Behavior of ar plasma formed in a high-density plasma source - an ecr reactor

In order to develop the ultra-large scale integration(ULSI), low pressure and high density plasma apparatus are required for etching and deposit of thin films. To understand critical parameters such as the pressure, temperature, electrostatic potential and energy distribution of ions impacting on the wafer, it is necessary to understand how these parameters are influenced by the power input and neutral gas pressure. In the present work, a 2-D hybrid electron fluid-particle ion model has been developed to simulate one of the high density plasma sources-an Electron Cyclotron Resonance (ECR) plasma system with various pressures and power inputs in a non-uniform magnetic field. By means of numerical simulation, the energy distributions of argon ion impacting on the wafer are obtained and the plasma density, electron temperature and plasma electrostatic potential are plotted in 3-D. It is concluded that the plasma density depends mainly on both the power input and neutral gas pressure. However, the plasma potential and electron temperature can hardly be affected by the power input, they seem to be primarily dependent on the neutral gas pressure. The comparison shows that the simulation results are qualitatively in good agreement with the experiment measurements.

Discovery of non-zero neutrino mixing angle θ_13 using Daya Bay antineutrino detectors

The Daya Bay Reactor Antineutrino Experiment observed the disappearance of reactor $\bar{\nu}_e$ from six $2.9~GW_{th}$ reactor cores in Daya Bay, China. The Experiment consists of six functionally identical $\bar{\nu}_e$ detectors, which detect $\bar{\nu}_e$ by inverse beta decay using a total of about 120 metric tons of Gd-loaded liquid scintillator as the target volume. These $\bar{\nu}_e$ detectors were installed in three underground experimental halls, two near halls and one far hall, under the mountains near Daya Bay, with overburdens of 250 m.w.e, 265 m.w.e and 860 m.w.e. and flux-weighted baselines of 470 m, 576 m and 1648 m. A total of 90179 $\bar{\nu}_e$ candidates were observed in the six detectors over a period of 55 days, 57549 at the Daya Bay near site, 22169 at the Ling Ao near site and 10461 at the far site. By performing a rate-only analysis, the value of $sin^2 2\theta_{13}$ was determined to be $0.092 \pm 0.017$.

Methanol synthesis from CO2 using a silicone rubber/ceramic composite membrane reactor

A one-dimensional isothermal pseudo-homogeneous parallel flow model was developed for the methanol synthesis from CO2 in a silicone rubber/ceramic composite membrane reactor. The fourth-order Runge-Kutta method was adopted to simulate the process behaviors in the membrane reactor. How those parameters affect the reaction behaviors in the membrane reactor, such as Damkohler number Da, pressure ratio p(r), reaction temperature T, membrane separation factor alpha, membrane permeation parameter phi , as well as the non-uniform parameter of membrane permeation L-1, were discussed in detail. Parts of the theoretical results were tested and verified; the experimental results showed that the conversion of the main reaction in the membrane reactor increased by 22% against traditional fixed bed reactor, and the optimal non-uniform parameter of membrane permeation rate, L-1.opt ,does exist. (C) 2003 Elsevier B.V All rights reserved.

Performance of a mixed-conducting ceramic membrane reactor with high oxygen permeability for methane conversion

A mixed-conducting perovskite-type Ba0.5Sr0.5Co0.8Fe0.2O3-delta (BSCFO) ceramic membrane reactor with high oxygen permeability was applied for the activation of methane. The membrane reactor has intrinsic catalytic activities for methane conversion to ethane and ethylene. C-2 selectivity up to 40-70% was achieved, albeit that conversion rate were low, typically 0.5-3.5% at 800-900 degreesC with a 50% helium diluted methane inlet stream at a flow rate of 34 ml/min. Large amount of unreacted molecular oxygen was detected in the eluted gas and the oxygen permeation flux improved only slightly compared with that under non-reactive air/He experiments. The partial oxidation of methane to syngas in a BSCFO membrane reactor was also performed by packing LiLaNiO/gamma -Al2O3 with 10% Ni loading as the catalyst. At the initial stage, oxygen permeation flux, methane conversion and CO selectivity were closely related with the state of the catalyst. Less than 21 h was needed for the oxygen permeation flux to reach its steady state. 98.5% CH4 conversion, 93.0% CO selectivity and 10.45 ml/cm(2) min oxygen permeation flux were achieved under steady state at 850 degreesC. Methane conversion and oxygen permeation flux increased with increasing temperature, No fracture of the membrane reactor was observed during syngas production. However, H-2-TPR investigation demonstrated that the BSCFO was unstable under reducing atmosphere, yet the material was found to have excellent phase reversibility. A membrane reactor made from BSCFO was successfully operated for the POM reaction at 875 degreesC for more than 500h without failure, with a stable oxygen permeation flux of about 11.5 ml/cm(2) min. (C) 2001 Elsevier Science B.V. All rights reserved.

Thin-zone TAP reactor as a basis of �state-by-state transient screening

Thin-zone TAP reactor is presented as a basis of the new state-by-state transient screening approach which has been proposed by the authors for non-steady-state kinetic characterization of industrial catalysts. The general thin-zone TAP reactor model is described, and its mathematical status is justified analytically. It is shown that this model provides high enough accuracy to be applicable in the wide conversion interval (up to 90%), which is an important advantage of this approach compared with the traditional differential reactor.

Multi-zone TAP-reactors theory and application - IV. Ideal and non-ideal boundary conditions

We study the influence of non-ideal boundary and initial conditions (BIC) of a temporal analysis of products (TAP) reactor model on the data (observed exit flux) analysis. The general theory of multi-response state-defining experiments for a multi-zone TAP reactor is extended and applied to model several alternative boundary and initial conditions proposed in the literature. The method used is based on the Laplace transform and the transfer matrix formalism for multi-response experiments. Two non-idealities are studied: (1) the inlet pulse not being narrow enough (gas pulse not entering the reactor in Dirac delta function shape) and (2) the outlet non-ideality due to imperfect vacuum. The effect of these non-idealities is analyzed to the first and second order of approximation. The corresponding corrections were obtained and discussed in detail. It was found that they are negligible. Therefore, the model with ideal boundary conditions is proven to be completely adequate to the description and interpretation of transport-reaction data obtained with TAP-2 reactors.

Dilute acid hydrolysis of cellulose and cellulosic bio-waste using a microwave reactor system

The dilute acid hydrolysis of grass and cellulose with phosphoric acid was undertaken in a microwave reactor system. The experimental data and reaction kinetic analysis indicate that this is a potential process for cellulose and hemi-cellulose hydrolysis, due to a rapid hydrolysis reaction at moderate temperatures. The optimum conditions for grass hydrolysis were found to be 2.5% phosphoric acid at a temperature of 175 degrees C. It was found that sugar degradation occurred at acid concentrations greater than 2.5% (v/v) and temperatures greater than 175 degrees C. In a further series of experiments, the kinetics of dilute acid hydrolysis of cellulose was investigated varying phosphoric acid concentration and reaction temperatures. The experimental data indicate that the use of microwave technology can successfully facilitate dilute acid hydrolysis of cellulose allowing high yields of glucose in short reaction times. The optimum conditions gave a yield of 90% glucose. A pseudo-homogeneous consecutive first order reaction was assumed and the reaction rate constants were calculated as: k(1) = 0.0813 s(-1); k(2) = 0.0075 s(-1), which compare favourably with reaction rate constants found in conventional non-microwave reaction systems. The kinetic analysis would indicate that the primary advantages of employing microwave heating were to: achieve a high rate constant at moderate temperatures: and to prevent 'hot spot' formation within the reactor, which would have cause localised degradation of glucose.

Non-invasive VHF monitoring of low-temperature atmospheric pressure plasma

A real-time VHF swept frequency (20–300 MHz) reflectometry measurement for radio-frequency capacitive-coupled atmospheric pressure plasmas is described. The measurement is scalar, non-invasive and deployed on the main power line of the plasma chamber. The purpose of this VHF signal injection is to remotely interrogate in real-time the frequency reflection properties of plasma. The information obtained is used for remote monitoring of high-value atmospheric plasma processing. Measurements are performed under varying gas feed (helium mixed with 0–2% oxygen) and power conditions (0–40 W) on two contrasting reactors. The first is a classical parallel-plate chamber driven at 16 MHz with well-defined electrical grounding but limited optical access and the second is a cross-field plasma jet driven at 13.56 MHz with open optical access but with poor electrical shielding of the driven electrode. The electrical measurements are modelled using a lumped element electrical circuit to provide an estimate of power dissipated in the plasma as a function of gas and applied power. The performances of both reactors are evaluated against each other. The scalar measurements reveal that 0.1% oxygen admixture in helium plasma can be detected. The equivalent electrical model indicates that the current density between the parallel-plate reactor is of the order of 8–20 mA cm-2 . This value is in accord with 0.03 A cm-2 values reported by Park et al (2001 J. Appl. Phys. 89 20–8). The current density of the cross-field plasma jet electrodes is found to be 20 times higher. When the cross-field plasma jet unshielded electrode area is factored into the current density estimation, the resultant current density agrees with the parallel-plate reactor. This indicates that the unshielded reactor radiates electromagnetic energy into free space and so acts as a plasma antenna.

Enhancement of the stability of microporous silica films in non-aqueous solvents at elevated temperature

The effect of Al incorporation and pH adjustment during hydrolysis of the silica precursor on the thermal and structural stability of ordered microporous silica films with a 2D structure is presented. The structural stability of the films was determined from a combination of LA XRD/TEM data with porosity data obtained from ethanol adsorption isotherms. Thermogravimetric analysis and MR data were used to determine the template removal and the thermal stability. Stability of aluminium incorporated silica films has further been examined in several organic solvents with different polarity. A solvent with a higher polarity interacts more strongly with the films; the long-order structure disappeared after exposure to polar solvents. After exposure to non-polar solvents, the pore size uniformity was retained after 48 h. The samples with an Al/Si ratio of 0.007 showed the smallest d-spacing shift after exposure to hexane. The stability was further tested in the hydrogenation of phenylacetylene performed in a batch reactor over 1 wt.% Pd/Si(Al)O-2/Si (Al/Si = 0.007) films at 30 degrees C and 10 bar H-2 with hexane as solvent. No deactivation was observed in two subsequent hydrogenation runs. (C) 2009 Elsevier Inc. All rights reserved.

Optimization of heat transfer characteristics, flow distribution, and reaction processing for a microstructured reactor/heat-exchanger for optimal performance in platinum catalyzed ammonia oxidation

The present work is focused on the demonstration of the advantages of miniaturized reactor systems which are essential for processes where potential for considerable heat transfer intensification exists as well as for kinetic studies of highly exothermic reactions at near-isothermal conditions. The heat transfer characteristics of four different cross-flow designs of a microstructured reactor/heat-exchanger (MRHE) were studied by CFD simulation using ammonia oxidation on a platinum catalyst as a model reaction. An appropriate distribution of the nitrogen flow used as a coolant can decrease drastically the axial temperature gradient in the reaction channels. In case of a microreactor made of a highly conductive material, the temperature non-uniformity in the reactor is strongly dependent on the distance between the reaction and cooling channels. Appropriate design of a single periodic reactor/heat-exchanger unit, combined with a non-uniform inlet coolant distribution, reduces the temperature gradients in the complete reactor to less than 4degreesC, even at conditions corresponding to an adiabatic temperature rise of about 1400degreesC, which are generally not accessible in conventional reactors because of the danger of runaway reactions. To obtain the required coolant flow distribution, an optimization study was performed to acquire the particular geometry of the inlet and outlet chambers in the microreactor/heat-exchanger. The predicted temperature profiles are in good agreement with experimental data from temperature sensors located along the reactant and coolant flows. The results demonstrate the clear potential of microstructured devices as reliable instruments for kinetic research as well as for proper heat management in the case of highly exothermic reactions. (C) 2002 Elsevier Science B.V. All rights reserved.

A kinetic study of ammonia oxidation on a Pt catalyst in the explosive region in a microstructured reactor/heat-exchanger

The application of an aluminum-based microstructured reactor/heat-exchanger for measuring reaction kinetics in the explosive region is presented. Platinum-catalyzed ammonia oxidation was chosen as a test reaction to demonstrate the feasibility of the method. The reaction kinetics was investigated in a wide range of conditions [NH3 partial pressure: 0.03-0.20 atm, O-2 partial pressure: 0.10-0.88atm; reactant flow 2000-3000 cm(3) min(-1) (STP); temperature 240-360degreesC] over a supported Pt/Al2O3 catalyst (mass of Al2O3 layer in the reactor, 1.95 mg; Pt/Al molar ratio, 0.71; Pt dispersion, 20%). The maximum temperature non-uniformity in the microstructured reactor was ca. 5degreesC, even at conditions corresponding to an adiabatic temperature rise of 1400degreesC. Based on the data obtained, a previous kinetic model for ammonia oxidation was extended. The modified 13-step model describes the data in a considerably wider range of conditions including those with high ammonia loadings and high reaction temperatures. The results indicate the large potential of microstructured devices as reliable tools for kinetic research of highly exothermic reactions.

Numbered-up gas-liquid micro/milli channels reactor with modular flow distributor

Gas-liquid processing in microreactors remains mostly restricted to the laboratory scale due to the complexity and expenditure needed for an adequate numbering-up with a uniform flow distribution. Here, the numbering-up is presented for multi-phase (gas-liquid) flow in microreactor suitable for a production capacity of kg/h. Based on the barrier channels concept, the barrier-based micro/milli reactor (BMMR) is designed and fabricated to deliver flow non-uniformity of less than 10%. The BMMR consists of eight parallel channels all operated in the Taylor flow regime and with a liquid flow rate up to 150. mL/min. The quality of the flow distribution is reported by studying two aspects. The first aspect is the influence of different viscosities, surface tensions and flow rates. The second aspect is the influence of modularity by testing three different reaction channels type: (1) square channels fabricated in a stainless steel plate, (2) square channels fabricated in a glass plate, and (3) circular channels (capillaries) made of stainless steel. Additionally, the BMMR is compared to that of a single channel regard the slug and bubble lengths and bubble generation frequency. The results pave the ground for bringing multi-phase flow in microreactor one step closer for large scale production via numbering-up. © 2012 Elsevier B.V.

Transient distributions of composition and temperature in a gas-solid packed bed reactor by near-infrared tomography

Near-infrared diffuse tomography was used in order to observe dynamic behaviour of flowing gases by measuring the 3D distributions of composition and temperature in a weakly scattering packed bed reactor, subject to wall effects and non-isothermal conditions. The technique was applied to the vapour phase hydrogen isotopic exchange reaction in a hydrophobic packing of low aspect ratio made of platinum on styrene divinyl benzene sulphonate copolymer resin. The results of tomography revealed uneven temperature and composition maps of water and deuterated water vapours in the core-packed bed and in the vicinity of the wall owing to flow maldistribution. The dynamic lag between the near-wall water vapour and deuterated water vapour compositions were observed suggesting that the convective transfer which was significant near the wall at the start, owing to high porosity, was also effective at large conversions. (C) 2012 Elsevier B.V. All rights reserved.

Design of a radio frequency heated isothermal micro-trickle bed reactor

A near-isothermal micro-trickle bed reactor operated under radio frequency heating was developed. The reactor bed was packed with nickel ferrite micro-particles of 110. μm diameter, generating heat by the application of RF field at 180. kHz. Hydrodynamics in a co-current configuration was analysed and heat transfer rates were determined at temperature ranging from 55 to 100. °C. A multi-zone reactor bed of several heating and catalytic zones was proposed in order to achieve near-isothermal operations. Exact positioning, number of the heating zones and length of the heating zones composed of a mixture of nickel ferrite and a catalyst were determined by solving a one dimensional model of heat transfer by conduction and convection. The conductive losses contributed up to 30% in the total thermal losses from the reactor. Three heating zones were required to obtain an isothermal length of 50. mm with a temperature non-uniformity of 2. K. A good agreement between the modelling and experimental results was obtained for temperature profiles of the reactor. © 2013 Elsevier B.V.

Kinetics of the photocatalysed oxidation of NO in the ISO 22197 reactor

The photocatalytic reactor described in the NOx removal ISO 22197-1:2007 is used to study the kinetics of the process, using a film of P25 TiO2 which has either been conventionally pre-irradiated in a stream of air, or unconventionally in a stream of NO (1 ppmv). In the former case it is shown that the system does not achieve steady state exit levels of NO, probably due to the gradual accumulation of HNO3 on the surface of the photocatalyst. The NO-preconditioned TiO2 film demonstrated excellent steady-state levels when monitored as a function of NO concentration, [NO] and UV irradiance, ρ. However, in this case the photocatalytic reaction under study is NOT NOx removal, but the conversion of NO to NO2. It is shown that the kinetics of this steady state process fit very well to a kinetic expression based on a disrupted adsorption reaction mechanism, which has also been used by others to fit their observed (non-steady state) kinetics for NOx removal on conventionally-(air) preconditioned films of P25. The appropriateness of this model for either system is questioned, since in both systems the kinetics appear to have a significant mass transport element. These findings suggest that mass transport and non-steady-state kinetics are likely to be significant features for most active photocatalytic samples, where the %NO conversion is >7%, and so limits the usefulness of the NOx removal ISO 22197-1:2007.