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By Boxun Lu, Juan Wei, Kun Chen, Wanlin Wang, Lejun Zhou

"Slag system is an indispensable part during the continuous casting process, and playing various important roles like absorbing inclusions, modifying heat transfer rate, preventing oxidation of molten steel, etc. to ensure the smooth process and excellent slab quality. However most slags contains more than 8% fluorides which tend to introduce a series of environmental and health problems. This study involves the research of the removal of fluorine through the chemical composition optimization. Through the studies of CCT, DHTT, XRD and SEM, it has been successfully founded that the crystalline phase of Ca11Si4B2O22 discovered in this study shows very similar crystallization property as Cuspidine (Ca4Si2O7F2), which is the most important crystalline phase in the current fluorine bearing slags. Moreover, the optimized free/low fluorine slag shows the opportunity to replace conventional high-fluorine mold slag for casting medium carbon steels that is regarded as the bottleneck of green slag development for continuous casting.IntroductionMold flux has been widely used in continuous casting to control heat transfer, lubricate the strand, absorb inclusions, provide insulation and prevent oxidation of the molten steel[1-3]. It usually contains fluorides, like CaF2, NaF etc., which are used to control the viscosity and solidification temperature of mold fluxes [4-5]. However, the presence of fluoride leads to corrosion of equipment, serious environmental pollution (toxic volatiles and water pollution), and high processing cost of cooling water[6-7]. Therefore, the study of low or free fluorine mold flux is of interest and attracts worldwide attention.S. Y. Choi et al. [4] used B2O3 as a substitute for cuspidine in steel B2PB2) however, B2O3 content was extremely high (up to 30 w%). Other studies have investigated F-free mold flux by adding or optimizing components as MgO, Li2O, B2O3 et al[8-11]. However, most of these focused on the melting and viscosity issues or for low or ultra-low carbon steels, where crystallization tendency is not significantly strong. Very few studies regarding to the development of low/free Fluorine mold flux for casting medium carbon (MC) steels have been conducted, due to the difficulty of the crystallization and heat transfer control without the formation of cuspidine."

Jan 1, 2014

By Craig A. Johnson

Cyanide speciation and behavior have been examined at three active heap leach operations, three heaps undergoing rinsing, and three sites with cyanide contaminated groundwater, all in the southwestern U.S. Data from these studies demonstrate that strong cyanometallic complexes of iron and cobalt can play ?an important role in cyanide behavior throughout the lifetimes of heap leach operations. In active circuits, we find evidence that significant amounts of cyanide combine with iron and cobalt to form strong cyanometallic complexes, and that these species can be adsorbed, probably onto iron hydroxides, or precipitated as insoluble cyanometallic compounds. When spent heaps are rinsed, the release of this cyanide is likely controlled by the slow kinetics of desorption from, or dissolution of, solids that have gone largely uncharacterized. We find evidence that strong cyanometallic complexes can give rise to transient free cyanide in some settings by rapid photo dissociation where heap rinse effluent is exposed to sunlight in open channels or translucent sample bottles. Thus, these species can complicate the ,preparation of spent heaps for decommissioning, even where regulatory standards ?are based on weak acid dissociable cyanide. There is a critical need for information on the form and stability of adsorbed and precipitated cyanide in spent ore heaps, on the concentrations of strong cyanometallic complexes in mineral processing effluents -particularly the complexes of cobalt, and on the natural attenuation of iron and cobalt cyanometallic complexes in both surface and subsurface waters.

Jan 1, 1998

By Kenji Matsuzaki

A mathematical simulation model of the Imperial Smelting Furnace operation has been developed for purpose of improving the furnace operation. The model consists of top, shaft and bottom regions, Analysis in the shaft region is based on differential heat and materials balances taking account of reaction kinetics and heat transfer rates, and those in the top and the bottom regions are based on heat and materials balances under a steady-state condition, Longitudinal distributions of process variables such as temperatures of gas, sinter and coke, gas composition and fractional conversion under a practical operating condition were calculated, With this model, the furnace performance under various operating conditions also can be shown reasonably predicted,

Jan 1, 2003

By Chen Wen, Li Zhao-jia, Zhao Qiang, Ning Shun-ming, Tang Sanchuan, Wang Hong-qiang

"The carbon-burdened and cold-bonded pelletizing-electrosmelting process is used to dispose low-grade manganese, and the qualified rich-manganese slag is obtained. On the condition that reduction roasting temperature was 1000?, reduction time was 45min, particle-size was -1mm, reductant dosage was 1.6%, basicity was 0.3, smelting temperature was 1410?, smelting time was 60min, it had a good effect on the melting between slag and metallographic phase, the manganese content was 32.58%, manganese recovery was 92.16% in the slag; while the iron content was 94.40%, iron recovery was 95.32% in the metallographic phase. It was proved by the demonstration tests.IntroductionManganese is an important raw material for steelmaking, which is extensively utilized in modern industry, the consumption of manganese for iron and steel industry accounts for 90% to 95%. After mining over 30 years, the high-grade manganese resources drop markedly, especially with the hypergrowth of steel industry, the domestic manganese is far from the requirement, as a result, we have to buy significant quantities of manganese overseas. Besides, the property of imported manganese is more and more complex, and the high-grade and lump manganese decrease year by year, while the fines and high-crystal water manganese are on the increase. Therefore, how to make effective use of domestic low-grade manganese and intensify the manganese’s smelting is an effective approach to reduce the cost of manganese series ferroalloy and improves market competitiveness[1-4]. It has important practical meaning."

Jan 1, 2012

By Aichun Dou

Au-Sb alloy sample in which the total amount of Cu and Ni is below 25% (wt. %). In practice, Cu and Ni were difficult to be dissolved in sulphuric acid solution by oxidative leaching under the atmospheric pressure conditions, because of the lower concentration of Cu and Ni in the sample. In this paper, pressure oxidation leaching in sulphuric acid system (POLS) followed by hydrochloric acid leaching (HAL) was employed to remove impurities in the Au-Sb alloy. The effects of variables in POLS on leaching ratios of different metals were investigated in detail. Under the optimal conditions: the concentration of H2SO4 is 1.5 mol/L, liquid-solid ratio is 7:1, the amount of oxidizer is 1.2 times of the theoretical amount, leaching time is 4h and leaching temperature is 427K, the leaching ratios of copper and nickel reached up to 99%, antimony, lead and silver were not dissolved in dilute sulphuric acid solution. The residue from POLS was then treated with hydrochloric acid solution in fixed conditions, the leaching ratio of antimony reached over 92%, the grade of gold in the ultima residue was enriched up to 66%.

Jan 1, 2016

By Chen Song

In the experiments of purifying the solution of chlorine leaching from nickel concentrate with N235, the effects of organic phase composition on purifying efficiency have been studied. From the results obtained, the optimal organic phase composition is found to be 25%N235+12%isomerous alcohol +63%sulfonic kerosene (VIV) and the saturated content of cobalt in organic phase is7.95 g*dm3. And then the serial experiment is carried out. The results show that at the given organic phase composition, the purified solution contains p(Ni) >200 gm dm3, p(Ni)l p(Co) >50000 and the contents of Cu, Fe, Mn, Zn meet the technical criterion of standard nickel electrolyte. The cobalt chloride solution contains p(Co) >I10 g L-1, p(Co) lp(Ni)>50000 and the enrichment of cobalt has been achieved.

Jan 1, 2006

By Qingchun Yu, Bin Yang, Yong Deng, Heng Xiong, Fei Wang, Minxiu Chen

"Metal aluminum produced by non-electrolysis process received much attention due to its lower energy consumption. In this paper, carbothermic reduction and carbothermic-chlorination of alumina in normal pressure and vacuum were studied. The products were examined by means of XRD, EDS and SEM. During the carbothermic reduction process using carbon reductant in normal pressure, no metal aluminum was found. However, when coal was used as reductant, a mixture containing metallic aluminum, A14C3, and silicon was obtained, but metallic aluminum couldn't be separated from the mixture. During the carbothermic-chlorination process in vacuum, Al404C and Al4C3 were produced by the reaction between alumina and carbon, and Al Ch gas reacted with Al404C and Al4C3 to produce Al Cl gas. Metallic aluminum was produced due to the disproportionation of A!Cl gas and condensed on the collecting plate. Meanwhile, the initial temperature of carbothermic reduction of alumina reduced in vacuum compared with that in normal pressure.IntroductionIndustrial production of primary aluminum is carried out in alumina cell by the so-called Hall- Heroult process, necessitating the use of very high currents of low voltage. The alumina from which metallic aluminum is gained must be chemically pure, otherwise impure metal results. The main drawbacks of the electrolytic production are its very high energy consumption, the release ofperfluorocarbons, and the high specific C02 emissions [1]. During the past years, there were a lot of attempts to produce metallic aluminum by carbothermic reduction of A1203 [2, 3]. Cox [4] determined the vapor pressure over the A1203-C system and performed X-ray diffraction analysis of condensed products. It was demonstrated that an increase in the carbon content in the system leaded to the sequence of transitions: A1203~Al404C~A1zoc~A14C3 ~AI [5]. In any carbothermic reduction process for aluminum, extremely high temperatures (2000 °C ) were required [6]. In spite of considerable effort, the carbothermic reduction of alumina to aluminum remains a formidable technical challenge, due to the high temperatures required, and to the formation of aluminum carbide and oxycarbide byproducts [7]."

Jan 1, 2013

By Matti Hämäläinen

Outokumpu has developed a new chloride leaching process, HydroCopper?, for copper concentrates. The process utilizes the cupric ion as oxidant, which is able to dissolve chalcopyrite. After solution purification monovalent copper is precipitated as cuprous oxide, Cu2O, using sodium hydroxide. Copper product is produced from Cu2O by reduction, melting and casting. An essential part of the new process is chlor-alkali electrolysis, which regenerates the reagents used. All impurity metals are removed before Cu2O precipitation, because otherwise they would report to the copper product, impairing its quality. A multistage solution purification scheme has been developed consisting of firstly, chemical precipitation of impurity metals by pH increase, secondly, cementation of silver and thirdly, removal of trace multivalent ions using ion exchange. This paper describes the characteristics of solution purification in the HydroCopper? process based on the laboratory tests and pilot runs made by Outokumpu Research Oy.

Jan 1, 2003

By I. M. Richardson, M. Janssen, I. J. Bennett, V. A. Popovich

The most critical processing step during the manufacture of screen-printed crystalline solar cells is firing aluminium and silver contacts, which generates residual stresses and solar cell bowing. In this paper, an alternative Ag contact formation mechanism is proposed and aspects related to electrical contact properties, residual stresses and layer delamination are investigated. It is found that there are two main processing parameters affecting the uniformity and delamination of the Ag/Si interface, namely the peak firing temperature and the silicon surface roughness. Silicon surface polishing gives a better wetting of the silicon surface by the glass layer, resulting in a good contact and lower incidence of large voids, compared to the case of highly textured surfaces. The non-uniformity in the glass layer and large voids at the Ag/Si interface (in the case of a textured surface) are expected to have a negative effect on the mechanical strength of the solar cell.

Jan 1, 2015

By Marta Cabral, C. A. Nogueira, F. Margarido

"Physical processing of spent batteries which includes shredding and sieving operation is the first step for chemical treatment by hydrometallurgy. A laboratory study was carried out to evaluate physical processing efficiency, by analysing the resulting particle size, of alkaline and saline mignon-type Zn-MnO2 batteries. After shredding with a tip shredder, results obtained showed that alkaline batteries were more efficiently size reduced than saline batteries. Difference in particle size distribution was larger for granulometric fraction -20+11.2 mm and also higher for saline batteries. Average diameters (d50) for saline and alkaline batteries were respectively 9.1 and 6.2 mm. Chemical composition carried out on several granulometric fractions allowed to identify metals distribution through size categories. This analysis showed that zinc concentration with the grain size was almost constant, while manganese decreased when particle size increased. More than 95% of iron scarp from the battery cases had a particle size higher than 5.6 mm.IntroductionRecycling process of spent batteries includes physical unit operations which involves a fragmentation step in order to open the battery cases and to allow the access of chemical reactants to the electrode materials, on further chemical unit operations. Shredders are usually used for that purpose, using cutting mechanisms and allowing efficient fracture of residues in order to promote further processing of the contained materials. Batteries are complex products with a large variety of sizes and shapes which causes serious difficulties for predicting and carrying out its fragmentation.Domestic-type batteries are essentially of the Zn-Mn systems and with cylindrical shape, varying from the large size Mono (or D) type to the small size Micro (or AAA) type [1]. Recycling of batteries involves collection, sorting [2] and metallurgical processing [3, 4]. In some processes, the first step of metallurgical processing is dismantling and size reduction by shredding. Research work on spent batteries considering grinding/shredding and physical separation of fractions is scarce [5-7], but investigation in this domain is very necessary."

Jan 1, 2008

By Liu bing-guo, Peng Jin-hui, Guo Sheng-hui, Kong dong-cheng, Hu jin-ming, Zhang Li-bo

The novel technology of calcination to prepare triuranium octaoxide（U3O8）from ammonium uranyl carbonate in microwave fields was investigated on the basis of the temperature rising characteristics of ammonium uranyl carbonate, triuranium octaoxide (U3O8), and their mixture. The result of experiments show that ammonium uranyl carbonate had weak capability to absorb microwave energy, while triuranium octaoxide has the very strong capability to absorb microwave energy and the sample temperature increased rapidly with an increase mixture ratio of triuranium octaoxide. The optimal calcination conditions were as follows: microwave power 700 W, calcination time 10 min and 60 g in this experiments range, respectively. Under these conditions the value of total uranium and 4 U of triuranium octaoxide was 84.28% and 31.02%, respectively. It is feasible to prepare triuranium octaoxide by calcination from ammonium uranyl carbonate, which mixed with small amounts of triuranium octaoxide under microwave fields.

Jan 1, 2015

By Sevinc Yildirim, Cigdem Oruclus

"Metal-Porous Silicon (PS) based structures dipped in water show the direct hydrogen fuel cell behavior. The effect of the thickness of the cupper (Cu) film on the electrical properties of direct hydrogen fuel cell is studied by fabricating Cu/Porous Silicon/n-Silicon/Indium structures. PS samples were produced electrochemical etching of n-type single crystalline silicon with a resistivity of 1,25 Ocm and (111) orientation. The thin films of Cu with different thickness between 200 and 600 nm were deposited on PS surface by electron-beam technique. Investigation of the effect of Cu layer on the performance of the structure indicates that the performance parameters such as open circuit voltage (Voc) and short circuit current (Isc) strongly depend on the Cu layer thickness. It was observed that the divice with an 350 nm Cu layer exhibits the highest open circuit voltage (0,5 V), short circuit current (0,01 mA) and power density (10 W.m-2).IntroductionHydrogen is the most attractive and ultimate candidate for a future fuel and an energy carrier. Hydrogen is recognized as the environmentally desirable clean fuel of the future since it can be used directly in different types of hydrogen fuel cells [1]. In the past years, the rise in portable electronics requires the development of miniature fuel cells compatible with standard silicon micro fabrication technology. Most silicon micro-fuel cells have used the polyperfluo-rosulfonic acid membranes (Nafion R) as a proton exchange membranes (PEM) that is not really integrated with standard micro fabrication techniques [2-5]. The composite materials such as inorganicorganic hybrid materials (Nafion-silica, Nafion-borosiloxane etc) are next generation of proton conducting membrane [4-8]. But, fuel cells run on pure hydrogen gas, which can be produced with other energy resources. Hydrogen smallest atom and thus the H2 gas can leak easiliy. The application of hydrogen for power sources has been greatly restrained due to the lack of safe and convenient generation and storage methods.A kind of hydrogen fuel cells Metal-PS-Si structures used as an energy water directly. There is no need pure hydrogen. Cu-PS-Si Schottky-type fuel cells with as proton-conducting membrane and the thin-film cupper catalist and water as fuel, which are interesting for fabrication of lowcost miniature fuel cells. Generation of the open-circuit voltage and short-circuit current has been observed by Cu-PS-Si structure dipping in different hydrogen-containing solution."

Jan 1, 2014

By J. W. Matousek

Copper losses in smelter slags are :typically normalized with some form of the distribution coefficient, written as the ratio of the weight percent assays of metal in slag to the metal in matte or its inverse: L(s/m) = %(Cu)/%[Cu] or L(m/s) = %[Cu]/%(Cu) However, this simple approach ignores the dynamics of the smelting process. It overlooks the effect of the chemical work done in producing a given matte grade from concentrates of different grades -- or from a single concentrate blended with varying quantities of copper bearing precipitates or reverts. This paper examines the combined influences of matte grade and the work done in smelting on the copper content of smelting furnace slags. A simple model for the relationship is proposed.

Jan 1, 1999

By M. Tangstad, H. Mølnäs, J. D. Steenkamp

"Temperature affects several aspects of pyrometallurgical systems, including thermodynamics and reaction kinetics. Reliability of temperature measurements in laboratory and plant applications is thus important from process, safety and financial perspectives. This case study briefly introduces different techniques utilized for temperature validation, and demonstrates temperature validation on laboratory scale utilizing the wire-bridge method. Pt/Ptl3Rh thermocouple hot junctions were constructed by mechanically connecting thermocouple wires through a pure metal bridge consisting of copper, gold, nickel or palladium wire. When heating the wire-bridge thermocouple alongside a regular Pt/Ptl3Rh thermocouple, temperature offsets were quantified as the wirebridge thermocouple short-circuited at the melting points of the pure metals. At the melting points of gold (1064°C) and palladium (1555°C), average measured temperature offsets were -2.1°C ± 2.3°C and 0.2°C ± 0.4°C, respectively. Results from the copper and nickel wire-bridges were inconclusive. The paper concludes with a discussion on the potential industrial applications of the technique.IntroductionThermocouples are probably the simplest of all temperature sensors, but are widely utilized due to simplicity, versatility and ability to handle a variety of experimental conditions and industrial applications. Additionally, thermocouples are often the only option in research laboratories requiring high temperature measurements, and a high level of reliability is usually required from thermodynamic, kinetic as well as safety points of view.The study presented here originated from a test program where the compatibility between different types of carbon-based refractory materials and industrial slag produced in silicomanganese furnaces were investigated on a laboratory scale utilizing the static crucible test[l]. Due to the nature of the silicomanganese production process, the compatibility tests were to be conducted at 1600CC[2]. Details of the experimental set-up utilized for the compatibility tests are discussed in the Experimental Set-up and Method Statement section later in this paper."

Jan 1, 2012

By Vaughan R. Voller

"Over the last ten years an increasing number of heat and mass transfer models of solidification processes have been presented in the literature. A key component in these models is the coupling between thermal and solute fields. This is achieved by developing relationships based on the behavior at the microscopic scale in the casting (typically a secondary dendrite arm space). An important class of models in this respect are models that describe the local scale redistribution of solute alloy components-collectively referred to as microsegregation models. This paper explores this class of models.IntroductionModeling takes a key role in processing materials for properties. This is particularly time in solidification processes where current computer techniques allow for a detailed treatment of the critical macroscopic phenomena. Typically these macro scale models consist ·of three main coupled components.1. A model of flow in the melt and solid + liquid mushy region.2. A model of heat transfer.3. A model of solute transport.The focus of this paper is the solute transport component, in particular the manner in which process scale transport is coupled to transport ·at the local scale of the solid-liquid interface. This step requires a modeling of the redistribution of solutes at the scale of the secondary arm spaces in the dendritic mushy region-a process referred to as microsegregation. Basic microsegregation models use the limit assumptions of no mass diffusion in the solid (Gulliver-Scheil [l]) or complete diffusion in the solid (equilibrium lever rule) in a fixed and space. Recently, however, more sophisticated microsegregation models that account for finite mass diffusion and coarsening of the arm space have been developed [2-19]. In this paper governing equations for a general microsegregation model for a multi-component alloy in a coarsening and spacing _are introduced. From these general equations various models for a binary system are developed and tested"

Jan 1, 2000

By Shaohua Ju, Huang Chang-yuan, Lu Shuaidan, Peng Jin-hui, Wu Guoqin, Yaqian Wei, Zhang Li-bo

"The contrastive studies of microwave and conventional roasting copper residue from zinc hydrometallurgical was carried. The experimental results showed that the microwave roasting has the higher dechlorination rate in the same condition such as temperature, heat preservation time and atmosphere. When the samples with 100 mesh grain size, the Cl content turned from 14.27% to 1.33% and the dechlorination rate achieved over 90% at 400°C with 2h microwave roasting. And in the same conditions, the materials' dechlorination rate after conventional roasting just reached around 78%. The phase changes of the roasting process was investigated with X-ray diffraction analysis.IntroductionCl element can be accumulated gradually in the solution of Zinc hydrometallurgical system. When Cl content in electrolysis solution comes up to 100 mg/L, the stability of electrodeposits process would be severely affected [ 1]. It would not only accelerate the consumption of cathode and anode plate, elevate the power consumption, but also cause serious corrosion of device, increase production costs and lower the quality of electrolytic zinc [2]. Thus, C1- contained in the solution should be removed before electrodeposits."

Jan 1, 2013

By Oleg Ostrovski

Industrial pyrometallurgical processes in ferrous metallurgy are based on carbothermal reduction of metal oxides. Carbothermal reduction of stable oxides requires high temperatures. Lowtemperature reduction can be implemented by using methane-containing gas with high carbon activity, or by carbothermal reduction under reduced CO partial pressure. Under standard conditions, methane is thermodynamically unstable above 550 °C and decomposes to solid carbon and hydrogen. At appropriate CH4/H2 ratio and temperature, carbon activity in the methane-containing gas phase can be well above unity relative to graphite, which provides favorable thermodynamic conditions for reduction. To maintain these conditions, the rate of reduction/carburisation should be higher than the rate of solid carbon deposition. The paper discusses reduction of pure manganese and chromium oxides at relatively low temperatures, and constraints in reduction of manganese and chromium ores. Reduction of metal oxides by carbon in hydrogen as an alternative use of natural gas is also discussed.

Jan 1, 2014

By Shizhe Liu, Bing Li, Heng Wang, Zuxin Zhao

In this paper, cyclic voltammetry and chronoamperometry have been applied to investigate the effects of Nd2O3 concentration on the anode effects, critical potential for the anode effects and Nd2O3 reduction in LiF-NdF3-Nd2O3 melts at 950℃. The results show that the oxidation peaks in the potential of about 2.7V are attributed to the oxygen ions oxidation and the peak current density increases with Nd2O3 concentration increase from 0 to 0.5wt%. The critical potential caused the anode effects shifts to 0.3V more positive value as Nd2O3 content in the melts decreases from 0.01wt% to 0.5wt%. The cyclic votammograms on W electrodes in the LiF-NdF3-Nd2O3 melts present two pairs of reduction and oxidation peaks, indicating that the reduction of Nd ions in the LiF-NdF3-Nd2O3 melts in two steps rather than one step.

Jan 1, 2014

By Yoshio Waseda, Tetsuya Uda, Tom H. Okabe

"Halide salt has been tested as a reductant for producing titanium powder directly from TiCl4. From the results of thermodynamic investigation for several rare earth chloride systems, DyCl2 was found to be used for the reduction of TiCl4 instead of the conventional metallic reductant. When TiCl4 was fed into molten salts containing DyCl2 at 1073K, titanium powder of several ten micron meters in diameter was obtained. In contrast to the sponge titanium produced by the conventional Kroll process, the present new process using a halidothermic reduction in a reactive molten salt appears to be suitable for producing metal powder. From the thermodynamic point of view, the resultant DyCl3 can be reduced to DyCl2 by magnesium. By utilizing the multivalent halide redox couple, some possible ways of titanium powder production directly from TiCl4 by magnesiothermic reduction are shown to be feasible. This can also be applied to the development of a new continuous titanium reduction process.1 IntroductionTitanium and its alloys show attractive mechanical properties such as strength-to-weight, rigidity-to-weight ratios and excellent corrosion resistance. Nevertheless, the application of titanium alloys is limited compared to other structural materials (e.g. steels, aluminum alloys) because of its high cost of production. Currently, almost all of titanium is produced by metallothermic reduction of TiCl4 by magnesium (Kroll process)[1] in an airtight metallic reactor. This process is batch type and labor intensive. Therefore, many attempts to develop new process for producing titanium are investigated so far."

Jan 1, 2000

By Hector Carreon

This paper presents experimental data for the magnetic field produced by thermoelectric currents around uncracked hard-alpha inclusions in a Ti?6Al?4V specimen under external thermal excitation for different nitrogen content ranging from 1.6% to 5.9%. According to our preliminary results, the magnetic flux density measurements were found to be rather sensitive to changes in nitrogen content with the exception of the intrinsic material background magnetic signal that affected deeply the detectability of inclusions and imperfections in non-contacting thermoelectric measurements. Hopefully, these preliminary results can help identify a non-destructive test method that can detect material inclusions with a level of nitrogen that could be detrimental to Ti?6Al?4V alloy components.

Jan 1, 2009