Polymer-grafted Al2O3-nanoparticles for controlled dispersion in poly(ethylene-co-butyl acrylate) nanocomposites

We report a model system to control the dispersion and inter-particle distance of polymer-grafted Al₂O₃-nanoparticles in high molecular weight poly(ethylene-co-butyl acrylate). The proposed methods make it possible to extend the use of surface initiated atom transfer radical polymerization (SI-ATRP) in combination with more commercial grades of silanes and particles, showing the versatility of this polymerization process. The nanoparticles were surface-modified by an amine-terminated silane, forming multilayered silane coatings to which moieties capable of initiating ATRP were attached. Subsequently, “short” (DP: 117) and “long” (DP: 265) chains of poly(n-butyl acrylate) were grafted from the particles via SI-ATRP. The graft density was found to be in accordance with the density of the accessible amine groups and could therefore be assessed directly after the initial silanization step using UV–Vis spectrometry. From AFM micrographs, the grafted nanoparticles were found to be well-dispersed in the matrix. This observation was corroborated by a novel simulation method capable of transforming the inter-particle distances from 2D to 3D, for the closest and more distant neighbors. Further, we calculated the deviation ratios and concluded that the dispersions were homogeneous and that the inter-particle distances were related to the graft length. The homogeneous dispersions were explained by dominating enthalpic contributions of the polymer grafts to the nanocomposites in combination with shielding of the nanoparticle core–core attraction by the silane multilayer (similar to bimodal systems).     

Mechanistic modelling of kinetics and mass transfer for a solid–liquid system: Leaching of zinc with ferric iron

A systematic approach was developed to consider liquid–solid reactions with rough solid particles and shrinking particle model. The model is able to predict the reactivities of both non-porous and porous solid particles; the reaction order with respect to the solid material varies from zero (non-porous slab) to one (porous particle).As a model system, leaching of zinc sulphide (sphalerite) with ferric iron in an acidic environment was considered. The modelling was based on experimental data obtained in a batch reactor system, for which both conventional mixing and ultrasound was applied. Rival models based on plausible reaction mechanisms were derived and discriminated qualitatively and with regression analysis. The best model described the leaching reaction as a stepwise process, where ferric ions react with solid zinc sulphide in consecutive surface reaction steps. Shrinking particle model along with the surface roughness approach was used. The model predicts first order behaviour with respect to zinc sulphide, while the reaction order with respect to ferric iron varies from one to two as the reaction progresses. This is in accordance with experimental observations. The intrinsic kinetics, liquid–solid mass transfer and the effect of ultrasound were well described by the best kinetic model.     

Experimental and DEM study of segregation of ternary size particles in a blast furnace top bunker model

Size segregation of pellets in the top bunker (hopper) of a blast furnace is an important factor affecting the radial distribution of the charged burden and indirectly also the distribution of gas in the shaft and cohesive zone. This paper studies size segregation of ternary size pellets during the discharging process of a hopper model through experiments and simulations. The simulations, which are based on the discrete element method (DEM), are first validated using four experimental cases applying different bunker filling methods. The effects of various variables, such as fine mass fraction, particle friction coefficients, diameter ratio of fine to coarse and filling method (random, layered or industrial filling), as well as the interaction with wall (static and rolling friction) on the segregation are investigated. The results show that even though many factors affect the extent of segregation during the discharging process, the most important factors are the filling method, diameter ratio of fine to coarse, wall-particle static and rolling friction, interparticle rolling friction as well as mass fraction of fine particles. Reducing wall-particle rolling or static friction or the fraction of fine particles decreased the extent of size segregation.     

Sintering of Multilayered Porous Structures: Part I‐Constitutive Models

Theoretical analyses of shrinkage and distortion kinetics during sintering of bilayered porous structures are carried out. The developed modeling framework is based on the continuum theory of sintering; it enables the direct assessment of the cofiring process outcomes and of the impact of process controlling parameters. The derived “master sintering curve”‐type solutions are capable of describing and optimizing the generic sintering shrinkage and distortion kinetics for various material systems. The approach utilizes the material‐specific parameters, which define the relative kinetics of layer shrinkages such as the relative intensity of sintering, and employs the conversion between real and specific times of sintering. A novel methodology is also developed for the determination of the ratio of the shear viscosities of the layer's fully dense materials. This new technique enables the determination of all input parameters necessary for modeling sintering of bilayers using experimental techniques similar to optical dilatometry applied to each individual layer and to a symmetric trilayered porous structure based on the two‐layer materials utilized in the bilayered system. Examples of sintering different porous bilayered systems are presented to justify the capability of the model in predicting and optimizing sintering kinetics.     

On the high‐gasification rate of Brazilian manganese ore in chemical‐looping combustion (CLC) for solid fuels

The high rate of char gasification observed when using a Brazilian manganese ore as compared to ilmenite is investigated in a batch fluidized‐bed reactor. Experiments were carried out at 970°C using petroleum coke, coal and wood char as fuel with a 50% H₂O in N₂ as fluidizing gas. A manufactured manganese oxygen carrier was also used, however, which presented a slower char conversion rate than the manganese ore. It is concluded that decrease in H₂ inhibition and oxygen release are unlikely to be the main responsible mechanisms for the ore's unexpected gasification rate. The ore was also mixed in different ratios with ilmenite and it was observed that the presence of even small amounts of ore in the bed resulted in increased gasification rate. Thus, the high‐gasification rate for the manganese ore could be due to a contribution from the impurities in the ore by catalyzing the gasification reaction. © 2013 American Institute of Chemical Engineers AIChE J, 59: 4346–4354, 2013     

Deep Kernel Density Estimation for Photon Mapping

Recently, deep learning-based denoising approaches have led to dramatic improvements in low sample-count Monte Carlo rendering. These approaches are aimed at path tracing, which is not ideal for simulating challenging light transport effects like caustics, where photon mapping is the method of choice. However, photon mapping requires very large numbers of traced photons to achieve high-quality reconstructions. In this paper, we develop the first deep learning-based method for particle-based rendering, and specifically focus on photon density estimation, the core of all particle-based methods. We train a novel deep neural network to predict a kernel function to aggregate photon contributions at shading points. Our network encodes individual photons into per-photon features, aggregates them in the neighborhood of a shading point to construct a photon local context vector, and infers a kernel function from the per-photon and photon local context features. This network is easy to incorporate in many previous photon mapping methods (by simply swapping the kernel density estimator) and can produce high-quality reconstructions of complex global illumination effects like caustics with an order of magnitude fewer photons compared to previous photon mapping methods. Our approach largely reduces the required number of photons, significantly advancing the computational efficiency in photon mapping.     

Elongational flow mixing for manufacturing of graphite nanoplatelet/polystyrene composites

Manufacturing strategy is of prime importance for the appropriate incorporation of filler into a polymeric matrix, and this in particular refers to nanofillers. Herein, direct‐graphite nanoplatelets are used as filler in polystyrene. The as‐received filler material contained microscopic size agglomerates formed by nanoscopic size graphite nanoplatelets. Refining of the microagglomerates (break‐up) and production of, desirably, single graphene layers (exfoliation) is the ultimate target for controlling production and thus properties of the present materials. Several processing methods including microcompounding, roll‐milling/calendering, Brabender mixing chamber, and solvent processing are used and compared with elongational flow mixing by a newly developed mixer. For the present system, sonication with surfactant assistance solvent processing yields both good micro deagglomeration and production of thin graphene nanostacks/layers. Also the elongational flow mixing efficiently refines the microagglomerates. Solvent processing and microcompounding are more efficient than the other processes in the production of exfoliated thin graphene stacks/layers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

On the synthesis and characterization of new low temperature curing powder coatings cured with radiation

The synthesis and characterization of a new type of low temperature curing powder coating is described. The type of materials used were mixtures of an amorphous methacrylate-functional prepolymer and crystalline acrylate and methacrylate monomers. The introduction of a crystalline component in an amorphous resin mixture was shown to markedly reduce the melt viscosity and thus enhance the flow properties of the powder coating. Curing experiments showed the advantage of using photoinitiation compared to thermal initiation. The reaction was much faster and the problem with oxygen inhibition could be avoided. Department of Polymer Technology, S-100 44 Stockholm, Sweden.