Thermal properties of bio flour-filled polypropylene bio-composites with different pozzolan contents

In this study, the thermal properties of bio-flour-filled, polypropylene (PP) bio-composites with different pozzolan contents were investigated. With increasing pozzolan content, the thermal stability, 5% mass loss temperature and derivative thermogravimetric curve (DTG_max) temperatures of the bio-composites slightly increased. The coefficient of thermal expansion (CTE) and thermal expansion of the bio-composites decreased as the pozzolan content increased. The glass transition temperature (T _g), melting temperature (T _m) and percentage of crystallinity (X _c) of the bio-composites were not significantly changed. The thermal stability, thermal expansion and X _c of the maleic anhydride-grafted PP (MAPP)-treated bio-composites were much higher than those of non-treated bio-composites at 1% pozzolan content due to enhanced interfacial adhesion. X-ray diffraction (XRD) analysis confirmed the crystallinity of pozzolan-added bio-composites. From these results, we concluded that the addition of pozzolan in the bio-composites was an effective method for enhancing the thermal stability and thermal expansion.     

Effect of poly (lactic acid)‐graft‐glycidyl methacrylate as a compatibilizer on properties of poly (lactic acid)/banana fiber biocomposites

The main aim of this study was to synthesis of poly (lactic acid) (PLA)‐graft‐glycidyl methacrylate (GMA) as well as its influence on the properties of PLA/banana fiber biocomposites. PLA‐graft‐GMA graft copolymer (GC) was synthesized by melt blending PLA with GMA using benzoyl peroxide and dicumyl peroxide as initiators. Graft copolymerization was confirmed by FTIR and ¹H‐NMR spectroscopic studies. PLA/silane treated banana fiber (SiB) biocomposites with various GC concentrations were prepared by melt blending followed by injection molding techniques. The influence of GC content on the mechanical, thermal and moisture resistance properties of the composite was investigated. The addition of 15 wt% GC content in the biocomposite provided optimum tensile and flexural strength, which is attributed to the greater compatibility between fiber and PLA matrix. The thermal properties of biocomposites have been evaluated using thermogravimetric analysis which provided evidence of improved interfacial adhesion between SiB and PLA by the addition of GC. Additionally, GC enhanced the moisture absorption resistance of biocomposites. These results indicated that GC is indeed a good candidate as a compatibilizing agent to improve the compatibility in PLA/fiber biocomposites. Copyright © 2015 John Wiley & Sons, Ltd.     

Compatibilization of the PBA/PMMA core/shell latex interphase. I. Effect of PMMA macromonomer

In this work poly(methyl methacrylate) (PMMA) macromonomer is used as a compatibilizing agent in a poly(butyl acrylate) (PBA)/PMMA core/shell latex system. The incorporation of the PMMA macromonomer was achieved by copolymerizing it with BA monomer using miniemulsion polymerization. PBA seed latex was also synthesized without the macromonomer present to compare the compatibilizing effects with the PMMA macromonomer. The second stage methyl methacrylate monomer was added semi-continuously to the PBA seed latexes under monomer-starved conditions. Solid-state ¹³C-NMR [H]T₁ρ relaxation studies were used to determine the effect of PMMA compatibilizer on these PBA/PMMA core/shell latex interphase regions. The thickness of the interphase of the core/shell particles prepared with and without the PMMA macromonomer compatibilizing agent are calculated to be in the range of 15–16 nm and 10–12 nm, respectively. Electron microscopy revealed that the seed latex prepared with the PMMA macromonomer achieved a more uniform coverage with the second stage PMMA polymer as compared to the latex synthesized without the compatibilizing agent present. It is concluded that the PMMA macromonomer is effective in increasing the thickness of the interphase region and also the amount of interfacial PMMA. © 1996 John Wiley & Sons, Inc.     

Effect of compatibilization on thermal degradation kinetics of HDPE-based composites containing cellulose reinforcements

Dynamic thermogravimetric analysis under nitrogen flow was used to investigate the thermal decomposition process of high-density poly(ethylene) (HDPE)-based composites reinforced with cellulose fibers obtained from the recycling of multilayer carton scraps, as a function of the cellulose content and the compatibilization. The Friedman, Flynn–Wall–Ozawa, and Coats–Redfern methods were used to determine the apparent activation energy (E _a) of the thermal degradation of the cellulose component into the composites. E _a has been found dependent on the cellulose amount and on the cellulose/polymer matrix interfacial adhesion. In particular, it has been evidenced an increase of the cellulose thermal stability as a consequence of the improved interfacial adhesion between the components in NFR composites.     

Thermal and microstructural characterization of compatibilized polystyrene/natural fillers composites

Composites of polystyrene (PS) with cellulose microfibres and oat particles, obtained by melt mixing, were examined. The compatibilization of the composites was carried out by addition of maleic anhydride-functionalized copolymers (SEBS-g-MA, PS-co-MA) and poly(ethylene glycol) to improve the fibre–matrix interfacial interactions. The plain components and their composites were characterised by FT-IR, DSC, TGA, SEM microscopy and mechanical tests. The properties of the various systems were analysed as a function of both fibre and compatibilizer amount. The compatibilized PS composites showed enhanced fibre dispersion and interfacial adhesion as a consequence of chemical interactions between the anhydride groups on the polymer chains and the hydroxyl groups on the fibres, as demonstrated by FT-IR spectroscopy. DSC analysis pointed out a neat increase of T _g of composites on addition of SEBS-g-MA, as compared to PS-co-MA. The thermal stability of composites was also influenced by the type and amount of fibres, as well as by the structure and concentration of compatibilizer. The effect of the reactive copolymers on the composites properties was accounted for on the basis of the polymer–polymer miscibility and chemical interactions at the matrix/filler interface.     

Capabilities of polymer-modified monodisperse colloidal silica particles as biomaterial carrier

 Polymer modification of monodispersed colloidal silica (0.5 μm) with poly(maleic anhydride-co-styrene) (P(MA-ST)) and poly (maleic anhydride-co-methyl methacrylate) (P(MA-MMA)) and application of the composite particles to biomaterial carriers were investigated. The reaction of bovine serum albumin(BSA)-immobilized P(MA-MMA)/SiO₂ with the anti-BSA antibody showed higher sensitivity in immunological agglutination test than BSA–P(MA-ST)/SiO₂, though immobilization efficiency of BSA on P(MA-MMA)/SiO₂ was lower than that on P(MA-ST)/SiO₂. Alkaline phosphatase and glucose oxidase immobilized on the composite particles exhibited extremely low activities, but α-chymotrypsin immobilized on P(MA-MMA)/SiO₂ and its derivative particles showed the relative activity of 12.5% and 16.1% to the native enzyme, respectively. Grafting of a hydrophilic polymer of poly(acrylic acid) to P(MA-ST)/SiO₂ let to an increase of the immobilized α-chymotrypsin activity to give the maximum relative activity of 55.5%. Received: 23 August 1996 Accepted: 16 October 1996     

Thermal and electrochemical characteristics of plasticized polymer electrolytes based on poly(acrylonitrile-co-methyl methacrylate)

The thermal and electrochemical characteristics of plasticized polymer electrolytes composed of poly(acrylonitrile-co-methyl methacrylate) [P(AN-co-MMA)], a plasticizer [a mixture of ethylene carbonate and propylene carbonate], and LiCF₃SO₃ were investigated. The incorporation of a MMA unit into the matrix polymer was effective for an increase in the compatibility between the matrix polymer and the plasticizer. The comparative investigation of the interfacial resistance of the Li/polymer electrolyte/Li cell for the PAN-based and the P(AN-co-MMA)-based polymer electrolytes showed that the MMA unit could improve the stability of the polymer electrolyte toward the Li electrode, which is probably due to the enhanced adhesion of the polymer electrolyte to the Li electrode. Received: 14 July 1997 / Accepted: 14 May 1998     

Biodegradable compositions by reactive processing of aliphatic polyester/polysaccharide blends

Commercially available biodegradable aliphatic polyesters, i.e., high molecular weight poly(ϵ-caprolactone) (PCL) and polylactide (PLA), were melt blended with a well-known natural and biodegradable polysaccharide: starch either as corn starch granules or as thermoplastic corn starch after plasticization with glycerol. Conventional melt blending yielded compositions with poor mechanical performances as a result of lack of interfacial adhesion between the rather hydrophobic polyester matrix and the highly hydrophilic and moisture sensitive starch phase. Interface compatibilization was achieved via two different strategies depending on the nature of the polyester chains. In case of PLA/starch compositions, PLA chains were grafted with maleic anhydride through a free radical reaction conducted by reactive extrusion. The maleic anhydride-grafted PLA chains (MAG-PLA) allowed for reinforcing the interfacial adhesion with granular starch as attested by TEM of cryofracture surface. As far as PCL/starch blends were concerned, the compatibilization was achieved via the interfacial localization of amphiphilic graft copolymers formed by grafting of PCL chains onto a polysaccharide backbone such as dextran. The PCL-grafted polysaccharide copolymers were synthesized by controlled ring-opening polymerization of ϵ-caprolactone proceeding via a coordination-insertion mechanism. These compatibilized PCL/starch compositions displayed much improved mechanical properties as determined by tensile testing as well as a much more rapid biodegradation as measured by composting testing.     

Polymer blends of polyamide-6 (PA6) and poly(phenylene ether) (PPE) compatibilized by a multifunctional epoxy coupler

A tetrafunctional epoxy monomer, N,N,N′-N′-tetraglycidyl-4,4′-diaminodiphenyl methane (TGDDM), has demonstrated to be a highly efficient reactive compatibilizer in compatibilizing the immiscible and incompatible polymer blends of polyamide-6 (PA6) and poly(2,6-dimethyl-1,4-phenylene ether) (PPE). This epoxy coupler can react with both PA6 and PPE to form various PA6-co-TGDDM-co-PPE mixed copolymers. These interfacially formed PA6-co-TGDDM-co-PPE copolymers tend to anchor along the interface to reduce the interfacial tension and result in finer phase domains and enhanced interfacial adhesion. A simple one-step melt blending has demonstrated to be more efficient in producing a better compatibilized PA6/PPE blend than a two-step sequential blending. The mechanical property improvement of the compatibilized blend over the uncompatibilized counterpart is very drastic, by considering the addition of a very small amount, a few fractions of 1%, of this epoxy coupling agent. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1805–1819, 1998     

Preparation and optical properties of novel bioactive photonic crystals obtained from core-shell poly(styrene/α-<Emphasis Type="Italic">tert</Emphasis>-butoxy-ω-vinylbenzyl-polyglycidol) microspheres

Optical properties of polymer microspheres with polystyrene cores and polyglycidol-enriched shells poly(styrene/α-tert-butoxy-ω-vinylbenzyl-polyglycidol) (P(S/PGL) particles with number average diameters D _n determined by scanning electron microscopy equal 237 and 271 nm), were studied before and after immobilization of ovalbumin. The particles were synthesized by emulsifier-free emulsion copolymerization of styrene and polyglycidol macromonomer (poly(styrene/α-tert-butoxy-ω-vinylbenzyl-polyglycidol)) initiated with potassium persulfate. Molar fraction of polyglycidol units in the interfacial layer of the microspheres determined by XPS was equal 42.6 and 34.0%, for the particles with D _n equal 137 and 271 nm, respectively. Colloidal crystals from the aforementioned particles were prepared by deposition of particle suspensions on the glass slides and subsequent evaporation of water. It was found that optical properties of colloidal crystals from the P(S/PGL) microspheres strongly depend on modification of their interfacial layer by covalent immobilization of ovalbumin. The coating of particles with ovalbumin resulted in decreasing their refractive index from 1.58 to 1.52.     

Fabrication and characterization of gamma-irradiated recycled (thermoplastic/elastomer) matrix filled with feldspar composites

A composite of waste polyethylene, recycled waste rubber powder and reactive compatibilizing agent maleic anhydride, 60/40/2 mass%, was loaded with increasing contents, up to 20 mass%, of the reinforcing filler, feldspar [K (Al SiO₃O₈)]. The composites were gamma-irradiated at various doses up to 150 kGy. Selected physical, mechanical, and thermal parameters were investigated as functions of radiation dose and filler content. Gamma irradiation led to a significant improvement in the properties for all composites irradiated with 150 kGy. Similarly, the increase in feldspar content provided substantial improvement in properties as a result of development in the interfacial adhesion between the filler particles and composite components. The results were confirmed by examining the fracture surfaces using scanning electron microscopic techniques.     

Bile salt structural effect on the thermodynamic properties of a catanionic mixed adsorbed monolayer

The interfacial effects of two bile salts (sodium deoxycholate (NaDC) and sodium dehydrocholate (NaDHC)) in a catanionic mixed adsorbed monolayer have been investigated at 25 °C. The surfactant interfacial composition, the interfacial orientation of the molecules and the energy changes are analysed to show a thermodynamic evidence of the hydrophobic BSs effect during its intercalation into interfacial adsorbed didodecyldimethyl ammonium bromide (DDAB) molecules. Both mixed systems (NaDC–DDAB and NaDHC–DDAB) have analogous adsorption efficiencies, which are similar from a pure DDAB monolayer and superior to that obtained for both bile salts molecules. Nevertheless, their adsorption effectiveness is different: NaDC causes an increment of Γ while NaDHC produces the opposite effect. The adsorption efficiency in surface tension reduction is due to the existence of interfacial synergistic interactions (confirmed by the analysis of β ^γ and ΔG _ad ⁰ values). Maximum synergistic interaction is seen for α _BSs = 0.4. The hydrophobic steroid backbone of NaDHC molecule presents a deep interfacial penetration than NaDC. This fact causes a great disturbance of DDAB hydrocarbon tails and conduces to a large separation of molecules (high A _m values) which explains the reduction of adsorption effectiveness (low Γ _m values).     

Effects of different compatibilizing agents on the interfacial adhesion properties of polypropylene/magnesium oxysulfate whisker composites

The effects of maleic anhydride-grafted polypropylene(PP-g-MAH) and maleic anhydride-grafted polyolefin elastomer(POE-g-MAH) on interfacial adhesion properties of the polypropylene/magnesium oxysulfate whiskers(PP/MOSw) composites were investigated via mechanical, thermal, ATR-FTIR and rheological tests. Although significant increases in yield strength and Young's modulus were observed in PP-g-MAH treated composites, a sharp decline in these properties was observed in POE-g-MAH treated composites. ATR-FTIR results indicated that esterification occurred between the hydroxyl groups of MOSw and the carbonyls of anhydrides of both compatibilizers but POE-g-MAH was still incompatible with the PP matrix, as verified by the presence of shoulder peaks in DTG curves and numerous voids in SEM micrographs. On the other hand, PP-g-MAH was highly compatible with the PP matrix, as evidenced by the peaks in DTG curves and vague interfaces with wrapped melts on the surface of MOSw. Rheological behaviors also confirmed that introducing PP-g-MAH resulted in a transition from liquid-like to solid-like, which was attributed to the stronger interfacial adhesion between MOSw and the PP matrix. POE-g-MAH treated composites, in contrast to PP-g-MAH, maintained liquidlike rheological behaviors as typical molten polymers. There is likely a MOSw network formed in the PP/15PP-gMAH/15 MOSw composite as suggested by the significant deviation of G′ versus G″ plots and the two crossover frequencies observed in plots of tan? versus frequency.     

Polyethylene-supported poly(acrylonitrile-co-methyl methacrylate)/nano-Al2O3 microporous composite polymer electrolyte for lithium ion battery

Nano-Al₂O₃ was doped in poly(acrylonitrile-co-methyl methacrylate) (P(AN-co-MMA)), and polyethylene(PE)-supported P(AN-co-MMA)/nano-Al₂O₃ microporous composite polymer electrolyte (MCPE) was prepared. The performances of the prepared MCPE for lithium ion battery use, including ionic conductivity, electrochemical stability, interfacial compatibility, and cyclic stability, were studied by scanning electron spectroscopy, linear sweep voltammetry, and electrochemical impedance spectroscopy. It is found that the nano-Al₂O₃ significantly affects the MCPE performances. Compared to the MCPE without any nano-Al₂O₃, the MCPE with 10 wt.% nano-Al₂O₃ reaches its best performances. Its ionic conductivity is improved from 2.0 × 10⁻³ to 3.2 × 10⁻³ S cm⁻¹, its decomposition potential is enhanced from 5.5 to 5.7 V (vs Li/Li⁺), and its interfacial resistance on lithium is reduced from 520 to 160 Ω cm². Thus, the battery performance is improved.     

Compatibilization of immiscible poly(lactic acid)/poly(ε-caprolactone) blend through electron-beam irradiation with the addition of a compatibilizing agent

The aim of this study was to compatibilize immiscible poly(lactic acid) (PLA)/poly(ε-caprolactone) (PCL) blend by using electron-beam radiation method with the addition of a compatibilizing agent. Glycidyl methacrylate (GMA) was chosen as the compatibilizing agent, in the expectation that the GMA plays a role as a monomeric compatibilizer and a reactive agent at the interface between the PLA and the PCL phases. Compatibilization process has been investigated through the melt mixing of the PLA/PCL and the GMA by using a twin-screw extruder and the exposure of the PLA/PCL/GMA mixture to electron-beam radiation at room temperature. The melt mixing process was performed to locate the GMA at the interface, thereby expecting a finer morphology due to the GMA as the monomeric plasticizer. The exposure process was carried out to induce definite interfacial adhesion at the interface through electron-beam initiated cross-copolymerization by the medium of the GMA as the reactive agent. To investigate the results of this compatibilization strategy, the morphological, mechanical, and rheological properties of the blend were analyzed. The morphological study clearly showed the reduced particle size of dispersed PCL domains and significantly improved interfacial adhesion by the electron-beam irradiation with the addition of the GMA. The stress–strain curves of the blends irradiated at less than 20 kGy showed the typical characteristics of ductile materials. The tensile properties of the blend were strongly affected by the dose of irradiation.     

Kinetics analysis of colloidal crystallization of silica spheres modified with polymers on their surfaces in acetonitrile

 The nucleation and growth rates in the colloidal crystallization of silica spheres (136 nm in diameter) modified with polymers on their surface were measured by time-resolved reflection spectroscopy. The polymers were poly(maleic anhydride-co-styrene) [P(MA-ST)] and poly(methyl methacrylate) (PMMA). The induction period for nucleation decreased sharply when the sphere concentration increased. The crystal growth process consisted of a fast growing step leading to metastable crystals (rate v ₁) and a slow growth rate accompanied by the formation of stable crystals. The crystal size of the P(MA-ST)/SiO₂ particles decreased from 0.4 to 0.06 mm, whereas v ₁ increased from 13 to 37 μm/s, when the particle concentration increased. The slow step was also observed for almost all the samples but was not analyzed since the rate was too small. For PMMA/SiO₂ dispersions, the crystal size (0.17–0.3 mm) and v ₁ (43–166 μm/s) did not show any relation to the particle concentration but showed a linear relationship with the molecular weight of PMMA. These results suggest the important role of the excluded-volume effects of the polymer layers around the silica surface. The contribution of the repulsion due to the electrical double layers is still effective in the colloidal crystallization in acetonitrile. Received: 6 June 2001 Accepted: 20 September 2001     

Surface modification of CaCO3 filler and its characterization using inverse gas chromatography (IGC)

A CaCO₃ filler was treated by generally used coupling agents and a special one — ethylene-octene copolymer (POE)-g-maleic anhydride (MAH). Fourier transform infrared spectroscopy (FTIR) results show that the special coupling agent POE-g-MAH, in a chemical reaction with CaCO₃, can produce an interfacial layer stronger than simple physical adhesion attained with usual coupling agents. Inverse gas chromatography (IGC) was used to investigate the surface free energy of CaCO₃ after surface modification and to optimize the monolayer content of coupling agents. Based on the IGC results, it can be deduced that the monolayer cover is around 1.9% for CaCO₃ treated with a titanate coupling agent. Scanning electron microscope (SEM) observation results show that the separated morphology existed in the ternary composites containing CaCO₃ after surface treatment with coupling agents, whereas the core-shell morphology was obtained in the ternary composites with POE-g-MAH. The encapsulation of the CaCO₃ filler treated with POE-g-MAH was caused by the strong chemical reaction between the elastomer and CaCO₃ particles. __________ Translated from Journal of Northwestern Polytechnical University, 2007, 25(2): 274–278 [译自: 西北工业大学学报]     

POE-g-PMAH反应性增容PA1010/PP共混物的性能研究

乙烯-辛烯共聚物-g-聚马来酸酐(POE-g-PMAH)作为反应性增容剂,采用熔体共混的方法制备了PA1010/PP共混物,通过扫描电镜(SEM)、力学性能、傅立叶变换红外光谱(FTIR)和示差扫描量热(DSC)测试,研究了POE-g-PMAH对PA1010/PP共混物的增容作用.结果表明,POE-g-PMAH的加入可以减小共混物的相区尺寸,当PA1010/PP/POE-g-PMAH=70/30/15时,分散相尺寸小而均匀;FTIR结果表明接枝在POE上的马来酸酐基团和PA1010在熔融共混期间发生了化学反应;DSC研究结果表明共混体系中PA1010和PP的结晶温度和结晶度随POE-g-PMAH的加入而降低,表明POE-g-PMAH的增容作用对PA1010和PP的结晶有抑制作用.力学性能测试结果表明随着POE-g-PMAH的增加,共混物的冲击强度逐渐增加,当POE-g-PMAH含量增加到15%时,干态冲击强度达到21.13 kJ/m2,是不加增容剂的3.1倍,而拉伸和弯曲强度可以保持较高水平.POE-g-PMAH的增容机理在于其支链中的马来酸酐能与PA1010中的胺基(NH2—)发生化学反应,而主链POE与PP有较好的亲和性,从而降低界面张力,减少相区尺寸,大幅度提高力学性能.     

Thermal decomposition of solid state poly(β-L-malic acid)

Thermal decomposition process of solid state poly(β -L-malic acid) was traced by DSC combined with FT-IR. Melting temperature of this partially crystallized polymer was detected at 46-60°C. The thermal decomposition initiated at ca 185°C accompanied by an evolution of gaseous products. In contrast to the cleavage reaction in the aqueous polymer solutions which gives L-malic acid and corresponding dimer of L-malic acid, the solid state poly(β -L-malic acid) decomposed at above the decomposition temperature giving not the constituent L-malic acid but fumaric acid at the first stage of the reaction then, maleic and maleic anhydride. This revised version was published online in July 2006 with corrections to the Cover Date.     

Structure–property relationship in PCL/starch blend compatibilized with starch‐g‐PCL copolymer

The polycaprolactone (PCL)/starch blends were prepared by using the starch‐g‐PCL (SGCL) graft copolymers as compatibilizers, and their mechanical properties were correlated with the compatibilizing effect of the SGCL copolymers having various molecular structures. The modulus and strength of the PCL/starch blend were decreased, whereas the percent elongation and the toughness were increased remarkably with the addition of SGCL having appropriate graft structure. These property changes were analyzed in terms of the PCL crystallinity and the interfacial adhesion between the PCL matrix and starch dispersion phases, which were dominated by the compatibilizing effects of the SGCL copolymers. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2430–2438, 1999