Poly(butylene terephthalate) Toughening with Butadiene-Epoxy-Functionalized Methyl Methacrylate Core–Shell Copolymer

Butadiene glycidyl methacrylate-functionalized-methyl methacrylate (PB-g-MG) core–shell copolymer was used to toughen poly(butylene terephthalate) (PBT). Fourier transform infrared (FTIR) spectra and torque tests showed that compatibilization reactions took place between the carboxyl and/or hydroxyl groups of PBT and the epoxy groups of PB-g-MG. Phase morphology results showed that the PB-g-MG core–shell particles dispersed in the PBT matrix uniformly. The addition of PB-g-MG significantly improved the mechanical properties of PBT. The elongation at break and the impact strength increased with the increase of PB-g-MG content. SEM results showed that the shear yielding properties of the PBT matrix was the main toughening mechanism. The relationship between complex viscosity and angular frequency of the PBT/PB-g-MG blends indicated that the melt viscosity was higher than that of pure PBT.     

The Mechanical Properties,Compatibility, and Thermal Stabilities of POE-Graft-Methyl Methacrylate and Acrylonitrile(POE-g-MAN)/ Styrene-Acrylonitrile Copolymer (SAN Resin) Blends

POE-graft-methyl methacrylate and acrylonitrile (POE-g-MAN) was prepared by graft copolymerization of methyl methacrylate (MMA) and acrylonitrile (AN) onto polyethylene-octene copolymers (POE) with suspension polymerization. POE-g-MAN/SAN resin blends (AOMS) were prepared by blending POE-g-MAN with styrene-acrylonitrile copolymer (SAN resin). The mechanical properties, compatibility, and thermal stabilities of AOMS were studied. The notched impact strength of the blends reached 54.0 kJ/m² when the AN/(MMA + AN) ratio (f_AN) of POE-g-MAN, benzoyl peroxide dosage, and POE content in AOMS were 15 wt%, 1.0 wt%, and 25 wt%, respectively. Transmission electron microscopy analysis showed that the highest toughness occurred when the size of POE-g-MAN particles and the surface-to-surface inter-particle distance were proper. Scanning electron microscopy analysis indicated that the AOMS fracture surface had plastic flow visible, which looked like a fibril morphology when the AN/(MMA + AN) ratio (f_AN) of POE-g-MAN was 15 wt%. The toughening mechanism of AOMS was shear yielding of the matrix, which endowed AOMS with remarkable toughness. Dynamic mechanical thermal analysis showed that the compatibility of the POE phase and SAN phase improved after graft copolymerization of MMA and AN onto POE. When the grafting chain polarity was appropriate, the miscibility between POE-g-MAN and SAN resin was the best. Thermogravimetry analysis showed that thermal stability of AOMS increased with increasing AN units in POE-g-MAN.     

Study on the Morphological and Mechanical Properties of Nylon 6/ABS/Nano-SiO2 Composites

The mechanical properties and morphology of the composites of nylon 6, acrylonitrile-butadiene-styrene (ABS) rubber, and nano-SiO₂ particles were examined as a function of the nano-SiO₂ content. A mixture with separation and encapsulation microstructures existed in the nylon 6/ABS/nano-SiO₂ at lower nano-SiO₂ content, and ABS and nano-SiO₂ improved the toughness synergistically, while obvious agglomeration appeared at higher nano-SiO₂ content and the impact strength decreased. Moreover, the addition of nano-SiO₂ particles also affected the dispersion of the rubber phase, resulting in the appearance of smaller rubber particles. The deformation and toughening mechanisms of the composites were also investigated; they resulted from rubber voiding, crack forking, and plastic deformation of the matrix.     

Properties of Poly(butylene terephthalate)/Bisphenol A Polycarbonate Blends Toughening with Epoxy-Functionalized Acrylonitrile–Butadiene–Styrene Particles

Glycidyl methacylate functionalized acrylonitrile–butadiene–styrene particles (ABS-g-GMA) prepared via an emulsion polymerization method were used to toughen poly(butylene terephthalate) (PBT)/bisphenol A polycarbonate (PC) blends. DMA results showed PBT was partially miscible with PC and the addition of ABS-g-GMA improved the miscibility between PBT and PC. DSC tests further testified that the introduction of ABS-g-GMA improved the miscibility of PBT and PC according to the T_m depression criterion. SEM displayed a very good dispersion of ABS-g-GMA particles in the PBT/PC blends and the dispersed phase size of PC decreased due to the compatibilization effect of ABS-g-GMA. The mechanical properties showed that the addition of 10 wt% ABS-g-GMA was sufficient to induce a super-tough fracture behavior to the PBT/PC blends and a notched impact strength of more than 1000J/m was achieved. The Vu-Khanh test showed that stable crack propagation took place for PBT/PC blends with the addition of ABS-g-GMA and led to ductile failure.     

Reactive Compatibilization of Poly(Butylene Terephthalate)/Acrylonitrile-Styrene-Acrylate Blends by Epoxy Resin: Morphology and Mechanical Properties

The effect on the notched Izod impact strength of poly(butylene terephthalate) (PBT) by blending it with acrylonitrile-styrene-acrylate (ASA) was examined. Epoxy resin (ER) was demonstrated to be an efficient compatibilizer for the partially compatible blends of PBT/ASA. It requires only a very small amount of ER to improve the toughness of the PBT/ASA blends drastically. Furthermore, there exists an optimum proportion of ER added to achieve maximum notched Izod impact strength. Transmission electron microscopy (TEM) observation suggests that the ER in the PBT/ASA/ER blends suppressing the tendency of coalescence of ASA, leading to better dispersion of the ASA particles. Field emission scanning electron microscopy (FESEM) shows that ER enhances the phase dispersion and the interfacial adhesion between the PBT and ASA phases, it improves the compatibility between PBT and ASA. The compositions in the interphase was continuous, which results in multiphase composites with a graded interphase. It is suggested that enhanced interphase adhesion was necessary to obtain improved dispersion, fine phase morphology, and better toughness.     

Toughening Effect of Poly(ethene-co-1-butene)-graft-methyl Methacrylate and Acrylonitrile on Styrene-acrylonitrile Copolymer (SAN)

Poly(ethene-co-1-butene)-graft-methyl methacrylate-acrylonitrile (PEB-g-MAN), synthesized by suspension grafting copolymerization of methyl methacrylate and acrylonitrile onto PEB, was blended with styrene-acrylonitrile copolymer (SAN). The mechanical properties, phase structure, toughening mechanism, miscibility, and thermal stability of the SAN/PEB-g-MAN blends were studied using a pendulum impact tester, tension tester, scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic mechanical analysis (DMA), and thermogravimetric analysis (TG). The results showed that PEB-g-MAN has an excellent toughening effect on SAN resin. The notched impact strength of the blends (containing 25 wt% PEB) was 63.3 kJ/m², which was nearly 60 times that of SAN resin. The brittle-ductile transition of SAN/PEB-g-MAN blends occurred when the weight percentage of PEB was between 17.5 and ～20 wt%. SAN and PEB-g-MAN were partially miscible. The toughening mechanism of the blends changed with the PEB content. When the PEB content was low, the toughening mechanism of the blends was branching and termination of cracks with slight cavitation. As the content of PEB increased, the toughing mechanism gradually changed from branching and termination of crack with slight cavitation to both branching and termination of crack and cavitation, to extensive cavitation, and finally to shear yielding accompanied by cavitation. The phase structure of the blends changed from a “sea-island’’ structure to a cocontinuous structure as the PEB content increased. ATG analysis showed that the thermal properties of the SAN resin in the blends were enhanced by adding the PEB-g-MAN.     

Acrylic coatings exhibiting improved hardness, solvent resistance and glossiness by using silica nano-composites

To prepare nano-composite emulsion acrylic resins with improved surface hardness and solvent resistance, nano-silica particles were treated with surfactants. The monomers of methyl methacrylate/butylacrylate were co-polymerized on the surface of dispersed silica particles. Several emulsions with different silica contents and copolymer mole fractions were prepared. Finally the emulsions were modified to water-based acrylic coatings and improved properties such as surface hardness, solvent resistance and glossiness were determined. The study of coatings was directed to find the improved resin by optimum surface properties. Size distribution and morphology of latexes were characterized by Fourier transform infrared spectroscopy, dynamic light scattering, transmission electron microscopy and scanning electron microscopy. The glass transition temperature of nano-composites was measured and discussed its relation with silica contents, monomer mole fractions and improved properties of coatings. The optimum pendulum hardness of coatings was on 0.46 methyl methacrylate mole fraction and 120 g silica content. An increase in pendulum hardness of nano-composites with the addition of modified silica was observed. DLS and TEM studies indicate that silica particles were dispersed homogenously through the polymer matrix.     

Annealing effect on adhesion properties of poly(butylene terephthalate)

Injection-molded poly(butylene terephthalate) (PBT) is generally annealed at a temperature above the operating temperature to remove residual internal stress and obtain high-dimensional stability. However, this annealing treatment causes poor adhesion property and affected quality and lifetime for the products. In this study, a plausible mechanism for why such problems are caused by the annealing treatment is proposed using additive free PBT. After PBT was annealed under given conditions, surface structure and adhesion strength with an epoxy adhesive were examined. Surface roughness of the PBT film monotonically increased with increasing annealing time, and the tensile adhesive strength concurrently decreased. In addition, the height difference between hill and valley of the surface after adhesive failure became larger, meaning that the failure took place in the PBT phase beneath the interface with the epoxy region. Based on these findings, it was claimed that the poor adhesion of PBT after the annealing treatment originated from a weak boundary layer, which was formed at the outermost surface of PBT. Finally, the presence of the weak boundary layer was directly confirmed by transmission electron microscopy.     

Carboxylated acrylo nitrile butadiene rubber latex/kaolin nanocomposites: preparation and properties

Carboxylated nitrile butadiene rubber (XNBR)–based nanocomposites with varying amounts of nanokaolin were produced by latex stage mixing. Sonication of the unmodified kaolin and the technique adopted for the preparation of the composite have helped to get a uniform dispersion of clay in XNBR matrix. Nanokaolin caused enhancement in the mechanical properties of the composites. Proper dispersion of the clay particles, partial exfoliation/intercalation of clay, and interaction of clay with the polar rubber latex made nanokaolin good reinforcing filler in XNBR latex. Swelling studies conducted in methyl ethyl ketone showed a decrease in the swelling index and solvent uptake confirming the hindrance exerted by clay and the possible clay–rubber interaction. Increase in complex modulus obtained from the strain sweep analysis is a further evidence for better rubber filler interaction. The composites were characterized by the scanning electron microscopy, X-ray diffraction analysis, and atomic force microscopy.     

Crystallization,Flame Retardancy and Mechanical Properties of Poly(Butylene Terephthalate)/Brominated Epoxy/Nano-Sb2O3 Composites Dispersed By High Energy Ball Milling

Nano-Sb2O3 particles and brominated epoxy resin (BEO) powders were dispersed in poly (butylene terephthalate) (PBT) by high energy ball milling (HEBM). Then the nanocomposites were prepared by a twin screw extruder. The influence of the nano-Sb2O3 particles on the crystallization, thermal stability, flame retardancy and mechanical properties of the PBT/BEO/nano-Sb2O3 composites were investigated by X-ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), limiting oxygen index (LOI), UL-94 tests and scanning electron microscopy (SEM). The results showed that the nano-Sb2O3 particles improved the crystallizability, thermal stability and flame retardancy properties of the PBT/BEO/nano-Sb2O3 composites. When the content of nano-Sb2O3 particles was 2.0?wt%, the LOI of nano-Sb2O3/BEO/PBT composites increased from 22.0 to 27.8 and the tensile strength reached its maximum value (62.44?MPa), which indicated that the optimum value of flame retardancy and mechanical properties of PBT/BEO/nano-Sb2O3 composites were obtained.     

Rheological Properties,Morphology, and Thermal Performance of E‐MA‐GMA/PC Blend

Blends of ethylene–methyl acrylate–glycidyl methacrylate terpolymer (E‐MA‐GMA, a random terpolymer) and polycarbonate (PC) were prepared in a Haake torque rheometer and the rheological properties, phase morphology, and thermal behavior were investigated. The graft reactions of PC terminal hydroxyl groups with the epoxy groups of E‐MA‐GMA and the in situ formation of the E‐MA‐GMA‐g‐PC copolymers at the interface were illustrated by the improved mixing torque and melt viscosity in E‐MA‐GMA/PC blends. Typical variation and significant deformation of the dispersed phase was observed in E‐MA‐GMA/PC blends with different composition, where PC was the matrix. With the E‐MA‐GMA content increasing, a complex co‐continuous phase structure with some dispersed E‐MA‐GMA particles wrapped in the continuous PC phase was present, indicating strengthened interfacial adhesion. When the E‐MA‐GMA content was higher than the PC component, fibrous structure of the dispersed PC phase in the E‐MA‐GMA matrix was caused by shear flow and interfacial interaction. DSC studies showed that the melting point of E‐MA‐GMA shifted to lower temperature with the increase of PC content, indicating that the enhanced interaction and graft structure hindered the process of crystallization and crystal growth.     

Morphology,miscibility and mechanical properties of PMMA/PC blends

This study deals with some results on morphology, miscibility and mechanical properties for polymethyl methacrylate/polycarbonate (PMMA/PC) polymer blends prepared by solution casting method at different concentration between 0 and 100 wt%. Dynamic storage modulus and tan δ were measured in a temperature range from 30 to 180°C using dynamical mechanical analyzer (DMA). The value of the storage modulus was found to increase with the addition of the PC in the matrix. Transition temperature of pure PMMA and pure PC is found to be 83.8 and 150°C, respectively. The result shows that the two polymers are miscible for whole concentration of PC in PMMA. The distribution of the phases in the blends was studied through scanning electron microscopy (SEM). Also the mechanical properties like elongation at break and fracture energy of the PMMA/PC blends increase with the increase in concentration of PC in PMMA.     

Toughened Poly(Trimethylene Terephthalate) by Blending with a Functionalized Metallocenic Poly(Ethylene-Octene) Copolymer

New toughened poly(trimethylene terephthalate) (PTT) materials were obtained by melt blending with maleic anhydride grafted poly(ethylene-octene) (POEg). Rheological properties, mechanical properties, and morphological characteristics of PTT/POEg blends at four different compositions—95/5, 90/10, 80/20, and 70/30—were studied. The melt viscosity of the blends shows a linear decrease on increasing the POEg content. The addition of rubbery POEg to the PTT matrix increases the impact strength, while tensile properties decrease. Scanning electron microscopy (SEM) displayed a very good dispersion of POEg particles in the PTT matrix. Differential scanning colorimetry (DSC) experiments showed that for all samples the melting point was almost constant and the crystallinity did not show obvious differences. SEM results showed shear yielding of the PTT matrix was the major toughening mechanism.     

Preparation of low density TiO2/poly (methyl methacrylate) composite particles by emulsifier-free emulsion polymerization

Based on the 3-(trimethoxysilyl) propylmethacrylate (MPS) modified TiO₂ particles, the TiO₂/poly (methyl methacrylate) (PMMA) composite particles have been prepared successfully via emulsifier-free emulsion polymerization in water. A facile floating-sinking method is proposed to roughly evaluate the composite particles’ density. Chemical component of obtained composite particles was identified by Fourier transform infrared spectra (FTIR). The morphology and grain size of the composite particles were investigated by field-emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). Thermal analysis of the composite particles was measured by differential thermal analysis-thermo gravimetric analysis (DTA-TGA). The zeta potential and electrophoretic mobility of composite particles with suitable density in water was measured by dynamic light scattering (DLS).     

Morphology and thermal properties of clay/PMMA nanocomposites obtained by miniemulsion polymerization

Miniemulsion polymerization was used as the synthetic method to produce clay/poly(methyl methacrylate) nanocomposites. Two kinds of interfacial interactions clay–polymer particle were observed by electron microscopy, one where the polymer particles are adhered on the surface of the larger fragments of clay, and another where nanometric fragments of clay are encapsulated by polymer particles. Variations in the glass transition temperature (T_g) and thermomechanical properties of the matrix, as function of clay content, were observed. In particular, at the highest clay loading (1.0 wt%) depression of T_g and thermomechanical properties were observed. The increased clay–polymer matrix interfacial area appears to be the conditioning factor that determines such behavior.     

Stress whitening and yielding mechanism of rubber-modified PVC

Structure-property relationships were investigated for blends of grafted rubbery polymers with PVC. Increasing grafting levels as well as higher blending temperatures improved the dispersion of the graft copolymers in PVC, lowered the impact strength, and reduced stress whitening. Presuming a mechanistic connection between impact strength and stress whitening, the causes of whitening due to mechanical deformations were studied by a variety of methods. Electron microscopy of stress-whitened zones revealed a large number of cavities formed by rupture of rubber particles, which correlated with the extent of whitening. Density measurements and quantitative evaluations of the volume increase due to the cavities in the stress-whitened zones were in agreement and proved that crazing did not significantly contribute to either volume dilation or stress-whitening. Light scattering studies indicated the existence of reflecting planes oriented at an angle of 55 to 64° to the direction of the applied stress, depending on the particle size of the modifier in the blends. The orientation of the scattered light could not be attributed to the cavities in the rubber particles because of their smallness (< 0.5 μm). An explanation was finally found by transmission light microscopy at various resolving powers. It was demonstrated that the ruptured rubber particles were accumulated in bands which corresponded to shear bands in the PVC matrix. Thus it was concluded that the rubber particles improved the impact strength of PVC by initiating shear bands and not by generating crazes.     

Interaction of Domains in Ternary Polymer Melt Blends with Separate Dispersions of the Inner Phases

The morphology evolution in three immiscible ternary polymer systems characterized by separate dispersions of the dispersed phases (i.e., no encapsulation phenomena takes place) was characterized. The components used were three of the following: commercial atactic poly(methyl methacrylate) (PMMA) and polystyrene (PS), crystallizable poly(butylene terephthalate) (PBT) and isotactic polypropylene (PP) and glass microspheres (GMS). In System I PMMA/PS/PP (primary dispersed phase/matrix/secondary, or minor, dispersed phase), all of the components were liquid on blending at 190°C. In System II PP/PS/PBT and System III PP/PSyGMS, at 190°C, the minor PBT and GMS dispersed phases were nondeformable. It was shown that small portions (0.5–1.0 wt%) of the PP minor dispersed phase added to the binary PMMA/PS blend produced a dual action: (a) transition of the PMMA dispersed phase to a cocontinuous one and (b) simultaneous substantial (up to a 6-fold) growth of the degree of dispersion of the blend. Moreover, these effects were accompanied by about a three-fold reduction of the threshold PMMA concentration (C*) at which it formed its own co-continuous phase in the ternary blend compared to that in the PMMA/PS binary mixture. The observed phenomena took place regardless of whether the domains of the minor dispersed phase were liquid (System I) or solid (Systems II and III), and was strongly related to the domain sizes of this phase and blend composition. A mechanism underlying the outlined behavior is proposed.     

Synthesis and Characterization of Multi-layered Core/Shell Particles by Sequential Emulsion Polymerization

A series of core/shell particles were prepared by sequential emulsion polymerization. The core/shell particles consisting of poly(methyl methacrylate) core grafted with using rubbery layer [poly(butyl acrylate)co-(styrene)] and then glassy layer [poly(methyl methacrylate)-co-(ethyl acrylate)] were prepared. The conditions which led to controlled particle size and morphology were discussed. A highly cross-linked structure was formed in both the cores and the shells by using a cross-linking agent, which could prevent the migration of hydrophobic shells to the inside of the particles. The core/shell particles were characterized by Fourier-transform infrared spectroscopy, solid state ¹³C-NMR. Thermogravimetric analysis (TGA) and differential scanning calorimeter (DSC) were used to determine the thermal stability and glass transition temperature of the core/shell particles, respectively. Results of the particle size analysis indicate that particle sizes were decreased when there is a rubbery layer as outer layer (0.44 μm) whereas it increases when there is a glassy layer as outer layer (324 μm). Scanning electron microscopy (SEM) also confirms the multi-layers formation in the polymer.     

POSS纳米复合物链运动的固体NMR研究

利用固体NMR技术、并结合TEM技术研究了POSS掺杂到不同聚合物体系后POSS复合物的链段运动及结构特点,其中聚合物包括聚甲基丙烯酸正丁酯（PBMA）和聚甲基丙烯酸甲酯（PMMA）. 实验结果表明：POSS能很好的分散在这2种聚合物中,形成纳米结构的复合物;其中POSS在PBMA中形成的复合物表现出较强的链段运动性,而在PMMA中则表现出较低的运动性;同时,2D HETCOR的结果表明这2种聚合物本身结构特点不同,POSS/PBMA复合物中聚合物部分与POSS部分间的距离较近,而在POSS/PMMA中则较远.     

Fracture Micromechanisms of Polypropylene/Polycarbonate/Poly(styrene-b-(ethylene-co-butylene)-b-styrene) (PP/ PC/SEBS) Ternary Blends: The Effects of SEBS Content

Ternary blends of polypropylene/polycarbonate/poly(styrene-b-(ethylene-co-butylene)-b-styrene) (PP/PC/SEBS) with varying SEBS contents were produced via melt blending in a co-rotating twin-screw extruder. The phase morphology of the resulting ternary blends and its relationship with bending and impact behaviors were studied. Transmission optical microscopy (TOM) of the crack tip damage zone and scanning electron microscopy (SEM) of impact fractured surfaces were performed to characterize the fracture mechanism. With increasing SEBS content in the PP/PC/SEBS ternary blends, the number of PC/SEBS core-shell particles increased and the size of the core-shell particles enlarged. It was shown that with an SEBS content of 5%, the crack initiation resistance decreased and then was almost unchanged with further increase of SEBS content, while resistance to crack growth increased continuously with increasing of SEBS content. Preliminary analysis of the micromechanical deformation suggested that the high impact toughness observed for samples containing 20 and 30 wt% of SEBS could be attributed to cavitation of the rubbery shell and, consequently, shear yielding of the matrix. This plastic deformation absorbed a tremendous amount of energy. Due to low interfacial adhesion between PC particles and PP matrix in samples containing 5 and 10 wt% of SEBS, debonding occurred too early, so the occurrence of matrix shear yielding was delayed and resulted in premature interfacial failure and, hence, rapid crack propagation.