Thermal techniques to study complex elastomer/filler systems

The transfer of heat through an elastomeric matrix is important for both the processing of the material and its subsequent lifetime. Thermal conductivity can be used to evaluate the influence of different polymers and fillers on heat transfer. Additionally, the dispersion of the filler has an effect on heat transfer and thermal conductivity measurements can be used to provide semi-quantitative estimations of filler dispersion. The degradation of sulfur-crosslinked elastomer systems has been studied for many years. The degradation of the crosslinks (changes in sulfur rank) and degradation of the polymer backbone by thermal and/or oxidative processes have been studied extensively using many techniques including thermal analysis (references). However, the degradation of the crosslinked-polymer 'network' is less well understood. The relationship of the crosslink network to this degradation process is a key to both the long term and higher temperature performance of the sulfur-crosslinked elastomer. The changes in physical properties observed upon exposure of sulfur-crosslinked elastomers can be monitored using dynamic mechanical analysis. Subsequently, other thermal techniques can be used to monitor the chemistry that is occurring during these degradations. Thermal desorption/mass spectroscopy and dynamic scanning calorimetry are used to complete the picture of the degradation processes taking place. Examples of these techniques will be provided to illustrate the utility of the analytical approach, the chemistry involved in these degradation processes and the effect of changes in the polymer, cure package and other ingredients. This revised version was published online in August 2006 with corrections to the Cover Date.     

Polyaniline-coated silica gel

Silica gel microspheres 7 and 15 μm in diameter were coated with an overlayer of polyaniline camphorsulfonate or hydrochloride during the oxidative polymerization of aniline. Coated silica gel and polyaniline precipitate were separated using a difference in sedimentation rate. In an alternative approach, the microspheres were modified with polyaniline in the presence of 35 nm colloidal silica. This technique prevented the macroscopic precipitation of polyaniline. Coatings of neat, 3-aminopropyl- and octadecyl-modified silica gel with polyaniline hydrochloride were compared. The surface composition of coated microspheres was characterized by X-ray photoelectron spectroscopy. Potential applications of particles in electrorheology, organic catalysis, and in modeling of conductivity behavior in composites are demonstrated.     

CuO/γ-Al2O3单分散催化剂的XAFS研究

采用XAFS方法研究浸渍法制备并于低温焙烧的CuO/γ-Al2O3催化剂的局域结构.对于CuO负载量小于单层分散阈值的CuO/γ-Al2O3(0.4mmol/100m2),结果表明,CuO物种是以层状分散的孤立原子簇存在于γ-Al2O3载体表面,其第一近邻Cu-O配位环境的结构与晶态CuO的相似,键长和配位数分别为0.195nm和4.对于CuO负载量等于单层分散阈值的CuO/γ-Al2O3(0.8mmol/100m2),已有少量的CuO纳米颗粒生成.对于CuO负载量大于单层分散阈值的CuO/γ-Al2O3(1.2mmol/100m2),其结构与多晶CuO的相近.基于CuO在γ-Al2O3载体上的三种不同分散状态的结构特点,我们提出了CuO/γ-Al2O3催化剂的结构模型.     

Dispersion state and catalytic properties of vanadia species on the surface of V_2O_5/TiO_2 catalysts

The dispersion state and catalytic properties of anatase-supported vanadia species are studied by means of X-ray diffraction (XRD), laser Raman spectroscopy (LRS), H2 temperature-programmed reduction (TPR) and the selective oxidation of o-xylene to phthalic anhydride. The almost identical values of the experimental dispersion capacity of V2O5 on anatase and the surface vacant sites available on the preferentially exposed (001) plane of anatase suggest that the highly dispersed vanadium cations are bonded to the vacant sites on the surface of anatase as derived by the incorporation model. When the loading amount of V2O5 is far below its dispersion capacity, the dispersed vanadia species might mainly consist of isolated VOx species bridging to the surface through V-O-Ti bonds. With the increase of V2O5 loading the isolated vanadia species interact with their nearest neighbors (either isolated or polymerized vanadia) through bridging V-O-V at the expenses of V-O-Ti bonds, resulting in the increase of the ra     

Spectroscopic study of solid-state photoreaction in organic crystal: Photopolymerization of dimethyl ester of α,α′-dicyano-p-phenylenediacrylic acid and diethyl ester of p-phenylenediacrylic acid

Raman spectroscopy has been used to study solid-state photopolymerization reactions in dimethyl ester of α,α′-dicyano-p-phenylenediacrylic acid (p-CPAMe) and diethyl ester of p-phenylenediacrylic acid (p-PDAEt). The reactants and products were characterized by infrared and Raman spectroscopy. Excitation and emission spectra suggest that in p-CPAMe exciton–phonon coupling is strong, but in the other monomer it is very weak. Raman phonon spectroscopic study reveal that in both the samples the reaction mechanism is homogeneous in the initial stages. However, in the later stages the reaction becomes heterogeneous in p-PDAEt. In p-CPAMe the lattice becomes disordered with the progress of polymerization and finally becomes amorphous whereas in p-PDAEt the lattice remains highly ordered. © 1992 John Wiley & Sons, Inc.     

A stream tube model for miscible flow

A simple theoretical model is described for deriving a 1-dimensional equation for the spreading of a tracer in a steady flow at the field scale. The originality of the model is to use a stochastic appoach not in the 3-dimensional space but in the 1-D space of the stream tubes. The simplicity of calculation comes from the local relationship between permeability and velocity in a 1-D flow. The spreading of a tracer front is due to local variations in the cross-sectional area of the stream tubes, which induces randomness in travel time. The derived transport equation is averaged in the main flow direction. It differs from the standard dispersion equation. The roles of time and space variables are exchanged. This result can be explained by using the statistical theory of Continuous Time Random Walk instead of a standard Random Walk. However, the two equations are very close, since their solutions have the same first and second moments. Dispersivity is found to be equal to the product of the correlation length by the variance of the logarithm of permeability, a result similar to Gelhar's macrodispersion.Nomenclature A total cross-section area of the sample - C (resident) concentration of tracer - D,D ^* dispersion coefficient - F flux of tracer - G probability distribution function for permeability in the stream-tube segments - I tracer intensity (mass crossing a surface per unit time) - K permeability - L length of the medium - M number of stream tubes in the medium - N number of segments along a stream tube - P pressure - Q total flow rate in the sample - a length of an elementary stream-tube segment - g probability distribution function for permeability in the space - i, j indices, tube numbers - q flow rate in each stream tube - s variable cross-section area of a stream tube - t, t time - u front velocity - x space variable in the flow direction - small local variation in time - , _t longitudinal, transverse dispersivity - porosity of the porous medium - correlation length in the permeability field - viscosity of the fluid - time for filling an elementary stream tube segment - standard deviation of a stochastic variable - probability distribution of arrival times (Gaussian)     

Co-monotone allocations,Bickel-Lehmann dispersion and the Arrow-Pratt measure of risk aversion

For every integrable allocation (X ₁,X ₂, ...,X _n ) of a random endowmentY= _i ^=1/n X _i amongn agents, there is another allocation (X ₁*,X ₂*, ...,X _n *) such that for every 1in,X _i * is a nondecreasing function ofY (or, (X ₁*,X ₂*, ...,X _n *) areco-monotone) andX _i * dominatesX _i by Second Degree Dominance.If (X ₁*,X ₂*, ...,X _n *) is a co-monotone allocation ofY= _i ^=1/n X _i *, then for every 1in, Y is more dispersed thanX _i * in the sense of the Bickel and Lehmann stochastic order.To illustrate the potential use of this concept in economics, consider insurance markets. It follows that unless the uninsured position is Bickel and Lehmann more dispersed than the insured position, the existing contract can be improved so as to raise the expected utility of both parties, regardless of their (concave) utility functions.     

A class of nonlinear relativistic partial differential equations in elementary particle theory

In mathematical approaches to elementary particle theory, the equation [² - ²/t²]=m² ;+g ³ has been of interest [1,2]; it describes a quartically self-coupled neutral scalar meson field. This paper applies the decomposition method [3-6] to obtain accurate non-perturbative timedevelopment of the field for this equation, or variations involving other nonlinear interactions, without the use of cutoff functions or truncations.     

Three-Dimensional Modeling of the Turbulent Plasma Jet Impinging upon a Flat Plate and with Transverse Particle and Carrier-Gas Injection

Modeling results are presented concerning the turbulent thermal plasma jet impinging normally on a substrate and with transverse injection of feedstock particles and their carrier gas from a single injection tube. The k- two-equation model is employed to model the turbulence, and particle dispersion is studied considering the interaction between the moving particles and turbulent eddies and considering the effect on particle trajectories of the random variation of the turbulent fluctuating velocities in their magnitude and direction. A well-validated three-dimensional (3-D) computer code is used in the modeling. The 3-D effects due to the carrier gas injection on the jet flow field and thus on the particle trajectories and heating histories are shown to be appreciable. The radial location of the injection tube with respect to the plasma jet is shown to be a critical parameter for the study of 3-D effects, besides the carrier-gas/plasma stream mass flux ratio. Particle dispersion considerably widens the distribution of the particle trajectories and heating histories. In addition, although pertinent swirl number is often rather small, swirling may also affect the modeling results.     

制备方法对WO_3/ZrO_2结构的影响

用XRD、比表面测定、LRS定性和定量的方法对用Zr（OH）4和已晶化的ZrO2作载体制得的两类WO3／ZrO2催化剂进行了表征．揭示了样品比表面、载体物相、活性组分的存在状态与制备方法、WO3含量、焙烧温度之间的关系．结果表明，WO3能单层分散在ZrO2上；单层覆盖在Zr（OH）4上的WO3使载体在焙烧时晶粒生长受阻，形成介稳的四方ZrO2，并阻止载体微粒间的烧结，使从Zr（OH）4出发制得的WO3／ZrO2比表面明显增大，在WO3含量达到单层分散容量时以上作用表现得最充分；WO3与Zr（OH）4（或四方ZrO2）在高温（～800℃）可能发生了某种化学结合，开创出超强酸位．用以上观点可对文献中已报导的主要实验事实作出较满意的解释.