Controlling the phase stability of polymer blends through the introduction of impenetrable interfaces

In this work, the effect of the introduction of modified solid surfaces into polymer blends on the phase‐separation process was investigated. Glass fibers with surfaces having different chemistries were introduced into polystyrene–poly(methyl methacrylate) blends. The glass fibers used either had fully hydrated surfaces or had surfaces covered with a random copolymer, poly(styrene‐co‐methyl methacrylate). The copolymer was synthesized by free‐radical polymerization of styrene and methyl methacrylate in the presence of previously vinyl silane‐treated glass fibers. The copolymerization and grafting procedures were investigated by FTIR and thermal analysis. Blends containing the fibers were studied using FTIR microscopy and optical microscopy. FTIR microscopy results showed that the composition of the phases in the blends was shifted by using fibers with different surface chemistries. Fibers with grafted copolymers were capable of narrowing the immiscibility region in the phase diagram, while fully hydrated fibers were able to expand the gap. It was proposed that interfacial interactions regulated by a hydrophilic–hydrophobic type of forces were responsible for guiding the described phase‐separation process. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1619–1627, 2003     

聚丙烯接枝马来酸酐增容聚酰胺6／聚丙烯体系吸湿性能及力学性能的研究

以聚丙烯接枝马来酸酐(PP-g-MAH)为相容剂，利用其与聚酰胺6(PA6)在共混过程中的反应增容作用，实现了与聚丙烯(PP)之间的相容性共混，改变其用量，制备了系列具有不同组成的PA6／PP合金，研究了不同组成合金材料的吸湿性能及其在干态和充分吸湿状态时的冲击强度和拉伸性能。结果表明，向PA6／PP合金体系中加入相容剂PP-g-MAH后，可以改善合金的相界面，形成相容性的合金结构，明显降低合金材料的吸湿量及吸湿速率，但进一步增大相容剂PP-g-MAH的用量时，只能明显降低合金材料吸湿过程初期的吸湿速率，不能进一步显著降低合金材料的吸湿量。在相容剂PP-g-MAH用量一定时，随着PA6／PP合金体系中PA6组分含量的提高，合金在干、湿态条件下的冲击强度、拉伸强度、断裂伸长率均呈近似线性变化。对于具有相同基本组成的合金，随着相容剂PP-g-MAFI用量的增加，材料在干、湿态条件下的拉伸强度均有提高，杨氏模量则在干态时有所提高，在湿态时影响不显著，在干、湿态时断裂伸长率以及冲击强度均没有产生显著影响。     

Effect of styrene–isopren–styrene addition on the recycled polycarbonate/acrylonitrile–butadiene–styrene polymer blends

Interfacial agents as compatibilizers have recently been introduced into polymer blends to improve microstructure and mechanical properties of thermoplastics. In this way, it is possible to prepare a mixture of polymeric materials that can have superior mechanical properties over a wide temperature range. In this study, an incompatible blend of Polycarbonate (PC) and Acrylonitrile Butadiene Styrene (ABS) Copolymer were made compatible by addition of 5, 10, and 20% Styrene–Isopren–Styrene Copolymer (SIS). The mixing operation was conducted using a twin‐screw extruder. The morphology and the compatibility of the mixtures were examined by SEM and DSC techniques. Furthermore, the elastic modulus, tensile and yield strengths, percentage elongation, hardness, melt flow index, Izod impact resistance, heat deflection temperature (HDT), Vicat softening point values of polymer alloys of various ratios were determined. It was found that addition of SIS to the structures decreased the tensile strength, yield strength, elastic modulus, and hardness, whereas it increased Izod impact strength and percentage elongation values. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 559–566, 2006     

Effect of compatibilization on the performance of biodegradable composites using cotton fiber waste as filler

The usefulness of cotton waste as a source of reinforcing fibers for the preparation of cost‐effective and biodegradable composites has been investigated. Biodegradable polyester (bionolle 3020) is melt‐compounded together with cotton fibers. Maleic anhydride‐grafted bionolle (bionolle‐g‐MA) is used as a compatibilizer. The grafting reaction is carried out in an intensive mixer in the presence of dicumyl peroxide as initiator. The effects of fiber and compatibilizer content as well as graft content are evaluated by mechanical property measurements and scanning electron microscopy. The compatibilizer improved all mechanical properties significantly. Moreover, the water absorption and swelling of composites decreased, while the thermal stability increased slightly. Also, the biodegradation of the polyester bionolle 3020, as well as that of its composites with cotton fibers, were studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1825–1835, 2003     

Polymer nanocomposite powders and melt spun fibers filled with silica nanoparticles

Nanocomposite powders from polypropylene filled with surface modified and unmodified fumed silica have been prepared from polymer solution to achieve improved mixing and have been forwarded to fiber melt spinning. The surface of the fumed silica was modified with dodecyl alkoxy silanes. Crystallization velocity and viscosity of the PP nanocomposites thereof were determined to ensure good melt spinning processing conditions for all composite compositions. Upon addition of untreated filler particles, a shear thinning and an increased crystallization velocity of the polymer melt was found, while only minor changes were detected in the presence of surface modified fumed silica particles. The composites and the polymer fibers made from these powder composites by melt spinning were mainly characterized by optical microscopy (OM), scanning electron microscopy (SEM), mechanical measurements, differential scanning calorimetry (DSC), and solid‐state NMR. The unmodified fumed silica was found to have a strong influence on the mechanical fiber properties, while the surface modified silica only a small one. Fibers were additionally characterized with respect to the uniformity, the PP crystallinity, moisture absorption, and the water contact angle. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 218–227, 2007     

Thermooxidative degradation of natural rubber/clay composite

The clay is treated with a reducing agent and an acid so as to obtain a clay containing various metal components with a variable‐valence state. Then, the clay is coprecipitated with natural rubber (NR) latex to prepare a vulcanized NR/clay composite. The degradation process of the NR/clay composite under hot air condition was studied dynamically by using a Fourier transform infrared spectrometer attaching an in situ sample cell and was also investigated using the TGA method. The test result obtained from the infrared spectrometry indicated that under low decomposition temperature, the decomposition products of the test samples mainly are ethylene, low molecular olefinic hydrocarbon, and carbonyl compounds. As the decomposition temperature rises, the low molecular olefinic hydrocarbon content decreases, the olefine with longer chain is formed, and a lot of alkane decomposition products are formed at the same time. When the content of the metal components with a variable‐valence state in clay such as Cu, Mn, Co, and Fe increases, the oxidation products containing the carbonyl group, the olefinic hydrocarbon, and CO₂ in the decomposition product of the test sample also increase. The TGA result clearly shows a shoulder peak that appears by the side of the main peak on the DTG curve of NR/clay composite. With the increase in the content of metal components with variable‐valence state in clay, the initial degradation temperature of the test sample (T₀), the degradation peak temperature (T_p1), and the final degradation temperature (T_f1) in first‐stage reaction, as well as the degradation peak temperature (T_p2) and the last final degradation temperature (T_f) in second‐stage reaction of all the test samples more or less shift to the direction of low temperature; besides, the activation energy (E) of the reaction of the test samples more or less decreases. This means that the metal components with variable‐valence state promote the oxidative degradation of the clay–rubber masterbatch. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3809–3815, 2006     

Reactive Compatibilizer Precursors for LDPE/PA6 Blends, 4

Summary: The effectiveness of some thermoplastic elastomers grafted with maleic anhydride (MA) or with glycidyl methacrylate (GMA) as compatibilizer precursors (CPs) for blends of low density polyethylene (LDPE) with polyamide‐6 (PA) has been studied. The CPs were produced by grafting different amounts of MA or GMA onto a styrene‐block‐(ethylene‐co‐1‐butene)‐block‐styrene copolymer (SEBS) (KRATON G 1652), either in the melt or in solution. A commercially available SEBS‐g‐MA copolymer with 1.7 wt.‐% MA (KRATON FG 1901X) was also used. The effect of the MA concentration and of other characteristics of the SEBS‐g‐MA CPs was also studied. The specific interactions between the CPs and the blends components were investigated through characterizations of the binary LDPE/CP and PA/CP blends, in the whole composition range. It was demonstrated that the SEBS‐g‐GMA copolymers display poor compatibilizing effectiveness due to cross‐linking resulting from reactions of the epoxy rings of these CPs with both the amine and the carboxyl end groups of PA. On the contrary, the compatibilizing efficiency of the MA‐grafted elastomers, as revealed by the thermal properties and the morphology of the compatibilized blends, was shown to be excellent. The results of this study confirm that the anhydride functional groups possess considerably higher efficiency, for the reactive compatibilization of LDPE/PA blends, than those of the ethylene‐acrylic acid and ethylene‐glycidyl methacrylate copolymers investigated in previous works.

SEM micrograph of the 75/25 LD08/PA blend (with 2 phr SEBSMA1).     

Blends of i‐PP and SBS. I. Influence of the in situ compatibilization on the morphology

This article concerns the in situ compatibilization of immiscible isotactic polypropylene/butadiene‐styrene‐butadiene triblock copolymer blends (i‐PP/SBS) by means of a reactive mixture. For this purpose, maleated PP (PP‐MAH) and SBS (SBS‐MAH) were used as functionalized polymers and 4,4′‐diaminediphenylmethane was used as a coupling agent between maleated polymers, resulting in a graft copolymer. Binary blends i‐PP/SBS, nonreactive ternary blends i‐PP/PP‐MAH/SBS, and reactive ternary blends i‐PP/PP‐MAH/SBS‐MAH with varying diamine and anhydride molar ratios were prepared. Torque measurements suggest a graft copolymerization during the melt blending for ternary reactive blends, but the extension of the grafting does not vary with the diamine and anhydride molar ratio, but with the elastomer concentration. The morphology of the blends was investigated by scanning electron microscopy. The morphology of binary and ternary nonreactive blends is similar, exhibiting elastomer domains disperse in the i‐PP matrix, whose sizes increase with elastomer concentration. On the other hand, the elastomer domain size in the ternary reactive blends is practically independent of the blends composition and of the diamine and anhydride molar ratio. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 847–855, 2002     

In situ formation and compounding of polyamide 12 by reactive extrusion

The anionic polymerization of lauryllactam was initiated at 270°C using sodium hydride as an initiator and N,N′‐ethylene‐bisstearamide (EBS) as an activator (NaH:EBS molar ratio of 2). Polymerization occurred in less than 2 min and was successfully performed in an internal mixer and a twin‐screw extruder with corotating intermeshing screws (Werner & Pfleiderer ZSK 25). The content of residual monomer, as determined by thermogravimetric analysis, was lower than 0.5 wt %. Molecular weight, as measured by size exclusion chromatography, was governed by the lauryllactam:NaH molar ratio calculated on a M_n of 25 kg/mol at a constant NaH:EBS molar ratio of 2. Blends were prepared in situ by polymerization of lauryllactam solutions of various polymers. When poly(ethylene‐co‐butylacrylate) (Lotryl®; Atofina) was dissolved in lauryllactam, rubber‐toughened polyamide 12 blends were obtained. Mechanical properties of the injection‐molded polymers were examined by stress–strain as well as notched Charpy impact tests at different temperatures. Blend morphologies were imaged by scanning electron microscopy (SEM). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 344–351, 2003     

In situ composite of nano SiO2-P(VDF-HFP) porous polymer electrolytes for Li-ion batteries

Nano SiO₂-P(VDF-HFP) composite porous membranes were prepared as the matrix of porous polymer electrolytes through in situ composite method based on hydrolysis of tetraethoxysilane and phase inversion. SEM, TEM, DSC and AC impedance analysis were carried out. It is found that the in situ prepared nano silica was homogeneously dispersed in the polymeric matrix, enhanced conductivity and electrochemical stability of porous polymer electrolytes, and improved the stability of the electrolytes against lithium metal electrodes. The in situ composite method was found to be much better than the direct composite method in lowering the interfacial resistance between electrolyte and lithium metal electrode. Moreover, cycle test of lithium batteries using lithium metal as anode and sulfur composite material as cathode showed that the electrolyte based on in situ composite of silica presented stable charge-discharge behavior and little capacity loss of battery.