Study of the size and numerical concentration of the free volume of carbon filled HDPE composites by the positron annihilation method

In this paper, the size and numerical concentration of free volume of high density polyethylene/carbon black (HDPE/CB) composite were investigated by positron annihilation lifetime spectroscopy (PALS). The PALS were measured in two series of samples, one with various CB contents in the composites and the other with changing the temperature of HDPE/CB composite containing 25 phr CB. It was found that the important parameters of PALS show their fluctuation around the percolation threshold. The conductivity of HDPE/CB is controlled by CB contribution, and that can be reflected in o-Ps lifetime. The temperature dependence of positron lifetimes reveals that the existence of glass transition temperatures and the size of free volume holes increases when temperature increases above glass transition. The results observed from the second set of samples suggest that positive temperature coefficient is in some way related with free volume expansion. The experiment facts implied that the conductivity of HDPE/CB was related with not only the size of free volume holes but also the number of free volume holes. The Doppler-broadening of HDPE/CB was also investigated.     

INVESTIGATION OF MICROSTRUCTURE AND CONDUCTIVE MECHANISM OF HIGH DENSITY POLYETHYLENE/CARBON BLACK PARTICLE COMPOSITE BY POSITRON ANNIHILATION LIFETIME SPECTROSCOPY

The microstructure and conductive mechanism of high density polyethylene/carbon black (HDPE/CB) compositewere investigated by positron annihilation lifetime spectroscopy (PALS). The PALS were measured in two series of samples,one with various CB contents in the composites and the other with various γ-irradiation doses in HDPE/CB compositecontaining 20 wt% CB. It was found that CB particles distribute in the amorphous regions, the CB critical content value inHDPE/CB composite is about 16.7 wtO/ and the suitable γ-irradiation dose for improving the conductive behavior ofHDPE/CB composite is about 20 Mrad. T'he result observed for the second set of samples suggests that γ-irradiation causesnot only cross-linking in amorphous regions but also destruction of the partial crystalline structure. Therefore, a suitableirradiation dose, about 20 Mrad, can induce sufficient cross-linking in the amorphous regions without enhancing thedecomposition of crystalline structure, so that the positive temperature coefficient (PTC) effect remains while the negativetemperature coefficient (NTC) effect is suppressed. A new interpretation of the conductive mechanism, which might providea more detailed explanation of the PTC effect and the NTC effect has been proposed.     

Gas permeation parameters and other physicochemical properties of a polymer of intrinsic microporosity: Polybenzodioxane PIM-1

A detailed study of gas permeation, thermodynamic properties and free volume was performed for a novel polymer of intrinsic microporosity (PIM-1). Gas permeability was measured using both gas chromatographic and barometric methods. Sorption of vapors was studied by means of inverse gas chromatography (IGC). In addition, positron annihilation lifetime spectroscopy (PALS) was employed for investigation of free volume in this polymer. An unusual property of PIM-1 is a very strong sensitivity of gas permeability and free volume to the film casting protocol. Contact with water in the process of film preparation resulted in relatively low gas permeability (P(O₂) = 120 Barrer), while soaking with methanol led to a strong increase in gas permeability (P(O₂) = 1600 Barrer) with virtually no evidence of fast aging (decrease in permeability) that is typical for highly permeable polymers. For various gas pairs (O₂/N₂, CO₂/CH₄, CO₂/N₂) the data points on the Robeson diagrams are located above the upper bound lines. Hence, a very attractive combination of permeability and selectivity is observed. IGC indicated that this polymer is distinguished by the largest solubility coefficients among all the polymers so far studied. Free volume of PIM-1 includes relatively large microcavities (R = 5 Å), and the results of the PALS and IGC methods are in reasonable agreement.     

Studies of self-diffusion of poly(dimethylsiloxane) chains in PDMS model networks by pulsed field gradient NMR

We have measured the diffusion of poly(dimethylsiloxane) (PDMS) chains in PDMS model networks by using a pulsed field gradient NMR technique. The model networks have been prepared by tetrafunctional endliking of linear PDMS chains having molecular weights M_n of 3,700 and 7,400 g mol^?1. The diffusants have been incorporated in the networks by immersing pieces of them in PDMS linear chains with molecular weights M_n between 3,000 and 12,000 g mol^?1 and molecular weight distributions M_w/M_n between 1.1 and 1.7. Although spin-echo attenuation results were fitted to a model which takes into account polydispersity of the diffusant, these results did not exhibit any dependency upon the molecular weight distribution. The self-diffusion coefficients of PDMS chains in the PDMS model networks were found to be smaller than in the melt, and the exponents for the diffusion coefficient dependence on M_n in the networks were found to be about-1.3. Free diffusion will give an exponent equal to-1, whereas free volume contributions or behavior intermediate between free and entangled diffusion will increase the magnitude of the exponent.     

DAMAGE OF SILICONE RUBBER INDUCED BY PROTON IRRADIATION

In this paper, the damage to methyl silicone rubber induced by irradiation with protons of 150 keV energy wasstudied. The surface morphology, tensile strength, Shore hardness, cross-linking density and glass transition temperaturewere examined. Positron annihilation lifetime spectrum analysis (PALS) was perfomed to reveal the damage mechanisms ofthe rubber. The results showed that tensile strength and Shore hardness of the rubber increased first and then decreased withincreasing irradiation fluence. The PALS characteristics τ_3 and I_3, as well as the free volume V_f, decreased with increasingirradiation fluence up to 10~(15) cm~(-2), and then increased slowly. It indicates that proton irradiation causes a decrease of freevolume in the methyl silicone rubber when the fluence is less than 10~(15)cm~(-2), while the free volume increases when thefluence is greater than 10~(15)cm~(-2). The results on cross-linking density indicate that the cross-linking induced by protonirradiation is dominant at smaller proton fluences, increasing the tensile strength and Shore hardness of the rubber, while thedegradation of rubber dominates at greater fluence, leading to a decrease of tensile strength and Shore hardness.     

Effects of organophilic montmorillonite on hydrogen bonding, free volume and glass transition temperature of epoxy resin/polyurethane interpenetrating polymer networks

Epoxy resin nanocomposites containing organophilic montmorillonite (oM) and polyurethane were prepared by adding oM to interpenetrating polymer networks (IPNs) of epoxy resin and polyurethane (EP/PU). The dispersion degree of oM in EP/PU matrix was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Fourier transform infrared spectrometry (FT-IR) showed that strong interactions existed between oM and EP/PU matrix, and oM had some effect on hydrogen bonding of these EP/PU IPNs nanocomposites. Positron annihilation spectroscopy (PALS) and differential scanning calorimetry (DSC) measurements were used to investigate the effect of oM and PU contents on free volume and glass transition temperature (T_g) of these nanocomposites. The PALS and DSC results clearly showed that the presence of oM led to a decrease in the total fractional free volume, which was consistent with increasing T_g upon addition of oM, ascribed to increasing hydrogen bonding in interfacial regions of oM and EP/PU matrix and enhancing the miscibility between EP phase and PU phase. In addition, with increasing PU content, the total fractional free volume increased, corresponding to decreasing T_g.     

The strain-sensing behaviors of carbon black/polypropylene and carbon nanotubes/polypropylene conductive composites prepared by the vacuum-assisted hot compression

The strain-sensing behaviors of carbon black (CB)/polypropylene (PP) and carbon nanotubes (CNTs)/PP conductive composites prepared by the vacuum-assisted hot compression were studied and compared. When ten extension-retraction cycles were applied, it was found for CB/PP, the value of the maximum responsivity (ΔR/R ₀, ΔR—the instantaneous variation of the resistance during the test, R ₀—the original resistance) decreased gradually with increasing the cycle number, but it began to rise from the seventh cycle. The value of the min ΔR/R ₀ increased during the whole test. While for CNTs/PP, both the values of the max and min ΔR/R ₀ decreased rapidly. It is suggested that the different behaviors mainly depend on the distinction in the dimension of the conductive fillers and the preparation technique.     

Free Volume of Montmorillonite/Styrene‐Butadiene Rubber Nanocomposites Estimated by Positron Annihilation Lifetime Spectroscopy

Summary: The size and concentration of free‐volume holes of two kinds of montmorillonite (MMT)/styrene‐butadiene rubber (SBR) nanocomposites were investigated by positron annihilation lifetime spectroscopy (PALS). Strong interfacial interaction caused an apparent reduction of the free‐volume fraction of rubber probably by depressing the formation of free‐volume holes in the interfacial region. Interfacial interaction in MMT/SBR nanocomposites was weaker than that in SBR filled with carbon black.

Dependence of normalized o‐Ps intensity of four kinds of composites on filler volume fraction.     

Positron annihilation lifetime study of PTFE/silica composites

Positron annihilation lifetime spectroscopy (PALS) was used to study the microstructure of PTFE/silica composites. The positron lifetimes (τ_n) and intensities (I_n) of PTFE and the composites (30-62% silica) were measured at room temperature as a function of specimen thickness. Four lifetime components were found in PTFE and the composites. The longer lifetime components, τ₃ = 1.4 ns and τ₄ = 4.4 - 4.1 ns, were interpreted to be due to the presence of two different sized free volume cavity distributions within the PTFE/silica composites. A strong silica concentration dependence was found in the bulk intensities (I_3b and I_4b). The I_3b value increased from 13.0% in PTFE to 28.2% in the 62% composite, while the I_4b value decreased from 17.5% in PTFE to 4.5% in the 62% composite. The smaller-void size, free volume fraction (τ₃I_3b) values increased linearly between 0 and 100% silica concentration, while the larger void size, free volume fraction (τ₄I_4b) values decreased nonlinearly with silica concentration. Since silica has a long lifetime component (τ₃ = 1.6 ns), this behavior is ascribed to silica particles occupying the large free volume cavities (370 ų) in the PTFE/silica composites. © 1996 John Wiley & Sons, Inc.     

Free volume and microstructural investigation of poly(ethylene terephthalate)-g-acrylic acid (PET-g-AA) copolymer films

Acrylic acid (AA) was grafted onto PET films by preirradiation method using a ⁶⁰Co γ-radiation source. Microstructural investigation of the PET-g-AA copolymers has been carried out by wide angle X-ray diffraction (WAXD), dynamic mechanical analysis (DMA) and positron annihilation lifetime spectroscopy (PALS) techniques. The WAXD results showed only marginal variation in the crystallinity of the graft copolymers. Dynamic mechanical analysis showed an increase in the temperature of the α-relaxation and the tan δ value of subroom temperature secondary relaxations. From the PALS results, a complex variation of the free volume parameters, i.e. the o-positronium lifetime (τ₃), its intensity (I₃), fractional free volume (f_v) and the intermediate lifetime component was observed for the graft copolymers. Multiple phenomena of the effect of secondary relaxations, additive behavior of the individual polymer free volume parameters and effects from interfacial defects have been invoked to understand the fluctuational nature of the free volume properties in the graft copolymers.     

炭黑填充聚苯乙烯熔体流变行为

研究了炭黑(CB)填充聚苯乙烯(PS)熔体的稳态和动态流变行为. CB/PS复合体系在CB体积分数φ=0.06时发生逾渗转变. 结果表明, 低应变区熔体模量降低主要归因于粒子-粒子及粒子-高分子间作用力的破坏, 高应变下模量的急剧下降则主要与高分子链间解缠结有关. 采用“两相”模型拟合线性动态流变行为, 发现应变放大因子A_f(φ)、填充相模量及松弛指数与温度有关. A_f(φ)~φ关系符合Guth方程和扩散控制的粒子簇聚集模型. “粒子相”形状参数与聚集体分维度均随温度升高而有所降低, 说明CB粒子聚集体因团聚而趋于各向同性, 应变放大效应减弱. “粒子相”特征模量G'_f1(φ)和G"_f0(φ)与φ关系满足标度律. 当φ > 0.06时, G'_f1(φ)和G"_f0(φ)及其标度指数均随温度升高而明显降低, 其G'_f1(φ)变化幅度略大于G"_f0(φ), 说明“粒子相”弹性与黏性组分具有不同的温度依赖性. 随着温度升高, 扩散控制的CB粒子团聚过程加快, 应变放大效应减弱.     

Transport properties of water in hydroxypropyl methylcellulose

The relation between the self-diffusion coefficient, D_self, of water and the free volume hole size, V_h, has been investigated in a hydroxypropyl methylcellulose (HPMC)-water system in the water content range 0.08-0.36 w/w, at room temperature. Furthermore, the thermal properties of the water in the HPMC-water system, as measured with differential scanning calorimetry (DSC) and the tensile storage, E′, and tensile loss, E″, moduli, of the HPMC-water systems, as determined with dynamic mechanical analysis (DMA), have been probed. Pulsed-field gradient nuclear magnetic resonance (PFG NMR) was used to measure the D_self of water and positron annihilation lifetime spectroscopy (PALS) was used to measure the ortho-Positronium (o-Ps) lifetime in the HPMC-water system. The glass transition temperature of the HPMC was found to be reduced by the water to room temperature in the water content range 0.10-0.15 w/w. The relation between ln D_self of water and the inverse free volume hole size of the HPMC-water system was non-linear. Furthermore, the PALS measurements showed that molecular water co-existed with water clusters in the HPMC-water system.     

Thermal stability of poly(methyl methacrylate)/silica nano- and microcomposites as investigated by dynamic-mechanical experiments

The thermal stability of poly(methyl methacrylate) (PMMA) filled with silicon dioxide particles was investigated by means of rheological tests. The change in the storage modulus G′ was measured, which is a very sensitive method to detect molecular changes in polymers. The long-term thermal stability of the composites was found to depend on the temperature of the melt, the size of the silica particles, which ranged from nano- to micrometers, and the volume fraction of the filler. For high temperatures and a large surface area of the silica particles the behaviour of the composites differs significantly from that of the pure polymer. Pure PMMA degrades at high temperatures, which correlates with a decrease of G′. In contrast an increase in G′ with increasing temperature and filler surface was measured for the composite materials. This behaviour is explained by chemical reactions of the PMMA molecules with the silica particles. Effects of that kind were not found for SiO₂ filled polystyrene.     

Ferrimagnetism in the rare earth titanium (III) oxides, RTiO3; R = Gd,Tb, Dy,Ho, Er,Tm

The series of compounds RTiO₃, R = Gd, Tb, Dy, Ho, Er, and Tm, were obtained as single-phase materials via solid state reaction between Ti₂O₃ and R₂O₃ at ca. 1500°C in welded molybdenum crucibles under argon; YbTiO₃ and LuTiO₃ could not be obtained as single-phase materials using this procedure. Lattice constants for all compounds were determined from powder X-ray data and are compared with previous results. All of these materials order magnetically between 30 and 70 K. From the appearance of the χ^?1_m vs T curve the type of order can be identified as ferrimagnetic. High-temperature susceptibility data have been fit to a two-sublattice molecular field model and the intra- and intersublattice interaction constants have been extracted. It is found that the TiTi interaction is ferromagnetic and relatively constant from R = Gd to R = Lu. Low-temperature magnetization field data suggest the existence of complex magnetic structures, large magnetocrystalline anisotropy, or both. The magnetic properties of the RTiO₃ series are compared to those of the chemically similar and better-known RMO₃ phases where M = Al, V, Cr, Mn, and Fe. The observed differences are shown to follow from the sign of the M-M interaction, which is ferromagnetic for M = Ti and antiferromagnetic for M = V, Cr, Mn, and Fe, together with the implications of the crystal symmetry for the R-M interaction.     

Effect of nitrile butadiene rubber/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/YSZ fillers for PMMA denture base on the thermal and mechanical properties

This study is to investigate the effect of nitrile butadiene rubber (NBR as impact modifier) together with Al₂O₃/YSZ (toughening) as filler loading in PMMA denture base on the thermal and mechanical properties. PMMA matrix without fillers was mixed between PMMA powder and 0.5 mass% of BPO, and it is used as the control group. The liquid components consist of 90% of methyl methacrylate (MMA) and 10% as the cross-linking agent of ethylene glycol dimethacrylate. The denture base composites were fabricated by incorporating PMMA powder and BPO and fixed at 7.5 mass% NBR particles and filler loading (1, 3, 5, 7 and 10 mass%) of Al₂O₃/YSZ mixture filler by (1:1 ratio) as the powder components. The ceramic fillers were treated with silane (γ-MPS) and the powder/liquid ratio (P/L) according to dental laboratory practice. The TGA data obtained show that the PMMA composites have better thermal stability compared to unreinforced PMMA, while DSC curves show slightly similar Tg values. DSC results also indicated the presence of unreacted monomer content for both reinforced and unreinforced PMMA composites. The fracture toughness, Vickers hardness and flexural modulus values were statistically increased compared to the unreinforced PMMA matrix (P?<?0.05).     

Transcrystallization in nanofiber bundle/isotactic polypropylene composites: effect of matrix molecular weight

Polyamide 66 (PA 66) nanofiber bundles were first electrospun and then introduced into isotactic polypropylene (iPP) melts to prepare nanofiber bundle/iPP composites. To reveal the influences of matrix molecular weight (M _n ) on the transcrystalline layer, three kinds of iPP with different M _n were adopted. Polarized optical microscope was employed to investigate the transcrystallinity. In the presence of PA 66 nanofiber bundle, the heterogeneous nucleation distinctly happened in iPP melts. Moreover, the higher the iPP M _n , the denser the nuclei. Both a decrease in matrix M _n and an increase in isothermal crystallization temperature led to an increase in the induction time. The maximum temperature at which the transcrystalline layer can be optically observed increased with the increase of M _n . The growth rate of transcrystallinity decreased with the increasing M _n and crystallization temperature. Moreover, selective melting of the transcrystalline layers confirmed that it was merely composed of α form crystal for all composites.     

Poly(methylmethacrylate-dimethylsiloxane) triblock copolymers synthesized by transition metal mediated living radical polymerization: bulk and surface characterization

Well-defined poly(MMA-b-DMS-b-MMA) triblock copolymers were prepared by copper(I) mediated living radical polymerization. This was achieved by polymerization of methylmethacrylate (MMA) with different concentrations of 2-bromoisobutyrate terminated polydimethylsiloxane (PDMS). The polymerization occurred in controlled manner with the molecular weight found by ¹H NMR close to that predicted and a narrow molecular weight distribution (M_w/M_n∼1.2). Copolymers were obtained with M_n=2100, 4900, 10 100 and 29 500 g mol⁻¹ respectively with poly(MMA) (PMMA) terminal blocks and a central PDMS block of 5500 g mol⁻¹ in each case.DSC analysis showed most of the poly(MMA-b-DMS-b-MMA) triblock copolymers exhibits two T_g’s, one at low temperature corresponding to the T_g of PDMS microphase and a second at high temperature corresponding to the T_g of the PMMA microphase. TEM images show microphase segregation morphology in bulk for the triblock copolymers, with a higher degree of segregation for copolymers containing higher PDMS content. XPS measurements were performed to determine the chemical composition at the surface. For all the copolymers PDMS enrichment is observed at the surface. Copolymers containing higher percentage of PDMS exhibit higher phase separation and better enrichment of PDMS at the surface. The surface tension determined by contact angle measurements of the copolymer film containing 59 mol% of PDMS was 19.15 mN m⁻¹.     

A positron annihilation study on the microstructure of cyanate ester resin toughened by carboxyl‐terminated butadiene‐acrylonitrile rubber system

The toughness of cyanate ester (CE) resin matrix improves significantly with the addition of carboxyl‐terminated butadiene‐acrylonitrile rubber (CTBN). The curing behavior of the system was studied by differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. The results show that carboxyl groups on the CTBN chain have a slight activation effect on the CE curing reaction at the beginning of the curing process. Phase separation was found to be the main toughening mechanism for CE/CTBN composites. The existence of macro‐size pores induced by the decomposition of a small amount of the low weight molecular part of CTBN might be another toughening mechanism. It is confirmed that positron annihilation lifetime spectroscopy (PALS) is still valid in such a system where macropores filled with gas molecules exist. When a high weight percentage of CTBN (>8%) was added to CE, free‐positron annihilation was found to be the dominant annihilation process in the macropores. For CTBN weight percentage higher than 8%, the contribution of ortho‐positronium (o‐Ps) annihilation in the macropores to τ₃ and I₃ was found to be insignificant. It is effective to use PALS as a probe of free‐volume properties in such systems by determining the changes in the τ₃ and I₃ of the composite. The compatibility and interfacial adhesion of the composites can be estimated from the changes in the free‐volume properties of the composites. Copyright © 2008 John Wiley & Sons, Ltd.     

Physico-mechanical and free volume behaviour of guar gum filled polyurethane/polyacrylonitrile biodegradable composites

A series of different weight ratios of guar gum viz. 5, 10, 20 and 30 were incorporated into polyurethane/polyacrylonitrile (PU/PAN, 50/50) semi interpenetrating polymer networks (SIPNs) using polyethylene glycol-400, 4,4′-diphenyl methane diisocyanate, acrylonitrile, benzoyl peroxide and new metallic catalyst. The obtained polymer composites were subjected to biodegradation studies using specific fungi Aspergillus niger. The composites are characterized for physico-mechanical properties like density and tensile behaviour of the specimens before and after biodegradation. The positron annihilation lifetime spectroscopy (PALS) was used to monitor the content of free volume before and after biodegradation. The extent of degradation was examined by change in tensile behaviour and surface morphology. The influences of fungi on mechanical and morphological behaviour of filled IPNs are found to be interesting. The free volume changes in the composite systems correlates well with the mechanical properties.