Intercalative polymerization of cyclic esters in layered silicates: thermal vs. catalytic activation

Poly(ε-caprolactone) layered silicate nanocomposites were synthesized by in situ intercalative ring-opening polymerization (ROP) of ε-caprolactone. The polymerization was promoted by thermal or catalytic initiation starting from either non-modified natural sodium-montmorillonite (MMT-Na) or montmorillonite modified by different ammonium cations bearing either non-functional alkyl chains or chains terminated by carboxylic acid or hydroxyl functions. The resulting compositions were analyzed by small-angle X-ray diffraction and transmission electron microscopy. The clay dispersion depended on the structure of the alkyl ammonium. Exfoliated nanocomposites were formed when hydroxyl-containing alkyl ammonium was used; otherwise, partially intercalated/partially exfoliated structures were observed. Moreover, owing to the inherent catalytic properties of the montmorillonite surface, it was also possible to prepare intercalated nanocomposites by in situ polymerization of ε-caprolactone in presence of non-modified montmorillonite-Na (MMT-Na) without any added catalyst.     

Properties of hydrophobically-modified graphene oxide (HG)/butyl rubber (IIR) nanocomposites prepared by shear mixing process

Abstract

Butyl rubber (IIR)/hydrophobically modified graphene oxide (GO) (HG) nanocomposites were prepared via shear-induced compounding. Hydrophilic GO was synthesized through the chemical oxidation of graphite (GP) and modified hydrophobically by octadecylamine which has a hydrophobic long alkyl chain. The obtained HG was characterized by Fourier transform infrared and wide-angle X-ray diffraction (WAXD) patterns. It was well dispersed in toluene for more than 30 days under stationary condition. The IIR/HG nanocomposites were prepared by the shear mixing process and followed by thermal vulcanization process through compression molding. Their properties were studied using oscillating disk rheometer, universal testing machine, differential scanning calorimetry, thermogravimetric analysis, WAXD patterns, and scanning electron microscope analysis. The hydrophobic HG was dispersed at the nanoscale within IIR matrix, and the resulting nanocomposites had significantly reduced curing time. The overall tensile properties were enhanced.     

Banana fiber/chemically functionalized polypropylene composites with in-situ fiber/matrix interfacial adhesion by Palsule process

Chemically functionalized maleic anhydride (MAH)-grafted polypropylene matrix has been used (in place of polypropylene as matrix with compatibilizer) to process banana fiber/chemically functionalized polypropylene (BF/CFPP) composites, without using any compatibilizer and without any fiber modification by Palsule process. Fiber/matrix interfacial adhesion generated, in-situ, due to interactions between BF and the MAH of the CFPP matrix has been established by Fourier transform infrared spectroscopy and scanning electron microscopy. Mechanical properties of the BF/CFPP composites developed by Palsule process with in-situ fiber/matrix interfacial adhesion in this study have been found to be higher than those of the matrix and it increases with increasing amounts of fibers in composites, and are better than properties of literature reported BF/polypropylene composites processed with compatibilizers. Measured modulus of BF/CFPP composites compares well with values predicted by rule of mixtures, Hrisch model, Halpin-Tsai equations and its modified Nielsen version, and with Palsule equation. The feasibility of developing natural fiber/MAH grafted polyolefin composites by Palsule process without using any compatibilizer and without any fiber treatment is demonstrated.     

Preparation of conductive nanocomposites based on poly (aniline-co- butyl 3-aminobenzoate) and poly (aniline-co-ethyl 3-aminobenzoate) by solution blending method

The polyaniline (PANI) is a widely studied conducting polymer due to its application in several devices such as biosensor, gas sensor etc. Known methods to produce PANI composites may be essentially reduced to two distinct groups: synthetic methods based on aniline polymerization in the presence of or inside a matrix polymer, and blending methods to mix a previously prepared PANI with a matrix polymer. Poly (aniline-co-butyl 3-aminobenzoate) (ANI-co-BAB) and poly (aniline-co-ethyl 3-aminobenzoate) (ANI-co-EAB) are prepared as conducting copolymers in nanoscale by chemical oxidation method under ultrasonic irradiation. The different molar ratio of aniline to butyl 3-aminobenzoate and ethyl 3-aminobenzoate are used in the preparation of copolymers. Conductive nanocomposites based on ANI-co-BAB or ANI-co-EAB with poly (styrene-alt-maleic acid) (PSMAC), and polystyrene are prepared by solution blending method. The obtained conductive composites formed films with good homogeneity and flexibility. The conductivity of the obtained nanocomposites is measured with a four-probe method. The electrical conductivity of the composites (ANI-co-EAB)/PSMAC/PS and (ANI-co-BAB)/PSMAC/PS are 24?×?10^?5?S?cm^?1 and 31?×?10^?5?S?cm, respectively. Our results show that the (ANI-co-BAB)/PSMAC/PS composite has more conductivity than (ANI-co-EAB)/PSMAC/PS composite. The copolymers and composites in nanoscale are characterized by FT-IR and ¹H NMR spectral data. The surface morphology was studied using SEM analysis. Also, their grain size is measured using XRD studies.     

Use of flow microcalorimetry and dynamic mechanical thermal analysis for probing interphase structure in poly(styrene-b-butadiene-b-styrene)/magnesium hydroxide composites

Interactions between magnesium hydroxide (Mg(OH)₂ particles (both untreated and treated with 16-methyl heptadecanoic acid (isostearic acid)) and low molar mass poly(styrene) (PS) and poly(butadiene) (PB) have been studied by flow microcalorimetry (FMC) and have been related to the interphase structure in poly(styrene-b-butadiene-b-styrene) (SBS)/Mg(OH)₂ composites using dynamic mechanical thermal analysis (DMTA). The FMC studies revealed that both polymers adsorbed strongly onto an untreated magnesium hydroxide surface though the PB showed greater irreversible adsorption from the heptane carrier fluid. Diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) studies on filler samples removed from the FMC cell after the adsorption-desorption cycle confirmed strong polymer filler interaction. Adsorption of the low molar mass samples of PS and PB onto a pre-adsorbed monolayer of isostearic acid on Mg(OH)₂ resulted in a very significant reduction in polymer adsorption activity due to blockage of adsorption sites. DMTA studies revealed that strong adsorption of PS and PB blocks of SBS onto untreated filler in composites containing 60% w/w Mg(OH)₂ gave rise to phase mixing that led to an 18 °C reduction in the T _g of the PS phase relative to that in the unfilled matrix. However, in equivalent composites based on isostearic acid treated filler a smaller reduction (10 °C) was observed, therefore reflecting reduced filler-matrix interaction and reduced phase mixing.     

A Study on Compatibility and Properties of POE/PS/SEBS Ternary Blends

Ethylene‐α‐olefin copolymer (POE)/polystyrene (PS)/poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) (SEBS) blends were prepared via melt blending in a co‐rotating twin‐screw extruder. The effects of SEBS copolymer on the morphology and rheological and mechanical properties of the blends were studied. Scanning electron microscopy (SEM) photos showed that the addition of SEBS copolymer resulted in finer dispersion of PS particles in the POE matrix and better interfacial adhesion between POE and PS compared with POE/PS blends, which exhibited a very coarse morphology due to the immiscibility between them. Interestingly, the tensile strength increased from 12.5 MPa for neat POE to 23.5 MPa for the POE/PS/SEBS (60/10/30) blend, whereas the tensile strengths of POE/PS (85.7/14.3) blend and POE/SEBS (66.7/33.3) blend were only 10.5 and 16.5 MPa, respectively. This indicates that both SEBS copolymer and PS have a synergistic reinforcing effect on POE. Dynamic mechanical thermal analysis (DMTA) and dynamic rheological property measurement also revealed that there existed some interactions between POE and SEBS as well as between SEBS and PS. DMTA results also showed that the storage modulus of POE increased when PS and SEBS were incorporated, especially at high temperature, which means that the service temperature of POE was improved.     

Microhardness Studies of the Interphase Boundary in Rubber‐Softened Glassy Polymer Blends Prepared with/without Compatibilizer

Abstract

The interphase boundary of incompatible polymer blends such as poly(methyl methacrylate) (PMMA)/natural rubber (NR) and polystyrene (PS)/NR, and of compatible blends such as PMMA/NR/epoxidized NR (ENR) and PS/NR/styrene–butadiene–styrene (SBS) block copolymer, where ENR and SBS were used as compatibilizers, was studied by means of microindentation hardness (H) and microscopy. Cast films of neat PMMA and PS, and blended films of PMMA/NR, PS/NR, PMMA/NR/ENR, and PS/NR/SBS were prepared by the solution method using a common solvent (toluene). Hardness values of 178 and 173 MPa were obtained on the surfaces of the neat PMMA and PS, respectively. After the inclusion of soft phases, the binary (incompatible) and the ternary (compatible) blend surfaces show markedly lower H‐values. Scanning electron and optical microscopy reveal a clear difference at the phase boundary of the surface of compatible (smooth boundary) and incompatible (sharp boundary) blends. The compatibilized blends were characterized by using microhardness measurements, as having the thinnest phase boundary (～30 µm), while incompatible blends were shown to present a boundary of about 60 µm. The hardness values indicate that the compatibilizer is smoothly distributed across the interface between the two blend components. Results highlight that the microindentation technique, in combination with microscopic observations, is a sensitive tool for studying the breadth and quality of the interphase boundary in non‐ or compatibilized polymer blends and other inhomogeneous materials.     

Stably dispersible P3HT/ZnO nanocomposites with tunable luminescence by in-situ hydrolysis and copolymerization of zinc methacrylate

In this paper, the copolymer shell with the internal hydrophobic polymethacrylate layer and the external hydrophilic poly(ethylene glycol) methyl ether groups was successfully bonded on the surface of ZnO nanocrystals through a simple sol–gel method, i.e., radical polymerization of zinc methacrylate (Zn(MA)₂) and poly(ethylene glycol) methyl ether methacrylate (PEGMEMA) and hydrolysis. The prepared ZnO@poly(methacrylate-co-poly(ethylene glycol) methyl ether methacrylate) (ZnO@PPEGMA) nanocrystals showed good dispersion and smaller particle size, due to the presence of copolymer shell. The optical properties of ZnO@PPEGMA nanocrystals were characterized by ultraviolet–visible (UV–vis) spectroscopy and photoluminescence (PL) spectroscopy. The results indicated that the absorption edge and PL emission in the UV region of ZnO@PPEGMA nanocrystals appeared obvious blue-shift, due to the smaller particle size. Incorporation of ZnO@PPEGMA nanocrystals into poly(3-hexylthiophene) (P3HT) matrix, the dispersion of P3HT/ZnO@PPEGMA nanocomposites was greatly improved and the nanocomposites possessed excellent photoluminescence stability. Meanwhile, it was observed that the PL emission of P3HT/ZnO@PPEGMA nanocomposites was enhanced significantly, due to the presence of copolymer shell and the improvement of compatibility of ZnO@PPEGMA in the P3HT matrix. The results showed that the P3HT/ZnO@PPEGMA nanocomposites could be potential candidates for optical applications.     

Assessment of thermal and antimicrobial properties of PAN/Zn-Al layered double hydroxide nanocomposites

Polyacrylonitrile-based Zn–Al layered double hydroxide composites (PAN/LDH) have been synthesised with different LDH content by in situ polymerisation technique. The nanocomposites were systematically studied by Fourier transform infrared spectroscopy, X-ray diffraction (XRD), thermo gravimetric analysis (TGA), field emission scanning electron microscope (FE SEM), high resolution transmission electron microscopy (HRTEM), energy dispersive spectroscopy (EDS) and antibacterial activity measurement. The successful formation of exfoliated nanocomposite was inferred from the XRD patterns and HRTEM images. The thermal decomposition of PAN was enhanced upon nanocomposite (PAN/LDH) formation. The antimicrobial activity of PAN/LDH nanocomposites is evaluated for antibacterial activity against some clinically important bacterial pathogens and the bacterial growth is monitored at different percentage of LDH. The PAN/LDH composites displayed considerable antibacterial activity, on the contrary the virgin PAN did not possess any antibacterial activity. The likely electrostatic interaction among LDH layers with charged surface of bacterial cell is assumed to be responsible for antimicrobial activity. The prepared nanocomposite has appreciable thermal stability in combination with antibacterial activities by which the material is suitable for packaging and fabrication in textile application.     

PVDF/PS/HDPE/MWCNTs/Fe3O4 nanocomposites: Effective and lightweight electromagnetic interference shielding material through the synergetic effect of MWCNTs and Fe3O4 nanoparticles

In this work, Polyvinylidene Fluoride (PVDF)/polystyrene (PS)/high density polyethylene (HDPE) ternary blends displayed a core-shell structure where HDPE was the core, PS was the shell, and this core-shell system dispersed in PVDF matrix. Here, multiwall carbon nanotubes (MWCNTs) and ferroferric oxide (Fe₃O₄) was incorporated. F-F composites with MWCNTs was in PS shell and Fe₃O₄ was in PVDF matrix and E-F composites with MWCNTs was in PS shell and Fe₃O₄ was in HDPE core were fabricated by melt blending. It was indicated that the core-shell morphology between PS and HDPE was well retained with the incorporation of Fe₃O₄ and MWCNTs. Both the electrical conductivity of F-F and E-F composites were similar without no obvious change with the incorporation of Fe₃O₄. Composites with greater than 20 dB shielding effectiveness were easy to obtain. The highest SE we observed was for the F-F composite with 1 vol% Fe₃O₄ and 1 vol% MWCNTs was 25 dB at 9.5 GHz, and the SE was over 20 dB in the whole measured frequency(X-band). The E-F composites with SE greater than 20 dB in X-band was at 2 vol% Fe₃O₄ and 1 vol% MWNCTs. Such effective and lightweight nanocomposites were obtained, resulting from the synergetic effect of MWCNTs and Fe₃O₄ nanoparticles.     

Synthesis and Characterization of Surface-modified Rutile Nanoparticles And Transparent Polymer Composites Thereof

Nanoparticles of rutile, a crystal modification of titanium dioxide, were synthesized in strongly acidic solutions by hydrolysis of titanium tetrachloride. The particles of average diameter 2nm were coated in situ with a layer of dodecylbenzenesulfonic acid (DBSA) and isolated as a powder. Remarkably, dispersions of this powder in toluene were essentially transparent at the visible wavelengths but absorbed UV radiation over a broad wavelength range. The DBSA-coated rutile was also embedded in poly(styrene) and a poly(carbonate), resulting in polymer nanocomposites acting as visually transparent UV filters.     

Synthesis and application of the solar cell of poly(3-hexylthiophene)/Fe N/titanium dioxide nanocomposite material

A series of nanocomposites of poly(3-hexylthiophene) with Fe N-doped TiO₂ (P3HT/Fe N/TiO₂) were synthesized by the chemical method in situ. The structure of the prepared composites was characterized using X-ray diffraction patterns (XRD), infrared spectroscopy (IR), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). Optical and electrochemical properties were determined using UV-vis spectroscopy, fluorescence spectroscopy, and cyclic voltammetry. These tests indicated that P3HT/Fe N/TiO₂ is a new p-n semiconductor. Two solar cells based on P3HT/Fe N/TiO₂ were manufactured and studied.     

COMPATIBILIZATION OF POLY(ETHYLENE OXIDE)/POLY(STYRENE) BLENDS: EFFECT OF THE MOLECULAR WEIGHT OF THE COMPATIBILIZER

The effect of the molecular weight and concentration of the compatibilizer maleic acid-alt-styrene copolymer (MAaS) on the compatibility behavior of incompatible poly(ethylene oxide)/poly(styrene) (PEO/PS) blends was studied by differential scanning calorimetry (DSC) and polarized light microscopy (PLM). PEO with [Mbar] _w = 100,000 (PEO₁₀₀) and PS with [Mbar] _w = 225,000 (PS₂₂₅) were used for this study. DSC measurements showed two T _g values that were shifted relative to those of the pure components. This result should be indicative that MAaS acts as a compatibilizer for the blend. Diminishing of the spherulitic growth rate G was observed as the content and molecular weight of MAaS increased in the blend. This result was confirmed by morphological analysis, by which it was possible to observe that the amorphous component diminished its droplike domains. Contact angle measurements suggest that the wettability of PEO drops on a PS/MAaS surface are larger in the system containing MAaS as the compatibilizer.     

Reaction‐Induced Phase‐Separation in Polyoxyethylene/Polystyrene Blends. II. Structure Development

Abstract

The morphology development in model polymer blends was investigated in relation to the processing pathway. Reaction‐induced phase separation was used to make polyoxyethylene (POE) and polystyrene (PS) blends from a solution of POE/styrene. As the styrene underwent polymerization by photo‐initiation with ultraviolet light, phase separation, and phase inversion were induced, whereby the POE became the matrix phase. Optical microscopy showed that liquid–liquid (L–L) phase separation occurred soon after the styrene polymerization was initiated. Nucleation and growth was identified as the mechanism of L–L phase separation. Polystyrene/styrene‐rich domains formed in a POE/styrene‐rich matrix. The domain size developed until arrested by the POE liquid–solid phase separating and crystallizing, since the experiments were conducted below the melt temperature of POE. The POE crystal growth process also followed a nucleation and growth mechanism. The time to the onset of crystallization was observed to decrease as the POE content increased, until the POE formed a saturated solution in styrene. As the crystallization onset time decreased, the PS‐rich domain size also decreased. The phase diagram previously established can now be used to describe (and predict) the number density and size of the PS‐rich domains in the POE matrix of the blends.     

Preparation and Properties of Polystyrene/Bacterial Cellulose Nanocomposites by In Situ Polymerization

Polystyrene/bacterial cellulose (PS/BC) nanocomposites were prepared via in situ polymerization. Scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), themogravimetry (TG), and mechanical testing were employed to characterize the PS/BC nanocomposites. The polystyrene filled in the network of the BC and a lamellar structure was formed. The FTIR results show that no chemical reaction between PS and BC occurred during the polymerization. These composites showed good mechanical properties.     

Study of Morphology and Mechanical Properties of In Situ PP/PS Alloy

The in situ polypropylene (PP)/polystyrene (PS) alloy was prepared in the presence of dicumyl peroxide (DCP). Purified styrene (St) and pre‐polymerized styrene (PSt), forming a dispersed PS phase in the PP matrix would react with PP matrix to form PP‐g‐PS graft co‐polymers acting as a compatibilizer in these alloys, leading to the formation of in situ PP/PS alloys with in situ compatibilizer during reactive blending in a mixer. The morphology development of the alloy was examined by scanning electron microscopy (SEM) and was described using the characteristic length L and the average characteristic length L_m. The shape of the dispersed PS phase was regular and the distribution of PS particles was uniform. Tensile properties of the alloy were improved with mixing time and fluctuated in a certain composition range.     

The Effect of Structure of the Clay Modifier on the Morphology and Properties of Polystyrene/Clay Nanocomposites Prepared via In Situ Suspension Polymerization

Polystyrene (PS)/organoclay nanocomposites were prepared via free radical suspension polymerization. Two kinds of organoclay were used, labeled KT and KD, modified by trimethyloctadecyl ammonium (TM) and dimethyldioctadecyl ammonium (DM) ions, respectively. Nanocomposites containing various amounts of both of the organoclay nanoparticles (1, 3, and 5 wt%) were prepared. The wide angle X-ray diffraction (WAXD) results revealed intercalation in both of the nanocomposites. The greatest improvement in thermal stability of the nanocomposites was achieved with 5 wt% of organo-MMT for both of the clays. The nanocomposite containing 3 wt% of KT organo-MMT showed the greatest improvement of storage modulus. When the organoclay content exceeded 3 wt%, the storage moduli decreased compared to the nanocomposite filled with 3 wt% of the organoclay. D-spacing calculations using Bragg's law and WAXD data showed that the KT and KD nanoparticles were intercalated within the PS matrix, but with different extents of intercalation. The styrene conversions of the as-polymerized nanocomposite samples were obtained by a gravimetric method. The results showed that conversion decreased with incorporation of organoclay in the reaction recipe. Particle size was also increased by increasing nanoclay content.     

Role of Styrene‐Ethylene/Propylene Block Copolymer in Controlling Morphology Development of PP/PS Blends during Mixing

The role of styrene‐ethylene/propylene (SEP) diblock copolymer in controlling morphology development of polypropylene/polystyrene (PP/PS) blends was studied by means of small angle laser scattering (SALS) and scanning electron microscopy (SEM). According to SALS, a certain amount of SEP was located at the phase boundary, forming a relatively thick transition layer penetrating into the homopolymers. The thickness of the transition layer was quantified in terms of Debye–Bueche light scattering theory. For PP/PS (1/99) and PP/PS (20/80) blends, the incorporation of SEP into PP/PS blends resulted in a decrease in domain size following an emulsification curve as well as a uniform size distribution, and consequently, a fine dispersion of PP domains in the PS matrix. However, for PP/PS (45/55) blends, the addition of SEP results in a nonmonotonous change in domain size. The morphology fluctuation of the fracture surfaces was analyzed using an integral constant Q based on Debye–Bueche light scattering theories. Variation of Q as a function of the concentration of SEP showed that, due to the penetrating transition layer, adhesion between phases was improved, making it possible for applied stress to transfer between phases and leading to a more uniform stress distribution when blends were broken; accordingly, a more complicated morphology fluctuation of the fracture surfaces appeared.     

Emulsion Polymerized Polystyrene/Montmorillonite Nanocomposite and its Viscoelastic Characteristics

A novel polystyrene (PS)/clay nanocomposite was synthesized using a simple emulsion polymerization method in the presence of sodium ion exchanged montmorillonite (Na‐MMT). Prior to the radical polymerization procedure with potassium persulfate (KPS) as an initiator, the hydrophobic styrene monomer was intercalated into hydrophilic clay layers using sodium dodecyl sulfate (SDS) as a surfactant. The FTIR spectra of the products showed the characteristic absorbance peaks of both the synthesized PS and Na‐MMT. The x‐ray diffraction patterns of the products exhibited an increase in the d ₀₀₁‐spacing, pointing to the intercalation of the PS chains into the intergalleries of the Na‐MMT. The enhancement of the thermal properties of the nanocomposite materials, such as the increase in the glass transition temperature of the PS, was investigated by differential scanning calorimetry (DSC). Furthermore, based on the viscoelastic properties of the products examined using a rotational rheometer with a parallel plate geometry, the nanocomposites were found to exhibit more rapid shear thinning and increased storage (G′) and loss (G″) moduli with increasing clay content.     

Approaches to the manufacture of layered nanocomposites

Clay-polymer nanocomposites, resulting from industrial research, have emerged as a new class of material because a low addition of clay in a polymer matrix causes dramatic improvement in mechanical and barrier properties. They represent the low volume fraction (<4 vol.%) end of the composition range. The question now is: what will emerge from attempts to explore the high volume fraction (>60 vol.%) end? Naturally occurring materials, such as nacre, show that a combination of a high platelet content in a polymer with a layered structure is strong and tough (4-10 MPa m^1/2), even if the reinforcement, aragonite in this case, is inherently brittle (∼1 MPa m^1/2). This achievement of nature has inspired the synthesis of materials to mimic the nacre structure using high aspect ratio reinforcements of high elastic modulus such as smectite clay tactoids. Preliminary successes were based on layer-by-layer assembly methods and it will be interesting to find out whether sufficient order can be obtained in composites assembled by more rapid manufacturing pathways. We are interested in the factors affecting dispersion, orientation and intercalation of platelets and here we survey the strategies that have been adopted in order to create organized structures of layered nanocomposites.