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By Bowen Li

Copper vermiculite is a special nanomaterial with excellent antibacterial and antifungal performance. By means of ion exchange, copper vermiculite containing up to 5.8wt% copper was prepared. The chemical and mineralogical characterization of the material was investigated in this study based on the XRD, AAS, TEM and EDS analysis, as well as the calculation of crystalline parameters and crystal chemical formula. Cu2+ and Mg2+ have similar atom radius and same electrovalence. Correspondingly, the structure character of copper vermiculite is very close to that of standard Mg-vermiculite. Most of the CU21 may have occupied the interlayer cationic positions in the form of hydrate in vermiculite. However, some may have entered into octahedral coordinate positions. The values of au and bo of the copper vermiculite crystal cell have no obvious change compared to that of original vermiculite micropowder, but the Co value decreased slightly, which is desirable for the stabilization of the Cu2+ in copper vermiculite.

Jan 1, 2003

By Susumu Okabe, Etsuji Kimura

"The Mitsubishi Continuous Copper Smelting and Converting Process is the typical applications of injection metallurgy to nonferrous metallurgical operation, where the top blowing multiple lance system is employed for the continuous feeding of the raw materials and reaction gases into the molten bath. This results in an effective dispersion of the reactants into a strongly agitated bath. These are considered as the major advantage of the process with respect to the high production efficiency. On the other hand, however, the strong agitation may cause a considerable amount of refractory wear, and the melt splash generated by the lancing may also have negative effects on the productivity, i.e. the increase in the refractory wear, the metal loss, the heat loss, and the accretion growth, etc. Therefore, the optimization of the blowing condition as wen as furnace design is very important to achieve a stable and efficient operation, and fundamental understanding of the injection, agitation, and splashing is badly needed.In this paper, fundamental aspects of the Mitsubishi Process regarding injection, especially splashing phenomena, are discussed. The splashing on a vertical plane caused by the top blowing gas injection onto liquid surface was investigated through physical model study. As a result of the study, the splashing rate on the furnace wan was wen correlated with the physical properties of the bath materials, gas velocity, cavity shape, lance/wall distance and ceiling position. Obtained equations were compiled in a computer program and have been successfully applied to the evaluation of the furnace design. IntroductionInjection metallurgy is an application of gas/solid-in-liquid dispersing operation to the metallurgical processing, and has been widely adopted in various fields in order to improve their efficiency or productivity. The dispersed small particles of gas or solid materials in the liquid phase result in increased interface area, and injected momentum causes an agitation and enhanced heat and materiel transfer. Typical examples of injection metallurgy are LD converter for steel making, PS converter, Noranda process, Isasme1t for copper making, and Mitsubishi Material's continuous copper smelting and converting process, and so on."

Jan 1, 1996

By Tatsuo Inoue, Marnoru Mizuno, Toru Matsuoka, Kenichiro Abe

"The distribution of particle reinforcements and the residual stresses in metal matrix composite are simulated by considering the motion of particles and the solidification of matrix associated with temperature variation in the course of centrifugal casting process. In the analysis, a heat conduction equation including heat generation due to latent heat and also mechanical work as well as heat input from successively accumulated element on the air/metal boundary is solved by the finite element technique. After the movement of particles subjected to the centrifugal force and drag are analyzed, the residual stresses are elucidated by using a unified constitutive equation which can describe the behavior both in liquid and solid states. Results of the simulation are compared with the experimental data, and the validity and utility of the procedure is confirmed.IntroductionProcess simulation of metal matrix composite (MMC) is required to determine the mechanical properties of the materials and the efficient process and conditions of the fabrication. Properties of bonding matrix with reinforcements in the course of the processing, for example, affects the strength of the composite, while the final costs of the productions depends on the efficiency of fabrication. Therefore, the simulation of processing of MMC is prerequisite in order to clarify the mechanism to fabricate the material which has been expected to maintain high mechanical properties and the cost performance.Some techniques of processing MMC[l] have been developed so far. Among them, the centrifugal casting technique [2-5] has many attractive characteristics as processing of the MMC: The centrifugal casting technique makes the reinforcements such as particles or short fibers to be distributed in the radial direction by the centrifugal force acting on reinforcements due to the difference in density between reinforcements and matrix. Since the distribution of reinforcements affect the mechanical properties of MMC, the composite with functionally gradient mechanical properties can be provided by the centrifugal casting technique."

Jan 1, 1994

By B. Q. Li, R. A. Mirshams

"A numerical algorithm is described for the simultaneous prediction of the thermomechanical behavior of the materials and microstructure evolption during metal forging. The numerical development is based on the finite element solution of the thermoviscoplastic deformation of metals coupled with the internal state variable model describing the microstructure evolution involving work hardening, recovery, recrystallization and grain size distribution. The finite element code for rigid viscoplastic deformation is developed based on the modification of the existing code for the thermal and fluid flow calculations. The code is tested against and compares well with the results reported in literature. The procedures for the integration of the · rnicrostructure model into the macro finite element model are described. Results are presented showing the characteristics of materials dynamics and mechanical deformation during simple metal forging processes.IntroductionIn industrial deformation processes such as hot rolling and forging, the workpiece undergoes both macroscopic plastic deformations and microstructural evolution. A computer model that allows to predict both materials dynamics and macroscopic deformation is obviously more useful for both fundamental understanding and deformation process optimization. For some industrial applications, especially those involving novel, light and high strength materials, such an integrated model is critical in that both materials and thermomechanical 'behavior during forging must be carefully controlled to obtain the products that meet the desired strength requirement [I]."

Jan 1, 2000

By T. T. Natarajan, Nagy EI-Kaddah

"Numerical simulation of electromagnetic confinement systems generally requires large CPU time due to the strong coupling between the electromagnetic and the free boundary problems. The present paper examines the accuracy and the computational efficiency of the most common numerical schemes used in modeling such systems. Levitation melting was taken as a test case. In this study, a comparison was made between the finite element and surface integral methods for electromagnetic field calculations. The computational efficiency of Lagrange and the modified Hestenes methods for solving the free boundary problem were investigated. The convergence of the Lagrange method was found to be much faster than the modified Hestenes method. It was also found that finite element method not only gives accurate solutions, but faster convergence to the final equilibrium shape than the surface integral method. The applications and the limitations of these techniques in modeling electromagnetic confinement systems will be discussed.IntroductionIn recent years there has been a growing interest in the use of electromagnetic forces for confinement of molten metals as a means to eliminate molten metal contamination during melting and to improve surface quality of cast products. Continuous casting of metal without contact of a mold is now a reality, and is being commercially applied for casting of aluminum slabs /1/, and copper rods /2/. New applications of electromagnetic confinement in melting and casting include containerless melting (Magnetic Suspension Melting) /3/, edge containment in twin roll casting, and meniscus shape control in continuous casting of steel /4/.Modeling of confinement systems involves the determination of the electromagnetic field and the equilibrium shape. These two problems are strongly coupled due to the dependence of the field on the shape of the melt. While significant advances have been made in computational electromagnetics /5/, the application of developed computational techniques to electromagnetic confinement problems is not a simple task. The principal difficulty in using these methods is that the solution domain is not known a priori. due to coupling between the electromagnetic field and the free boundary problems. These two problems have to be solved simultaneously, leading to an iterative solution procedure. As a result, numerical simulation of electromagnetic confinement systems are computationally intensive with computational time at least an order of magnitude larger than the fixed domain problems."

Jan 1, 1994

By Yongyong Gong, Qijie Zhai, Zhichen Zhang, Qixin Li, Zhishuai Xu

"Microstructure of semisolid slurry of Al-4.5wt.%Cu alloy was investigated with pulse magnetooscillation (PMO) treatment, the results showed that the PMO treatment can refine the crystal structures of Al-4.5wt.%Cu alloy significantly. The discharging frequency of PMO had a great effect on the solidified structure transformation of semisolid slurry of Al-4.5wt. %Cu alloy, and the primary a-Al particles become much finer and rounder with an increase of discharging frequency. However, over a certain discharging frequency, the grains of primary a-Al become coarse.IntroductionOver the last decade, a lot of attentions have been paid on metal rheoforming process [1-4], since it has higher mechanical properties of formed components, strength to weight ratio and age hardenablity. Nevertheless, semi-solid forming is always performed at high solid fractions (40%-60%), so it has the limitation of viscosity, a tends to be difficult to pour semisolid slurry into the hole of the shot sleeve. Therefore, a series of novel semi-solid slurry preparation methods and rheoforming techniques have been invented, such as, semisolid vibration treatment [5], rheocasting [6], pulsed magnetic field process [7], annulus electromagnetic stirring [8], via ultrasonic vibration process [9], equal channel angular extrusion (ECAE) process [l0] and straininduced melt activation (SIMA) process [11].The electromagnetic field is characterized by its effective grain refinement, green, convenient manipulation and without contamination of melt. The mechanisms of dendrite was fragmentation by electromagnetic field have also been largely proposed [12-14]. The broken dendrite arms then undergo a coarsening process to provide the globular structures and obtain much finer and rounder a-Al particles. When compared with other external electromagnetic techniques, Pulse Magneto-Oscillation (PMO) has obtained more fuvors, owing to narrower pulse width and much lower energy consumption. Furthermore, the PMO treatment can reach finer grains with shorter time treatment [16, 17]. This work aims to study the effects of different discharging frequency ofPMO treatment on the microstructure transition of the semisolid slurry of Al-4.5 wt.%Cu alloy."

Jan 1, 2014

By James M. Fragomeni

"The mechanical behavior of an Al-Li alloy was studied and related to the extrusion processing parameters, the plastic metal flow during defonnation, the anisotropy, and the microstructure. The extrusion temperatures, strain rates, extrusion ratios, billet temperatures, and extrusion geometries were varied during processing and correlated with the microstructure and properties. The extrusion processing variables were related to the mechariicar behavior, anisotropy, and microstructure through the ZenerHollomon parameter i.e., the temperature compensated strain rate. Based on optical and electron microscopy studies it was found that regardless of the extrusion conditions, the various microstructures for the most part were unrecrystallized for both the as-extruded and the solution heat-treated conditions. Smaller grain sizes were correlated to larger Zener-Hollomon parameters. The extrusion temperature and ratio did not significantly affect the strength or ductility as did the section geometry, which had a large affect on these mechanical properties. The anisotropy of the properties varied substantially when comparing the extruded longitudinal versus transverse grain orientations.IntroductionThe extrusion process also has a substantial influence on: the microsfructure and mechanical properties of a material that is Athens, Ohio, 45701 fonned The plastic defonnation that occurs during the extrusion process alters the grain size, crystallographic texture, anisotropy, subgrain size, dislocation density and various other microstructural features. Often the material being extruded is not homogeneous, therefore variations in the microstructure and properties occur across the cross-section of the final extruded product. The mechanical properties and microstructure can also vary with length since it is hard to maintain a constant temperature throughout the extrusion process. The extrusion temperature often varies from the heat generated during the extrusion process. The demonstration material that was extruded for this .study was an aluminum alloy containing 2.6wt, % lithium and 0.09wt.% zirconium. This alloy was strengthened by heat treatment causing nucleation, growth, and coarsening of coherent metastable o' (Al3Li) precipitates in the microstructure. The ? precipitates which are a consequence 9f artificially aging the AlLi alloy, are spherical, ordered, and coherent with the aluminum matrix and impede the dislocation glide inotion during plastic defonnation. Theo particles grow homogeneously in the matrix, and have the Cu3Au (L 12)"" superlattice crystal structure. Aluminum-lithium alloys are used primarily for aerospace structural applications since they have attractive properties such as a lower density and higher elastic modulus than conventional 2XXX and 7XXX alloys."

Jan 1, 2000

By Qin Li

An highly active absorbent with oxidization based on fly ash, lime and additives was prepared. Experiments of simultaneous desulphurization and denitrification were carried out using fixture bed and duct injection. The influential factors for the absorptive capacity of the absorbent were studied. The absorptive capacities of 120.7mg for SO2 and 43.7 mg for NOx were achieved at a Ca/(S + N) molar ratio 1.2, respectively, corresponding removal efficiencies of 87% and 76%, while spent absorbent appeared in the form of dry powder. The optimal temperature and humidity of flue gas treated with this process were shown to be approximately 50\\176 and 5% respectively. The mechanism of removal for SO2 and NOx was investigated. In comparison with traditional dry FGD, this process appears to have lower cost, less complicated configuration and simpler disposal of used absorbent. The valuable references can be provided for industrial application by this process. The foreground of application will be vast in China and in the world.

Jan 1, 2006

By Sui Xue

A process has been developed from laboratory-scale experiments for the aqueous processing of various lead-bearing wastes. The process exploits the limited solubility of lead in sulfate-rich solutions to effectively separate lead from other metals. The lead sulfate is then completely converted to lead carbonate using sodium carbonate and ammonium carbonate. The effectiveness of this conversion was observed to be sensitive to the solution pH and carbonate concentration. The final stage of the process uses low temperature calcination of the lead carbonate to form PbO. Yellow lead oxide (massicot) is readily formed if calcination is conducted at a temperature at or iibove 50G°C, wlule red iead oxide (iitharge) is formed at temperatures near 450°?C. A complete economical analysis of the process will be discussed.

Jan 1, 1996

By H. Saint-Raymond, F. Gruy, P. Gardin, M. Cournil

"The control of inclusion elimination is getting more and more important to obtain clean steel. This paper presents a methodology under development for predicting cluster growth and elimination in ladle - RH system. The first key point is to express the collision efficiency, which is very specific for alumina cluster due to the non-wetting fluid. Second, a description of the two-phase flow in the system is necessary. In our calculations with Fluent CFD package and Lagrangian approach for bubbles, bubble growth is implemented, which improves the predictions. Using global reactor decomposition makes possible the prediction of the time evolution of cluster distribution. Important effect of fractal dimension is demonstrated.IntroductionElaboration of new steel grades requires not only to have a high purity in terms of C, O and N content but also to eliminate particles such as alumina or slag droplets. Flow optimisation making easier inclusion elimination is then a key figure to satisfy cleanliness requirements. Mathematical models of flow and inclusion behaviour are widely used for this purpose (1, 2). But having a predictive tool is still a challenge, because the number of phases is important in steelmaking industry: liquid steel, slag layer, bubbles and inclusions (with a large range of composition and rheology). The paper presents the methodology which is developed at IRSID to predict oxygen content evolution during RH degassing.The main mechanisms which have to be considered are :-inclusion growth by turbulent aggregation of elementary inclusions (keeping in mind that liquid steel is a non-wetting medium for inclusions); the difficulty is to express collision efficiency for alumina particles,-inclusion removal by flotation; the difficulty for alumina clusters stems from the complex morphology of particle; fortunately, the use of fractal concept makes it possible to cope with this problem.The paper describes the general modelling of inclusion removal taking into account the previous mechanisms. Hydrodynamic parameters are obtained by means of Fluent CFD package and a specific coding is developed for cluster growth."

Jan 1, 2001

By K. Narayan Prabhu, W. D. Griffiths

"Heat transfer during the unidirectional solidification of a cast iron alloy against cast iron chills was investigated using an inverse modelling approach. Chills of thickness 100 mm and 10 mm were used, to simulate gravity die cruiting conditions and the use of chills in sand moulds. In both cases transient heat transfer, measured by the interfacial heat flux and heat transfer coeffieient; declined from initially high values in the first few seconds of solidification, to values about an order of magnitude lower which persisted for the remainder of the experiments. In the case of the thin chill it became saturated with heat until it was no longer in a position to extract further heat from ·the casting. These results were interpreted by studying the resistance to heat transfer from the casting offered by the ·casting-chill interface and the chill itself for example, the thermal resistance of the casting-chill interface can be influenced by the deformation of their respective surfaces and their subsequent relationship.IntroductionDie casting cast iron offers several advantages such as energy savings, higher mould yield, and better surface quality over the sand casting process1 • The process is· environmentally' friendly because of the elimination of the sand. However the design and construction of metallic moulds is expensive and a faulty die design may result in a defective casting: A simulation based process design of die castings would enable die designers and solidification modellings to try better designs of dies on the computer and arrive at a cost effective solution more quickly. This has numerous benefits for the die caster, as he would be able to produce sound castings with very short lead times.The success of a solidification model to predict accurately the thermal history and the location of hot, spots inside a solidifying casting depends to a large extent on the heat transfer data prescribed at the metal/mould interface. Many measurements of the heat transfer coeffident (or the heat flux) between a solidifying aluminum alloy and a chill have shown that the heat transfer coefficient is a function of most of the variables of the casting process2 - 8. However heat transfer studies during the solidification of ferrous alloys are rather limited. The high temperatures involved suggest that the contribution due to radiation heat transfer cannot be neglected."

Jan 1, 2000

By Fumito Tanaka

The Mitsubishi process is the sole pyrometallurgical process for the continuous production of blister copper from copper concentrates and has been successfully operated around the world. The development of calcium ferrite slag (CaO-FeOx-Cu20), the so-called "C-slag", has enabled continuous converting from matte to blister copper in the commercial scale operations. Commercial interests in the slag led to many papers over the CaO-FeOx slag. However, CU2O- bearing slag has not been studied well due to experimental difficulties. The authors have quantified the thermodynamic properties ofthe CaO-FeOx-Cu2O system. The results have been utilized to analyze various issues related to the converting furnace, such as the magnetite precipitation from the slag or from blister copper and to develop better controlling criteria for the continuous converting operation.

Jan 1, 2003

By Broggi Andrea

Condensates produced by SiO(g) and CO(g) have a crucial importance in silicon production. Condensation will follow the reactions 3 SiOðgÞ+COðgÞ→ 2 SiO2 + SiC and 2 SiO ðgÞ→Si+SiO2. Solid compounds generated during silicon production contain Si, SiO2 and SiC in different microstructures and amounts. In industrial systems, condensates limit the SiO(g) escape to the off-gas system. On the other hand, they can block the gas flowing from the high temperature zone, hence the necessity of studying an optimized condensation process. This review discusses SiO(g) condensation and its interaction with CO(g). The report gives an overview of the condensates found both at laboratory and at industrial scale. The two main compounds are the Si–SiO2 and the SiOx–SiC mixtures. The hypothesis on the mechanism of formation of SiC–SiOx condensates is presented through a wide selection of performed works. The advantages and disadvantages of the former experimental procedures are discussed.

By Guo Xueyi

The environmental impact assessment of the Imperial Smelting Process for metallic zinc and lead production in Shaoguan Smelter, China, was carried out by the life cycle assessment method. The detailed inventory analysis of the Input/Output in the process during 1998-2000 was conducted and the allocation was done among the main products of zinc, lead and sulfuric acid, according to the system expansion and substitution principle, The environmental impacts were assessed by using the following five Eco-indicators: Gross Energy Requirement (GER), Global Warming Potential (GWP), Acidification Potential (AP), Heavy Metal Toxicity (HMT) and Solid Waste Burden (SWB). The results from this study are useful to address the environmental situation of the technology practice in this smelter, and provide a scientific basis for the further improvement.

Jan 1, 2003

By Caisa Samuelsson

Experimental studies in laboratory-scale equipment have been carried out to study the vaporisation from dust generated during the copper converting process. In the present work the vaporisation of Zn, Pb, As, Sb, and Bi from a dust collected in the electrostatic precipitator after the copper converter were studied. The results show that Pb, Bi and As were vaporised to a high degree from the dust at a temperature above 900°C in a gas containing N2, SO2 and a small amount of H2. The vaporisation was high for these elements also in a gas containing N2, SO2 and 02 at temperatures above 1120°C. In an earlier study, thermodynamic calculations showed that it is possible to selectively condense metals at high temperature' in a gas atmosphere generated during a copper converting process. The present study was carried out to verify the thermodynamic model. The results indicate that it should be possible for a selective condensation of Zn at high temperature. The temperature required for a selective condensation of Zn is dependent upon the gas atmosphere, e.g., the oxygen potential.

Jan 1, 1998

By Jacqueline JAlexander

Two of the most important phenomena which govern the continuous casting process and determine the quality of the product are the fluid flow and the heat transfer. Steel flows into the mold through the ports of a bifurcated submerged entry nozzle (SEN), which directs the jet to the mold narrow faces where the superheat contained is dissipated on the solidifying shell. Many important aspects of the fluid flow in the mold are transient and difficult to control. However, the time-averaged flow pattern in the mold is greatly influenced by the nozzle geometry, the submergence depth and the mold dimensions. The aim of this work is to analyze the relationship between the heat transfer and the fluid flow pattern inside the mold using the CFD technique at several operating conditions.

Jan 1, 2009

By Gunther Schimmel

Ag exudation in four different alloys (Ag-Cd, Ag-Sn, Ag-Sn-In and Ag-Zn) is characterized. The amount of exuded material is correlated with the volume increase due to oxide formation in dependence of the alloy concentration and different densities of the oxide and matrix phases. It is shown that all four alloys show similar amounts of volume increases, but different amounts of exuded material. It is concluded that internal stresses due to the volume increase cannot be the dominant driving force for Ag exudation. A gradient in the chemical potential of Ag that originates from the O concentration gradient inherent to internal oxidation is suggested as driving force. The exudation behavior is thus governed by the variation of the activity of Ag in the Ag fcc phase in the Ag-Me-O system that differs between the alloying systems.

Jan 1, 2010

By Kimiaki Utsunomiya, Yasumasa Hattori, Yoshiaki Mori, Toyokazu Okubo

"The effect of various operating conditions on splashing behavior in a Peirce-Smith converter has been investigated with a 1/5.7 scale cold model. Dynamic similarity between the model and a commercial converter was attained by setting the modified Froude number in the model experiments in· the range for normal converter operation. It is known that for a given modified Froude number the dimensionless penetration length of gas into the liquid phase increases as the liquid density decreases. Moreover, penetration· length has a large effect on splashing behavior. Therefore, a heavy liquid, a mixture of water and lead concentrate was used as the liquid phase. It was concluded that the amount of splash dramatically decreases with a reduction in the buoyancy energy per, unit liquid mass and an increase in the horizontal distance between the tuyere tip and the edge of the mouth.IntroductionSubmerged gas injection is widely used in practice in ferrous and nonferrous pyrometallurgical operations to achieve large gas-liquid contact areas and good agitation of liquid for rapid chemical reaction. The common application in ·nonferrous industry is the Peirce-Smith converter with multi-tuyere for copper and nickel matte converting. This process has been used for over 100 years because of its effectiveness in mixing of the molten bath, as well as its merits of the engineering simplicity. However, the mechanisms which · determine the blowing performance is poorly understood, and the design and operating conditions of the Peirce-Smith converter varies widely from plant to plant, such as by diameter, length, mouth angle, tuyere position and level of molten matte. Smelters have continuously made an effort to increase converter productivity, implying maximum tuyere blowing rate. Above a certain critical blowing rate, splash of molten matte from the converter mouth becomes unacceptable because of dangerous ejection and accretion buildup around the converter mouth, which results in interference with effective hood sealing. In fact, a 1993 converter survey[!] reported that splash was a major limiting factor for blowing rate and 54% of responding plants from around the world regard it as a limiting condition[2]. In order to increase tuyere blowing rate a study of the effect of various operating conditions on splashing behavior is expected."

Jan 1, 2000

By Guy Xueyi

The environmental impact assessment of the Imperial Smelting Process for metallic zinc and lead production in Shaoguan Smelter, China, was carried out by the life cycle assessment method. The detailed inventory analysis of the Input/Output in the process during 1998-2000 was conducted and the allocation was done among the main products of zinc, lead and sulfuric acid, according to the system expansion and substitution principle, The environmental impacts were assessed by using the following five Eco-indicators: Gross Energy Requirement (GER), Global Warming Potential (GWP), Acidification Potential (AP), Heavy Metal Toxicity' (HMT) and Solid Waste Burden (SWB). The results from this study are useful to address the environmental situation of the technology practice in this smelter, and provide a scientific basis for the further improvement.

Jan 1, 2003

By Mamoru Kuwabara

A high-power sound which can transmit through any continuous elastic medium with less attenuation, particularly in liquid allows us to externally control the system of concern by using the acoustic radiation force or the cavitation phenomena. These functions may eliminate gravitational and/or atmospheric constraints which are often encountered in conventional operations for producing clean and advanced materials. This paper outlines the recent development in the field of sonoprocessing of materials. Cold model experiments in some vessels have been performed to simulate ultrasonic operations such as inclusion removal from liquid, degassing of melt, emulsification of two liquid phases, solidification processing, and decomposition of chemical species in waste water. High speed visual imaging is carried out for better understanding of the cavitation phenomena as well as the followed microjets during the processing. The radiation force acting on fine suspending objects in a fluid can be utilized for eliminating or rearranging/orienting the objects in the fluid. Acoustically induced cavitation phenomena in liquid can be utilized as an effective dynamic means to control interfacial phenomena as well as micro- and macro-mixing of liquid. Sonochemical and thermal effects in cavitation multi-bubble can be also useful in a waste water treatment.

Jan 1, 2006