Evaluation of mechanical properties of polypropylene/polycarbonate/SEBS ternary polymer blends using Taguchi experimental analysis

In this work, ternary polymer blends based on polypropylene (PP)/polycarbonate (PC)/poly(styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene) (SEBS) triblock copolymer and a reactive maleic anhydride grafted SEBS (SEBS‐g‐MAH) at fixed compositions are prepared using twin‐screw extruder at different levels of die temperature (235‐245‐255°C), screw speed (70‐100‐130 rpm), and blending sequence (M1‐M2‐M3). In M₁ procedure, all of the components are dry blended and extruded simultaneously using Brabender twin‐screw extruder, whereas in M₂ procedure, PC, SEBS, and SEBS‐g‐MAH minor phases are first preblended in twin‐screw extruder and after granulating are added to PP continuous phase in twin‐screw extruder. Consequently, in M₃ procedure, PP and SEBS‐g‐MAH are first preblended and then are extruded with other components. The influence of these parameters as processing conditions on mechanical properties of PP/PC/SEBS ternary blends is investigated using L9 Taguchi experimental design. The responding variables are impact strength and tensile properties (Young's modulus and yield stress), which are influenced by the morphology of ternary blend, and the results are used to perform the analysis of mean effect as well. It is shown that the resulted morphology, tensile properties, and impact strength are influenced by extrusion variables. Additionally, the optimum processing conditions of ternary PP/PC/SEBS blends were achieved via Taguchi analysis. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polypropylene/polystyrene blends prepared by diffusion and subsequent polymerization in polypropylene pellets after injection molding

PP/PS quasi‐nanoblend pellets were synthesized by diffusion and subsequent polymerization of styrene in iPP pellets via a two‐step procedure and then processed by injection molding. The PS distributions along the thickness direction of the molded bars were investigated by Micro‐FTIR, showing almost homogeneous distribution no matter whether the PS distribution in the blend pellets is homogeneous. The morphology of the molded bars was investigated by FESEM, revealing two types of particles (small spherical and bigger irregular‐shaped complex aggregates) and good interfacial adhesion between particles and matrix. The particles are mainly in nano and submicron sizes, and only few particles approach 1 μm. The mechanical properties of the molded bars were evaluated by uniaxial tensile testing, showing a significant reinforcing effect without significantly loosing ductility. The yield strength of all the blends increase 20–27% compared to neat PP and the elongations at break are all over 300%. The remarkable mechanical properties of the molded bars were correlated with their morphology. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43983.     

Nanostructured polymer blends: Synthesis and structure

Nanostructured polymer blends prepared via anionic ring opening polymerizations of cyclic monomers in the presence of a pre-made polymer melt exhibit a number of special properties over traditional polymer blends and homopolymers. Here, we report on a simple and versatile method of in situ polymerization of macrocyclic carbonates in the presence of a maleic anhydride polypropylene (mPP) matrix and a surface-active compatibilizer (i.e. PC grafted onto a mPP backbone generated in situ) to yield a micro- and nanostructured polymer blends consisting of a polycarbonate (PC) minor phase, and a polypropylene (PP) major phase. By varying the processing conditions and concentration of the macrocyclic carbonate it was possible to reduce the size of the PC dispersions to an average minor diameter of 150 nm. NMR and TEM characterizations indicate that the PC dispersions do not influence crystal content in the PP phase. Overall, the results point to a simple strategy and versatile route to new polymeric materials with enhanced benefits.     

In situ compatibilization of starch-zein blends under shear flow

Starch-zein blends show poor adhesion between the two phases. Aldehyde starch was investigated as compatibilizer for these blends. Wheat starch was oxidized under mild conditions using sodium hypochlorite in the presence of the 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) and NaBr to prepare aldehyde starch. The oxidized starch was characterized by Nuclear Magnetic Resonance and Rapid Visco-Analyzer. Starch-zein blends plasticized with water and glycerol were prepared using simple shear flow in an in-house developed shearing device. Different zein ratios were tested to study the influence of aldehyde starch on the properties of the final material. The morphology of the blends was observed with confocal scanning laser microscopy and scanning electron microscopy. Tensile tests were used to evaluate the performance of the material. Both microscopy and tensile tests indicated that the blends had improved adhesion between the zein and starch phases, probably by reaction between the aldehyde groups in the starch molecules and zein. The aldehyde starch also influenced the properties of the starch matrix (higher viscosity, larger breakdown), which shows that physical or chemical crosslinks were formed inside the starch matrix.     

PS/EPDM blends prepared by in situ polymerization of styrene

PS/EPDM blends formed by in situ polymerization of styrene in the presence of EPDM were prepared. EPDM has excellent resistance to factors such as weather, ozone and oxidation and it could be a good alternative for substituting polybutadiene‐based rubbers in PS toughening. The PS/EPDM blends present two phases, an EPDM elastomeric phase dispersed into a rigid matrix. The blends show higher thermal stability than polystyrene homopolymer due to the stabilizing effect of EPDM incorporation. The mechanical properties of in situ polymerized PS/EPDM blends with different compositions were evaluated before and after accelerated photoaging and compared with the properties of HIPS submitted to the same aging conditions. The blend containing 17 wt % of EPDM presents an increase in the impact resistance of 210% in comparison with the value of PS. Although the initial mechanical properties of HIPS are superior, a pronounced drop was observed after an exposure time. For example, after the aging period, all PS/EPDM blends showed higher strain at break than HIPS. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Kinetics-controlled compatibilization of immiscible polypropylene/polystyrene blends using nano-SiO2 particles

Rigid inorganic filler has been long time used as a reinforcement agent for polymer materials. Recently, more work is focused on the possibility that using filler as a compatibilizer for immiscible polymer blends. In this article, we reported our efforts on the change of phase morphology and properties of immiscible polypropylene(PP)/polystyrene(PS) blends compatibilized with nano-SiO₂ particles. The effects of filler content and mixing time on the phase morphology, crystallization behavior, rheology, and mechanical properties were investigated by SEM, DSC, ARES and mechanical test. A drastic reduction of PS phase size and a very homogeneous size distribution were observed by introducing nano-SiO₂ particles in the blends at short mixing time. However, at longer mixing time an increase of PS size was seen again, indicating a kinetics-controlled compatibilization. This conclusion was further supported by the unchanged glass transition temperature of PS and by increased viscosity in the blends after adding nano-SiO₂ particles. The compatibilization mechanism of nano-SiO₂ particles in PP/PS blends was proposed based on kinetics consideration.     

Molecular dynamics in semifluorinated side-chain polyesters as studied by broadband dielectric spectroscopy

The molecular dynamics in a variety of poly(ethylene isophthalate)s (PEIs) is studied by broadband dielectric spectroscopy (BDS). The materials comprise non-substituted main chain polyesters and polyesters with semifluorinated (oxydecylperfluorodecyl) side chains. Combining temperature-dependent small angle X-ray scattering (T-SAXS), differential scanning calorimetry (DSC) and BDS it can be shown that the microphase separated semifluorinated polymers exhibit independent dynamic glass transition relaxations taking place in the separate microphases. Additionally in the glassy state, the non-substituted polymers show an Arrhenius-type relaxation whose activation energy decreases gradually from 52 to 40 kJ/mol with increasing main chain flexibility. The semifluorinated polymers exhibit a relaxation assigned to fluctuations of the perpendicular component of the fluoroalkyl end group with activation energies between 38 and 40 kJ/mol. With increasing flexibility of the main chain, the dynamics of the backbone becomes faster for the non-substituted polymers while an opposite trend is observed in the oxydecylperfluorodecyl substituted side-chain materials. A detailed explanation of the molecular origin of the relaxations is provided.     

Continuous ultrasonic process for in situ compatibilization of polypropylene/natural rubber blends

The immiscible polypropylene (PP)/natural rubber (NR) blends of various concentrations were prepared by using a twin-screw extruder. The prepared blends were passed through the reactor where they were ultrasonically treated by an extrusion process. Mechanical properties and rheology of the obtained blends were studied, along with morphology by using the scanning electron microscopy and the atomic force microscopy (AFM). Mechanical properties of the treated blends were found to improve significantly in comparison with those of untreated blends. Under most treatment conditions, no significant differences in the viscosity of the treated and untreated blends were observed. The AFM studies revealed the development of interfacial layers, interfacial roughening and improved interfacial adhesion between PP and NR phases in the blends subjected to ultrasonic treatment. At the same time weak adhesion and delamination at the interface were found in the untreated blends. The improved interfacial adhesion, morphology and mechanical properties are believed to be due to the formation of in situ copolymer at the interface of two immiscible polymers caused by an ultrasonic treatment without the use of any chemicals.     

In situ compatibilization of polypropylene–polyethylene blends: a thermomechanical and spectroscopic study

Polypropylene (PP) and low density polyethylene (LDPE) were melt blended in proportions of 75/25, 50/50 and 25/75 w/w, respectively. Poly(propylene-g-maleic anhydride) (PP-g-MA) with 0.8 mol% maleic anhydride content and poly(ethylene-co-vinyl alcohol) (EVAL) with 7.5 mol% vinyl alcohol content were added at a 50/50 w/w proportion as in situ reactive compatibilizers. Four series of compatibilized blends were produced containing 2.5, 5, 10 and 20 wt% compatibilizer in the final blend. The compatibilization reaction was followed by a torque increase during mixing and by FTi.r. spectroscopy. A notable improvement in tensile strength, elongation at break and impact strength was observed for all blends after compatibilization and, in particular, for the blends containing 10 wt% compatibilizer. Scanning electron microscopy (SEM), aided by micro-Raman spectroscopy, was used for investigating the morphology of the blends.     

Comparison of carboxylated and maleated polypropylene as reactive compatibilizers in polypropylene/polyamide‐6,6 blends

Using reactive extrusion, polypropylene is functionalized with maleic anhydride and compared on an equimolar basis to polypropylene that is functionalized with an asymmetric, carboxylic acid containing peroxide. The grafting efficiency for the asymmetric peroxide is double that obtained for the maleic anhydride system. Moreover, the asymmetric peroxide yields a functionalized material with minimal molecular weight degradation and desirable mechanical properties, relative to maleic anhydride‐grafted polypropylene. In compatibilized blends of polypropylene and nylon 6,6, the polypropylene that was functionalized with the asymmetric peroxide is found to be an improved compatibilizer compared to that of maleic anhydride‐grafted polypropylene. The differences in mechanical properties of the two different functionalized polypropylene materials and their respective blends are rationalized on the basis of the grafting efficiency, molecular weight degradation during reactive extrusion, and effect of free functional species on the ability to form graft copolymers in compatibilized blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2398–2407, 2001     

Molecular dynamics and thermal analysis study of anomalous thermodynamic behavior of poly (ether imide)/polycarbonate blends

Molecular dynamics simulation used to study the binary polymer blend of poly (ether imide) (PEI) and polycarbonate (PC) showed that these polymer blends are immiscible. The Flory-Huggins interaction parameter, χ, calculated from simulation reached a minimum value at 80 wt% PEI. The simulation results showed that the concentration dependence of χ was mainly due to electrostatic interaction and van der Waals force. The simulation results were supported by differential scanning calorimetry (DSC) measurements. The DSC measurements showed that there are two distinct glass transition temperatures for all the blends' concentrations. However, at 80wt % PEI, the T_g of PEI-rich phase reached a minimum while that of the PC-rich phase was comparable to its pure form indicating that there is some partial miscibility of PC in the PEI rich phase, but no PEI is incorporated in the PC rich phase. From simulations, the χ versus concentration plot shows the same trend as the experimentally measured glass transition temperature versus concentration plot.     

Polyethylene/palygorskite nanocomposites: Preparation by in situ polymerization and their characterization

A naturally occurring clay mineral, palygorskite, which has the microstructure of nano-fibers, was used to support a metallocene compound, Cp₂TiCl₂. After activation by methylaluminoxane, the supported catalyst initiated an in situ ethylene polymerization resulting in the exfoliated dispersion of the nano-fibers into the polyethylene matrix. With no further chemical modification of the palygorskite after thermal treatment, the activity of the supported catalyst was found to be even higher than its solution counterpart under the same polymerization conditions. The addition of the filler in the polymer matrix led to an increase in composite rigidity as reflected by almost doubling the storage modulus at room temperature. Moreover, the filler affects the crystallization process, as observed by DSC and solid-state NMR, reducing the crystallinity up to 28% and the thickness of the rigid phase up to 22% compared with the neat sample.     

Surface mechanical properties of transparent poly(methyl methacrylate)/zirconia nanocomposites prepared by in situ bulk polymerization

Poly(methyl methacrylate)/zirconia (PMMA/ZrO₂) nanocomposites with ZrO₂ content as high as 15 wt% were prepared by modifying non-aqueous synthesized ZrO₂ nanoparticles with methacryloxypropyltrimethoxysilane (MPS) in tetrahydrofuran, dispersing MPS-functionalized ZrO₂ nanoparticles in MMA and following in situ bulk polymerization with controlled pre-polymerization time. The MPS-functionalized ZrO₂ nanoparticles showed an efficient crosslinking role in the polymerization, leading to a complete gel of PMMA at 5 wt% of ZrO₂ content. Homogeneous dispersion of the ZrO₂ nanoparticles at primary particle size level was observed in all nanocomposites, which results in good clarity of the obtained nanocomposites. Hardness tests (pendulum hardness tests and indentation tests) and anti-scratch tests (abrasion tests and nano scratch tests) were employed to probe the surface mechanical properties of the nanocomposites. The properties of nanocomposites as a function of ZrO₂ content, revealing from various characterization techniques, are not consistent and discussed in detail. At low ZrO₂ content, the mechanical properties are enhanced by the formed crosslinking structure. However, remarkable improvements of hardness and scratch resistance of PMMA were achieved when 15 wt% of ZrO₂ content was embedded.     

Effects of compatibilization of oxidized polypropylene on PP blends of PP/PA6 and PP/talc

The influence of compatibilization on the dynamic mechanical properties of polypropylene (PP) binary blends with polyamide‐6 (PA6), Talc, and oxidized PP (OPP) was investigated. The oxidation of PP homopolymer was performed in a internal mixer by using air as a oxidizing agent (under atmospheric pressure) and dodecanol‐1 as an accelerator at 180°C for 6½ h [Abdouss, M.; Sharifi‐Sanjani, N.; Bataille, P. J Appl Polym Sci 1999, 36, 10]. In the blends, OPP was used as a blend component and compared with PP over the whole concentration range. Pressed film blends of PP/OPP, PP/OPP/Talc, and PP/OPP/PA6 were examined by dynamic mechanical analyzer, thermal gravimetry analysis, and scanning electron microscopy. Mechanical properties such as tensile strength, modulus of elasticity, elongation, melt flow index, and hardness of the blends were measured. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2871–2883, 2004     

Intercalated structure of polypropylene/in situ polymerization-modified talc composites via melt compounding

Talc was modified with methyl methacrylate (MMA) or butyl acrylate (BA) via in situ polymerization. The talc/isotactic polypropylene (PP) composites with nano-sized intercalated structure were formed by melt compounding of PP with the modified talc. The results showed that the talc layers were partially delaminated, aligned along the flow direction, and uniformly dispersed in the PP matrix. The thickness of the PMMA-modified talc layers in the PP matrix was in the range 80-240 nm, while the PBA-modified talc was even thinner. PMMA or PBA macromolecules attached on the surface of talc layers hindered the crystallization of the PP component. Moreover, the aligned pristine talc layers promoted the orientation of the PP crystals. However, the extent of PP crystal orientation decreased in the presence of PMMA or PBA-modified talc.     

Compatibilization effects of styrenic/rubber block copolymers in polypropylene/polystyrene blends

Compatibilizing effects of styrene/rubber block copolymers poly(styrene‐b‐butadiene‐b‐styrene) (SBS), poly(styrene‐b‐ethylene‐co‐propylene) (SEP), and two types of poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) (SEBS), which differ in their molecular weights on morphology and selected mechanical properties of immiscible polypropylene/polystyrene (PP/PS) 70/30 blend were investigated. Three different concentrations of styrene/rubber block copolymers were used (2.5, 5, and 10 wt %). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to examine the phase morphology of blends. The SEM analysis revealed that the size of the dispersed particles decreases as the content of the compatibilizer increases. Reduction of the dispersed particles sizes of blends compatibilized with SEP, SBS, and low‐molecular weight SEBS agrees well with the theoretical predictions based on interaction energy densities determined by the binary interaction model of Paul and Barlow. The SEM analysis confirmed improved interfacial adhesion between matrix and dispersed phase. The TEM micrographs showed that SBS, SEP, and low‐molecular weight SEBS enveloped and joined pure PS particles into complex dispersed aggregates. Bimodal particle size distribution was observed in the case of SEP and low‐molecular weight SEBS addition. Notched impact strength (a_k), elongation at yield (ε_y), and Young's modulus (E) were measured as a function of weight percent of different types of styrene/rubber block copolymers. The a_k and ε_y were improved whereas E gradually decreased with increasing amount of the compatibilizer. The a_k was improved significantly by the addition of SEP. It was found that the compatibilizing efficiency of block copolymer used is strongly dependent on the chemical structure of rubber block, molecular weight of block copolymer molecule, and its concentration. The SEP diblock copolymer proved to be a superior compatibilizer over SBS and SEBS triblock copolymers. Low‐molecular weight SEBS appeared to be a more efficient compatibilizer in PP/PS blend than high‐molecular weight SEBS. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 291–307, 1999     

Microstructural evolution of electrically activated polypropylene/layered silicate nanocomposites investigated by in situ synchrotron wide-angle X-ray scattering and dielectric relaxation analysis

Electric field was found to facilitate the destruction of layer stacking and separation of silicate layers in polypropylene (PP)/layered silicate nanocomposites, resulting in the penetration of polymer chains into silicate galleries. In this study, we describe the real-time microstructural evolution of PP/clay nanocomposites under electric field investigated by in situ synchrotron wide-angle X-ray scattering (WAXS) analysis. We were able to identify two distinctive mechanisms for the formation of nanocomposites depending on the type of electric field. We observed that the exfoliation process prevails in the AC field, while the alignment of silicates parallel to the electric field predominates in the DC field. Dielectric relaxation analysis showed that the different mechanisms originate from different charge distributions of bound ions attached to the clay surfaces due to the applied electric field.     

PP/PA11共混物微、介观形态的分子模拟

采用分子动力学（MD）和介观动力学（MesoDyn）模拟方法研究了不同质量含量（10/90、30/70、50/50、70/30和90/10）PP/PA11共混物的相容性和介观形态结构。通过对MD模拟得到的Flory-Huggins相互作用参数（χ）和PP-PP、PA11-PA11及PP-PA11分子间C-C原子对径向分布函数的研究表明：当PP与PA含量为90/10时两者具有一定的相容性,而其它比例的相容性则较差。为了进一步研究共混物的介观形态结构,采用MesoDyn模拟方法在介观尺度对共混体系的介观形貌进行了研究,将通过MD模拟计算的分子间相互作用参数和其他结构参数（重复单元个数、聚合度和极限特征比等）转化为MesoDyn模拟的输入参数,实现了微、介观多尺度模拟的连接。