase domains elevated on the average height of PMMA-rich phase domains. In addition, continuous pits, networks and isolated droplets consisted of PS formed on the blend film surfaces with the decrease of polymer concentrations. The mechanism of the surface morphology evolution was discussed in detail.

Hydrazide-functionalized hollow porous poly(2-hydroxyethyl methacrylate-co-ethylene dimethacrylate) spheres for immobilization of enzyme

Hollow porous poly(2-hydroxyethyl methacrylate-co-ethylene dimethacrylate)(HEMA-co-EDMA) spheres were prepared by emulsifier-free emulsion polymerization, swelling, seed emulsion polymerization and extraction. Then the spheres activated with 2,4,6-trichloro-1,3,5-triazine were functioned with adipohydrazide (AH). After periodate oxidation of its carbohydrate moieties, horseradish peroxidase was immobilized on the hydrazide-functionalized hollow porous poly(HEMA-co-EDMA) spheres. The amount of immobilized enzyme was up to 43.4 mu g of enzyme/g of support. Moreover, the immobilized horseradish peroxidase exhibited high activity and good stability.

Influence of the degree of grafting on the morphology and mechanical properties of blends of poly(butylene terephthalate) and glycidyl methacrylate grafted poly(ethylene-co-propylene) (EPR)

Poly(ethylene-co-propylene) (EPR) was functionalized to varying degrees with glycidyl methacrylate (GMA) by melt grafting processes. The EPR-graft-GMA elastomers were used to toughen poly(butylene terephthalate) (PBT). Results showed that the grafting degree strongly influenced the morphology and mechanical properties of PBT/EPR-graft-GMA blends. Compatibilization reactions between the carboxyl and/or hydroxyl of PBT and epoxy groups of EPR-graft-GMA induced smaller dispersed phase sizes and uniform dispersed phase distributions. However, higher degrees of grafting (>1.3) and dispersed phase contents (>10 wt%) led to higher viscosities and severe crosslinking reactions in PBT/EPR-graft-GMA blends, resulting in larger dispersed domains of PBT blends. Consistent with the change in morphology, the impact strength of the PBT blends increased with the increase in EPR-graft-GMA degrees of grafting for the same dispersion phase content when the degree of grafting was below 1.8. However, PBT/EPR-graft-GMA1.8 displayed much lower impact strength in the ductile region than a comparable PBT/EPR-graft-GMA1.3 blend (1.3 indicates degree of grafting).

Isothermal crystallization behavior of the poly(L-lactide) block in poly(L-lactide)-poly(ethylene glycol) diblock copolymers: Influence of the PEG block as a diluted solvent

Isothermal crystallization kinetics and morphology of the poly(L-lactide) block in poly(L-lactide)poly(ethylene glycol) diblock copolymers were studied by differential scanning calorimetry (DSC) and polarized optical microscopy (POM), respectively. The results were compared with that of the PLLA homopolymer. The introduction of the PEG block accelerated the crystallization rate of the PLLA block and promoted to form ring-banded spherulites. The analysis of isothermal crystallization kinetics has shown that the PLLA homopolymer accorded with the Avrami equation. But the PLLA block of the diblock copolymers deviated from the Avrami equation, which resulted from increasing of the crystallization rate and occurring of the second crystallization process. The equilibrium melting temperature (T,,) of the PLLA block fell with its molecular weight decreasing. The conditions to obtain more regular ring-banded spherulites were below: the sample was the PLLA block of LA(5) EG(5); the crystallization temperature was about from 95 degrees C to 100 degrees C, which almost corresponded to regime II.

Preparation and characterization of post-derivatives from functional polystyrene (ATRP) with p-nitroaniline-azomethine phenol and their thermal and optical study

The functional polystyrene, (Cl-PS)(2)-CHCOOCH2CH2OH ( designated as XPSt and coded P2) was prepared by ATRP at 130(0)C using CuCl and bipyridine as catalysts, 2,2-dichloro acetate-ethylene glycol (DCAG) as multifunctional initiator and THF as solvent. 4-Nitoroaniline azomethine-4' phenol (P1) as chromophores were covalently linked to the functional end groups of the polymer by using simple displacement reaction. The functional polystyrenes, namely XPSt (P2) and (PS)(2)-CHCOOCH2CH2OH, designated as X-PSt and coded P3 and their post-derivatives, namely, DXPSt (P4) and DX-PSt (P5) respectively were characterized by IR, NMR and UV spectroscopies, gel permeation chromatography (GPC) and thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), polarising optical microscopy (POM) and XRD studies. DSC showed that incorporation of chromophores in the side chains of polymers towards the polystyrene moiety increases the rigidity of the polymer and subsequently, its glass transition temperature; however the incorporation of side chain towards the alcoholic functional group decreases the glass transition temperature. The post derivatives do not play any significant role to increase the thermal stability ( TGA).

Nonisothermal crystallization behavior of poly (L-lactide)-poly(ethylene glycol) dibloick copolymer

The nonisothermal crystallization behavior of poly (L-lactide)-poly(ethylene glycol) ( PLLA-PEG) diblock copolymer was studied by means of real-time WAXD, DSC and POM, and Ozawa equation was used to analyze the kinetics of PLLA-PEG under nonisothermal crystallization conditions. During the crystallization of the high-T-m block (PLLA), the low-T-m block (PEG) acts as a noncrystalline diluent, and the crystallization behavior of PLLA obeys the Ozawa theory. When the PEG block begins to crystallize, the PLLA phase is always partially solidified and the presence of the spherulitic microstructure of PLLA profoundly restricts its crystallization behavior, which results in that the overall crystallization process does not obey the Ozawa equation. Furthermore, the study of the crystalline morphology of PLLA-PEG at different cooling rates indicates that when the cooling rate is from low to high, the crystalline morphology undergoes a transformation from the ring-banded spherulites to the typical Maltese cross spherulites, which experiences the mixed crystalline morphologies of ring-banded and typical Maltese cross spherulites, and the spherulitic size becomes smaller.

Electrochemical study of PW12O403- in poly(ethylene glycol) electrolyte

The electrochemical properties Of PW12O403- (abbreviated as PW12) anion in poly(ethylene glycol) (PEG) have been studied by cyclic voltammetry, complex impedance and FT-IR spectroscopy. The PW12 anion in PEG-LiClO4 electrolyte shows reasonable facile electrochemistry, and the diffusion coefficients Of PW12 were measured with microelectrode. It is shown that ionic conductivity of polymer electrolytes based on low molecular weight PEG can be improved by the addition of PW12. The increase of conductivity is coupled with decrease of transient cross-links density of polymer chains which is evidenced by the downshift of C-O-C stretching mode. The phenomena are explained in view of ion-ion and ion-polymer interactions.

Electrochemical behavior of alpha-Keggin-type nanoparticles, Co(en)(3)(PMo12O40), in polyethylene glycol

The electrochemical behavior of alpha-Keggin-type nanoparticles, Co(en)(3)(PMo12O40) (abbreviated as PMo12-Co), have been studied in poly(ethylene glycol) for four different molecular weights (PEG, average MW 400, 600, 1000, and 2000 g mol(-1)) and containing LiClO4 (O/Li=100/1) supporting electrolyte. The diffusion coefficients of the PMo12-Co nanoparticles were determined using a microelectrode by chronoamperometry for PEG of different molecular weights that were used to describe the diffusion behavior of PMo12-Co nanoparticles in different phase states. Moreover, the conductivity of the composite system increases upon addition of PMo12-Co nanoparticles, which was measured by an a.c. impedance technique. FT-IR spectra and DSC were used to follow the interactions of PEG-LiClO4-PMo12-Co, and well described the reason that the PMo12-Co nanoparticles could promote the conductivity of the PEG-LiClO4-PMo12-Co system.

Pressure-dependent glass-transition temperatures of poly(methyl methacrylate)/poly(styrene-co-acrylonitrile) blends

The pressure-dependent glass-transition temperatures (T-g's) of poly(methyl methacrylate) (PMMA)/poly(styrene-co-acrylonitrile) (SAN) blends were determined by pressure-volume-temperature (PVT) dilatometry via an isobaric cooling procedure. The Gordon-Taylor and Fox equations were used to evaluate the relationships between the T-g's and compositions of the PMMA/SAN system at different pressures. The relationships were well fitted by the Gordon-Taylor equation, and the experimental data for T-g positively deviated from the values calculated with the Fox equation. Also, the influence of the cooling rate (during the PVT measurements) on T-g was examined.

Compatibilization of polyamide-6/syndiotactic polystyrene blends using styrene/glycidyl methacrylate copolymers

Blends of polyamide-6 (PA6) with syndiotactic polystyrene (sPS) were prepared using a series of styrene/glycidyl methacrylate (SG) copolymers as compatibilizers. These copolymers are miscible with sPS, and the epoxide units in SG are capable of reacting with PA6 end groups. These copolymers thus have the potential to form SG-g-PA6 graft copolymers at the PA6/sPS interface during melt processing. This study focuses on the effects of functionality and concentration of the compatibilizer on the morphological, mechanical and crystallization behaviors of the blends.. In general, SG copolymers are effective in reducing the sPS domain size and improving the interfacial adhesion. About 5 wt% glycidyl methacrylate (GMA) is the optimum content in SG copolymer that produces the best compatibilization. Both the strength and modulus of the blend have been improved on addition of the SG copolymers, accompanying a loss in toughness when higher concentration copolymer is added. Incorporation of SG compatibilizers to PA6/sPS blend has little influence on the crystallization behavior of PA6 component but resulted in a steady reduction in intensity of crystallinity peak of sPS and simultaneous crystallization of sPS with PA6 is observed.

Reverse atom transfer radical polymerization of (-)-menthyl methacrylate

The reverse atom transfer radical polymerization(RATRP) of (-)-menthyl methacrylate ((-)-MnMA) with AIBN(AIBN/CuCl2/bipyridine(bipy) or (-)sparteine((-)Sp) =1/2/4) initiating system in THF has been studied. The dependence of the specific rotation on molecular weight was investigated.