Mechanism of formation of fine rubber powder from ternary ethylene–propylene–diene vulcanizates

The process of comminution of EPDM vulcanizates with different content of plasticizer (paraffin oil) is studied. A sol–gel analysis is performed, and the crosslink density in the rubber powders obtained is determined. The surface morphology of these rubber powders is examined by scanning electron microscope. The surface of the particles shows characteristic regions of plastic and brittle fracture. A model of the structure of particles of rubber powders is proposed.     

Intense violet-blue photoluminescence in BaZrO3 powders: A theoretical and experimental investigation of structural order-disorder

Intense violet-blue photoluminescence (PL) emission at room temperature was verified in BaZrO₃ (BZO) powders with structural order-disorder. Ab-initio calculations, ultraviolet-visible absorption spectroscopy and PL were performed. Theoretical results showed that the local disorder in the network-formed Zr clusters present an important role in the formation of hole-electron pair. The experimental data and theoretical results are in agreement, indicating that the PL emission in BZO powders can be related to the structural order-disorder degree in the lattice.     

Segmental anisotropy in strained elastomers detected with a portable NMR scanner

Single-side NMR is particularly suitable for measurements of segmental anisotropy induced in elastomers by uniaxial forces or local strain. Proton transverse nuclear magnetic relaxation was investigated with the NMR-MOUSE by recording the Hahn-echo decay in cross-linked natural rubber bands. This provided information on the dependence of the Hahn-echo decay on the angle between the direction of the uniaxial stretching force and the axis Z defined direction perpendicular to the magnet pole faces of the NMR-scanner. The anisotropy effect on the Hahn-echo decay is correlated with the extension ratio, and it is more evident in the liquid-like regime of the decay. A weaker segmental anisotropy is detected by 1H solid- and Hahn-echo decays recorded by multi-pulse sequences. A qualitative understanding of the angular dependence is obtained by an analytical theory of the Hahn-echo decay adapted to the case of stretched elastomers and to strongly inhomogeneous magnetic fields. Using angular-dependent 1H residual second van Vleck moments and correlation times reported previously [P.T. Callaghan and E.T. Samulski, Macromolecules 30, 113 (1997)] from stretched natural rubber bands the segmental anisotropy measured in inhomogeneous magnetic fields by the Hahn-echo decay was numerically simulated. As an example of a macroscopic distribution of local segmental anisotropy, 1H Hahn-echo decays were measured by the NMR-MOUSE sensor in a stretched cross-linked natural rubber plate with a circular cut in the center.     

Variable energy gap of SiCN nanopowders

SiCN and SiC nanopowders were prepared by infrared laser pyrolysis of gaseous precursors starting from a SiH₄C₂H₂NH₃ gas mixture. The SiCN powders were composed of an amorphous phase ascribed to the ternary compound with a β-SiC crystalline phase, while the SiC powders consisted of β phase only. The chemical bonding and the local atomic order in the SiCN powders are much more complicated than those of pure SiCSi₃N₄ mixtures and are strongly dependent on the variation in the initial gas composition. The average grain size was estimated from X-raydiffraction (XRD) patterns and atomic force microscopy (AFM). The UV-VIS transmittance data were used for the bandgap determination in these new materials. Absorption studies suggested that the direct energy gap is more favourable in SiCN and SiC nanoparticles and is blueshifted with regard to the crystalline bulk (SiC). The change of type of band-to-band transition in SiC nanopowders, due to the size effects, and increasing of the energy gap value in SiCN powders with different local atomic arrangement, makes them attractive for blue-UV optoelectronic applications. PACS 61.46.+w; 78.70.Ck; 68.3.Ps; 78.40.-q     

Electron and probe microscopy investigation of the surface of elastomers modified with antifriction fillers

The surface of frost-resistant elastomers (rubbers) based on nitrile-butadiene rubber and propylene- oxide rubber (pure and modified with fillers: ultrafine PTFE and carbon black) is investigated. Tribological tests show that the addition of carbon black produced the greatest effect: the friction coefficient decreases to 0.2 and remains virtually constant during cooling. Surface and subsurface defects are detected by SEM. These defects can affect the processes in the zone of friction and destruction of the sliding surface of rubber. It is demonstrated that the modification of propylene-oxide rubber results in surface smoothing; the effect is the most pronounced in the samples modified with carbon black. The potential to use scanning probe microscopy for local investigation of the surface of rubber is assessed. A conclusion is made about the adhesive properties of surfaces based on the obtained force–distance curves. The investigation of vibration parameters of a probe in contact with the surface provides an opportunity to estimate the surface elasticity. It is shown that the addition of carbon black results in an increase in hardness of the rubber samples and a drastic reduction in adhesion. At the same time, the introduction of ultrafine PTFE leads to a slight enhancement of the adhesion and hardness. It is concluded that carbon black is the best modifying additive for the studied elastomers.     

Effects of powder flowability on the alignment degree and magnetic properties for NdFeB sintermagnets

The magnetic powders for sintered NdFeB magnets have been prepared by using the strip casting (SC), hydrogen decrepitation (HD) and jet milling (JM) techniques. The effects of powder flowability and addition of a lubricant on the alignment degree and the hard magnetic properties of sintered magnets have been studied. The results show that the main factor affecting powder flowability is the aggregation of magnetic particles for powders in a loose state, but it is the friction between the powder particles for powders that are in a compact state. The addition of a lubricant with suitable dose can slightly prevent the congregating of powders, obviously decrease the friction between the powder particles, improve the powder flowability, and increase the alignment degree, remanence and energy product density of sintered magnets. Mixing a suitable dose of lubricant and adopting rubber isostatic pressing (RIP) with a pulse magnetic field, we have succeeded in producing the sintered NdFeB magnet with high hard magnetic properties of B_r=14.57 KG, _jH_c=14.43 KOe, (BH)_max=51.3 MGOe.     

Enhancement of electromagnetic and microwave absorbing properties of gas atomized Fe-50 wt%Ni alloy by shape modification

In order to increase the electromagnetic parameters and improve the microwave absorbing properties in the range of 1–4 GHz, gas atomized Fe-50 wt%Ni alloys with spherical form were processed in a planetary mill. The morphology, phase composition and saturation magnetization of the FeNi alloy particles were investigated by means of scanning electron microscopy, X-ray diffraction and vibrating sample magnetometer. The complex permittivity, complex permeability and reflection loss of the microwave absorbing material made from Ethylene–Propylene–Diene Monomer rubber, and the Fe-50 wt%Ni alloys were also studied using vector network analyzer and transmission line theory. The results show that the shape of the atomized Fe-50 wt%Ni powders can be modified by mechanical milling. The flaky Fe-50 wt% Ni particles were prepared, and the aspect ratio increases with increasing the milling time from 10 to 30 h. Mechanical milling does not change the phase compositions of the FeNi alloys but decreases the peak intensity and broadens the peak width. The saturation magnetization decreases and the coercivity increases as the milling time increases. The electromagnetic parameters and microwave absorbing properties are enhanced with the increase of the aspect ratio. The rubber absorbers filled with flaky Fe-50 wt%Ni powders milled for 30 h exhibit the low reflection loss in the 1–4 GHz frequency range.     

Droplets of fine powders running uphill by vertical vibration

We observe "droplets" forming when an inclined surface initially covered by fine powders is vibrated vertically. Droplets move uphill in the direction of maximum local slope. The speed of droplets is nearly independent on their size whereas it is an increasing function of the plate acceleration and inclination. By evacuating the container we show that the interstitial air flow plays an important role on droplets forming and their drift.     

Looking for self-organized critical behavior in avalanches of slightly cohesive powders

We report results from a statistical analysis of avalanches of cohesive powders in a slowly rotated drum. Interparticle adhesion, which diminishes the effect of inertia and whose magnitude strongly fluctuates in a local scale, makes avalanches in slightly cohesive powders eligible for displaying self-organized criticality. However, the results show that avalanche sizes, time interval between avalanches, and maximum stable angle do not follow a power-law distribution. Otherwise, these parameters scale with powder cohesiveness.     

Investigation of Carbon Black Network in Natural Rubber with Different Bound Rubber Contents

A new method was applied to modify the surface activity of virginal carbon black (VCB). LA‐57, one kind of hindered amine light stabilizer, was adsorbed onto the carbon black surface through a strong shear force induced by the screws of a HAAKE internal mixer. The modified carbon black (MCB) was characterized by FT‐IR and thermogravimetric analysis (TGA). The bound rubber content of the natural rubber (NR) compounded with MCB and VCB varied with the fraction of LA‐57 on the MCB surface. The nonlinear effect at small strains, generally referred as the Payne effect, was investigated in the rubber compounds based on the different bound rubber contents. The NR compound containing the lowest bound rubber content had an obvious Payne effect. Based on the bound rubber content, the types of filler network varied from direct contact mode to the joint rubber shell mechanism.     

Measuring the solidification time of silicone rubber using optical inspection technology

A room temperature vulcanization silicone rubber was widely used as the mold making material due to its high elasticity, good heat-resistance and low surface energy. To enhance the efficiency of making the silicone rubber mold, accurately measuring the solidification time is an important issue. This study demonstrated a non-invasive measurement system to measure the solidification time of silicone rubber. The solidification time can be determined rapidly from the thickness of silicone rubber according to the predicted equation. The maximum relative error of the predicted equation is about 8.26%. The temperature rise of the silicone during the solidification process is an important phenomenon to determine the solidification behavior of silicone rubber. The solidification mechanism of silicone rubber mold is demonstrated.     

High-Energy Ball Milling of Some Intermetallics

High-energy ball milling of metallic powders has been used in recent years for the synthesis of alloys through reactions mainly occurring in solid state. The diffusive phenomena accompanying and promoting the reactions of formation are related to the microstructure acquired by the powders as a consequence of the intense mechanical deformations. The process induces a remarkable comminution of powder particles, inside of which domains of nanometric size are formed and compositional variations often occur. Several analytical techniques are suitable for following the structural evolution of the powders during milling. Among them, Mössbauer spectroscopy is suitable for obtaining detailed local information on the atomic arrangement of the treated materials, if one of the constituents is a Mössbauer isotope, and for detecting little changes occurring at an atomic scale. For these reasons Mössbauer spectroscopy is more sensitive than other analytical techniques especially in the early stages of the process. Some recent results are presented regarding in particular the Fe–Cu, Fe–Al, Fe–Al–Cu, NiAl(Fe) and Fe–Mn systems.     

电流体动力学技术制备的Sn-Bi纳米超微粉的微观结构特征

采用电流体动力学技术制备了Sn-Bi纳米超微粉,利用X射线衍射、透射电子显微镜和高分辨电子显微镜研究了Sn-Bi纳米超微粉的微观结构特征,结果表明：所制取的Sn-Bi纳米超微粉由四方结构的β-Sn单相过饱和固溶体和菱方结构的Bi单相过饱和固溶体所组成,这些纳米超微粉绝大部分为单晶结构,极少量为孪晶结构,小于10nm的颗粒为完整单晶,10nm以上的单晶颗粒中存在着位错．并对其结构形成机制进行了分析. 关键词：     

Interactions Between an Ionic Liquid and Silica,Silica and Silica,and Rubber and Silica and Their Effects on the Properties of Styrene-Butadiene Rubber Composites

An investigation of the effect of an ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate (BMI), on the properties of silica reinforced styrene-butadiene rubber (SBR), aimed to correlate the interactions between the ionic liquid and silica, silica and silica, and silica and rubber with the macro-properties and microstructure of SBR and SBR/silica vulcanizates is described. The interaction between the ionic liquid and silica was characterized by differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR), the interaction between silica and silica was characterized by a rubber processing analyzer (RPA), and the interaction between rubber and silica was characterized by the bound rubber content. The FTIR analysis revealed that BMI can react with the hydroxyl groups on the surface of silica, improving the compatibility between the rubber and silica. The RPA and bound rubber testing indicated that the interactions between silica and silica particles were weakened and the interaction between silica and rubber increased with the incorporation of BMI into the SBR rubber. The bound rubber content showed a maximum with a BMI content of 3 phr. At the same time, the dispersion of silica in SBR was improved with the incorporation of BMI. With the increase of BMI content, the curing rate was greatly improved and the crosslink density increased. BMI also increased the tensile strength and abrasion resistance of the SBR vulcanizates. Most important, the BMI significantly improved the dynamic properties of the rubber composites, especially the wet-skid resistance and rolling resistance. However, excessive BMI (beyond 3 phr) acted as a plasticizer and was detrimental to the mechanical properties, resulting in a decrease of tensile strength and abrasion resistance.     

Direct magnitude and phase imaging of myelin using ultrashort echo time (UTE) pulse sequences: A feasibility study

In this paper, we aimed to investigate the feasibility of direct visualization of myelin, including myelin lipid and myelin basic protein (MBP), using two-dimensional ultrashort echo time (2D UTE) sequences and utilize phase information as a contrast mechanism in phantoms and in volunteers. The standard UTE sequence was used to detect both myelin and long T2 signal. An adiabatic inversion recovery UTE (IR-UTE) sequence was used to selectively detect myelin by suppressing signal from long T2 water protons. Magnitude and phase imaging and T2* were investigated on myelin lipid and MBP in the forms of lyophilized powders as well as paste-like phantoms with the powder mixed with D₂O, and rubber phantoms as well as healthy volunteers. Contrast to noise ratio (CNR) between white and gray matter was measured. Both magnitude and phase images were generated for myelin and rubber phantoms as well white matter in vivo using the IR-UTE sequence. T2* values of ~ 300 μs were comparable for myelin paste phantoms and the short T2* component in white matter of the brain in vivo. Mean CNR between white and gray matter in IR-UTE imaging was increased from − 7.3 for the magnitude images to 57.4 for the phase images. The preliminary results suggest that the IR-UTE sequence allows simultaneous magnitude and phase imaging of myelin in vitro and in vivo.     

Thermal diffusivity and nuclear spin relaxation: a continuous wave free precession NMR study

Continuous wave free precession (CWFP) nuclear magnetic resonance is capable of yielding quantitative and easily obtainable information concerning the kinetics of processes that change the relaxation rates of the nuclear spins through the action of some external agent. In the present application, heat flow from a natural rubber sample to a liquid nitrogen thermal bath caused a large temperature gradient leading to a non-equilibrium temperature distribution. The ensuing local changes in the relaxation rates could be monitored by the decay of the CWFP signals and, from the decays, it was possible to ascertain the prevalence of a diffusive process and to obtain an average value for the thermal diffusivity.     

Synthesis of Cu2ZnSnSe4 compound powders by solid state reaction using elemental powders

The solid state reaction method was used to synthesize single phase and near stoichiometric Cu₂ZnSnSe₄ compound from elemental Cu, Zn, Sn and Se powders in a quartz tube furnace under an Ar flow at atmospheric pressure. These elemental powders were initially milled using zirconia balls. The α-CuSe phase was present in all of the milled powders because of the mechanical alloying effect between the Cu and Se powders. The solid state reaction mechanism was examined for the synthesis process. The phase analysis suggested that the Cu₂ZnSnSe₄ powder crystallized into the stannite phase with a high degree of crystallinity after near stoichiometric molar ratios of the powders was reacted at 500 °C for 6 h. This study showed that the solid state reaction method was a straightforward technique for the synthesis of the Cu₂ZnSnSe₄ compound powders from the elemental powders.     

Raman scattering studies on nanocrystalline BaTiO3 Part II—consolidated polycrystalline ceramics

BaTiO₃ dense ceramics with different grain sizes from 5.6 µm down to 35 nm were thoroughly studied by Raman spectroscopy. The temperature characteristics of optical phonons were compared with those obtained for powders. The micrograined ceramic revealed the well‐known spectrum profiles and transitions, typical for bulk BaTiO₃. On the other hand, the Raman spectra obtained for a nanograined ceramic with an average grain size of 35 nm revealed a tetragonally distorted pure BaTiO₃ phase showing a diffused phase transition behaviour with respect to temperature. Abnormality of phonon damping characteristics for the nanograined ceramic was demonstrated through comparison with powders with various crystallite sizes and the micrograined ceramic. The Curie temperature of the nanograined ceramic was estimated to be 105 °C from the temperature characteristic of a sharp peak at 307 cm⁻¹, which is one of the most specific tetragonal features for bulk BaTiO₃. In the present study, local stabilization of the tetragonal phase in ultra‐fine grains was experimentally demonstrated from comparison between the Raman spectroscopic results for powders and ceramics prepared through microemulsion‐mediated synthesis. Rather long phonon mean free paths can exist even in such ultra‐fine grains, but the phonon characteristics originating from various grains are diffused mainly because of the effect of internal stress. Copyright © 2007 John Wiley & Sons, Ltd.     

Phase evolution in gel-precipitated LaAlO3 ceramics

Lanthanum aluminate ceramic powders could be prepared by a combined gel precipitation process from metal chlorides using ammonia. A slight modification in the conventional gel precipitation technique was carried out by introducing a step of ultrasonication followed by centrifugal washing of the gel. The dried gels produced pure phase lanthanum aluminate powders on calcination at 1100 °C for the combined gel-precipitated powders, and at 600 °C for the washed gel. The phase evolution was studied and it was found that the delay in obtaining monophasic LaAlO₃ in the combined gel-precipitated powder owed to the crystallization of an impure phase LaOCl. This phase was not detected in the washed gel (WG) powders. TEM micrographs showed a uniform morphology for the calcined WG powders, which were in contrast to the irregular particles in the gel-precipitated (GP) powders. The uniform morphology was assigned to the ultrasonic effects during washing of the gel.     

Microstructural analysis of TiC reinforced ferrous surface composites processed by accelerated electron beam irradiation

The present study aims to analyze microstructures of TiC reinforced ferrous surface composites processed by accelerated electron beam irradiation. Two kinds of powder/flux mixtures, i.e., TiC and (Ti + C) powders with 40 wt% of CaF₂ flux, were deposited evenly on an AISI 304 stainless steel substrate, which was then irradiated with electron beam. TiC agglomerates and pores were found in the surface composite specimen processed by irradiation of TiC powders because of insufficient melting of TiC powders. In the specimen processed by irradiation of Ti and C powders having lower melting points than TiC powders, a lot of large TiC carbides were precipitated in the melted region, together with a few TiC agglomerates or pores. This indicated the more effective TiC precipitation obtained from the melting of Ti and C powders, instead of TiC powders. The hardness of the surface composite layer was about two times higher than that of the AISI 304 substrate mainly due to the precipitation of TiC carbides.