High-power laser beam shaping by inseparable two-dimensional binary-phase gratings for surface modification of stamping dies

For surface modification of stamping dies, an inseparable two-dimensional binary-phase gratings is introduced to implement the wavefront transformation of high-power laser beams. The design and fabrication of the gratings are described in detail. Two-dimensional even sampling encoding scheme is adopted to overcome the limitations of conventional Dammann grating in the design of two-dimensional output patterns. High diffractive efficiency (>70%) can be achieved through the transformation of the Gaussian laser beam into several kinds of two-dimensional arrays in focal plan. The application of the binary-phase gratings in the laser surface modification of ductile iron is investigated, and the results show that the hardness and the wear resistance of the sample surface were improved significantly by using the binary-phase gratings. (C) 2008 Elsevier Ltd. All rights reserved.

Numerical Simulation of Reactive Extrusion Processes for Activated Anionic Polymerization

In order to deal with the complicated relationships among the variables of the reactive extrusion process for activated anionic polymerization, a three-dimensional equivalent model of closely intermeshing co-rotating twin screw extruders was established. Then the numerical computation expressions of the monomer concentration, the monomer conversion, the average molecular weight and the fluid viscosity were deduced, and the numerical simulation of the reactive extrusion process of Styrene was carried out. At last, our simulated results were compared with Michaeli's simulated results and experimental results. (C) 2007 Elsevier B.V. All rights reserved

Preparation and properties of polyether pentaerythritol mono-maleate grafted linear low density polyethylene by reactive extrusion

A reactive type nonionic surfactant, polyether pentaerythritol mono-maleate (PPMM) was synthesized in our laboratory. PPMM was adopted as functionalizing monomer and grafted onto linear low density polyethylene (LLDPE) with a melt reactive extrusion procedure. FT-IR was used to characterize the formation of grafting copolymer and evaluate their degree of grafting. The effects of monomer concentration, reaction temperature and screw run speed on the degree of grafting were studied systematically. Isothermal crystallization kinetics of LLDPE and LLDPE-g-PPMM samples was carried out using DSC.

Grafting acrylic acid onto polypropylene by reactive extrusion with pre-irradiated PP as initiator

In this paper, the modification of polypropylene (PP) with acrylic acid (AA) by reactive extrusion using pre-irradiated PP (rPP) as initiator was investigated. It was found the relatively high graft degree (Gd) and slight degradation of modified PP was obtained when 20 wt% rPP was used. This result can be explained in terms of effective concentration of free radicals.

Analysis of chemical calorific effect during reactive extrusion processes for free radical polymerization

In the reactive extrusion process for polymerization, the chemical calorific effect has a great influence on the temperature. In order to quantitatively analyze the polymerization trend and optimize the processing conditions, the phenomena of the chemical calorific effect during reactive extrusion processes for free radical polymerization were analyzed. Numerical computation expressions of the heat of chemical reaction and the reactive calorific intensity were deduced, and then a numerical simulation of the reactive extrusion process for the polymerization of n-butyl methacrylate was carried out. The evolutions of the heat of chemical reaction and the reactive calorific intensity along the! axial direction of the extruder are presented, on the basis of which reactive processing conditions can be optimized.

Investigation of the gel effect in reactive extrusion processes for free radical polymerization

The gel effect in the reactive extrusion process for free radical polymerization in a closely intermeshing co-rotating twin screw extruder was investigated. First the reaction kinetic model was constructed mainly on the basis of entanglement theory. Next, numerical calculation expressions for the initiator and monomer concentrations, monomer conversion, average molecular weight and apparent viscosity were deduced. Finally, the evolution of the above variables were shown and discussed for the example of butyl methacrylate. The simulated results of the monomer conversion are in good agreement with experimental results.

Computer simulation of reactive extrusion processes for free radical polymerization

The reactive extrusion for polymerization is an integrated polymer processing technology. A new semi-implicit iterative algorithm was proposed to deal with the complicated relationships among the chemical reaction, the macromolecular structure and the chemorheological property. Then the numerical computation expressions of the average molecular weight, the monomer conversion, and the initiator concentration were deduced, and the computer simulation of the reactive extrusion process for free radical polymerization was carried out, on basis of which reactive processing conditions can be optimized.

Study on reactive extrusion processes of block copolymer

The anionic copolymerization process of styrene-buradiene (S/B) block copolymer in a closely intermeshing co-rotating twin screw extruder with butyl-lithium initiator was studied. According to the anionic copolymerization mechanism and the reactive extrusion characteristics, the mathematical models of monomer conversion, average molecular weight and fluid viscosity during the anionic copolymerization of S/B were constructed, and then the reactive extrusion process was simulated by means of the finite volume method and the uncoupled semi-implicit iterative algorithm. Finally, the influence of the feeding mixture composition on conversion was discussed. The simulated results were nearly in agreement with the experimental results.

Numerical simulation of reactive extrusion processes of PA6

To analyze the complicated relationships among the variables during the reactive extrusion process of polyamide 6 (PA6), and then control the chemical reaction and the material structures, the process of continuous polymerization of caprolactam into PA6 in a closely intermeshing co-rotating twin screw extruder was simulated by means of the finite volume method, and the influences of three key processing parameters on the reactive extrusion process were discussed. The simulated results of an example were in good agreement with the experimental results.

Free radical grafting of polyethylene with vinyl monomers by reactive extrusion

The free radical grafting of polyethylene with vinyl monomers by reactive extrusion was studied numerically. Numerical computation expressions of key variables, such as the concentrations of the initiator and polymer, grafting degree, average molecular weight and apparent viscosity, were deduced. The evolutions of the above variables were predicted by means of an uncoupled semi-implicit iterative algorithm. The monomer conversion monotonically increases with decreasing throughput or increasing initial initiator concentration; with increasing barrel temperature, the monomer conversion first increases then decreases. The simulated results are nearly in good agreement with the experimental results.

Kinetics study on melt grafting copolymerization of LLDPE with acid monomers using reactive extrusion method

Graft copolymerization in the molten state is of fundamental importance as a probe of chemical modification and reactive compatibilization. However, few grafting kinetics studies on reactive extrusion were carried out for the difficulties as expected. In this work, the macromolecular peroxide-induced grafting of acrylic acid and methyl methacrylate onto linear low density polyethylene by reactive extrusion was chosen as the model system for the kinetics study; the samples were taken out from the barrel at five ports along screw axis and analyzed by FTIR, H-1 NMR, and ESR. For the first time, the time-evolution of reaction rate, the reaction order, and the activation energy of graft copolymerization and homopolymerization in the twin screw extruder were directly obtained. On the basis of these results, the general reaction mechanism was tentatively proposed. It was demonstrated that an amount of chain propagation free radicals could keep alive for several minutes even the peroxides completely decomposed and the addition of monomer to polymeric radicals was the rate-controlled step for the graft copolymerization.

Neodymium oxide co-catalyzed melt free radical grafting of maleic anhydride onto co-polypropylene by reactive extrusion

Rare earth oxide, neodymium oxide (Nd2O3), CO-catalyzed melt grafting of maleic anhydride (MAH) onto co-polypropylene (co-PP) in the presence of dicumyl peroxide (DCP) was carried out by reactive extrusion. The experimental results reveal that the addition of Nd2O3 as a coagent leads to an enhancement in both MFR and the grafting degree of MAH, along with a simultaneous decrease in the gel content. When the Nd2O3 concentration is 6.0 mmol%, the increment of the grafting degree of MAH maximally is up to about 20% compared with the related system without adding Nd2O3, and the gel content decreases simultaneously to a very low level of about 3%. Attenuated total reflection FTIR (ATR-FTIR) indicates that the gel in the graft copolymers mainly arise from the cross-linking reaction between ethylene units of co-PP. A reasonable reaction mechanism has been put forward on the basis of our experimental results and other mechanisms reported in the literature. We also tentatively explain above results by means of synergistic effect between DCP and Nd2O3, which causes a higher concentration of the macroradical, in particular the tertiary macroradical.

Neodymium oxide-assisted melt free-radical grafting of maleic anhydride on isotactic-polypropylene by reactive extrusion

Rare earth oxide, neodymium oxide (Nd2O3), -assisted melt free-radical grafting of maleic anhydride (MAH) on isotactic-polypropylene (i-PP) was carried out by reactive extrusion. The experimental results reveal that the addition of Nd2O3 into reactive system leads to an enhancement of the grafting degree of MAH, along with an elevated degradation of i-PP matrix. When Nd2O3 content is 4.5 mmol %, the increment of the grafting degree of MAH (maximally) is up to about 30% compared with that of the related system without adding Nd2O3, while the severest degradation of i-PP matrix simultaneously occurs. On the basis of the reaction mechanism of PP-g-MAH proposed before, the sequence of beta-scission and grafting reaction is discussed in detail. It is found that, for the reactive system studied, most tertiary macroradicals first undergo beta-scission, and then, grafting reaction with MAH takes place at the new radical chain ends. The imported Nd2O3 has no effect on the aforementioned reaction mechanism, whereas it enhances the initiating efficiency of the initiator, dicumyl peroxide (DCP).