Investigation of thermally conducting phase‐change materials based on polyethylene/wax blends filled with copper particles

This article reports on the morphology, melting and crystallization behavior, thermal stability, tensile properties, and thermal conductivity of phase‐change materials (PCM) for thermal energy storage. These materials were based on a soft Fischer‐Tropsch paraffin wax (PCM) blended with low‐density polyethylene, linear low‐density polyethylene, and high‐density polyethylene. These immiscible blends were melt‐mixed with copper (Cu) microparticles (up to 15 vol %) to improve the thermal conductivity in the matrix material. The presence of the Cu microparticles in the PCMs did not significantly change the crystallization behavior, thermal stability, or tensile properties of the blend composites in comparison with the corresponding polyethylene/wax blends and polyethylene/Cu composites. The observed differences were related to the fact that the wax seemed to have a higher affinity for the Cu particles than any of the polyethylenes, and so it crystallized as a layer around the Cu particles. The thermal conductivity of the samples increased almost linearly with increasing Cu content, but the samples had slightly lower values than the corresponding polyethylene/Cu composites, probably because of the lower thermal conductivity of the wax. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Biodegradable polymer blends of poly(3-hydroxybutyrate) and starch acetate

The thermal behaviour and phase morphology of poly(3-hydroxybutyrate) (PHB) and starch acetate (SA) blends have been studied by differential scanning calorimetry, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy and polarizing optical microscopy. PHB/SA blends were immiscible. The melting temperatures of PHB in the blends showed some shift with increase of SA content. The melting enthalpy of the PHB phase in the blend was close to the value for pure PHB. The glass transition temperatures of PHB in the blends remained constant at 9°C. The FTIR absorptions of hydroxyl groups of SA and carbonyl groups of PHB in the blends were found to be independent of the second component at 3470cm^-1 and 1724cm^-1, respectively. The crystallization of PHB was affected by the addition of the SA component both from the melt on cooling and from the glassy state on heating. The temperature and enthalpy of non-isothermal crystallization of PHB in the blends were much lower than those of pure PHB. The crystalline morphology of PHB crystallized from the melt under isothermal conditions varied with SA content. The cold crystallization peaks of PHB in the blends shifted to higher temperatures compared with that of pure PHB. ©1997 SCI     

Mechanical properties and morphology of polyethylene–polypropylene blends with controlled thermal history

The effect of time–temperature treatment on the mechanical properties and morphology of polyethylene–polypropylene (PE–PP) blends was studied to establish a relationship among the thermal treatment, morphology, and mechanical properties. The experimental techniques used were polarized optical microscopy with hot‐stage, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and tensile testing. A PP homopolymer was used to blend with various PEs, including high‐density polyethylene (HDPE), low‐density polyethylene (LDPE), linear low‐density polyethylene (LLDPE), and very low density polyethylene (VLDPE). All the blends were made at a ratio of PE:PP = 80:20. Thermal treatment was carried out at temperatures between the crystallization temperatures of PP and PEs to allow PP to crystallize first from the blends. A very diffuse PP spherulite morphology in the PE matrix was formed in partially miscible blends of LLDPE–PP even though PP was present at only 20% by mass. Droplet‐matrix structures were developed in other blends with PP as dispersed domains in a continuous PE matrix. The SEM images displayed a fibrillar structure of PP spherulite in the LLDPE–PP blends and large droplets of PP in the HDPE–PP blend. The DSC results showed that the crystallinity of PP was increased in thermally treated samples. This special time–temperature treatment improved tensile properties for all PE–PP blends by improving the adhesion between PP and PE and increasing the overall crystallinity. In particular, in the LLDPE–PP blends, tensile properties were improved enormously because of a greater increase in the interfacial adhesion induced by the diffuse spherulite and fibrillar structure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1151–1164, 2000     

In situ fiber composites based on metallocene polyethylene matrices

Binary blends of metallocene polyethylenes with polyethylenes and polypropylene were made in a co‐rotating twin‐screw extruder. A stretching process was carried out afterwards in the melt state at the extruder's exit to study the effect of the induced orientation on their thermal and tensile properties. Capillary rheometry was performed to the neat polymers to determine the viscosity ratios of the blend components as a function of the shear rate. SEM and Micro‐Raman analyses were done to study the morphology of the stretched and nonstretched blends. As expected, an increase in the modulus and tensile stress was obtained through blending. Additionally, the elastomeric behavior of the metallocene polyethylene (mPE) sample is observed in all blends and it was not lost through blending. Nevertheless, all blends without stretching exhibited a negative deviation of the linear additivity rule of blending. The stretching of the blends made with metallocene polyethylenes as matrices and other types of PEs as dispersed phase did not improve the tensile properties, although some differences in the dispersed phases were found by DSC, and microfibrils could be seen in the drawn mPE/HDPE blend. However, blending with PP produced an improvement in the modulus and tensile stress of the drawn samples in comparison to their undrawn counterpart. The tensile stresses of PP blends are more sensitive to the drawing process than the modulus, which can be attributed to the appearance of large fibril fractions during this process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

聚烯烃包覆石蜡相变材料的结构和初步热性能

分别以低密度聚乙烯（LDPE）和乙烯-辛烯共聚物（POE）为包覆材料,以石蜡为相变材料,制备了定形相变材料,采用SEM、DSC和流变性能对其进行分析表征。SEM电镜显示了两种不同的表面形貌;DSC测试表明石蜡加入量越多,潜热越大,POE/石蜡体系的潜热高于LDPE/石蜡体系;流变性能研究表明,石蜡的加入在固态时提高了基体的储能模量,对于LDPE/石蜡体系,LDPE为连续相;对于POE/石蜡体系,由于POE和石蜡熔融温度非常接近,分辨不出谁是连续相谁是分散相。     

Crystalline and thermal behavior of poly(ethylene terephthalate)/polyphenoxy blends

Poly(ethylene terephthalate) (PET)/polyphenoxy blends were prepared by melt blending. Crystalline and thermal behaviors of PET/polyphenoxy blends were verified by use of DSC. The experiment results show that the initial temperature, peak temperature, and ending temperature of cold crystallization increase with increasing phenoxy content. On the contrary, the onset melting temperature, finishing melting temperature, and peak temperature in the first heating and the secondary heating processes decrease with increasing phenoxy content. The crystallization enthalpy and melting enthalpy, as well as the crystallization rate, decrease with increasing phenoxy content. Avrami exponents of the blends are slightly higher than that of pure PET and almost independent of phenoxy content. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 878–885, 2005     

The effect of expanded graphite on the thermal stability,latent heat,and flammability properties of EVA/wax phase change blends

This article reports on the morphology, melting and crystallization behavior, thermal stability, flammability and thermal conductivity of shape‐stabilized phase‐change materials (PCM) for thermal energy storage, based on a soft Fischer–Tropsch paraffin wax, the PCM, blended with ethylene vinyl acetate (EVA). These immiscible blends were melt‐mixed with expanded graphite (EG) (up to 9 wt%) to improve the thermal conductivity and flame resistance of the material. It was observed that the EG particles agglomerate in the absence of wax, but disperse much better in the EVA/wax blend, probably because the wax penetrates in between the EG layers (there seems to be a better interaction between wax and EG than between EVA and EG) and separates the layers, giving rise to smaller and better dispersed EG particles. This gives rise to better thermal conductivity and flame resistance. There were no significant changes in the melting temperature of EVA in the EVA/EG composites, while the crystallinities of EVA were observably lower in the presence of EG. The thermal stability and flammability results show an increase in thermal stability and flame resistance of EVA, which further improved in the presence of wax because of the smaller and better dispersed EG particles in these systems. POLYM. ENG. SCI., 55:1255–1262, 2015. © 2015 Society of Plastics Engineers     

Morphology and properties of poly(vinylidene fluoride)/silicone rubber blends

Blends of poly(vinylidene fluoride) (PVDF) and silicone rubber (SR) were prepared through melt mixing. The morphology, rheology, crystallization behavior, mechanical properties, dynamic mechanical properties and thermal properties of the PVDF/SR blends were investigated. The blend with 9 wt % of SR showed spherical shape of disperse phase whereas the blend with 27 wt % of SR resulted in irregular shape of rubber phase. The rheology showed that the complex viscosity and storage modulus of the blends decreased with increasing the SR content. The mechanical properties of the blends were decreased with increasing the SR content but that were significantly improved after dynamical vulcanization. The crystallization temperature of PVDF phase in PVDF/SR blends was increased. The incorporation of SR improved the thermal stability of PVDF/SR blends, and the temperature at 10% mass loss of the blends increased to about 489°C compared with 478°C of the pure PVDF. The mass of residual char in experiment of the blends was lower than that obtained in theory. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39945.     

Blends of high density polyethylene and ethylene/1‐octene copolymers: Structure and properties

The morphology formation in the blends comprising a high density polyethylene (HDPE) and selected ethylene/1‐octene copolymers (EOCs) was studied with variation of blend compositions using atomic force microscopy (AFM). The binary HDPE/EOC blends studied showed well phase‐separated structures (macrophase separation) in consistence with individual melting and crystallization behavior of the blend components. For the blends comprising low 1‐octene content copolymers, the lamellar stacks of one of the phases were found to exist side by side with that of the another phase giving rise to leaflet vein‐like appearance. The formation of large HDPE lamellae particularly longer than in the pure state has been explained by considering the different melting points of the blend components. The study of strain induced structural changes in an HDPE/EOC blend revealed that at large strains, the extensive stretching of the soft EOC phase is accompanied by buckling of HDPE lamellar stack along the strain axis and subsequent microfibrils formation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1887–1893, 2007     

Biodegradable polymer blends of poly(3-hydroxybutyrate) and poly(DL-lactide)-co-poly(ethylene glycol)

The melting and crystallization behavior and phase morphology of poly(3-hydroxybutyrate) (PHB) and poly(DL-lactide)-co-poly(ethylene glycol) (PELA) blends were studied by DSC, SEM, and polarizing optical microscopy. The melting temperatures of PHB in the blends showed a slight shift, and the melting enthalpy of the blends decreased linearly with the increase of PELA content. The glass transition temperatures of PHB/PELA (60/40), (40/60), and (20/80) blends were found at about 30°C, close to that of the pure PELA component, during DSC heating runs for the original samples and samples after cooling from the melt at a rate of 20°C/min. After a DSC cooling run at a rate of 100°C/min, the blends showed glass transitions in the range of 10–30°C. Uniform distribution of two phases in the blends was observed by SEM. The crystallization of PHB in the blends from both the melt and the glassy state was affected by the PELA component. When crystallized from the melt during the DSC nonisothermal crystallization run at a rate of 20°C/min, the temperatures of crystallization decreased with the increase of PELA content. Compared with pure PHB, the cold crystallization peaks of PHB in the blends shifted to higher temperatures. Well-defined spherulites of PHB were found in both pure PHB and the blends with PHB content of 80 or 60%. The growth of spherulites of PHB in the blends was affected significantly by 60% PELA content. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1849–1856, 1997     

Phase morphology,thermomechanical, and crystallization behavior of uncompatibilized and PP‐g‐MAH compatibilized polypropylene/polystyrene blends

In this article, we discuss the phase morphology, thermal, mechanical, and crystallization properties of uncompatibilized and compatibilized polypropylene/polystyrene (PP/PS) blends. It is observed that the Young's modulus increases, but other mechanical properties such as tensile strength, flexural strength, elongation at break, and impact strength decrease by blending PS to PP. The tensile strength and Young's modulus of PP/PS blends were compared with various theoretical models. The thermal stability, melting, and crystallization temperatures and percentage crystallinity of semicrystalline PP in the blends were marginally decreased by the addition of amorphous PS. The presence of maleic anhydride‐grafted polypropylene (compatibilizer) increases the phase stability of 90/10 and 80/20 blends by preventing the coalescence. Hence, finer and more uniform droplets of PS dispersed phases are observed. The compatibilizer induced some improvement in impact strength for the blends with PP matrix phase, however fluctuations in modulus, strength and ductility were observed with respect to the uncompatibilized blend. The thermal stability was not much affected by the addition of the compatibilizer for the PP rich blends but shows some decrease in the thermal stability of the blends, where PS forms the matrix. On the other hand, the % crystallinity was increased by the addition of compatibilizer, irrespective of the blend concentration. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42100.     

Effect of EVA copolymer on properties of different polyethylenes in silane crosslinking process

Abstract

The effect of molecular structure of polyethylene (PE) [low density PE (LDPE), linear LDPE and high density PE] and silane/peroxide concentration on the grafting level and gel content in silane crosslinking process has been studied. The effect of incorporation of ethylene vinyl acetate (EVA) copolymer on the rate of crosslinking and thermal properties of PEs has been reported. The order of gel content was LDPE>linear LDPE>high density PE. With the incorporation of EVA, the rate of crosslinking increased. The degree of crystallinity did not change with crosslinking significantly. However, the shape of melting and crystallisation peaks changed, and two regions due to gel and sol parts were formed. In EVA/PE blends, two melting points were observed for both crosslinked and uncrosslinked samples. The SEM images showed the droplet matrix morphology with the EVA as the dispersed phase, especially for EVA/LDPE blend. The EVA/PE blends failed in hot set test, while the origin of PEs passed the hot set test successfully.     

乙烯-醋酸乙烯酯共聚物对茂金属聚乙烯的改性研究

以添加不同比例的茂金属聚乙烯 (mLLDPE) /乙烯 醋酸乙烯酯 (EVA)共混物为研究对象 ,考察了EVA含量对mLLDPE/EVA共混物的力学性能、热性能、流变性能、动态力学性能和形态结构的影响。研究结果表明 ,EVA添加到mLLDPE中 ,增加了mLLDPE的剪切敏感度、降低了mLLDPE的熔融粘度、改善了mLLDPE的流动性和加工性 ;在一定的添加比例范围内mLLDPE和EVA具有很好的相容性 ,可以在改善mLLDPE加工性能、引入极性基团的同时又保持与纯mLLDPE相近的力学性能 ,但会导致共混物材料的刚性下降 ,柔性增加。热分析数据说明 ,mLLDPE/EVA共混体系中 ,在EVA含量较小时共混物存在大量共晶 ,与mLLDPE有很好的相容性 ,无论是熔融曲线还是降温曲线都只出现一个峰。当EVA含量增大时 ,mLLDPE/EVA共混物出现相分离 ,曲线出现双峰 ,但两峰值呈现靠近趋势 ,预示mLLDPE/EVA共混物中仍存在少量共结晶     

Viscoelastic and adhesion properties of EVA/tackifier/wax ternary blend systems as hot-melt adhesives

Two types of wax were added to a ethylene vinyl acetate (EVA) copolymer/aromatic hydrocarbon resin (tackifier) blend in the molten state and the miscibility, viscoelastic and adhesion properties of ternary blends as hot-melt adhesives (HMAs) were investigated. Miscibility and viscoelastic properties were studied using differential scanning calorimetry (DSC), Brookfield viscometry and dynamic mechanical thermal analysis (DMTA), and their adhesion strength was determined in terms of single lap shear strength. DSC thermograms of both types of waxes showed their melting peaks in a similar region to that of EVA/tackfier blend. It was difficult to evaluate the miscibility of ternary blends using DSC because the melting peaks of the waxes overlapped with those of the EVA/tackifier blend, although the glass transition temperature (T _g) of the ternary blend systems slightly increased with increasing wax concentration. However, their storage modulus (E′) increased slightly and loss tangent (tan δ) showed different peaks when two types of wax were added to the EVA/tackifier blend. Therefore, the miscibility of EVA/tackifier blend altered with addition of waxes. In addition, their melt viscosity decreased with increasing wax concentration. Furthermore, the adhesion strength of the ternary blends decreased with increasing wax concentration, despite the increment of storage modulus. These results suggested that the ternary blends of EVA/tackifier/wax were heterogeneous.     

Rheological and mechanical properties in polyethylene blends

Melt rheology and mechanical properties in linear low density polyethylene (LLDPE)/low density polyethylene (LDPE), LLDPE/high density polyethylene (HDPE), and HDPE/LDPE blends were investigated. All three blends were miscible in the melt, but the LLDPE/LDPE and HDPE/LDPE blends exibiled two crystallization and melting temperatures, indicating that those blends phase separated upon cooling from the melt. The melt strength of the blends increased with increasing molecular weight of the LDPE that was used. The mechanical properties of the LLDPE/LDPE blend were higher than claculated from a simple rule of mixtures, whiele those of the LLDPE/HDPE blend conformed to the rule of mixtures, but the properties of HDPE/LDPE were less than the rule of mixtures prediction.     

Melt blending of ultra high molecular weight and high density polyethylene: The effect of mixing rate on thermal,mechanical, and morphological properties

The blends of two different ultra high molecular weight polyethylenes (UHMWPE) and high density polyethylene (HDPE) were prepared in melt at different compositions and mixing rates in Brabender Torque Rheometer. The temperature build-up due to the internal friction during melt blending was recorded and evaluated with respect to the change in the torque. The temperature at maximum torque was considered the fusion point temperature of the UHMWPE in the blend. This fusion point temperature was found to depend on the composition, mixing rate, and molecular weight. The effect of mixing rate on the mechanical properties (measured as yield and tensile strengths and elongation at break), thermal oxidative degradation and melting behavior were studied. The morphology of the blends were investigated by optical microscopy.     

Crystallization—morphology—polymer processing correlations for IUPAC low density polyethylenes

The crystallization behavior of three IUPAC low density polyethylene samples has been characterized by thermal analysis. Their rates of crystallization only are directly correlatable with their film forming ability in film blowing technology. The IUPAC samples possessed essentially indistinguishable physical properties, including differential scanning calorimetry (DSC) melting curves and rheological characteristics, but their propensity for crystallization was found readily to parallel their film forming ability and other characteristics associated with end-use performance. The application of thermal analysis to assess crystallization is a unique diagnostic tool for measuring polymer film processability, which is well illustrated here using a few simple experiments made on the original polymer specimens and a polymer blend. Although all samples exhibit similar small-angle X-ray periodicities, the morphological differences assessed, particularly by microtomy-optical microscopy, correlate with, and complement, the results of phase transformation kinetics responsible for film properties. Fractography-scanning electron microscopy proves to be inferior to optical methods for revealing the morphology of these low density polyethylenes.     

Binary mixtures of polyethylene and oxidized wax: Dependency of thermal and mechanical properties upon mixing procedure

The influence of the preparation procedure on the thermal and mechanical properties of linear low‐density polyethylene (LLDPE)– and LDPE–oxidized wax blends was investigated. It was found that mechanically mixed blends show reduced thermal stability as well as ultimate mechanical properties (stress and strain at break) compared to that of extrusion mixed blends. However, the structure of the blend and consequently its thermal and mechanical behavior also depend on the initial morphology of polyethylene. DSC measurements show miscibility up to high wax contents in both blend types, but increasing the amount of wax in LDPE blends induces increasing crystallinity. As a result, the LDPE/wax blends show improved thermal stability of between 20 and 50°C at low wax concentrations. Although the elasticity modulus of the blends increases, increasing the amount of wax generally degrades the mechanical properties. The main reason for this is the reduced number of tie chains. Changes in the average concentration of tie chains with increasing wax content were calculated and a correlation was made with the ultimate properties of the blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2446–2456, 2003     

Crystallization,melting behavior,and morphology of BPP/HDPE blend

The crystallization, melting behavior, and morphology of a low ethylene content block propylene–ethylene copolymer (BPP) and a high-density polyethylene (HDPE) blend were studied. It was found that the existence of ethylene–propylene rubber (EPR) in BPP has more influence on the crystallization of HDPE than on that of PP. This leads to the decreasing of the melting temperature of the HDPE component in the blends. It is suggested that the EPR component in BPP shifted to the HDPE component during the blending process. The crystallinity of the HDPE phase in the blends decreased with increasing BPP content. The morphology of these blends was studied by polarized light microscopy (PLM) and SEM. For a BPP-rich blend, it was observed that the HDPE phase formed particles dispersed in the PP matrix. The amorphous EPR chains may penetrate into HDPE particles to form a transition layer. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 69: 2469–2475, 1998     

Calorimetric studies of PP/Mater‐Bi blends aged in soil

Blends of polypropylene and a commercial biodegradable additive (Mater‐Bi AF05H) were subjected to a soil burial test for 1 year. The effect of the degradation process on the morphology of the blend was studied by differential scanning calorimetry. The melting and crystallization temperatures, degree of crystallinity, lamellar thickness distribution, and crystallization kinetics were analyzed for both the nondegraded and degraded blends and for the pure components before blending and degradation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3446–3453, 2006