POLY(3-HYDROXYBUTYRATE)-BASED COPOLYMERS AND BLENDS: INFLUENCE OF A SECOND COMPONENT ON CRYSTALLIZATION AND THERMAL BEHAVIOR*

Isotactic poly(3-hydroxybutyrate) (P3HB) is an aliphatic polyester obtained by bacterial fermentation. This truly biodegradable polymer has been widely investigated, mainly with the aim to replace conventional plastics, which cause environmental pollution. To improve its properties, extensive studies have been conducted to modify it properly by copolymerization or blending with other polymers. Macroscopic properties of polymers, particularly of polymer blends, are strongly affected by their microstructure, especially by the allocation of different phases and their level of dispersion and adhesion. In nonreactive blends, the adhesion level is mainly determined by the similarity between the chemical structure of the components, and the arrangement of the phases is remarkably controlled by the crystallization conditions. The superstructure of the crystalline phases accounts for the mechanical resistance of the blend, but the composition and the distribution of the amorphous phases also play an important role, especially with respect to toughness properties. This article reviews data on thermal properties and the crystallization process of P3HB and its copolymers, both alone and in the presence of other polymers. In particular, copolymers of 3-hydroxybutyrate with 3-hydroxyvalerate and with 4-hydroxybutyrate and blends of P3HB and the copolymers with atactic poly(3-hydroxybutyrate), poly(vinyl acetate), poly(vinyl alcohol), poly(ethylene oxide), poly(methylene oxide), poly(epichlorohydrin), and poly(methyl methacrylate) are considered. Major attention is directed toward the influence of miscibility and composition on solidification kinetics and crystal structure with the objective to provide an overview of the current state of the art.

     

单壁碳纳米管-聚合物复合材料的拉曼光谱表征(英文)

本文在粗糙金属表面上制作了单壁碳纳米管—聚乙烯醇复合材料,并利用表面增强拉曼散射讨论了碳纳米管与聚乙烯醇之间的相互作用     

Nonisothermal Crystallization Kinetics of Ethylene Vinyl Alcohol Copolymer with Poly(oxypropylene)diamine Intercalated Montmorrilonite

Films of ethylene vinyl alcohol copolymer (EVOH) and EVOH containing poly(oxypropylene)diamine intercalated montmorrilonite were prepared by solution casting. The nanostructures and viscosity were characterized by small angle x-ray scattering (SAXS), transmission electron microscopy (TEM) and rheological testing. The nonisothermal crystallization kinetics of the samples were investigated by the Ozawa's and Mo's methods and the crystallization activation energy by Kissinger's model. The SAXS and TEM analysis demonstrated that the nanoplatelets, with an intercalated structure, were dispersed in the EVOH matrix. The rheological tests showed that the incorporation of the modified clay could increase the viscosity of the composite system. The Mo's method more successfully described the nonisothermal ctystallization behavior of neat EVOH and its nanocomposites as compared with the Ozawa's method. Adding the nanoclays had a heterogeneous nucleation effect to accelerate the crystallization of EVOH despite hindering the macromolecular chains movement.     

Characterization of Poly(Vinyl Alcohol) Membranes Cross-Linked by Aldehyde-Substituting Cyclotriphosphazene

A new type of cross-linker, based on cyclotriphosphazene with six aldehyde groups, was used for the cross-linking of poly(vinyl alcohol) membranes. FTIR-ATR analysis indicated that cyclophosphazene reacted with poly(vinyl alcohol) by forming C–O–C bonds. TGA and DTG analysis showed that cross-linking improved the thermal stability. The swelling degree and pervaporation properties of cross-linked PVA membranes were also characterized. With increasing cross-linker concentration, swelling degrees and flux decrease while separation factors increase. Compared with PVA membranes cross-linked by glutaraldehyde, PVA membranes cross-linked by cyclophosphazene exhibited better selectivity and permeation rate.     

Crystallization Morphology and Behavior of Polypropylene Composites Containing Microencapsulated Flame Retardant

With shells of melamine-formaldehyde (MF), urea-melamine-formaldehyde (UMF), or poly(vinyl alcohol)-melamine-formaldehyde (VMF), microencapsulated ammonium polyphosphate (APP) was prepared by in-situ polymerization for use as a flame retardant in polypropylene (PP). Microencapsulated APP showed rougher surface, smaller size, and narrower size distribution compared with APP. The results of polarized optical microscopy (POM) showed that the additives resulted in a decrease of the spherulite size and less perfection in crystal geometry of PP composites. Due to the interaction and alignment of the PP polymer chains at the surface, the surface modification of APP influenced the formation and further development of PP crystals remarkably. The crystallization and melting behaviors of the PP composites were affected by the rough surface of the microencapsulated APP, which was helpful for the formation of β-crystals and decreased the crystal growth rate compared with APP.     

Properties of nano-ZnO/poly(vinyl alcohol)/poly(ethylene oxide) composite thin films

A series of poly(vinyl alcohol)/nano-ZnO composites were prepared by dispersing nano-ZnO in aqueous solutions containing mixtures of the biodegradable polymers poly(vinyl alcohol) (PVA) and poly(ethylene oxide) (PEO), and composite thin films were prepared by casting. The introduction of nano-ZnO into PVA/PEO mixed solutions significantly decreased the resistivity of the solutions. Ultraviolet absorption, thermal behaviour and visco-elastic properties of the thin films were determined as a function of nano-ZnO content up to 15 wt%. Optimum film properties were obtained with 1 wt% nano-ZnO, higher proportions of nano-ZnO resulting in agglomeration of ZnO particles and deterioration in film properties. The Forouhi and Bloomer model was used for the modelling of ZnO thin films.     

Isothermal and non-isothermal crystallization kinetics of PVA + ionic liquid [BDMIM][BF4]-based polymeric films

The effect of ionic liquid (IL), 1-butyl-2,3-dimethylimidazolium tetrafluoroborate [BDMIM][BF₄], on crystallization behavior of poly(vinyl alcohol) (PVA) has been studied by isothermal and non-isothermal differential scanning calorimetry techniques. The PVA + IL based polymer electrolyte films have been prepared using solution casting technique. To describe the isothermal and non-isothermal crystallization kinetics, several kinetic equations have been employed on PVA + IL based films. There is strong dependence of the peak crystallization temperature (T_c), relative degree of crystallity (X_t), half-time of crystallization (t_1/2), crystallization rate constants (Avrami K_t and Tobin A_T), and Avrami (n) and Tobin (n_T) exponents on the cooling rate and IL loading.     

Nanocomposites of Poly(vinyl alcohol) Reinforced with Chemically Modified AL2O3: Synthesis and Characterization

The surface of α-alumina (Al₂O₃) nanoparticles was first modified with γ-aminopropyltriethoxy silane as a coupling agent. Then a series of poly(vinyl alcohol)/ surface modified Al₂O₃ nanocomposite suspensions were prepared in ethanol by a simple ultrasonic irradiation process. Composite films with 5, 10, and 15 wt % of inorganic Al₂O₃ nanoparticles were achieved after solvent evaporation. The formation of the composite materials were confirmed by Fourier transform infrared spectroscopy, X-ray diffraction, field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and optical transparencies. The FE-SEM and TEM results showed a homogenous dispersion of nanoscale inorganic particles in the poly(vinyl alcohol) matrix. TGA thermographs showed that the thermal stability of the prepared Al₂O₃-reinforced nanocomposites was improved, increasing with increasing content of the nanoparticles. According to the optical transparencies, the optical clarity of poly(vinyl alcohol)/Al₂O₃ nanocomposite films was only slightly affected by the presence of the Al₂O₃ content.     

Effect of carbon nanotubes dispersion on morphology, internal structure and thermal stability of electrospun poly(vinyl alcohol)/carbon nanotubes nanofibers

The current work reports the effect of multi walled carbon nanotubes and single walled carbon nanotubes dispersion on morphological, structural and thermal degradation of electrospun poly(vinyl alcohol) (PVA)/carbon nanotubes (CNTs) dispersed in sodium dodecyl sulfate (SDS) (PVA/CNTs–SDS) composites nanofibers. (PVA/CNTs–SDS) nanocomposites fibers were elaborated using the traditional electrospinning process to disperse and align CNTs into the fibers, especially for low CNTs loading fraction: 0.3 and 0.7 wt%. The morphology of the electrospun fibers was studied using the scanning electronic microscopy. The average diameter of the fibers changes significantly after the incorporation of the CNTs in the PVA. Furthermore, Fourier transform infrared spectroscopy elucidated the effect of CNTs on the crystallization of the PVA which was confirmed by X-ray diffraction analysis. Thermogravimetric analysis showed that the thermal stability of the composite fibers depends on the loading fraction and on the type of carbon nanotubes.     

Liposomal Templating,Association with Mammalian Cells,and Cytotoxicity of Poly(vinyl alcohol) Physical Hydrogel Nanoparticles

The assembly, cellular internalization, and cytotoxicity of nanoparticles based on physical hydrogels of poly(vinyl alcohol) (PVA) are reported. PVA nanoparticles are assembled using a liposomal templating technique followed by removal of the lipids using isopropanol, a process that requires the presence of a custom‐made block copolymer, poly(vinyl alcohol‐b‐vinyl pyrrolidone), to avoid aggregation of the nanoparticles. Polymer hydrogelation is induced via incubation in aqueous isopropyl alcohol solution, which results in PVA hydrogel nanoparticles (PVA HNP) with excellent colloidal stability and stability towards disintegration over at least 24 h. Pristine PVA HNP are found to be remarkably stealth‐like and exhibit negligible cellular internalization. This feature is likely inherent with the low fouling nature of PVA and makes PVA HNP attractive for targeted drug delivery with a low level of association with non‐targeted cells and tissues. Blending PVA with varied amounts of collagen results in colloidal hydrogel particles with a well pronounced tendency towards association with mammalian cells, specifically hepatocytes and endothelial cells. The association of PVA HNP elicits minimal changes in cellular proliferation, making these novel hydrogel particles convenient tools for drug delivery applications and creation of implantable artificial organelles and sensors.     

Collagen fibril formation in poly(vinyl alcohol) and poly(vinyl pyrrolidone) films

The formation of collagen fibrils in poly(vinyl alcohol) (PVA) and in poly(vinyl pyrrolidone) (PVP) was investigated using Atomic Force Microscopy (AFM). The water solutions of PVA and PVP containing 1%, 3% and 5% of collagen were cast onto glass plate. After slow solvent evaporation thin polymeric films were obtained. AFM images showed the fibril formation in both, PVA and PVP films containing collagen. The amount of collagen in PVA and PVP matrix has an important effect on the structure and size of collagen fibril formed. The diameter of collagen fibrils in PVA films is bigger than the diameter of collagen fibrils formed in PVP films.     

Alkaline poly(vinyl alcohol)/poly(acrylic acid) polymer electrolyte membrane for Ni-MH battery application

Ionics - Alkaline polymer electrolyte membrane with high ionic conductivity of 0.019 S cm−1 at room temperature was prepared from poly(vinyl alcohol) and acrylic acid...     

Specific features of the internal photoelectric effect of the Cu(II)/Fe(III) oxalate complex with ethylenediamine in an insulating polymer film

Physics of the Solid State - The electrical and photoconductive properties of films of the composites based on poly(vinyl alcohol) with additions of the (NH4)[Cu(en)2Fe(C2O4)3] · 2DMSO...     

The polymorphism of poly(vinylidene fluoride) V. The effect of hydrostatic pressure on the melting behavior of copolymers of vinylidene fluoride

The high-pressure melting behavior of samples of vinylidene fluoride copolymerized with vinyl fluoride, trifluoroethylene, or tetrafluoroethylene indicate that the copolymers have a lower entropy of melting than the poly(vinylidene fluoride) homopolymers in the same phase. As the comonomer size increases, the entropy of melting decreases. High-pressure crystallization of copolymers of 91-9 mole% vinylidene fluoride-trifluoroethylene and 93-7 mole% vinylidene fluoride-tetrafluoroethylene results in a high-melting form of phase I (planar zig-zag).     

Solution-grown crystals of poly(vinyl alcohol)

The growth mechanism and crystalline texture of solution-grown crystals of poly(vinyl alcohol) have been studied by electron microscopy. From morphological data it is shown that single crystals of poly(vinyl alcohol) (PVA) have two growth faces, i.e., the (100) and (101) fold planes. It is suggested that the parallelogrammic single crystals grow from the center by molecular folds. The rate of addition on the (100) plane is about three times larger than that on the (101) plane. Twinning of the PVA crystals takes place at the (100), (001), (101), and (101) planes at the time of the nucleation or during the growth. The single crystal and twins of PVA are corrugated lamellae. Granulated structure is observed on the surface in a figure similar to the external form of the crystals. Dark-field micrographs show that the PVA single crystals possess a mosaic structure with the arrangement of the blocks deviating slightly from parallel alignment in the lamella. The reactivities of single crystals to various aldehydes indicate that the single crystals contain crystal lattice defects.     

Spectral Properties of Amphiflavins in Polymer Matrices

The parameters characterizing the absorption, fluorescence and phosphorescence of 10-dodecylisoalloxazine (DIA), 10-octadecylisoalloxazine (OIA) 3-methyl-10-dodecylisoalloxazine (MDIA) embedded into polymeric matrices (polystyrene – PS, polymethacrylate methyl – PMM and poly(vinyl alcohol) – PVA) were studied. It was found that both the polarity of microenvironment and its structure influenced the changes of the spectral properties of the examined amphiflavins.     

Electrical conductivity studies on PVA/PVP-KOH alkaline solid polymer blend electrolyte

A series of conducting thin-film solid electrolytes based on poly (vinyl alcohol)/ poly (vinyl pyrrolidone) (PVA/PVP) polymer blend was prepared by the solution casting technique. PVA and PVP were mixed in various weight percent ratios and dissolved in 20 ml of distilled water. The samples were analyzed by using impedance spectroscopy in the frequency range between 100 Hz and 1 MHz. The PVA/PVP system with a composition of 80% PVA and 20 wt.% PVP exhibits the highest conductivity of (2.2±1.4) × 10⁻⁷ Scm⁻¹. The highest conducting PVA/PVP blend was then further studied by adding different amounts of potassium hydroxide (KOH) ionic dopant. Water has been used as solvent to prepare PVA/PVP-KOH based alkaline solid polymer blend electrolyte films. The conductivity was enhanced to (1.5 ± 1.1) × 10⁻⁴ Scm⁻¹ when 40 wt.% KOH was added. Paper presented at the International Conference on Functional Materials and Devices 2005, Kuala Lumpur, Malaysia, June 6 – 8, 2005.     

High ionic conductive behavior of cyanoethylated polyvinylalcohol- and polyacrylonitrile-based electrolytes

New type polymer electrolyte films based on poly(acrylonitrile), (PAN), and cyanoethylated poly(vinyl alcohol), (CN-PVA), were prepared and their conducting behaviors were investigated. CN-PVA was prepared from poly(vinyl alcohol), (PVA) and acrylonitrile in the presence of sodium hydroxide and quaternary ammonium halide as a phase transfer catalyst. Free standing PAN- and CN-PVA-based electrolyte films were prepared by casting the propylene carbonate (PC) solution containing PAN, CN-PVA and LiClO₄ and removing some amount of PC. Ionic conductivity of the electrolyte film, (PAN)10(CN-PVA) 10(LiClO₄)8(PC)4 composite film was 14.6 mS cm^− 1 at 30 °C and 22.4 mS cm^− 1 at 60 °C. FTIR results for the electrolyte films suggest that the nitrile groups in the CN-PVA matrix mainly interact with the lithium ions in the films and enhance dissolution of the lithium salt in the electrolyte films.     

Strengthening Porous PVA with TiO_2 Structure by an Ice-Templating Method

A poly vinyl alcohol(PVA) scaffold with aligned porous is strengthened by in-situ combining with TiO_2. The increased freezing rate can be used to further increase the strength of aligned porous materials. The strengthened porous PVA exhibits aligned interconnected porous structures and shows a significant enhancement in tensile testing and compression strength testing.     

Studies on mechanical and swelling behavior of polymer networks on the basis of the scaling concept. 6. Gels immersed in polymer solutions

In order to describe the mechanical and swelling behavior of gels immersed in polymer solutions, theoretical considerations based on both classical and scaling theories are discussed and compared with experimental findings. Three situations are studied: (1) the gel is separated from the surrounding solution by a semipermeable membrane; (2) the gel is immersed in the semidilute solution of a chemically identical polymer; (3) the gel is directly immersed in the semidilute solution of a chemically different polymer. An attempt is made to take into account the effect of the penetrating polymer on the elastic modulus and the swelling pressure of the gel. Experimental data referring to chemically cross-linked poly(vinyl alcohol) and poly(vinyl acetate) networks are presented. It was found that the concentration of the free chains inside moderately cross-linked networks may be considerable even for polymers having relatively long chains (27,000 < < M _n < 130,000). Experimental results indicate that the presence of free chains only slightly alters the elastic modulus; however, the swelling pressure is considerably affected by the penetrating polymer. The analysis of mechanical and equilibrium deswelling measurements carried out on several series of gel homologues shows that scaling theory satisfactorily describes the experimental data.