On the compatibility of low density polyethylene/hydrolyzed collagen blends. II: New compatibilizers

Compatibility/compatibilization of low density polyethylene (LDPE) and hydrolyzed collagen (HC) in the presence of some reactive compatibilizing agents (CA), like acrylic acid functionalized low density polyethylene (LDPE-g-AAc) and bismaleinimide-functionalized low density polyethylene (LDPE-g-BMI) have been discussed. It has been established that, by 20-30 wt% HC incorporation in LDPE matrix, in the presence of LDPE-g-AAc and LDPE-g-BMI compatibilizing agents, materials with good mechanical and surface properties can be obtained. Because of the high reactivity of bismaleinimide, the efficacity of LDPE-g-BMI as a compatibilizing agent is higher than that of LDPE-g-AAc.     

A study of melting of low density polyethylene by in situ WAXD

Analysis of low density polyethylene using in situ wide-angle X-ray diffraction shows that the melting process takes place over a broad temperature range with continuous destruction of lamellar laterals. This process exhibits decreasing rate as the temperature increases, indicating that in general each lamellae has less order in outer regions than in central ones. The shifts in angular position of the amorphous halo as a function of the temperature show that the amorphous phase in a semicrystalline sample is less disordered compared to that in an overall melted sample. As the temperature increases the unit cell parameter a increases, generating a crystalline phase density reduction.     

The influence of various deformation histories on elongational properties of low density polyethylene

Summary The elongational viscosity of low density polyethylenes depends on the mechanical history as is demonstrated on the samples IUPAC A and IUPAC C and some other specimens. IUPAC C which stems from the same batch as IUPAC A but has undergone an additional extrusion shows a significantly lower elongational viscosity whereas the shear viscosity remains nearly unchanged. The elastic behaviour measured by the recoverable strain is not influenced by a mechanical pretreatment. The viscosity decrease is found to be canceled to its greatest extent after dissolving the sample in xylene and evaporating the solvent. Pure elongation seems to be more effective in creating the viscosity decrease than pure shear. A similar effect could not be found for linear polyethylene and polystyrene. This result leads to the assumption that the branched molecules give rise to a mechanically induced change of the entanglement structure which can be reverted by dissolving. The evidence of the elongational behaviour for film blowing is discussed.Dedicated to Professor Dr. Reif on the occasion of his 60th birthday.     

Nonisothermal crystallization kinetics and melting behavior of bimodal medium density polyethylene/low density polyethylene blends

Nonisothermal crystallization kinetics and melting behavior of bimodal-medium-density- polyethylene (BMDPE) and the blends of BMDPE/LDPE were studied using differential scanning calorimetry (DSC) at various scanning rates. The Avrami analysis modified by Jeziorny and a method developed by Mo were employed to describe the nonisothermal crystallization process of BMDPE. The BMDPE DSC data were analyzed by the theory of Ozawa. Kinetic parameters such as the Avrami exponent (n), the kinetic crystallization rate constant (Z_c), the peak temperatures (T_p) and the half-time of crystallization (t_1/2) etc. were determined at various scanning rates. The appearance of double melting peaks and the double crystallization peaks in the heating and cooling DSC curves of BMDPE/LDPE blends indicated that the BMDPE and LDPE could crystallize respectively.     

Influence of mechanical history on the crystallization behaviour and morphology of low density polyethylene

Summary If a virginal LDPE melt is sheared a memory is frozen during crystallization inasmuch as after remelting the nucleation density and the rate of crystallization are strongly increased as compared with the original material. This is not caused by the introduction of impurities into the melt during shearing.Part of this memory is recovered by annealing or solvent treatment. This reversible contribution is discussed in terms of a shear-induced increase of trans conformations in the melt, which is partly frozen on pelletizing and which becomes active again on remelting.The non-recoverable part of the memory must be due to changes of molecular structure. Since other parameters do not change it is supposed that a change of the long-chain branching frequency during shearing is the reason for the irreversible effects.Blown films produced from LDPE pellets, which originate from a strongly sheared melt and consequently have an increased crystallization rate, are known to have improved processing and end-use properties (maximum draw-down speed, optical quality). The film blowing process itself is shown to introduce an additional mechanical history into the LDPE melt such that differences of the crystallization kinetics of the starting pellets are completely equalized. A different crystallization behaviour of pellets, therefore, cannot be responsible for the differing film properties, which are more likely influenced by the different viscoelastic response of the melt.Dedicated to Professor Dr. Werner Reif on the occasion of his 60th birthday.     

Electrical breakdown in high‐density polyethylene/graphite nanosheets conductive composites

The electrical breakdown is investigated in high‐density polyethylene/graphite nanosheets (HDPE/GNs) conductive composites. A sample suffers electrical breakdown when the applied field exceeds the critical electrical breakdown field below which the sample reaches a stable state. It is found that the ratio of the critical electrical breakdown resistance to the linear resistance assumes a fixed value Y, which is found to be about 1.30 in HDPE/GNs conductive composites. The value Y is independent of GNs' content, sample size, breakdown cycle, but depends on the property of GNs. The critical breakdown field E_b scales with the resistance R₀ as with the exponent y_b = 0.46 ± 0.02, which is close to the value predicted in mean‐field theory but higher than the value given by the singly connected bonds networks. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 576–582, 2009     

Dynamic vulcanization of reclaimed tire rubber and high density polyethylene blends

Dynamic vulcanization of reclaimed tire rubber (RTR) and HDPE blends was reported. The effect of blend ratio, methods of vulcanization, i.e. sulphur, peroxide, and mixed system and the addition of compatibilizer on mechanical, thermal, and rheological properties were investigated. The blend with highest impact strength was obtained from 50/50 RTR/HDPE vulcanized by sulphur. Increasing the RTR content to more than 50% resulted in a decrease in the impact strength of blend, most likely due to the increasing carbon black content. For tensile strength, the presence of rubber and carbon black, however, unavoidably caused a drop in this property. Comparing among three methods of vulcanization, sulphur system seems to be the most effective method. Results from solvent swelling ratio, glass transition temperatures and viscosity indicated that the sulphur vulcanization created the highest degree of cross-link and filler-matrix interaction in the RTR/HDPE blend. Morphology of the blends was also assessed by scanning electron microscopy (SEM).     

Modification of surface properties of high and low density polyethylene by Ar plasma discharge

Structural changes induced by Ar plasma discharge in low and high density polyethylene (LDPE and HDPE) were studied by different techniques. AFM and SEM methods were used to determine surface morphology, the changes in chemical structure were followed using FTIR and UV-vis spectroscopy. The content and the depth profile of incorporated oxygen was determined by RBS method. The degree of polymer ablation was determined gravimetrically. Standard goniometry was used to determine contact angle and to follow aging of plasma modified polymer. As a result of plasma treatment a lamellar structure or spherulites appear on the surface of HDPE and LDPE, respectively. Pronounced increase of the surface roughness is observed on HDPE contrary to LDPE. Plasma treatment for 400 s leads to the ablation of the surface layer of about 0.6 and 1 μm thick for LDPE and HDPE, respectively. Plasma treatment results in oxidation of the polymer surface layer which is more pronounced in HDPE. Concentration maximum of incorporated oxygen lies 25 nm beneath the sample surface in both polymer types. After exposure to plasma discharge carbonyl, carboxyl and amide groups were detected in the polymer surface layer together with CC bonds either in aromatic or in aliphatic structures. Immediately after the plasma treatment strong decline of the contact angle is observed, the decline being larger in HDPE. Later, in aged specimens the contact angle increases rapidly. The increase, which may be due to rearrangement of degraded structures, is stronger in the specimens exposed to plasma for longer times.     

A novel zinc chelate complex containing both phosphorus and nitrogen for improving the flame retardancy of low density polyethylene

A novel metal chelate complex containing phosphorus, nitrogen and zinc (II) ion was synthesized and used as the flame retardant of low density polyethylene (LDPE). The zinc chelate complex was synthesized by reacting zinc acetate with the ligand of tetraethyl (1,2-phenylenebis(azanediyl)) bis (2-hydroxylphenylmethylene) diphosphonate (TEPAPM). The chemical structure of the target Zn-TEPAPM was confirmed by FTIR, ¹H NMR, ¹³C NMR and ³¹P NMR spectra. The flame retardancy and thermal behavior of LDPE containing various amount of Zn-TEPAPM were investigated by limiting oxygen index test, thermogravimetric (TG) analysis and cone calorimetry. The results show that Zn-TEPAPM can greatly increase the thermal stability, the char formation and smoke suppression ability of LDPE. The TG curves show that even when the filler content of Zn-TEPAPM is as low as 1 wt% in LDPE, the onset degradation temperature of LDPE is increased from 429 °C to 442 °C, and the maximum degradation temperature is increased from 469 °C to 488 °C. Also, a reduction of 32% for the peak heat release rate (PHRR) is obtained in the cone test. Moreover, Zn-TEPAPM is demonstrated to be a very effective synergist of ammonium polyphosphate (APP). When 1 wt% of Zn-TEPAPM was introduced into the LDPE/APP (mass ratio 80/19) blend, the PHRR value is reduced by 32%, compared with that of LDPE/APP blend without Zn-TEPAPM, and the char layer becomes more compact and intact.     

Compatibilizing effect of isocyanate functional group on polyethylene terephthalate/low density polyethylene blends

To evaluate the compatibilizing effects of isocyanate (NCO) functional group on the polyethylene terephthalate/low density polyethylene (PET/LDPE) blends, LDPE grafted with 2-hydroxyethyl methacrylate-isophorone diisocyanate (LDPE-g-HI) was prepared and blended with PET. The chemical reaction occurred during the melt blending in the PET/LDPE-g-HI blends was confirmed by the result of IR spectra. In the light of the blend morphology, the dispersions of the PET/LDPE-g-HI blends were very fine over the PET/LDPE blends. DSC thermograms indicated that PET microdispersions produced by the slow cooling of the PET/LDPE-g-HI blends were largely amorphous, with low crystallinity, due to the chemical bonding. The tensile strengths of the PET/LDPE-g-HI blends were higher than those of the PET/LDPE blends having a poor adhesion. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 447–453, 1998     

Effects of charge trapping in gamma irradiated and accelerated aged low-density polyethylene

The effects of gamma irradiation in air and accelerated aging of low-density polyethylene (LDPE) were studied through dielectric loss (tan δ) analysis in the temperature range from 25 to 325 K and using thermally stimulated discharge current (TSDC) measurements. The radiation-induced oxidation was observed using IR spectroscopy. The influence of radiation dose and accelerated aging on the intensities and the positions of the γ and β dielectric relaxation maxima were correlated with maxima of TSDC measurements, and found to be strongly dependent upon the changes in the microstructure of the amorphous phase and on the surface of the crystallites induced by oxidation and crosslinking.     

Lamellar structure in melt crystallized low density polyethylene

The investigation of representative details in the lamellar microstructure of LDPE observed after controlled chlorosulfonation using both EM and SAXD is reported. For this purpose melt crystallized PE with two branch contents (=0.28 and 2.53 branches per 10²CH²) has been prepared using Kanig's technique over a range of temperatures and treatment times. During the first treatment hours the selective incorporation of electron-dense atoms at the lamellar surface produces a macroscopic weight increase, swelling of the sample and a concurrent decrease of the SAXS intensity. The main result, however, is that the thickness of the lamellar structure does not vary with treatment time. After long chlorosulfonation times a saturation of electron-dense atoms within the surface layer and a reduction in the lateral dimensions of the lamellae take place. Optimum conditions for revealing the representative morphology are such as to lead to a weight increase of 50% for PE with=0.28 of branches and only to an increase of 10% for material of branch content represented by an value of 2.53.On leave from Inst. Estructura de la Materia, Madrid-6. Spain     

玉米芯与低密度聚乙烯混合物在氢气气氛下的催化热解研究

本文研究了在氢气氛围及HZSM-5、H-Beta、NaY和TiO2催化剂作用下玉米芯与LDPE混合物(重量比2∶8)的共热解情况。通过催化热解所得油相液体的烃族分析及碳数分布发现:在催化剂作用下,油相液体的碳数分布变窄,共同热解所得气体产率最高的是H-Beta催化体系,液体产率最高的是NaY,残渣量最多的是TiO2催化体系。催化共热解所得油相液体的碳数分布主要集中在C4~C19之间,使用NaY可获得高品位的油相液体,其研究法辛烷值(RON)为97.5;水相液体中的主要物质是醋酸,加入催化剂后其含量明显增加。四种催化剂中,醋酸生成量最多的是NaY催化剂,其次是HZSM-5,最后是H-Beta和TiO2。其中在NaY催化体系作用下生成的水相液体组分中,醋酸含量为57.8%。     

Structural effects on thermal properties and morphology in XLPE

This study investigated the morphological, thermal and mechanical changes with increasing crosslink density for two low density polyethylenes (LDPE). A reference LDPE was compared with an LDPE containing a higher number of vinyl groups that was introduced via a copolymerisation with a diene. During crosslinking, two reactions simultaneously occur in the copolymer, i.e. a reaction of the vinyl groups and combination crosslinking. After crosslinking with a low amount of peroxide, the majority of the crosslinks originate from reacted vinyl groups in the LDPE containing the higher number of vinyl groups, whereas the crosslinks in the reference LDPE originate from combination crosslinking, thus leading to different crosslinked structures for the two polymers. The melt temperature, crystallisation temperature, and degree of crystallinity were measured using a Differential Scanning Calorimeter. Thermal fractionation studies and morphology studies were also made. The Differential Scanning Calorimetry results show a decrease in those properties for both materials along with a concurrent change in the morphology when the crosslink density increased. The results deviate slightly between the materials.     

Rheological investigation of the influence of molecular structure on natural and accelerated UV degradation of linear low density polyethylene

Metallocene and Ziegler-Natta (ZN) linear low density polyethylenes (LLDPEs) of different branch types and contents as well as linear high density polyethylene (HDPE) were exposed to natural and accelerated weather conditions. The degree of UV degradation of exposed samples was measured by rheological techniques and results were compared with unexposed polymers. Dynamic shear measurements were performed in an ARES rheometer in the linear viscoelastic range. The degree of enhancement or reduction in viscosity and elasticity was used as a measure of the degree of cross-linking or chain scission, respectively. The degradation results of LLDPE suggest that both cross-linking and chain scission are taking place. Chain scission dominated the degradation at high levels of short chain branching (SCB) and long exposure times. The degradation mechanism of m-LLDPE and ZN-LLDPE is similar; however, m-LLDPE showed a higher degradation rate than ZN-LLDPE of similar M_w and average SCB. ZN-LLDPE was found to be more stable than a similar m-LLDPE. Comonomer type had little influence on degradation. Dynamic shear rheology was very useful in revealing the influence of different molecular parameters and it exposed the degradation mechanism.     

Comparison of near-infrared and Raman spectroscopy for the determination of the density of polyethylene pellets

In this study, we compare near-infrared (NIR) and Raman spectroscopy for the determination of the density of linear low density polyethylene (PE) (in a pellet form). As generally known, Raman spectral features are more selective than those of NIR for most chemical samples. NIR spectroscopy has been more extensively used for the quantitative analysis of polymers, but Raman spectroscopy is the better choice as long as the problem of reproducibility of Raman measurements (especially for solid samples), mostly resulting from insufficient sample representation due to probing only localized chemical information and the sensitivity of sample placement with regard to the focal plane, can be overcome. To improve sample representation and reproducibility of Raman measurements, we have employed the wide area illumination (WAI) Raman scheme, capable of illuminating a laser onto a large sample area (28.3 mm²) for Raman spectral collection (a 6-mm laser spot with a focal length of 248 mm). Diffuse reflectance NIR spectra of PE pellets were collected using a sample moving system which allowed for the scanning of large areas. The prediction error was 0.0008 g cm⁻³ for Raman spectroscopy and 0.0011 g cm⁻³ for NIR spectroscopy. The harmonization of inherently selective Raman features and a reproducible spectral collection with correct sample representations using the WAI scheme led to an accurate determination of the density of the PE pellets.     

A dielectric study of molecular relaxations in irradiated high density polyethylene

The molecular relaxation behaviour of high density polyethylene (HDPE), exposed to gamma radiation in air to various absorbed doses (up to 700 kGy), has been investigated by dielectric loss (tanδ) analysis. All relaxation zones (γ, β and α, in order of increasing temperature), between 25 K and the melt temperature, were studied in the frequency range from 1 kHz to 1 MHz. The changes observed in the dielectric relaxation spectra were related to the modifications in the structural and morphological parameters attributed to exposure of the samples to radiation. Radiation-induced changes in the crystal fraction, oxidative degradation and degree of network formation, observed by wide angle X-ray scattering (WAXS), differential scanning calorimetry (DSC), infrared spectroscopy (IR) and gel measurements, were well connected with the changes in intensity, position and activation energy of α and γ relaxations. Complete disappearance of the already weak β relaxation with irradiation is attributed to the more restricted chain segment mobility in the net structure, but the contribution due to radiation-induced increase in crystallinity should also be taken into account.     

Morphology studies and ac electrical property of low density polyethylene/octavinyl polyhedral oligomeric silsesquioxane composite dielectrics

This paper presents the results of morphological and ac electrical investigations on low density polyethylene (LDPE) composites with octavinyl polyhedral oligomeric silsesquioxane (POSS). It has been shown that at low loadings, the frequency dependence of dielectric constant and dielectric loss for the LDPE/POSS composites showed unusual behaviors when compared with conventional (micro-sized particulates) composites. The ac breakdown strength was measured and statistical analysis was applied to the results to determine the effects of POSS loadings on the dielectric strength of LDPE. The morphological characterization showed that the presence of POSS additives apparently altered the supermolecular structure of LDPE and resulted in more homogeneous morphology when compared with the neat LDPE. The structure-property relationship was discussed and it was concluded that the final dielectric properties of the composites were determined not only by the incorporation of POSS additives but also by the supermolecular structure of LDPE. Rheological analyses of LDPE/POSS composite were also performed and the results showed that the octavinyl-POSS had good compatibility with LDPE.     

Effect of crystal form and particle size of titanium dioxide on the photodegradation behaviour of ethylene-vinyl acetate copolymer/low density polyethylene composite

The photodegradation behaviour of ethylene-vinyl acetate copolymer (EVA)/low density polyethylene (LDPE) composite containing four different types of titanium dioxide (TiO₂) was investigated through colour difference, Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and mechanical tests. The results showed that the performance losses of composites were qualitatively correlated with the degradation degree. The vinyl acetate (VA) groups in EVA were sensitive to UV light and the photodegradation mainly occurred in the amorphous region. The chain scission and annealing effect facilitated the secondary crystallization of composites. The heterogeneous nucleation effect of TiO₂ on the crystallization of composites was related to the particle size of TiO₂. The micro rutile TiO₂, micro anatase TiO₂ and their mixture (rutile/anatase = 13/87) exhibited a photo-stabilising effect, while the nano mixed crystals TiO₂ (rutile/anatase = 20/80) had an opposite effect.     

Morphology and crystallization of blends of linear low density polyethylene with a semiflexible liquid crystalline polymer

The morphology and the crystallization behavior of blends of linear low density polyethylene (LLDPE) with an experimental sample of a semiflexible liquid crystalline polymer (SBH 112 by Eniricerche, Italy) have been studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM) and scanning electron microscopy (SEM). The blends possess a two-phase morphology, due to immiscibility of the two components. SEM observations show that dispersion of the minor SBH phase is favored at low (相似文献