HDPE／NBR共混物结构和性能的研究

本文对高密度聚乙烯(HDPE)/丁腈橡胶(NBR)共混物的组成、结构、性能和相互作用进行了研究。实验结果表明:少量的NBR能大幅度提高HDPE的冲击韧性和耐环境应力开裂性能。WAXD显示NBR在共混物中呈现一定程度的取向;TEM显示NBR能以平均粒径为0.2 μm的尺寸分散于HDPE中,且形成较牢固的结合;DMA分析发现HDPE与NBR间相互作用而引起α、γ、T_(?)转变温度发生变化。本文对HDPE与NBR相互作用的机理进行了讨论。     

Evident improvements in the rigidity,toughness, and electrical conductivity of PVDF/HDPE blend with selectively localized carbon nanotube

In this work, carbon nanotube (CNT) was used to fabricate poly(vinylidene fluoride) (PVDF)/high density polyethylene (HDPE) blend-based nanocomposites via a Haake mixer. Scanning electron microscopy confirmed that the CNT was mainly selectively located in the HDPE dispersed domains. Thermogravimetric analysis revealed that CNT addition improved the thermal stability of the blend (up to 61 °C increase at 3-phr CNT loading at 40 wt% loss) in air environment. Differential scanning calorimetry results revealed the enhanced nucleation of individual PVDF and HDPE upon crystallization in the composites; the presence of CNT inceased the stability of PVDF crystals. CNT addition increased the heat distortion temperature of the blend by up to 27 °C at 3-phr CNT loading. The complex viscosity and storage modulus increased due to the CNT pseudo-network formation in the reduce-sized HDPE phase of the composites. The rigidity of the blend was significantly improved after the addition of CNT. The impact strength of the blend increased by up to 66% after 2-phr CNT loading, and the electrical resistivity of the blend decreased by up to nine orders at 3-phr CNT loading due to the double percolation-like morphology formation.     

Effect of arrangement of nano and micro barium titanate (BaTiO3) particles on the enhanced dielectric constant of high‐density polyethylene (HDPE)/BaTiO3

The aim of this study is to improve the dielectric and mechanical properties of HDPE/BaTiO₃ composites by binary BaTiO₃ particles, when the volume fraction of BaTiO₃ is constant. In this study, it was found that the pack density of binary BaTiO₃ particles in HDPE/BaTiO₃ composite relies on particle ratio and volume fraction of small particles. It is found that the addition of 50 vol % 1600 nm BaTiO₃ particles can boost the dielectric constant of HDPE control from 2 to 30 (14 times higher) at 40 Hz and 19 (8.5 times higher) at 40 MHz, respectively. When the particle ratio was 4, the substitution of 10 vol % 1600 nm BaTiO₃ particles by 10 vol % 400 nm BaTiO₃ particles can further enhance the dielectric constant of HDPE/L‐BT (10/10) from 30 to 50 (67% increase) at 40 Hz and from 19 to 42 (121% increase) at 40 MHz, respectively, without greatly influencing the volume resistivity of HDPE composites. In addition, the thermal conductivity of HDPE with binary BaTiO₃ particles were all above 2.0 W/(m•K). © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1101–1108     

Effect of Ultraviolet Irradiation on Structure and Properties of HDPE and HDPE/STC Blends

Abstract

Some oxygen‐containing groups such as C?O and C–O were introduced onto high‐density polyethylene (HDPE) chains by an ultraviolet irradiation technique without the addition of any additives, and this method causes no chemical pollution to the environment. This groups content increases with irradiation time. Gelation took place in the HDPE irradiated for 16?hr, and the gel content also increases with irradiation time. After irradiation, the crystal shape and crystalline plane spacing of HDPE remained unchanged; the melting temperature decreased, whereas the crystallinity and hydrophilicity increased. Due to the introduction of polar groups, the interfacial interaction between sericite–tridymite–cristobalite (STC) particles and irradiated HDPE, and the mechanical properties of irradiated HDPE/STC (60/40) blend were improved. Compared with the yield and impact strength of HDPE/STC (60/40) blend, those of the corresponding blend irradiated for 16?hr were increased from 25.1?MPa and 56?J/m to 29.1?MPa and 283?J/m, respectively.     

Volume‐exclusion effects in polyethylene blends filled with carbon black,graphite, or carbon fiber

Conductive polymer composites possessing a low percolation‐threshold concentration as a result of double percolation of a conductive filler and its host phase in an immiscible polymer blend afford a desirable alternative to conventional composites. In this work, blends of high‐density polyethylene (HDPE) and ultrahigh molecular weight polyethylene (UHMWPE) were used to produce ternary composites containing either carbon black (CB), graphite (G), or carbon fiber (CF). Blend composition had a synergistic effect on electrical conductivity, with pronounced conductivity maxima observed at about 70–80 wt % UHMWPE in the CB and G composites. A much broader maximum occurred at about 25 wt % UHMWPE in composites prepared with CF. Optical and electron microscopies were used to ascertain the extent to which the polymers, and hence filler particles, are segregated. Differential scanning calorimetry of the composites confirmed that the constituent polymers are indistinguishable in terms of their thermal signatures and virtually unaffected by the presence of any of the fillers examined here. Dynamic mechanical analysis revealed that CF imparts the greatest stiffness and thermal stability to the composites. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1013–1023, 2002     

Dielectric,thermal, and mechanical properties of CeO2‐filled HDPE composites for microwave substrate applications

Cerium oxide‐filled high density polyethylene (HDPE) composites for microwave substrate applications were prepared by sigma‐blend technique. The HDPE was used as the matrix and the dispersion of CeO₂ in the composite was varied up to 0.5 by volume fraction, and the dielectric properties were studied at 1 MHz and microwave frequencies. The variations of thermal conductivity (k_eff), coefficient of thermal expansion (α_c) and Vicker's microhardness with the volume fraction of the filler were also measured. The relative permittivity (ε_eff) and dielectric loss (tan δ) were found to increase with increase in CeO₂ content. For 0.4 volume fraction loading of the ceramic, the composite had ε_eff = 5.7, tan δ = 0.0068 (at 7 GHz), k_eff = 2.6 W/m °C, α_c = 98.5 ppm/°C, Vicker's microhardness of 18 kg/mm² and tensile strength of 14.6 MPa. Different theoretical approaches have been used to predict the effective permittivity, thermal conductivity, and coefficient of thermal expansion of composite systems and the results were compared with the experimental data. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 998–1008, 2010     

Enhancing dielectric and mechanical behaviors of hybrid polymer nanocomposites based on polystyrene,polyaniline and carbon nanotubes coated with polyaniline

The dielectric and mechanical properties of hybrid polymer nanocomposites of polystyrene/polyaniline/carbon nanotubes coated with polyaniline(PCNTs) have been investigated using impedance analyzer and extensometer. The blends of PS/PANI formed the heterogeneous phase separated morphology in which PCNTs are dispersed uniformly. The incorporation of a small amount of PCNTs into the blend of PS/PANI has remarkably increased the dielectric properties. Similarly, the AC conductivity of PS/PANI is also increased five orders of magnitude from 1.6 × 10~(-10) to 2.0 × 10~(-5) S·cm~(-1) in the hybrid nanocomposites. Such behavior of hybrid nanocomposites is owing to the interfacial polarization occurring due to the presence of multicomponent domains with varying conductivity character of the phases from insulative PS to poor conductor PANI to highly conductive CNTs. Meanwhile, the tensile modulus and tensile strength are also enhanced significantly up to 55% and 160%, respectively, without much loss of ductility for three phase hybrid nanocomposites as compared to the neat PS. Thereby, the hybrid nanocomposites of PS/PANI/_P CNTs become stiffer, stronger and tougher as compared to the neat systems.     

Binary and ternary blends of high‐density polyethylene with poly(ethylene terephthalate) and polystyrene based on recycled materials

Binary blends of recycled high‐density polyethylene (R‐HDPE) with poly(ethylene terephthalate) (R‐PET) and recycled polystyrene (R‐PS), as well as the ternary blends, i.e. R‐HDPE/R‐PET/R‐PS, with varying amounts of the constituents were prepared by twin screw extruder. The mechanical, rheological, thermal, and scanning electron microscopy (SEM) analyses were utilized to characterize the samples. The results revealed that both R‐HDPE/R‐PET and R‐HDPE/R‐PS blends show phase inversion but at different compositions. The R‐PET was found to have much higher influence on the properties enhancement of the R‐HDPE compared to R‐PS, but at the phase inverted situation, a significant loss in the tensile strength of R‐HDPE/R‐PET blend was observed due to the weak interaction at this morphological state. However, the ternary blends with higher loading of second phase, namely greater than 50 wt% of R‐PET+R‐PS, demonstrated better mechanical properties than the binary blends with the same content of either R‐PET or R‐PS. Copyright © 2009 John Wiley & Sons, Ltd.     

Morphology and properties of nanostructured materials based on polypropylene/poly(butylene succinate) blend and organoclay

Nanostructured materials based on organically modified montmorillonite (OMMT) and polypropylene (PP)/poly(butylene succinate) (PBS) blend were prepared via melt-mixing of PP, PBS, and OMMT in a batch mixer. The weight ratio of PP and PBS was 70:30, and the OMMT loading varied from 0.5 to 5 wt%. The surface morphologies of unmodified and OMMT-modified blend were studied by field-emission scanning electron microscopy. Results showed that the particle size of the dispersed PBS phase was significantly reduced with the addition of a small amount of OMMT (1.5 wt%). Upon the addition of 5 wt% of OMMT, the domain size of the dispersed PBS phase changed significantly from the unmodified blend, and a homogeneous dispersion of very fine particles of PBS was observed. The degree of dispersion of silicate layers in the blend matrix was characterized by X-ray diffraction and transmission electron microscopy. The improved adhesion between the phases and the fine morphology of the dispersed phase contributed to the significant improvement in the properties and thermal stability of the final nanocomposite materials. On the basis of these results, we describe a general understanding of how the morphology is related to the final properties of OMMT-incorporated PP/PBS blend.     

High density polyethylene/hydrogenated oligo(cyclopentadiene) blends: Phase structure,thermal and mechanical properties

The article discusses the influence of an oligomeric resin, hydrogenated oligo (cyclopentadiene) (HOCP), on the morphology and properties of its blends with high density polyethylene (HDPE). HDPE/HOCP blends after solidification contain three phases: the crystalline phase of HDPE and two amorphous phases, one rich in amorphous HDPE and the other in HOCP. DSC thermograms and the loss modulus behaviors show that the γ transition is influenced by HOCP molecules and, in addition to the α_c transition of HDPE, there is another transition that is attributed to the HOCP-rich phase. The hypothesis of the two amorphous phases is confirmed by the optical microscopy observations performed on isothermally crystallized blend films. © 1994 John Wiley & Sons, Inc.     

Morphology,structure, and properties of in situ compatibilized linear low‐density polyethylene/polystyrene and linear low‐density polyethylene/high‐impact polystyrene blends

Blends of linear low‐density polyethylene (LLDPE) with polystyrene (PS) and blends of LLDPE with high‐impact polystyrene (HIPS) were prepared through a reactive extrusion method. For increased compatibility of the two blending components, a Lewis acid catalyst, aluminum chloride (AlCl₃), was adopted to initiate the Friedel–Crafts alkylation reaction between the blending components. Spectra data from Raman spectra of the LLDPE/PS/AlCl₃ blends extracted with tetrahydrofuran verified that LLDPE segments were grafted to the para position of the benzene rings of PS, and this confirmed the graft structure of the Friedel–Crafts reaction between the polyolefin and PS. Because the in situ generated LLDPE‐g‐PS and LLDPE‐g‐HIPS copolymers acted as compatibilizers in the relative blending systems, the mechanical properties of the LLDPE/PS and LLDPE/HIPS blending systems were greatly improved. For example, after compatibilization, the Izod impact strength of an LLDPE/PS blend (80/20 w/w) was increased from 88.5 to 401.6 J/m, and its elongation at break increased from 370 to 790%. For an LLDPE/HIPS (60/40 w/w) blend, its Charpy impact strength was increased from 284.2 to 495.8 kJ/m². Scanning electron microscopy micrographs showed that the size of the domains decreased from 4–5 to less than 1 μm, depending on the content of added AlCl₃. The crystallization behavior of the LLDPE/PS blend was investigated with differential scanning calorimetry. Fractionated crystallization phenomena were noticed because of the reduction in the size of the LLDPE droplets. The melt‐flow rate of the blending system depended on the competition of the grafting reaction of LLDPE with PS and the degradation of the blending components. The degradation of PS only happened during the alkylation reaction between LLDPE and PS. Gel permeation chromatography showed that the alkylation reaction increased the molecular weight of the blend polymer. The low molecular weight part disappeared with reactive blending. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1837–1849, 2003     

A comparative study on the AC/DC conductivity,dielectric and optical properties of polystyrene/graphene nanoplatelets (PS/GNP) and multi-walled carbon nanotube (PS/MWCNT) nanocomposites

Polystyrene/graphene nanoplatelets (PS/GNP) and polystyrene/multi-walled carbon nanotube (PS/MWCNT) nanocomposites were prepared through solution mixing processing. The effect of carbon filler (CF) (GNP or MWCNT) doping on the DC/AC electrical conductivity, dielectric characteristics and optical parameters (absorption coefficient, α and band gap energy, E_g) of nanocomposites were investigated and compared for similar doping concentrations. The observed behavior of the DC surface conductivity for PS/CF nanocomposites was explained according to the classical percolation theory, where the percolation thresholds (ϕ_c) for PS/GNP and PS/MWCNT nanocomposites were determined as 12.0 vol% and 3.81 vol% and the critical exponents (t) were calculated as 2.19 and 2.13, respectively. These results indicate that CFs create three dimensional CF network in PS matrix. The dielectric relaxation properties and the AC conductivity studied by means of Broadband Dielectric Spectroscopy (BDS) measurements, showed that the presence of carbon fillers significantly enhanced the capacitive/charge storage capabilities of the nanocomposites. The optical band gap energies (E_g) of PS/GNP and PS/MWCNT nanocomposites were obtained by using Tauc method. From applicative point of view, with their enhanced dielectric and AC conductivity properties of the PS/GNP and PS/MWCNT nanocomposites have the potential to be used in energy storage and electromagnetic interference (EMI) shielding applications.     

Synthesis,structure and dielectric properties of a novel Gd coordination polymer based on 2-（ pyridin-4-yl ）- 1H-i midazole-4,B -dicarboxylate

A new Gd coordination polymer based on 2-（pyridin-4-yl）-I H-imidazole-4,5-dicarboxylate （H3PIDC） has been synthesized under hydrothermal conditions, formulated as {[Gd3（HPIDC）3（PIDC）（H2O）4].3H2O}n （1）. The compound crystallizes in the monoclinic system, space group C2/c with a=20.951（7）, b = 9.515（3）, c = 27.483（10） A,β= 106.176（6）°, Z = 4, V= 5262（3） A3, C40 H45 Gd3 N12 O30, Dc = 2.071 g/cm3, Mr=1645.63, λ （MoKa）=0.71073A, μ=3.846mm-1, F（000）=3204, the final R=0.0390 and wR= 0.1332. Complex 1 is a two-dimensional MOF built up from T-shaped 3-connected HPIDC2 , PIDC3 and 4-connected metal nodes. Dielectric constant of complex 1 was measured at different frequencies with temperature variation.     

Nanocomposite of montmorillonite with telechelic sulfonated poly(butylene terephthalate): Effect of ionic groups on clay dispersion, mechanical and thermal properties

Telechelic ionomeric poly(butylene terephthalate) nanocomposites with organically modified clays have been prepared by the melt intercalation technique both in Brabender mixer and in twin screw-extruder. The presence of ionic groups tethered at the end of the polymer chains permits electrostatic interaction between the polymer and the surface of an organically modified clays providing a thermodynamic driving force for the dispersion of the clay platelets in the polymer matrix. The improved dispersion has been verified by TEM and XRD analyses. Nanocomposites with telechelic polymers present therefore consistently higher thermo-mechanical properties and improved thermal and hydrolytic stability respect to nanocomposites with standard PBT. Nanocomposite obtained using PBT with 3% telechelic ionic groups and with 5% of clay present a heat deflection temperature that is 48 °C higher compared to that of the commercial material. The presence of the clay also slightly increases the thermal and hydrolytic stability respect to standard PBT.     

Elaboration of poly(ethyleneimine) coated poly( , -lactic acid) particles. Effect of ionic strength on the surface properties and DNA binding capabilities

Poly( , -lactic acid) (PLA)-based particles, obtained by the emulsification–diffusion process, were surface-modified by electrostatic adsorption of poly(ethylenimine) (PEI). The amount of immobilized PEI and the conformation of the polycation at the interface were dependent on the ionic strength of the media. In the absence of salt, or at low ionic strength, the adsorbed amounts of PEI, the surface charge and the critical concentration for coagulation (CCC) of the modified particles were lower than when the adsorption was achieved at elevated ionic strength. Moreover, at low salt concentration, isotherms were of Langmuir type, suggesting the formation of monolayers. The differences in PEI surface conformation had consequences on the DNA binding capacity of the particles, on the plasmid DNA conformation at the interface and on the DNA release in various media. When PEI was adsorbed in a 50 mM phosphate buffer, the amount of bound plasmid and the strength of binding were higher than when PEI was adsorbed in water. From these differences in physico-chemical properties, one can expect differences in transfection or immunization performances of the vectors.     

Influence of the β‐crystalline phase on the mechanical properties of unfilled and calcium carbonate‐filled polypropylene: Ductile cracking and impact behavior

The β‐crystalline form of isotactic poly(propylene) (PP) has been long recognized to have a greater mechanical absorption capacity than the α‐crystalline form. This is of major importance for improving impact properties and crack resistance of injection‐molding parts. Unfilled PP samples together with calcium carbonate‐filled PP samples having various β/α‐phase ratios, with nearly constant morphological parameters, have been investigated from the standpoint of ductile crack propagation and impact behavior. The presence of the β‐crystalline phase turned out to improve both properties. The β spherulites are notably more prone to craze initiation than α spherulites that display a propensity for cracking. Subsequent crack propagation appears to be faster in the latter ones. The plastic zone ahead from the crack tip broadens, and the specific plastic energy increases with increasing β‐phase content. The lower elastic limit of the β phase is likely to promote the early crazing. However, the suspected higher density of tie molecules in β spherulites provides more numerous and stiffer microfibrils. The impact strength of PP is also improved by the presence of β crystals as a result of greater energy‐absorption capabilities. However, filled samples turned out insensitive to the β phase. A discussion is made about the origins of the β‐phase‐induced improvement of the mechanical properties. The possible role of the β → α transition is also explained. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 31–42, 2002     

Synthesis,structure, and properties of chiral liquid crystal monomers and polymers based on menthol

To study structure–mesomorphism relationships of the monomers and polymers based on menthol, four new chiral monomers ( M₁ – M₄ ) and the corresponding homopolymers ( P₁ – P₄ ) with menthyl group were synthesized. Their chemical structures, formula, phase behavior, and thermal stability were characterized by FTIR, ¹H NMR, ¹³C NMR, elemental analyses, differential scanning calorimetry, polarizing optical microscopy, X‐ray diffraction, and thermogravimetric analysis. The selective reflection of light was investigated with ultraviolet/visible spectrometer. The influence of the mesogenic core rigidity, spacer length, and menthyl steric effect on the mesomorphism of M₁ – M₄ and P₁ – P₄ was examined. By inserting a flexible spacer between the mesogenic core and the terminal menthyl groups, four target monomers and polymers could form the expected mesophase. Moreover, their melting temperature (T_m), glass transition temperature (T_g), clearing temperature (T_i), and mesophase range (ΔT) increased with increasing the mesogenic core rigidity; whereas the T_m and T_g decreased, T_i and ΔT increased with an increase of the spacer length. M₁ and M₂ showed monotropic and enantiotropic cholesteric phase, respectively, whereas M₃ and M₄ all revealed chiral smectic C (SmC*), cholesteric and cubic blue phases. In addition, with increasing temperature, the selective reflection of light shifted to the long wavelength region at the SmC* phase range and to the short wavelength region at the cholesteric range, respectively. P₁ and P₂ only showed a smectic A (SmA) phase, whereas P₃ and P₄ exhibited the SmC* and SmA phases. All the obtained polymers had very good thermal stability. © 2012 Wiley Periodicals, Inc. J. Polym. Sci. Part A: Polym Chem, 2012     

Ternary structure design based on hydrogen bonding for transparent and flame retardant PMMA with good mechanical properties

The synthesis of intrinsic flame retardant copolymer by copolymerization with reactive flame retardants is the most potential method to prepare transparent and flame retardant poly (methyl methacrylate) (PMMA) at present,but the main challenge of this method is that the copolymer usually has poor mechanical properties and heat resistance. In this work, the hydrogen bond enhancement strategy is adopted, and the flame retardant PMMA with excellent comprehensive properties is obtained by ternary copolymerization with methyl methacrylate (MMA) as matrix unit, diethyl (methacryloyloxymethyl) phosphonate (DEP) as flame retardant unit and methacrylamide (MAA) as hydrogen bond unit. Due to the formation of intermolecular hydrogen bond via MAA unit, the storage modulus, flexural strength and impact strength of the terpolymer containing 15 mol% MAA are 48%, 19%, and 24% higher than those of the copolymer of MMA and DEP, and its hardness, glass transition temperature and load thermal deformation temperature (increased by 7°C) are also superior. Moreover, owing to the gas-phase dilution and charring flame retardancy of MAA unit, the terpolymer shows increased limiting oxygen index (24.3%) and UL94 rating (V-1). This work not only provides a promising flame retardant PMMA for practical application, but also offers a new strategy to design flame retardant polymers with good mechanical properties.