Mechanical properties and morphology of crosslinked PP/PE blends and PP/PE/propylene–ethylene copolymer blends

Blending is an effective method for improving polymer properties. However, the problem of phase separation often occurs due to incompatibility of homopolymers, which deteriorates the physical properties of polyblends. In this study, isotactic polypropylene was blended with low-density polyethylene. Crosslinking agent and copolymers of propylene and ethylene (either random copolymer or block copolymer) were added to improve the interfacial adhesion of PP/LDPE blends. The tensile strength, heat deflection temperature, and impact strength of these modified PP/PE blends were investigated. The microstructures of polyblends have been studied to interpret the mechanical behavior through dynamic viscoelasticity, wide-angle X-ray diffraction, differential scanning calorimetry, picnometry, and scanning electron microscopy. The properties of crosslinked PP/PE blends were determined by the content of crosslinking agent and processing method. For the material blended by roll, a 2% concentration of peroxide corresponded to a maximum tensile strength and minimum impact strength. However, the mechanical strength of those products blended by extrusion monotonously decreased with increasing peroxide content because of serious degradation. The interfacial adhesion of PP/PE blends could be enhanced by adding random or block copolymer of propylene and ethylene, and the impact strength as well as ductility were greatly improved. Experimental data showed that the impact strength of PP/LDPE/random copolymer ternary blend could reach as high as 33.3 kg · cm/cm; however, its rigidity and tensile strength were inferior to those of PP/LDPE/block copolymer blend.     

Toughening of polylactide by melt blending with linear low‐density polyethylene

Melt blending of polylactide and linear low‐density polyethylene (LLDPE) was performed in an effort to toughen polylactide. In addition, two model polylactide‐polyethylene (PLLA‐PE) block copolymers were investigated as compatibilizers. The LLDPE particle size and the impact resistance of binary and ternary blends were measured to determine the extent of compatibilization. For the amorphous polylactide (PLA), toughening was achieved only when a PLLA‐PE block copolymer was used as a compatibilizer. For the semicrystalline polylactide (PLLA), toughening was achieved in the absence of block copolymer. To decrease the variability in the impact resistance of the PLLA/LLDPE binary blend, as little as 0.5 wt % of a PLLA–;PE block copolymer was effective. The differences that were seen between the PLA and PLLA binary blends were investigated with adhesion testing. The semicrystalline PLLA did show significantly better adhesion to the LLDPE. We propose that tacticty effects on the entanglement molecular weight or miscibility of polylactide allow for the improved adhesion between the PLLA and LLDPE. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3757–3768, 2003     

The Use of Ethylene/Propylene Copolymers as Compatibilizers for Recycled Polyolefin Blends

Compatibilizing effects of ethylene/propylene (EPR) diblock copolymers on the morphology and mechanical properties of immiscible blends produced from recycled low‐density polyethylene (PE‐LD) and high‐density polyethylene (PE‐HD) with 20 wt.‐% of recycled poly(propylene) (PP) were investigated. Two different EPR block copolymers which differ in ethylene monomer unit content were applied to act as interfacial agents. The morphology of the studied blends was observed by scanning‐ (SEM) and transmission electron microscopy (TEM). It was found that both EPR copolymers were efficient in reducing the size of the dispersed phase and improving adhesion between PE and PP phases. Addition of 10 wt.‐% of EPR caused the formation of the interfacial layer surrounding dispersed PP particles with the occurrence of PE‐LD lamellae interpenetration into the layer. Tensile properties (elongation at yield, yield stress, elongation at break, Young's modulus) and notched impact strength were measured as a function of blend composition and chemical structure of EPR. It was found that the EPR with a higher content of ethylene monomer units was a more efficient compatibilizer, especially for the modification of PE‐LD/PP 80/20 blend. Notched impact strength and ductility were greatly improved due to the morphological changes and increased interfacial adhesion as a result of the EPR localization between the phases. No significant improvements of mechanical properties for recycled PE‐HD/PP 80/20 blend were observed by the addition of selected block copolymers.     

The mechanical behavior of blends of polyethylene,polypropylene, and an ethylene–propylene block copolymer at −20°C

Compatibilization is necessary for most binary blends which display poor mechanical properties. The addition of an ethylene–propylene block copolymer to a blend of isotactic polypropylene and linear low-density polyethylene alleviates the problem of poor adhesion at the interface. This was observed through the improvement in overall performance of the blend. It was noted that it is not solely the “interfacial agent” which is responsible for the improvement in impact strength of this blend. © 1992 John Wiley & Sons, Inc.     

Effects of organoclay on the compatibility and interfacial phenomena of PE/EVA blends with UCST phase behavior

The compatibilization effects of organically modified nanoclay on the miscibility window, phase separation kinetics, biphasic morphology, interfacial tension, and final properties of polyethylene/ethylene vinyl acetate copolymer blends exhibiting UCST behavior have been investigated. Regardless of blend composition, intercalated nanoclay decreases the phase transition temperatures to lower values and changes the symmetry of phase diagram. The miscibility of PE and EVA phases in the amorphous regions of nanocomposites noticeably enhances and finer biphasic morphology is obtained by the incorporation of organoclay. The pinning influence of the nanofiller on polymer chain diffusion causes much slower phase separation kinetics for the nanocomposites. Similar to conventional compatibilizers such as block copolymers, the interfacial activity of nanoclay leads to a sharp decline in the interfacial tension of PE/EVA up to 2‐orders of magnitude. Moreover, the results show that imposing restrictions on the phase separation phenomenon increases the impact strength of the virgin blend and related nanocomposite. However, this improvement has been much more noticeable in the presence of nanoparticles, which is due to the simultaneous roles of organoclay as an effective compatibilizer and reinforcement. POLYM. COMPOS., 35:2329–2342, 2014. © 2014 Society of Plastics Engineers     

Mechanical properties and failure mode of thermoplastic elastomers from natural rubber/poly(methyl methacrylate)/natural rubber-g-poly(methyl methacrylate) blends

The mechanical properties and fracture behavior of natural rubber/poly-(methyl methacrylate) blends were investigated as a function of composition, graft copolymer concentration, and mixing conditions. The mechanical properties and failure behavior vary with the blend ratio, graft copolymer concentration, and mixing conditions. Various two-phase models were used to fit the experimental mechanical properties. Mechanical properties such as stress–strain behavior, tensile strength, tensile modulus, tear strength, and Izod impact strength were evaluated as a function of compatibilizer concentration. The domain size of the dispersed phase decreases with graft copolymer concentration followed by a leveling off at higher concentration. The mechanical properties attain a maximum value at the leveling point, which is an indication of interfacial saturation and the attainment of maximum interfacial adhesion between the homopolymers. Tensile and tear fracture surfaces were examined by scanning electron microscopy. The detachment of the dispersed domains from the matrix is an indication of no adhesion between the two phases in the case of uncompatibilized blends. Microfibrils between the matrix and the dispersed phase indicate a sign of interfacial adhesion between the phases in the case of compatibilized blends. © 1997 John Wiley & Sons, Inc. J Appl Polm Sci 65:1245–1255, 1997     

Toughening of poly(l‐lactide) modified by a small amount of acrylonitrile−butadiene−styrene core‐shell copolymer

A small amount of acrylonitrile‐butadiene‐styrene (ABS) core shell copolymer particles are used to improve the toughness of poly(l ‐lactide) (PLLA) matrix. The incorporation of ABS copolymer dramatically increased the elongation yield at break of PLLA. For PLLA blend with 6.0 wt % ABS copolymer particles, the elongation yield at break increased by 28 times and the notched impact strength improved by 100% comparing with those of neat PLLA. Fourier transformed infrared (FTIR) and dynamic mechanical analysis (DMA) and scanning electron microscopy (SEM) measurement results indicated that the special polarity interaction between ester group of PLLA matrix and nitrile group of PSAN shell phase enhanced the interfacial adhesion between PB rubber phase and PLLA matrix and promoted the fine dispersion of ABS particles in PLLA matrix. Meanwhile, ABS core shell particles also showed a certain extent of effects on the crystallinity behavior of PLLA. A small amount of ABS particles became the nucleating sites, and then the degree of crystallinity of PLLA/ABS blends increased. However, the notched impact of PLLA blends decreased because of the aggregation of more ABS particles. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42554.     

Comparison of isotactic and syndiotactic polypropylene as matrix materials of hybrid composites

The structure/property relationships and morphology of glass bead–reinforced syndiotactic and isotactic polypropylene composites containing 0 to 20 vol% thermoplastic elastomer (TPE) were studied. Polystyrene-block-poly(ethylene-co-butylene)-block-polystyrene (SEBS) and the corresponding block copolymer grafted with maleic anhydride (SEBS-g-MA) were used as the TPEs. The Young's modulus of hybrid composites based on s-PP showed no dependence on the type of TPE used, whereas i-PP hybrid composites containing SEBS had a higher Young's modulus than composites containing SEBS-g-MA. A comparison of the data with theoretical predictions of Young's modulus and tensile yield stress gave strong evidence of two different morphologies for the hybrid composites. The increasing tensile yield stress of s-PP hybrid composites and i-PP hybrid composites containing SEBS-g-MA was attributed to an interlayer formation and in-situ encapsulation of glass beads, which resulted in core-shell particles with improved interfacial interactions. In contrast, SEBS in hybrid composites based on i-PP formed a separate dispersed phase. Crystallization and scanning electron microscopy studies also provided evidence of a core-shell morphology for hybrid composites based on s-PP. Results of lap-shear and peel tests confirmed strong interfacial interaction between glass and SEBS-g-MA and between SEBS and s-PP as well as i-PP. Only above a critical volume fraction did the TPE provide significant improvement of the notched Izod impact strength of hybrid composites based on s-PP or i-PP.     

Effects of Polystyrene Block Content on Morphology and Adhesion Property of Polystyrene Block Copolymer

Effects of polystyrene block content on adhesion property and phase structure of polystyrene block copolymers were investigated. Polystyrene-block-polyisoprene-block-polystyrene triblock and polystyrene-block-polyisoprene diblock copolymers with different polystyrene block contents in the range from 13 to 35 wt% were used. In the case of the low polystyrene block content (below 16 wt%), a sea-island structure was observed: near-spherical polystyrene domains having a mean diameter of about 20 nm were dispersed in polyisoprene matrix. The phase structure changed from a sea-island structure to a cylindrical structure with an increase of polystyrene block content (over 18 wt%). Peel strength decreased with an increase of polystyrene block content and the pure triblock copolymers had lower peel strength than their blends with the diblock copolymers. Pulse nuclear magnetic resonance studies indicated that molecular mobility of polyisoprene phase decreased with an increase of polystyrene block content, and the molecular mobility was lower in the pure triblock than in the blend. Thus, the peel strength was found to be related to molecular mobility. The adhesion strength of the block copolymer depended on the molecular mobility: high molecular mobility can promote interfacial adhesion.     

Dilatometric investigation of deformation mechanisms in polystyrene-polyethylene block copolymer blends: correlation between Poisson ratio and adhesion

To gain more insight into the deformation behaviour of blends containing polystyrene (PS), low density polyethylene(IdPE) and a PSPE block copolymer, tensile tests have been performed with simultaneous volume measurements. Assuming that shearing does not give rise to volume changes, it is shown that, after yielding, crazing is the only deformation mechanism of blends with a low PE and PSPE block copolymer content. Shearing becomes important at relatively high copolymer concentrations. This is explained by the formation of a semi-continuous low-modulus phase. The decrease of the Poisson ratio with PE content in PSPE blends, as opposed to an increase if some block copolymer has been added to these blends, shows that the Poisson ratio is very sensitive to adhesion between the components. Toughness of PSPE blends is discussed in terms of concentrations of craze nuclei. Too few craze nuclei give rise to brittle failure: the resulting low number of crazes cannot take over much of the deformation of the matrix. Too many craze nuclei cause brittle failure because chances are high that some of the high number of crazes formed will combine to produce a fatal crack. Therefore high toughness is only obtained at intermediate craze nuclei concentrations. The concentration of craze nuclei is shown to be dependent on the number of dispersed particles and the adhesion between these particles and the matrix.     

Morphology and Properties of Poly(L‐Lactide) (PLLA) Filled with Hollow Glass Beads

The morphology, crystalline behavior, and mechanical and thermal properties of poly(L ‐lactide)/hollow glass beads (PLLA/HGBs) composites were investigated. The incorporation of HGBs enhanced the crystallization rate and crystallinity of PLLA, but slightly decreased its elongation at break. In addition, HGBs acted as stress concentration points inducing the plastic deformation of PLLA, leading to increased Izod impact strength. Differential scanning calorimetry results show that annealed PLLA eliminated cold crystallization phenomenon in the region of 100–140 °C and presented a double melting peak around 150 °C. Moreover, annealing was demonstrated to be effective for the improvement of tensile modulus, strength, Izod impact strength and heat distortion temperature of the composites due to the increased crystallinity and more perfect crystals. Silane coupling agents can enhance the interfacial adhesion of the composites, and lead to better mechanical properties. Compared to neat PLLA, the HGBs filled PLLA composites did not exhibit an obvious increase of the density.

     

Mechanical properties and morphology of polypropylene composites. III. Short glass fiber reinforced elastomer modified polypropylene

The impact strength and rigidity of polypropylene composites can be significantly improved by application of short glass fibers instead of mineral fillers in elastomer-modified polypropylene. The properties of such composites are strongly dependent on the adhesive forces at the fiber-matrix interface. Poor adhesion results in interfacial fracture solely by fiber-matrix debonding, as evidenced by scanning electron microscopy on the fracture surfaces. This is accompanied by relatively low impact strengths. By contrast, increased adhesion leads to fracture not only by fiber-matrix debonding, but also by crack propagation through the elastomeric phase at the fiber surface. This mechanism is thought to be responsible for a remarkable increase of the impact strength. Appropriate compositions of polypropylene, glass fiber, and elastomer resulted in composite properties similar to, or even better than, those of a typical acrylonitrile-butadiene-styrene copolymer. The lengths of the fibers recovered from the test specimens were somewhat smaller than the critical fiber lengths as calculated by simple shear lag theory. The properties of the present composites should thus be regarded as minima, rather than as potential maxima. This suggests that current composites may be suitable for engineering applications.     

Toughening and reinforcing of polypropylene

To improve the mechanical properties of polypropylene (PP), some elastomers and fillers are used. The impact properties and tensile strength are affected by both the mineral additives and the polymer additives. There are also some changes in the thermal properties. To improve the interfacial adhesion, some low molecular polymers are added to assist the dispersion of the fillers and the uniformity of the various polymers with PP. The addition of low-density polyethylene (LDPE), high-density polyethylene (HDPE), or the styrene–butylene–styrene block copolymer (SBS) can improve the impact properties of PP. The propylene–ethylene copolymer has a more pronounced effect than does the physical blending of PP with PE. Calcium carbonate can reinforce PP resin. The ethylene–vinyl acetate copolymer (EVA) has an effect on the printing properties of the PP. © 1996 John Wiley & Sons, Inc.     

Influence of morphology on rheological and mechanical properties of SEBS-toughened,glass-bead-filled isotactic polypropene

The influence of morphology of glass-bead-filled isotactic polypropene containing 0–20 vol% thermoplastic elastomers (TPE) on mechanical and rheological properties was investigated. Polystyrene-block-poly(ethene-co-but-1-ene)-block-polystyrene(SEBS) and the corresponding block copolymer grafted with maleic anhydrid (SEBS-g-MA) were used as thermoplastic elastomers, realizing, in the first case, a three-phase morphology with separately dispersed glass beads and SEBS particles. In the second case, SEBS-g-MA forms an elastomeric interlayer between glass beads and polypropene matrix, comprising core–shell particles. Young's modulus and tensile yield stress of the hybrid composites decrease with an increase in TPE volume fraction due to low stiffness and strength of TPE. In comparison with the three-phase morphology of hybrid composites with SEBS, SEBS-g-MA interlayers effect a reduced stiffness of the hybrid composites but improve interfacial adhesion and, thus, tensile yield stress. Rheological storage and loss moduli increase with an increase in glass bead and TPE volume fraction. Due to improved interfacial adhesion, melt elasticity and viscosity are enhanced by the SEBS-g-MA interlayer when compared with separately dispersed SEBS. Consequently, the reduced stiffening effect of the glass beads due to SEBS-g-MA interlayer decreases mechanical elasticity, whereas improved interfacial adhesion, also promoted by the SEBS-g-MA interlayer, enhances tensile yield stress and melt elasticity. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2499–2506, 1998     

EOC-g-MAH共混增韧SGF/PP泡沫复合材料的制备及力学性能

采用型内二次发泡工艺制备了马来酸酐接枝乙烯-1-辛烯共聚物(EOC-g-MAH)共混增韧短玻璃纤维(SGF)/聚丙烯(PP)泡沫复合材料,考察了EOC-g-MAH含量对复合材料的泡孔形貌、微观结构和力学性能的影响。结果表明,EOC-g-MAH的引入改善了泡沫体的发泡效果,平均孔径减小约35%,泡孔密度提高近4倍且分布均匀。SGF与基体间的界面结合得到显著增强,且EOC-g-MAH在SGF表面形成了颗粒黏附结构,大幅提高了SGF/PP泡沫复合材料的冲击韧度,并在质量分数为8%时达到最大值,增幅为77%。随着EOC-g-MAH质量分数的增加,SGF/PP泡沫复合材料的抗弯强度先增加后降低,而压缩强度则呈近似线性下降的变化趋势。     

The interfacial properties and porous structures of polymer blends characterized by synchrotron small-angle X-ray scattering

Microvoids are induced upon uniaxial drawing of films made from immiscible polypropylene (PP)/polystyrene (PS) binary blends and ternary blends of PP, PS, and a block copolymer SEEPS. The shape of the uniaxially oriented microvoids is rod- or slit-like with a high aspect ratio. Synchrotron small-angle X-ray scattering (SAXS) is used to characterize the dimensions of these microvoids. Their scattering image is an intense azimuthally narrow equatorial streak on a two-dimensional SAXS pattern. This streak is analyzed to obtain the diameter, length and misorientation of the microvoids. The microvoids length is identified as an effective measure of the interfacial adhesion and strength between phase domains. Drawn films of binary blends of PP/PS are found to have the longest microvoids. The initial addition of the block copolymer SEEPS as a compatibilizer enhances the interfacial adhesion and shortens the length of microvoids. Further addition of compatibilizer induces the formation of aggregates of a composite PS/SEEPS dispersed phase, and this leads to reduced interfacial adhesion and a longer microvoids. Interfacial properties are also dependent on the mixing protocol used to produce the blends.

The transport property of the films is determined by porosity and the degree of interconnectivity. A convenient measure of the degree of interconnectivity is proposed. The degrees of interconnectivity of these films are in accordance with the interfacial adhesion and strength. Non-equatorial streaks are observed and attributed to the microvoids with a complex orientation and geometry, which are responsible for the interconnectivity among microvoids.     

PO／PS合金的相态结构与力学性能

以氢化ＳＢＳ（ＳＥＢＳ）为增容剂的聚烯烃／聚苯乙烯（ＰＯ／ＰＳ）合金，与聚烯烃相比具有更好的力学性能，尤其是抗冲击强度随机容剂的增加而大幅度提高，应用ＴＥＭ，ＳＥＭ、ＤＳＣ、偏光显微技术对一系列合金相形态，相容程度及分散相颗粒尺的考察研究发现，合金中分散相多数呈卵石状，随ＳＥＢＳ含量增加，分散相粒径显著变小，而合金抗冲击强度增大，分散相形态结构。颗粒尺寸与材料力学性能密切相联。     

Conversion of plastic/cellulose waste into composites. I. Model of the interphase

This article proposes a mechanism for a significant improvement in the mechanical performance of a simulated waste fraction, composed of an immiscible low-density polyethylene (LDPE) and high-impact polystyrene (HIPS) blend (70:30 proportion), when chemithermomechanical pulp (CTMP) fibers and maleic acid anhydride grafted styrene–ethylene/butylene–styrene block copolymer (MAH-SEBS) were added. SEM micrographs of composites showed an increased contact between the continuous LDPE phase and CTMP fibers when the functionalized compatibilizer (MAH-SEBS) was used. By employing a model study using LDPE and regenerated cellulose, we investigated the interphase properties between the plastic phase and the cellulosic component. The model study utilized ESCA, FTIR, and contact angle analysis to follow the reaction between the cellulose surface and the functionalized compatibilizer. All three methods showed that MAH-SEBS was bonded to the surface of the cellulose. The single-fiber fragmentation test showed that the adhesion between cellulose fibers and the plastic matrix was significantly improved for MAH-SEBS–modified samples. The effect of enhanced adhesion on increased mechanical properties of cellulose composites is also discussed, and a prediction of composite strength given, based on interfacial adhesion promotion and fiber properties. © 1995 John Wiley & Sons, Inc.     

废旧高密度聚乙烯/木粉复合材料的改性研究

采用自制的聚乙烯与三单体固相接枝共聚物(GPE)对废旧高密度聚乙烯/木粉复合材料进行改性。与其他界面改性剂相比,GPE能有效改善复合材料的界面相容性,提高复合材料的力学性能和耐热性,但对其流变性能影响不大。     

Studies of different kinds of fiber pretreating on the properties of PLA/sweet sorghum fiber composites

In this article, truly degradable composites were prepared using sweet sorghum fibers which are residue of ethanol fermentation industry as reinforcement and renewable resource‐based biodegradable polyester, poly(L ‐lactide) (PLLA) as matrix, they were fabricated by melt‐blending. The effect of different kinds of pretreatments (dilute sulfuric acid pretreatment, mild alkaline/oxidative pretreatment, steam explosion pretreatment) on mechanical properties of composites were investigated. Besides the composition of untreated and treated fibers as determined by Van soest method, Fourier transformed infrared (FTIR) spectroscopic and scanning electron microscopic (SEM) were also used to study the change of sweet sorghum fibers before and after pretreatments. Mechanical properties testing indicated that tensile strength and impact strength of PLLA/treated fibers were improved except the dilute sulfuric acid pretreated fibers reinforced PLA composite. The mild alkaline/oxidative pretreated fiber reinforced PLA composite showed highest tensile strength of 46.12 MPa and impact strength of 8.02 kJ/m² which was 15.5 and 33% higher than that of the control. The SEM of impact fracture surface and DMTA test were carried out to investigate the interfacial morphology and interfacial adhesion between the fiber and matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010