Raman and Wide-Angle X-Ray Diffraction Studies on Molecular Structure,Crystallinity, and Morphology of Uncompatibilized and Compatibilized Blends of High Molecular Weight Polyethylene/Nylon 12

Molecular structure, crystallinity and morphology of uncompatibilized and compatibilized blends of high molecular weight polyethylene (HMWPE) and Nylon 12 were investigated by using Fourier-transform (FT) Raman spectroscopy, wide-angle x-ray diffraction (WAXD), and scanning electron microscopy (SEM). One of the important purposes of the present study is to compare the present results for HMWPE/Nylon 12 with the previously obtained results for high-density polyethylene (HDPE/Nylon 12). Uncompatibilized and compatibilized blends of HMWPE/Nylon 12 with a Nylon 12 content ranging from 10 to 90 wt% at increments of 10 wt% were prepared. The compatibilized polymer blends were prepared by adding a small amount of maleic anhydride (MAH), and SEM images show that the addition of the small amount of MAH (0.5 wt%) yields a marked improvement of dispersion of HMWPE and Nylon 12. To evaluate the crystallinity of HMWPE from Raman spectra, the relative intensities of bands at 1418 and 1129 cm⁻¹ to the intensity of a band at 1000 cm⁻¹ (I₁₄₁₈/I₁₀₀₀ and I₁₁₂₉/I₁₀₀₀) were estimated for all the uncompatibilized and compatibilized blends of HMWPE/Nylon 12. From the comparison of the relative intensities (I₁₄₁₈/I₁₀₀₀ and I₁₁₂₉/I₁₀₀₀) between the uncompatibilized and compatibilized blends of HMWPE/Nylon 12 it was found that when the Nylon 12 content reaches 40 wt% the crystallinity of HMWPE in the compatibilized blends becomes higher than that of HMWPE in the uncompatibilized blends. The uncompatibilized and compatibilized blends of HMWPE/Nylon 12 (50/50) show quite different x-ray diffraction patterns; the compatibilized blend shows a significantly larger orientational effect in the x-ray pattern of HMWPE. It seems that the increase of interaction of MAH-HMWPE with the Nylon 12 matrix leads to the additional crystallinity.     

Crystallinity and rheology of HDPE/PA12 blends compatibilized with HDPE-alt-MAH

This work studies the crystallinity and rheology of HDPE/PA12 blends compatibilized with 2 wt% of HDPE-alt-MAH. Specimens of HDPE/PA12 blends were extruded and injected into a mold with 75/25, 50/50, and 25/75 HDPE/PA ratios. The Fourier-transform infrared spectroscopy (FTIR) analysis showed that no oxidation reaction occurred in the high-temperature processing and that stronger interactions between the components of the blends occurred in the polyamide's functional groups. The x-ray diffraction (XRD) analysis showed that the crystallinity degree of the blends and the mean crystallite sizes decreased with the addition of PA12 for both blends. The HDPE's lattice parameters were consistent with the values in the literature, whereas for the PA12, it was not possible to fit its lattice parameters. The rheology analysis evaluated the relationship between the shear stress and viscosity and found that the HDPE/PA 75/25 blend was the most pseudoplastic, presenting the best processability under high shear rates.     

聚环氧乙烷/聚乙基■唑啉共混体系结晶行为及相容性的研究

用偏光显微镜（ＰＬＭ）、ＤＳＣ、ＩＲ和ＷＡＸＤ等测试方法对聚环氧乙烷（ＰＥＯ）／聚乙基唑啉（ＰＥＯｘ）共混体系结晶行为及相容性进行了研究．结果表明，ＰＥＯ含量在３０％以上的共混体系中，几乎完全被球晶充满，非晶态ＰＥＯｘ作为微区分散在大球晶之间或之中；含量为２０％的共混体系照片上呈树枝状晶；含量低于１０％时则看不到结晶出现，体系形成单一的非晶相．对任何组成的共混物，均只出现单一的玻璃化转变温度（Ｔｇ），而且符合Ｆｏｘ方程揭示的规律；随ＰＥＯｘ组分含量的增加，共混体系的结晶度减小，熔点下降，并利用平衡熔点方程计算出ＰＥＯ与ＰＥＯｘ的相互作用能密度．非晶ＰＥＯ与ＰＥＯｘ热力学相容，其相容性是由于这两种分子间存在着特殊相互作用．ＰＥＯｘ的加入不会改变ＰＥＯ的晶胞参数．     

Microhardness of compatibilized blends of polypropylene with a semiflexible liquid-crystalline polymer

 The Vickers microhardness of blends of isotactic polypropylene and a semiflexible liquid-crystalline polymer (iPP/LCP 90/10 and 80/20 w/w), compatibilized with 2.5, 5 or 10 wt% PP-g-LCP copolymers with different composition has been studied. It has been shown that the microhardness values of uncompatibilized blends are close to the additive ones, while for compatibilized blends a strong positive deviation from additivity has been established. This result is interpreted by the increase in the degree of crystallinity of PP, by the decrease in the surface free energy of PP crystals and by the decrease in the surface free energy of the LC domains when the PP-g-LCP compatibilizer is present. The effect of the composition and concentration of the compatibilizer on the experimental hardness values has also been studied. The values of the microhardness/modulus of elasticity of some of the materials have been obtained. It is demonstrated that according to these values the compatibilized blends take a position closer to the elastic material in the elastic–plastic spectrum than the uncompatibilized blends. The results are interpreted by the compatibilizing efficiency of PP-g-LCP copolymers towards iPP/LCP blends. Received: 18 June 2001 Accepted: 4 October 2001     

Microhardness and thermal stability of compatibilized LDPE/PA6 blends

Microhardness tests, water absorption and thermogravimetric measurements have been performed on blends of low density polyethylene (LDPE) with different molar mass and polyamide 6 (PA6) compatibilized with 2 pph poly(ethylene-co-acrylic acid) (Escor 5001 by Exxon). The negative deviation of Vickers microhardness from the additivity has been interpreted by changes in the crystallinity of the blend components. The hardness values of the compatibilized blends that are lower than those of the corresponding uncompatibilized blends have been explained by the decrease of the degree of crystallinity of PA6 phase in the presence of Escor. The molar mass of LDPE almost does not influence on the hardness values. The lower water absorption of the compatibilized blends, caused by the formation of a copolymer between PA6 and the compatibilizer leads to microhardness values of the wet compatibilized blends higher than those of the corresponding uncompatibilized blends. The thermogravimetric measurements demonstrate that the thermal stability of blends increases in the presence of 2 pph Escor 5001. The results confirm the compatibilizing efficiency of Escor 5001 towards LDPE/PA6 blends in a wide composition range.     

Deformation mechanisms in nylon 6/ABS blends

The deformation mechanisms during fracture of a Nylon 6/ABS blend compatibilized with an imidized acrylic polymer were compared to those of an uncompatibilized blend. A postmortem examination of deformed zones in samples loaded to failure in a double-notch four-point-bend geometry was made using transmission electron microscopy (TEM). For the compatibilized blend, cavitation of the rubber particles followed by massive shear yielding of the polyamide matrix was concluded to be the sequence of events leading to toughness; while, for the brittle uncompatibilized blend, the evidence indicated that a lack of adhesion at the Nylon-ABS interface prevented the rubber particles from cavitating and the subsequent plastic deformation of the polyamide matrix. © 1994 John Wiley & Sons, Inc.     

The effect of various compatibilizers on thermal,mechanical, and morphological properties of polystyrene/polypropylene blends

The effects of various compatibilizers on thermal, mechanical and morphological properties of 50/50 polypropylene/polystyrene blends were investigated. Various compatibilizers, polystyrene-(ethylene/butylenes/ styrene) (SEBS), ethylene vinyl acetate (EVA), polystyrene-butylene rubber (SBR) and blend of compatibilizers SEBS/PP-g-MAH, EVA/PP-g-MAH, and SBR/PP-g-MAH were used. Differential scanning calorimetry, thermogravimetric analysis, wide-angle X-ray scattering, scanning electron microscopy, microhardness, and Izod impact strength were adopted. It was found that the influence of various compatibilizers was appeared on all the properties studied. The properties of the blends compatibilized with SEBS, EVA, and SBR are very distinct from those of blends compatibilized with blend of compatibilizers. Results show that compatibilized blends with the blend of compatibilizers EVA/PP-g-MAH, SBR/PP-g-MAH, and SEBS/PP-g-MAH or SBR were relatively more stable than the uncompatibilized blend and blend compatibilized with SEBS or EVA. The compatibilizer does not only reduce the interfacial tension or increase the phase interfacial adhesion between the immiscible polymers, but greatly affects the degree of crystallinity of blends.

     

Morphology and Mechanical Properties of Nylon 6/PBT Blends Compatibilized with Styrene/Maleic Anhydride Copolymer

The mechanical properties and dynamic mechanical properties of blends composed of Nylon 6 and poly(butylenes terephthalate)(PBT),with styrene/maleic anhydride(SMA)as compatibilizer,were studied.The observation on the morphologies of the etched surfaces of the cryogenically fractured specimens via scanning electron microscopy(SEM)demonstrated that in the compatibilized Nylon 6/PBT blends,there exists a finer and more uniform dispersion induced by the in-situ interfacial chemical reactions during the preparation than that in the corresponding uncompatibilized blends.On the other hand,the overall mechanical properties of the compatibilized blends could be remarkably improved compared with those of the uncompatibilized ones.Moreover,increasing the amount of the compatibilizer SMA leads to a more efficient dispersion of the PBT phase in Nylon 6/PBT blends.Furthermore,there exists an optimum level of SMA added to achieve the maximum mechanical properties.As far as the mechanism of this reactive compatibilization is concerned,the enhanced interfacial adhesion is necessary to obtain improved dispersion,stable phase morphology,and better mechanical properties.     

聚己内酯在聚己内酯/聚乙烯基甲基醚共混体系中的结晶研究

通过示差扫描量热(DSC)、广角X射线衍射(WAXD)、小角X射线散射(SAXS)研究了聚己内酯(PCL)/聚乙烯基甲基醚(PVME)共混体系中PCL的结晶行为.研究结果表明,共混聚合物中PCL的结晶度几乎不随体系的组成而发生变化.共混物中PVME的存在没有改变PCL的晶体结构,但是随着PVME含量的增加,片晶之间的距离则大,这主要是由于非晶层增厚引起的.     

Deformation of thermotropic liquid crystalline polymer droplets dispersed in a polyamide

The deformation of dispersed droplets of a thermotropic liquid crystalline polymer in a polyamide (nylon 6) matrix was studied by morphological observation. An immiscible binary blend and compatibilized ternary blends were studied. For the uncompatibilized blend, the morphology of the blends was that of a typical immiscible blend showing poor adhesion and no deformation of the dispersed phase. For the compatibilized blend, deformation of the dispersed TLCP phase was observed even if the viscosity of the matrix was lower than that of the TLCP phase. Compatibilizer addition improved the interfacial adhesion, hence enabled TLCP droplets to be deformed. A simple mechanism for the deformation of TLCP droplets was presented considering characteristic rheological properties of the TLCP melt.     

STUDY ON THE BLENDS OF NYLON 66 AND LIQUID CRYSTALLINE POLYESTERS

Blends of polyamide (Nylon 66) with two different kinds of liquid crystalline polyesters were studied in all the composition range. Homogeneous samples were obtained by coprccipitation from 2 wt%. solution of blends. The thermal properties, crystallinity and morphology of these blends were studied by using DSC, polarizing microscopy, and scanning electron microscopy. The phase transition and morphology of the blends are markedly-influenced by the composition of liquid crystalline polyesters. The mechanical behaviour of PHB/HNA-Nylon 66 blend was improved. although polyamidc (Nylon 66)with the liquid crystalline polyesters were incompatible, but a rather strong interaction between the polymers did exist.     

Non-isothermal crystallization behavior of Styrene butadiene rubber/high density polyethylene binary blends

The thermal and crystallization behavior of the blends are studied by differential scanning calorimetry and XRD. The presence of the amorphous component in the blend is found to influence the non-isothermal crystallization of HDPE. The addition of small quantities of SBR resulted in an increase in the rate of crystallization whereas nucleation is delayed. As compared to HDPE, larger crystallite size, a narrower size distribution, were observed in low SBR (~up to 30?wt%) content blends. The half time of crystallization also found to reduce as the SBR content in the blend increased. However, a lower degree of crystallinity was observed in these blends. The results thus show that incorporation of SBR in HDPE, while accelerating the rate of crystallization, lower the degree of crystallization. The reduction in the overall crystallization rate at high-SBR content is attributed to a decrease in the growth rate in the later stages of crystallization. It is observed that in dynamically cross-linked blends, the presence of crosslinked SBR that can acts as heterogeneous nuclei facilitated the nucleation of HDPE. However, the crystal growth may be impeded. As a result the overall crystallinity of the crosslinked blends found to decrease. From XRD profiles it had seen that addition of SBR and dynamic crosslinking does not exert an effect on the crystalline structure of HDPE. The dynamic vulcanization of SBR/HDPE blends enhanced the process of crystallization of HDPE phase. These conclusions are supported by the thermal characterization (DSC) results also.     

Thermogravimetric and dynamic mechanical analysis of LLDPE/EMA blends

The thermal stability of linear low density polyethylene (LLDPE)/ethylene methyl acrylate (EMA) blends was studied using thermogravimetry. The blend ratio as well as the presence of compatibilizer has significant effect on thermal stability of the blends. The compatibilization of the blends using LLDPE-g-MA has increased the degradation temperature. Phase morphology was found to be one of the most decisive factors that affected the thermal stability of both uncompatibilized and compatibilized blends. Dynamic mechanical behavior of the blend was studied by dynamic mechanical analysis. The storage modulus of the blends decreased with increase in EMA content. When compatibilized with LLDPE-g-MA the storage modulus of the blend increases. LLDPE-g-MA is an effective compatibilizer as it increases the thermal stability and modulus of the blend.     

Morphology of PC/SAN blends: effect of reactive compatibilization,SAN concentration,processing, and viscosity ratio

This article examines the effects of dispersed phase concentration, processing apparatus, viscosity ratio, and interfacial compatibilization using an SAN–amine compatibilizer on the morphology of blends of bisphenol A–polycarbonate (PC) with styrene–acrylonitrile (SAN) copolymers. For uncompatibilized blends, the dispersed phase particle size increased significantly with SAN concentration, and was found to exhibit a minimum at a viscosity ratio of approximately 0.35 for a fixed concentration of 30% SAN in the blend. Although the morphology of uncompatibilized PC/SAN blends mixed in a Brabender mixer, single‐ and twin‐screw extruders were quite similar, the twin‐screw extruder produced significantly finer morphologies in blends containing SAN–amine. The average particle size for blends compatibilized with the SAN–amine polymer was approximately half that of uncompatibilized blends and was relatively independent of viscosity ratio and dispersed phase composition. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 71–82, 1999     

Effect of compatibilizer on morphology and properties of HDPE/Nylon 6 blends

The compatibilization effect of linear low‐density polyethylene‐grafted maleic anhydride (LLDPEgMA) and high‐density polyethylene‐grafted maleic anhydride (HDPEgMA) on high‐density polyethylene (HDPE)/polyamide 6 (Nylon 6) blend system is investigated. The morphology of 45 wt %/55 wt % polyethylene/Nylon 6 blends with three compatibilizer compositions (5 wt %, 10 wt %, and 15 wt %) are characterized by atomic force microscopic (AFM) phase imaging. The blend with 5 wt % LLDPEgMA demonstrates a Nylon 6 continuous, HDPE dispersed morphology. Increased amount of LLDPEgMA leads to sharp transition in morphology to HDPE continuous, Nylon 6 dispersed morphology. Whereas, increasing HDPEgMA concentration in the same blends results in gradual morphology transition from Nylon 6 continuous to co‐continuous morphology. The mechanical properties, oxygen permeability, and water vapor permeability are measured on the blends which confirm the morphology and indicate that HDPEgMA is a better compatibilizer than LLDPEgMA for the HDPE/Nylon 6 blend system. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 281–290     

Thermal behaviour of styrene butadiene rubber/poly(ethylene-co-vinyl acetate) blends

The thermal behaviour of styrene butadiene rubber (SBR)/poly (ethylene-co-vinyl acetate) (EVA) blends was studied by using thermogravimetry (TG) and differential scanning calorimetry (DSC). The effects of blend ratio, cross-linking systems and compatibilization on the thermal stability and phase transition of the blends were analyzed. It was found that the mass loss of the blends at any temperature was lower than that of the components, highlighting the advantage of blending SBR and EVA. The addition of compatibilizer was also found to improve the thermal stability. DSC studies indicated the thermodynamic immiscibility of SBR/EVA system even in the presence of the compatibilizer. This is evident from the presence of two different glass transition temperatures, corresponding to SBR and EVA phases in both compatibilized and uncompatibilized blends.     

Morphology development of immiscible polymer blends during melt blending: Effects of interfacial agents on the liquid-solid interfacial heat transfer

This article reports on a new phenomenon: The presence of a compatibilizer accelerates the melting/plastification of an immiscible polymer blend during melt blending. The increase in the rate of melting as a result of the addition of a compatibilizer is believed to be one of the important factors responsible for the fact that the morphology of compatibilized blends develops much faster than that of their uncompatibilized counterparts. To substantiate the above statement, blends based on polypropylene (PP) and polyamide 6 (PA6) were used as model systems. The compatibilizer was a graft copolymer (PP-g-PA6) with PP as the backbone and PA6 as grafts. Its presence in a PP/PA6 blend accelerated the rate of melting of the PA6. This effect was observed only when the compatibilizer itself was molten and migrated to the interfacial layer between the PA6 and PP phases. It is likely that the presence of the compatibilizer increased the chain entanglements at the PP and PA6 interface and consequently reduced the thermal resistance of the interfacial layer. Detailed mechanisms are discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 3368–3384, 1999     

Poly(ethylene-co-vinyl alcohol) and poly(methyl methacrylate) blends: Phase behavior and morphology

In this work blends of poly(ethylene-co-vinyl alcohol) (EVOH) with different ethylene contents (27, 32, 38 and 44 mol%) and poly(methyl methacrylate) (PMMA) were prepared by mechanical mixing in the melted state. The miscibility and melting behavior as a function of blend composition and the ethylene content in EVOH copolymers were investigated by means of differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). The morphology of the cryofractured surfaces was examined by scanning electron microscopy (SEM). DSC and DMTA data show that EVOH/PMMA blends are immiscible, independent of EVOH and blend composition. The SEM analysis in agreement with DMTA analysis indicates that the morphology of phases depends on the blend composition, with phase inversion occurring as the concentration of one or other polymer component increases. However, the copolymer composition apparently does not affect the domain size distribution for blends containing 20 wt% of EVOH or 20 wt% of PMMA. A better phase adhesion is observed mainly for blends with 50 wt% of each polymer component.     

低密度聚乙烯/乙丙烯三元共聚(LDPE/EPO)共混体系的相容性及其结晶结构

DDV、DSC、WAXD、萃取和Raman光谱实验表明,在所有组成下,LDPE/EPO共混体系共晶相容.WAXD法测定表明,LDPE/EPO共混体系的结晶度随EPO组分含量的增加而降低,EPO未能进入LDPE晶胞中.     

Friction and wear mechanisms of polyamide 66/high density polyethylene blends

Polyamide 66 (PA66)/high density polyethylene (HDPE) blends having miscible structure were produced by compatibilization of HDPE grafted with maleic anhydride (HDPE‐g‐MAH). Mechanical and tribological properties of blends in different compositions were tested. It was found that the polymer blends greatly improved the mechanical properties of PA66 and HDPE. Blending HDPE with PA66 significantly decreased the friction coefficient of PA66; the friction coefficients of blends with different compositions were almost the same and approximately equal to that of pure HDPE; the blends with 80 vol % PA66 exhibited the best wear resistance. The transfer films, counterpart surfaces, and wear debris formed during sliding were investigated by Scanning Electron Microscopy (SEM), and Differential Scanning Calorimetry (DSC) analysis was further carried out on wear debris. These investigations indicated that the thermal control of friction model is applicable to PA66/HDPE blend, that is the friction coefficient of blend is governed by the HDPE component, which possesses a lower softening point relative to the PA66 component in this system. The wear mechanism of PA66/HDPE blend transforms from PA66 to HDPE as the HDPE content increases. PA66, as the component with higher softening point, increases the hardness of blend, enhances the ability of blend to form a transfer film on the counterface, and inhibits the formation of larger belt‐like debris of HDPE, at the same time, the presence of self‐lubricating HDPE in the system decreases the friction coefficient and the frictional heat, all of these factors are favorable for the wear resistance of PA66/HDPE blend. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2514–2523, 2005