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By Chandrakala Kari, Divyang Shah, Lakshmi Kanth Reddy, Kaushik Vakil, Sanjay Sarkar, Bhavin Desai

Gases rich in sulfur dioxide generated as a by-product of smelting and converting operations of copper concentrate contain selenium apart from zinc, lead, copper, cadmium, bismuth, antimony, and arsenic. The gaseous stream is heat exchanged in waste heat boiler, dust collected in electrostatic precipitator followed by cleaning in reverse jet scrubber to remove fumes, halogens and fine dust before passing to DCDA Monsanto catalytic converter to produce commercial grade sulfuric acid. The gas cleaning section of the acid plant uses water to scrub the smelting gases. During scrubbing, precipitated solids, known as sludge, settles at the bottom of the reverse jet scrubber containing 30 to 40 wt% copper and selenium up to 40 wt% selenium. In the existing process, the sludge collected during scrubber cleaning process is directly recycled to the smelter for copper recovery. However, the selenium is expected to again vaporize due to high oxidation potential during smelting and converting, causing accumulation of selenium in sludge. In present investigation, a roasting process has been developed to recover the selenium from acid plant sludge before charging it to smelter for copper recovery. Selenium is associated with copper in acid plant sludge as copper selenide, as determined by X-ray diffraction and electron microscopy. Thermodynamic and thermo-gravimetry study revealed that the copper selenide phase present in the sludge was amenable to oxidation at 600°C forming oxides of copper and selenium (Cu-Se-O). However, the dissociation of selenium from the copper oxide was made possible by sulfatation using sulfur dioxide between 450°C to 600°C, resulting into the formation of CuSO4(s) and SeO2(g). Lab scale experiments were carried out in vertical tubular furnace to determine the optimum roasting conditions with respect to roasting time, temperature and molar ratio of O2:SO2. Using these optimum conditions, selenium up to 90 wt. % in the form of SeO2 vapors could be recovered from the acid plant sludge in a large scale commercial roaster. Roasted sludge free from selenium and containing oxides and sulfates of copper could now be recycled in the smelter for copper recovery. INTRODUCTION There is an increasing demand for minor metals due to their use in innovative technologies. Similarly, the increase in demand for selenium is expected due to disruption in sectors related to renewable energy and photovoltaic battery. Selenium is a chalcogen and a non-metal with black or red crystalline appearance. Selenium is used in the glass industry to decolorize glass and to make red-colored glasses and enamels. It is also used in solar cells and as a photographic toner. Selenium is used as a brasses in stainless steel to improve its machinability. Selenium sulfide is used in anti-dandruff shampoos. In spite of the toxicity of its compounds, selenium is also an essential trace element for humans and animals. Selenium occasionally occurs free in nature, but more often occurs as selenides of iron, lead, silver and copper. There is an urgent need for the development of new methods for selenium recovery from the existing resources. Commercially, selenium is obtained only from anode mud produced during electrolytic refinery of copper.

Jan 1, 2019

By Robert D. Pehlke, Robert G. Blossey

The solubility of nitrogen in liquid iron alloys containing chromium and nickel has been measured in the temperature range 1550° to 1700°C at nitrogen pressures to 1 ah. The solubility surface has been determined for the iron corner of the liquid metallic ternary to 21 pct Cr and 11 pct Ni. The nitrogen solubility increases markedly with increasing chromium concentration. The effect of nickel and the bilinear effect of chromium and nickel are less pronounced. The solubility data are presented, and interaction coefficients are determined from them. THE solubility of nitrogen has been determined in liquid Fe-Cr-Ni binary and ternary alloys. The work in this laboratory has been directed toward a relatively limited composition range, that is to 20 pct Cr and 10 pct Ni. Humbert and Elliott1 studied the entire ternary; but their investigation was, understandably, limited in this region. The region considered here is of the greatest commercial interest. Knowledge of the solubility in these alloys is important for accurate control of the nitrogen levels in various stainless alloys. Also, the solution behavior is of theoretical interest because of its deviations from ideal dilute solution rules at moderate chromium levels. The nitrogen solubility in the iron binaries has been reviewed extensively by Pehlke and Elliott,2 particularly with respect to the dilute solution interaction parameters. More recently, there has been some interest in accurate descriptions of solute interactions in non-dilute solutions. Most of the investigators have adopted a power series fit to accommodate any non-linearity of the data. The Taylor series expansion is adopted here, using Scimar's notation3 for the interaction coefficients. An alternate method, instead of requiring higher-order expansions, is to restrict the range of the composition variables. A planar solubility surface may be fitted to the data and its range of validity determined. If the axes of this region are displaced from the usual origin—the solvent pure iron—a change in standard state is required for the solution reaction. The standard state for nitrogen in iron is commonly taken as the hypothetical 1 wt pct solution of nitrogen in pure iron. However, for an alloy of appreciable solute concentration, e.g., 13 pct Cr or 18 pct Cr-8 pct Ni, it would be convenient to use that base composition as the solvent and redefine the solution reaction in terms of that particular solvent. A brief derivation follows, defining the free energy of solution in an alloy solvent. Following the treatment by Darken and Gurry,4 for a nitrogen pressure of 1 atm: N (pure component) = N (1 wt pct in solvent) [l] AG=RT ln100/ wt pct N in solvent Taking this reaction for an alloy solvent less the same reaction for a pure iron solvent the relation between nitrogen in pure iron and an alloy is: N (1 wt pct in Fe) = N (1 wt pct in alloy) [2] AG = RT[ln(wt pct N in Fe) - ln(wt pct N in alloy)] Adding ½ N2(g) to each side and subtracting N (1 wt pct in Fe) = ½N2(g), the total free energy for solution of nitrogen in an alloy, referred to nitrogen at infinite dilution, is given by: ½N2 (g) = N (wt pct in alloy) L3] AG°3 = -RT ln(wt pct N in alloy )PN =1 atm Interaction parameters have their usual meaning when ?G°/RT is differentiated with respect to the proper composition coordinate. If desired, the dilute alloy treatment may be utilized with the new reference composition as the solvent. This has. indeed, been done by Small and pehlke5 in their analysis of nitrogen solution in liquid 18-8 alloys. The Sieverts' technique was used for this investigation on an apparatus previously described.6 The materials used in this program were: Ferrovac-E iron, 99.95 pct, Crucible Steel Co.: chromium, 99.95 pct, Union Carbide Metals Co.; nickel, 99.9 pct, International Nickel Co. Recrystallized alumina crucibles were used with no evidence of crucible-melt reaction. RESULTS The locations of the ternary compositions investigated are shown in Fig. 1. The data of Turnock7 and small8 have been alluded to in other papers.5'6 There were no departures from Sieverts' law observed for

Jan 1, 1969

By M. E. Wadsworth, A. S. Peck

Infrared spectra disclose that oleic acid will not adsorb on the surface of pure beryl unless the mineral is first activated with HF. The adsorption of oleic acid on HF activated beryl is attributed to the hydrogen bonding of oleic acid monomers to F-surface bridging sites. These sites are formed as a result of the reaction of HF with chemisorbed water or surface hydroxyl. Characteristic infrared spectra of physically adsorbed oleic acid are correlated with flotation at different pH at temperatures of 25°C and 75°C for colloidal and -60-mesh particles. The usual mode of occurrence of the beryllium mineral beryl, Be3A12Si6O18, is in granite pegmatites as pale green, white, or yellow crystals. A dark green gem variety, emerald, may be found in the wall rock of pegmatite veins or in mica schist. The most important beryl deposits in the United States are in the Black Hills District of South Dakota, and several mountain ranges of central and west-central Utah contain potential commercial sources of this mineral. Several papers have been published concerning the flotation of beryl with different conditioning reagents. Kennedy and O'Meara1 reported on the essential use of HF in the flotation of beryl from different ores. The use of calcium hypochlorite to separate HF activated beryl from feldspar after flotation with an amine collector was made by Runke.2 A report on the activation of beryl with different cations using sodium oleate collector was presented by Viswa-nathan and co-workers.3 Flotation of beryl with sulfonate collector and different activating salts was employed by Fuerstenau and Bhappu.4 The role of the surface charge or zeta potential in the flotation of beryl with different collectors and salts was also extensively investigated.5"7 Previous infrared investigations by the authors8 disclosed that the orthosilicate beryllium mineral, phenacite, reacts with oleic acid to form a chemisorbed oleate monolayer on the mineral surface. Thus, chemisorption is the effective mode of adsorption in the phenacite-oleate acid flotation system. In contrast, neither chemisorption or physical adsorption of oleic acid occur on the surface of pure beryl as evidenced in this study. Efforts were subsequently made to determine the mechanism of activation and collector adsorption for HF pretreated beryl. EXPERIMENTAL PROCEDURES Large, white, terminated crystals of beryl were obtained from Madagascar through Ward's Co., Monterey, Calif. The crystals were broken into -60-mesh fragments in a porcelain mortar. Part of this prepared material was ground to a powder with a Fisher Grinder using an agate mortar and pestle. The powder was transferred to a graduated cylinder and mixed with 500 ml of distilled water. After 5 min, the colloidal suspension was separated from the settled particles by decantation and used as a stock for infrared test determinations. Adsorption tests were performed by first transferring 20 ml of colloidal suspension to 50 ml glass centrifuge tubes. The solids were then centrifuged out and the liquid was discarded. Then, the solids were pretreated with one molar HC1 or one molar HF. After 15 min, the solids were again centrifuged out. The mineral solids were washed free of residual acid by repeated centrifuging and water washing operations. Then, 20 ml of distilled water was added to the solids, and the resultant suspension was used for test purposes. In the preparation of mineral for flotation tests, 1.5 g of -60-mesh beryl was deslimed by removing the colloidal fraction by three successive water washes and decantations. Then, the coarse particles were pretreated with either one molar HCl or one molar HF for 15 min. The mineral was next washed free of acid with distilled water, and 20 ml of distilled water was added to the beryl prior to collector conditioning. The conditioning of mineral with collector was performed in 50 ml centrifuge tubes to which either NaOH or HC1 was added for pH modification. One drop (6.0 mg) of U.S.P. reagent grade oleic acid or 2 ml of 0.01 molar sodium oleate was added to the pulp and stirred at about 1500 rpm for 3 min at a

Jan 1, 1968

By Janet A. Johnson, T. B. Borak, K. J. Schiager

INTRODUCTION In the USA regulatory agencies have adopted standards which limit the allowable concentration of ore dust in underground uranium mines. The American Conference of Governmental Industrial Hygienists has recommended a threshold limit value for silica which has been incorporated by reference in federal regulations (30 CFR 57, 1980). The Nuclear Regulatory Commission (NRC) imposes a limit for unprocessed uranium ore dust for reducing the exposure to radioactive materials from inhalation (10 CFR 20, 1980). We have been unable to trace the origin of the NRC standard. Recently the ICRP has published recommendations concerning limits for intakes of radionuclides by workers (ICRP, 1979). We have used the ICRP methodology to compute the dose equivalent commitment to lung and bone from inhalation of insoluble ore dust particles. These values were used to derive air concentrations which would provide an acceptable risk for induction of cancer from occupational exposure. Results indicate that the new ICRP recommendations are more restrictive than the present NRC standard for radioactivity. The maximum allowable dust load in a uranium mine will depend on both the concentration of silica (% Si02) and the amount of radioactivity (% U308). We have combined these standards assuming complete independence of biological hazard to establish boundary conditions for which either silica or radioactivity is the dominating factor. Based on these results we present suggestions for analysis of ore dust to insure compliance with regulatory agencies. SILICA STANDARDS Silicosis, fibrotic lung disease produced by crystalline silica, was one of the earliest forms of occupational disease to be recognized. The pulmonary lesions caused by silica, silicotic nodules, consist of concentrically arranged bundles of collagen fibers. Fusion of these nodules results in progressive massive fibrosis causing alveolar changes which decrease ventillation and blood flow in the lungs. The current Threshold Limit Value (TLV) for mineral dusts is based on the concentration of free silica. The standard is expressed in three forms: (1) Particle count standard: TLV (mppcf) = 300/(% Si02 + 10) (mppcf = million particles per cubic foot) (2) Respirable dust mass standard: TLV (mg/m3 ) = 10/(% respirable Si02 + 2) (3) Total dust standard: TLV (mg/m3 ) = 30/(% Si02 + 3) The most commonly used form is the respirable mass standard. These curent values for silica are based primarily on epidemilogical studies of Vermont granite workers and other occupationally exposed workers. In the Vermont study no cases of silicosis were seen in individuals employed after dust control measures were initiated and whose subsequent exposure averaged less than 5 mppcf. The free silica concentration in the airborne dust to which these workers were exposed averaged 25%. A concentration of 10 mppcf of granite dust is considered equivalent to 0.1 mg/m3 quartz. The current respirable mass standard allows a maximum silica concentration of 0.1 mg/m3. NIOSH (1974) has recommended a reduction in the current TLV for respirable silica to 0.05 mg/m3 Si02. As with radiation standards, the TLV for mineral dusts is an upper limit for time weighted average exposure. It is recommended that dust concentrations be maintained as far below the TLV as current practices permit. RADIATION STANDARDS The present concentration limit for airborne natural uranium in ore dust prior to chemical separation is 75 µg of uranium per m3 of air ( 10 CFR 20, 1980) . This corresponds to 1.85 Bq/m3 (50 pCi/m3 ) of natural uranium, U-238, U-235 and U-234 and is equivalent to 3.7 Bq/m3 (100 pCi/m3 ) of gross alpha activity with radioactive equilibrium between the long-lived alpha progeny through Ra-226. The origin or basis for this standard is not known, but it presumably includes both chemical toxicity and risk from somatic radiation injury. Recently the International Commission on Radiological Protection (ICRP, 1977) has published recommendations concerning the objectives and criteria for limiting radiation exposures. This was followed b y a revision of the limits for intake of radionuclides by workers (ICRP, 1979; ICRP, 1980). The previous compilation of limits for internal emitters was published by ICRP Committee II in 1959 (ICRP, 1959). The latest version includes new methodlogy outlined in ICRP Publication 26 (ICRP, 1977) as well as extensive metabolic information

Jan 1, 1981

On account of the increased work required from the assay office, owing to the large additions which have been made to the smelting and superphosphate plants during the last few years, it was found necessary to build a more extensive and up-to-date assay office than the one that had been in use since the starting of the works some twenty years back.A site was chosen adjacent to the main office, so as to be free from smoke and dust.. The building is constructed of red brick, the over-all dimensions being 109 ft. x 37 ft. The roof is of fibrous-cement slates, 31 ft. high, with a two-to-one rise, and overlaps the walls to the extent of 4 ft. 6 in. on all sides.Special care was taken to give light to all working benches, fume cupboards, and balance rooms. The main chemical room occupies the entire western end of the building, and the fire room the entire eastem end. Between these two rooms are the superphosphate, refinery, and gold-parting rooms on one side of the central passage, and three balance rooms, general office, and cloak room on the other side. The height of the roof affords ample space above these central rooms for storage purposes, and also maintains a fairly even temperature. The ceiling of the main chemical and fire rooms is carried immediately under the slates, which gives a total height in the centre of about 25 ft.

Jan 1, 1918

By G. R. Love, C. C. Koch

The changes in superconducting properties with aging time have been studied ,for the pecipitation reaction in a Tc-30 at. pct V alloy. Superconducting critical temperature, upper critical field, and relative critical current density were determined by ac susceptibility techniques. Aging produces changes in critical temperature of both matrix and precipitate which can be rationalized by compositional effects. maximum flux pinning (critical current density) occurs at a time during aging when subgrain boundaries are completely decorated with precipitates and the subgrain centers remain precipitate -free. The particular effectiveness as barriers to flux motion of planar defects which enclose regions of low deject density is discussed. THE precipitation of a second phase can dramatically modify the superconducting properties of type I1 super-conductors. According to Livingston and Schadler1 one might expect changes in the primary, secondary, and tertiary superconducting properties of the material. Changes in matrix chemistry caused by precipitation can alter the fundamental superconducting parameters; critical temperature, Tc, and thermody-namic critical field, Hc. The concimitant changes in electron mean free path (reflected in normal state resistivity) can affect the critical fields Hc 1, IIc2, Hc3. Finally, the presence of precipitate particles may hinder the motion of flux lines and may considerably improve the current-carrying capacity in high-field superconductors. The influence of precipitation on superconducting properties has been studied in a number of systems.2 Magnetization measurements have been used to study the influence of precipitates on flux pinning in lead-base alloys by Livingston3 and Evetts et al4 In these alloys precipitates induced magnetic hysteresis and flux trapping. The amount of hysteresis increased with the volume fraction of precipitate and decreased with coarsening of the precipitate. Jn an Al-Zn alloy5 and an A1-Ag alloy6 the initial precipitate size was presumably smaller than a coherence length and coarsening increased magnetic hysteresis5 and critical current density.6 The influence of precipitation on superconducting properties has also been studied in several of the commercially interesting Ti-Nb7-10 and zr-Nb11 alloys. The maximum in critical current density for these alloys was confined to a narrow range of either isothermal aging time" or isochronal aging temperature7 during the precipitation reaction. Thus, experimental evidence and theoretical considerations suggest there is an optimum precipitate size, spacing, and density, and a critical composition with respect to the matrix for flux pinning. What these "optimum" values might be and the relative importance of each is still not clear, although a few generalizations can be made. It is generally accepted1' that particle sizes smaller than the coherence length or larger than the inter-flux line spacing are poor pinning centers. In high Hc2 materials, precipitate sizes for maximum values of critical current density lie in the range of 50 to 2000Å,9,7 and there are indications that increasing dissimilarity between precipitate and matrix produces increasing pinning force.13 Because of several interesting features of the aging reaction in a Tc-30 pct V alloy, we have chosen to study the influence of precipitation on the superconducting properties of this alloy. The physical metallurgy14 and a survey of the superconducting properties" of the Tc-V alloy system have been reported. The Tc-V phase diagram is presented in Fig. 1. At 1500°C the Tc-30 pct V alloy is in the single phase 6 field. Samples quenched from the 6-phase field have a CsCl structure X-ray diffraction pattern at room temperature and it has been proposed that the 6 structure is closely related to the bcc lattice.14 When held isothermally below the eutectoid temperature, 115O°C, the 6 phase decomposes into the CsCl and hcp phases.

Jan 1, 1970

By R. D. Begley, A. W. Khair

Introduction The technique being investigated here uses a physical mine model which consists of a plexiglass room-and-pillar model 11.4 x 11.4 cm (4.5 x 4.5 in.). It is placed at the bottom of a larger plexiglass box 25.4 x 30.5cm (10 x 12 in.). The box is then filled with a model material representing geologic overburden. Sand has been selected because of its deformability under gravitational forces. The mine model is capable of creating a cavity and induces movement on the surface of the model material. This surface disturbance can be measured using a photographic technique called holographic interferometry. This paper discusses results of an investigation of the possibility of generating subsidence criteria using physical mine models and laser holographic interferometry. Problem Statement Subsidence appears to be widespread in two states - Pennsylvania and Illinois - although serious subsidence is found in localized areas of numerous other states (HRB Singer Inc., 1977). The US Bureau of Mines estimates that more than 1618 km2 (400,000 acres) of urban areas are threatened by subsidence. Pennsylvania and West Virginia contain 57% of these threatened areas, with the remainder being spread out over 16 states (Johnson and Miller, 1979). Events of subsidence have been reported in urban areas, including Pennsylvania (Gray et al., 1977) and Illinois (Mahar and Marino, 1981). One location has observed three episodes of subsidence beginning in 1950 (Bruhn et al., 1981). These subsidence events all occurred over abandoned room-and-pillar mines. Some mines have been abandoned more than 50 years (Bauer and Hunt,1981) . Available research does not offer much on the problem related to time dependent subsidence, especially those associated with the failure of remnant coal pillars. The physical modeling technique developed at West Virginia University is capable of measuring both instantaneous and time delayed subsidence. Laser Holographic Interferometry Laser holographic interferometry, or holometry, uses the interference properties of laser light to measure small movements of objects. The object requires only optical access and no surface instrumentation. This technique is closely related to photoelasticity. Both techniques rely on the uniqueness of the light reflected off or through an object in any given state of stress. The entire measurement process is done remotely without any surface instrumentation and without using a camera. The interferogram is constructed and visual observation will yield fringes on all areas that yielded or moved. The displacement represented by one fringe was determined by Wilson et al. (1977) and is given by the relationship: [d ='1(1) 2 cos 8 where d = displacement of one fringe 6 = incident angle of laser light A = wavelength of light (632.8 x 10-9 meters for Helium-Neon lasers)] In summary, holometry is capable of detecting very small movements of objects under study. It is a very sensitive process that requires laser light and vibration free experiments. Experimental Program Lab Facilities The primary components of the facilities were the laser and the optical table. The light source was 50 milli-watt, Helium-Neon laser. The optical table was a granite slab weighing nearly one ton. All experiments were performed on the optical table. It consists of a large table sitting on air cells similar to car innertubes. Six air cells were placed on top of two layers of wood and Styrofoam. Figure 1 is a schematic diagram of the vibration free table. Even with these precautions, the experiments still had to be performed at night to reduce potential traffic related vibrations. Room-and-pillar mine models consisting of three different pillar sizes were constructed out of plexiglass. The models were designed to represent three different extraction ratios. Figure 2 shows the models. The extraction ratios were determined by the tributary loading concept (Peng, 1978). These models were the primary component of a seam extraction simulator. A schematic of this simulation device is shown in Fig. 3.

Jan 1, 1986

By Ted D. Maki, Joseph B. Taylor

INTRODUCTION FMC's Paradise Peak mine, located 13 Ian (8 miles) south of Gabbs, Nevada, became opera¬tional in April of 1986 (Figure 1). It was designed and built by Davy McKee, who was instrumental in equipment design and selection. It is the 7th largest gold deposit in the United States with defined reserves of 10.9 mt (12 million st) containing 34 million gms (1.1 million tr oz) of recoverable gold and 933 million gms (30 million tr oz) of recoverable silver. The mine extracts ore by the open-pit method, taking advantage of a 1.5:1 stripping ratio. The mill operates at a 3600 mt/day (4000 st/d) capacity. Crushing is done in three stages to achieve an ore size of minus 0.635 cm (0.25 inches). Grinding further reduces the ore to 85% minus 100 mesh. The ground ore is treated with cyanide in agitated leach tanks and then washed in the counter-current decantation (OCD) thickeners. Zinc is added to the clarified, deaerated pregnant solution to precipitate the precious metals. The precipitate is acid digested to eliminate excess zinc, filtered and retorted to drive off contained mercury. The retorted precipitate is then fluxed, melted and poured through cascade molds. Dore bars are cleaned for shipment and the slag is sent to an in-house slag treatment system. ELECTROSTATIC SEPARATION The dry electrostatic slag treatment system at Paradise Peak is the first installation of its kind. Electrostatic separation has been widely used in mineral processing since the early 1950's. A brief discussion of the theory behind the process is helpful to those not familiar to electrostatic separation. Charging and sepa¬rating slags, dry minerals or other materials by ion bombardment is the most common form of electrostatic separation. Millions of tonnes of minerals are processed each year by this method. In an ion bombardment separation, granular material is fed onto a grounded metal cylinder (or roll) and charged by a corona-producing electrode placed above the roll's surface (Figure 2). While both conductors and non¬conductors become charged, only the conductor is able to lose its charge. The charged non¬conductor, as it rests on the roll's surface, "sees" an oppositely charged image of itself in the metal surface. It is attracted to the image charge, becomes electrostatically pinned to, and moves with the roll's surface. The conductive particle also sees an image and is attracted to it. But upon touching the roll's surface, it discharges rapidly to the grounded surface and is thrown free from the roll's surface with a projectile motion. In the case of precious metal slags, the con¬ductive particles would be metallic prills of dore metal; and the nonconductive particles would be the slag, free of metal. Middling grains, generally, are in the form of a metallic prill encased in or incompletely liberated from slag. LABORATORY TESTING A number of precious metal slag samples have been tested in the laboratory. It has been found that the composition of slags vary widely from one refinery operation to another. Typical laboratory procedure is to crush and size the slag followed by two-stage lab-scale electro¬static separation. The conductor fractions from the first and second pass are then combined as a prill concentrate; middlings fraction and clean slag tailings from the second pass are held separate. Selected results from laboratory testing are shown in Table 1. It is important to note in Table 1 that the assays represent overall silver and gold, not metallic values. From experience, the laboratory results are typically lower in grade and recovery than the industrial installations. This is largely due to the hydroscopic nature of precious metal slags coupled with the high local humidity in Carpco's Jacksonville, Florida, location. Relative humidity in Jacksonville can range form 60-95%, while most mining locations in the

Jan 1, 1987

By Blake M. Caldwell, Harrold D. Owen

The continued use of permanent-type, we11 completion Iras pointed LIP the need for more powerful through-tubing perforating equipment. A new expendable shaped charge perforator has been developed in which the charges are run through the tubing in a vertical position and then opened out to a horizontal position when at the desired shooting zone. The performance of this new tool is comparable to that of conventional casing type perforators. This paper describes the new tool and its applications. Performance data in targets rind under various actual well conditions are presented. INTRODUCTION The general acceptance and increasing use of pernianent-type well completion by the oil industry has indicated the need for through-tubing perforating equipment with performance comparable to that of conventional casing type perforators.'.' To achieve the performance desired, a new, expendable, shaped charge perforator has been developed with adequate power for effectively perforating both 51/2-in. and 7-in. casing below tubing. This has been accomplished without resulting severe damage to the casing and can he obtained under extremes of pressure and temperature. The design of this new tool is a radical departure from previous concepts of tubing guns since it was felt that the two major limitations imposed by previous designs severely handicapped performance. The first of these limitations was the restriction imposed upon the length of the charges by the necessary small inside diameter of the carrier. This resulted from the necessity for compromises in designing a hermetically sealed gun small enough to allow free passage through 2-in. tubing, yet with sufficient wall thickness to withstand some minimum pressure. In an effort to overcome this limitation, the charges were in some cases placed at an angle with the axis of the well with resulting loss in effective depth of penetration. The second limitation concerned the extreme distance of the charges from the casing when the gun was fired. An example of the latter situation is demonstrated by the fact that a conventional 13/4-in. tubing gun centralized in 51/2-in., 17-lb casing has a clearance of more than 1-9/16-in. on all sides. This means that a considerable portion of the force from each charge must be expended in penetrating this 1-9/16-in. of well fluid before it even reaches the casing. With the gun centered in 7-in., 23-lb casing, the amount of fluid penetration required of each jet is in excess of 21/4-in. In a situation where the 13/4-in. gun is touching one side of the 51/2-in., 17-lb casing, the jets from the charges on the opposite side have more than 3%-in. of fluid to penetrate. A similar situation in 7-in., 23-lb casing necessitates the penetration of more than 4-9/16-in. of fluid. The penetrating effect of the charges is severely impaired in passing through so much fluid. Under such conditions, there is usually insufficient force left to penetrate the casing. Previous studies have shown the decided disadvantage of having to shoot through such an excessive quantity of well fluid.'.' The problem. then, was how to position large powerful charges close to the casing prior to firing and still manage free passage through 2-in, tubing. The solution appeared to be in some method of folding sealed charge units in an open type, expendable. 13/4-in. carrier for travel through the tubing, and unfolding them upon their arrival at the shooting zone in the casing. It was desired to control the mechanism electrically from the surface through the regular shooting cable, making the release of the charges independent of the physical characteristics of the well, yet with a provision to prevent the gun from firing until the

Jan 1, 1955

By A. A. Nourbakhsha

The main application of refractories based on andalusite in ferrous metallurgy are in air heaters of blast furnaces, mobile mixers, and hot-metal transfer, pig iron ladle, steel-casting, and intermediate ladles. Three specific properties of andalusite are very interesting for the production of high-quality shaped and unshaped mullite refractories: being free of water, its crystal a remains stable without changing its density or volume after firing and therefore has no internal porosity .Graphite additives due to its great wetting ability play an important role in raising the property of refractory bodies. In order to improve properties of andalusite graphite bodies, oxidant agent for increasing in hot strength and oxidation resistance can not be avoided. In this research, firstly 8 pig iron ladles from ESC(esfahan Steel company) with different conditions selected and monitored during usage to determine of main factors affecting on corrosion of refractories. Results showed that tap to tap time, undischarged pig iron ,penetrated pig iron are the main ones.Literature studies showed that the graphite addition help to thermal shock resistance and liquid penetration(steel,pig iron) effect. In this research particle size distribution of aggregates containing andalusite and graphite determined by andreazen equation. Then different mixes with different percentage of graphite,Si, FeSi, SiC prepared by uniaxially pressing under 1500kgf/cm2 pressure by adding 4%wt novalak resin and 0.4%wt HMTA as hardner. Samples fired at 1100-1500oC under reduction atmosphere. According to specific standards density, porosity and CCS measured. Analytical tests such as XRD, SEM were carried out on sample selected from point of view of mechanical properties at different temperatures. Results showed that optimized amount of Si and Fe-Si for _-SiC formation in body is 4 and 6 %wt respectively at 1500OC. XRD and SEM analysis on sample with Fe-Si additives showed no destructive phase through the matrix, also SiC additives not only increase oxidation resistance but also no effect on thermo-mechanical properties.

Oct 1, 2011

By Arnulf Muan, Carlos Landolt

Equilibria involving Cu-Pt alloys, copper oxides, and atmospheres of known ox2gen pressures have been determined at 1000' and 1200 C. The data obtained have been used to calculate activity-composition relations in the alloys. A moderate negative deviation from ideality is found. At high copper concentrations, the results of the present study are in good agreement with those of previous investigators, whereas at low copper concentrations the activities obtained in this investigation are slightly higher than those reported previously. The present study is part of a research program dealing with the determination of phase relations and thermodynamic properties of copper-containing systems at high temperatures. The information available for such systems is very scanty, particularly for copper oxides and their combinations with other oxide components. Platinum is commonly used as a container in studies of oxide equilibria. To evaluate quantitatively the extent of reaction between the oxide and the container, a knowledge of activity-composition relations in Cu-Pt alloys is necessary. Such data are not available for Cu-Pt alloys in the temperature range of particular interest in the present research program, and particularly for alloys low in copper. Studies of various aspects of the systems Cu-Pt and Cu-0 have been reported in previous literature. The system Cu-Pt is known1 to form a continuous solid-solution series above 812.C, whereas ordered phases are present in certain composition ranges at lower temperatures. Thermodynamic data for the system have been reviewed by Hultgren et al.,' who presented free energies of mixing at 65Oo C, mainly derived from electromotive force cell measurements by Weibke and Matthes.3 Enthalpies of mixing at 640°C have been obtained by Oriani and Murphy4 with liquid tin calorime-try. Their results differ considerably from those derived from the temperature dependence of the data of Weibke and Matthes. Thermodynamic data for the disordered alloys have been obtained by Assayag,5 and more recently by Schmahl and Minzl,6 by Myles and Darby,7 and by McCormack, Myers, and Saxer.8 The two latter sets of data7'' became available after the present study was completed. In the system Cu-0+ two oxides are stable at high temperatures, CuO and CuzO+ each having only minor deviations from stoichiometry. Equilibria in the liquidus temperature region of the system Cu2O-CuO have been studied by Roberts and systemsmyth,9'10CuzO-CuO by Vogel and ocher,I1 by Osterwald,12 and recently the the present authors.13 The system is of the eutectic type with a eutectic temperature of 1083.C The composition of the eutectic liquid corresponds to Xcu0 = °.44, and the oxygen pressure of the coexisting gas phase is Po2 = 0.55 atm.13 Equilibrium oxygen pressures for coexistence of solid CuO and solid Cu2O have been determined by Schmahl and Muller,l4 by Gadalla, Ford, and white,l5 by Bidwell,16 and recently by the present authors.13 There is reasonably good agreement among the various sets of data. Free energies of formation of Cu2O(s) from the elements have been derived by Tretyakov,17 by Bidwell,16 by Kiukkola and wagner,18 by Pal'guev and Neuimin," and by Steele and Alcock,20 There is particularly good agreement among the latter three1'-20 sets of data. THEORETICAL BASIS Consider a subsolidus isothermal section of the system Cu-Pt-0, as shown in Fig. 1. Two phase as-

Jan 1, 1970

By L. W. Pommier, F. B. Brien

In order to determine the ability of cyclones with heavy liquids to preconcentrate ores, a study of the variables which govern the behavior of the solids in the apparatus has been made. To assess the test results, the cyclone products have been examined by sink and float analysis at various specific gravities and the results examined by the Tromp type curves. This analysis has allowed the development of the SG50 unit — specific gravity of the particles, 50% of which goes to overflow and 50% to underflow — rather than the d50 (size) unit used in classification. The results of tests using the closed circuit laboratory cyclone assembly with dry feed samples show the validity of the equation: Results indicate that 83% of the feed may be rejected containing 0.1% Sn. Recoveries in excess of 80% are obtained at a grade of 1.7% Sn from feed samples assaying 0.4% Sn. As water-wetted particles may comprise the plant feed, separate tests were performed to examine the effect of water in the feed material. Results indicate that the entrained water divides into two fractions, one of which is defined as free water and is rejected to the cyclone overflow, the other fraction forms an adhering envelope of water on the ore particles, altering their effective size and density. The presence of the envelope of water on the particles increases the ease with which the heavy liquid can be recovered but decreases the concentration efficiency. It is proposed that the detrimental effect of water in the cyclone may be minimized by using a higher feed pressure cx by the use of surfactants. A higher feed pressure, by increasing shearing forces, would reduce the thickness of the water envelope on the particles. The surfactants, by adsorbing on the particles and producing hydrophobic surfaces, would displace the water envelope and allow the heavy liquids to wet the modified surfaces. In both cases a larger proportion of the entrained water would report to the cyclone overflow as free water, thus minimizing the detrimental effect of water on the concentration efficiency. Additional testing is required on the behavior of water in the system; to determine the optimum particle size for the preconcentration step; to determine final particle size for optimum liberation and subsequent treatment of the products in present plants and to determine the efficiency with which the heavy liquids may be recovered from the products. For many years tin mining in Bolivia has been very important to the economy of the country. In recent years the tin content of the ore reserves has been steadily declining. An improvement in concentration efficiency is highly desirable in order to increase productivity from the present low-grade mine ores and to allow retreatment of the many millions of tons of tailings from past operations, some of which equal the present ores in tin content. A number of investigators have been or at present are working on various phases or approaches to the problem. Gravity concentration is used in Boliva today as it has been in the past to recover tin minerals from the mine ores. An objective of the work reported in this paper was to examine the possibility of treating present low-grade ores and sink-float tailings products, at a relatively coarse grind, in order to produce a higher grade feed material to the present gravity concentration plants. The possibility of using heavy liquids in cyclones to treat large tonnages with a minimum of outlay presented itself and is of particular interest since heavy liquids are now available with physical properties which lend themselves to simple recovery methods. Tests were carried out using a closed circuit laboratory cyclone assembly. It was desirable to determine the value of using the SG50 concept and Tromp curves for analyzing the cyclone concentration test results. The effects of entrained water on the behavior of ore particles in the cyclone were examined. THEORY AND TECHNICAL CONSIDERATIONS Three types of heavy liquids are available: aqueous solutions of very soluble salts, salts or mixtures of

Jan 1, 1964

By A. M. Gaudin, J. G. Morrow

FLOTATION requires the existence of a definite contact angle. This contact angle, the surface tension of the solution, and adsorption at the solid-fluid interface are quantitatively related. Adsorption of dodecylammonium acetate on hematite was measured for a wide range of concentrations of reagent in solution. Similar measurements for quartz have already been made. Contact angle measurements were then made on polished surfaces of hematite and of quartz immersed in aqueous dodecylammonium acetate solutions, and a functional relationship was sought between adsorption density at the mineral-solution interface and the contact angle. Finally, the surface tension of the aqueous amine acetate solutions was measured. These data were combined to give an evaluation of the work of adhesion for the three-phase system. Specular hematite was crushed and then ground dry in a laboratory porcelain mill, with flint pebbles, to pass a 200-mesh screen. The ground product was sized in a Haultain infrasizer, and one of the granular sizes (cone No. 3) was used in all adsorption tests. A hand magnet was used to remove magnetite and abraded iron. Quartz was removed in a Frantz isodynamic magnetic separator. The purified hematite was leached in aqua regia, washed with distilled water until the washings appeared free of electrolyte by conductance measurement, dried in a low-temperature oven, and stored in a pyrex container. The specific surface of the closely sized hematite was determined by the krypton gas adsorption method.' Three measurements gave an average value of 1350 sq cm per g. Chemical analysis showed Fe -69.37 pct, insol = 0.72 pct. The quartz used in the flotation tests had been prepared by Chang" for an earlier investigation. Demineralized distilled water was used for all test solutions. Dissolved salt content was of the order of 0.03 ppm, expressed in terms of sodium chloride, as estimated from conductance measurements. Dodecylammonium acetate was obtained from Armour & CO. in two forms, the unmarked compound and a preparation marked by carbon 14 in the hydrocarbon chain of the aminium ion. Specific activity of the active salt was 0.134 millicurie per g. The important physico-chemical constants for the primary amine salt have been reviewed by de Bruyn. The calculated effect of hydrolysis of amine salt on pH of aqueous solutions and the effect of pH on the distribution ratio of the alkylammonium ion to free amine are of particular interest. All other chemicals used in this investigation were of analytical reagent grade. A column method' was used for adsorption work. Attainment of equilibrium distribution in the adsorption column depends on the solid-solution contact time, hence upon the volume of solution passed. It was assumed that contact time required for equilibrium would be a maximum for the lowest reagent concentrations. On this premise it was demonstrated experimentally that the passage of 500 ml of solution through the mineral bed was adequate. An aliquot (1 to 5 cc) of the solution to be analyzed was transferred to a small pyrex cup and allowed to evaporate to dryness at room temperature; 4 or 5 mg of unmarked amine acetate were added to the dried sample and the cup and its contents were transferred to the combustion system for analysis. Evaporation at room temperature must be emphasized, as even slightly elevated temperatures result in loss of reagent. A laboratory model G Beckman pH meter equipped with a glass electrode was used to measure pH of amine acetate solutions. The technique of internal gas counting of radioactive carbon dioxide in a Geiger-Muller counter was used. Developed originally by Brown and Miller,- his method was adapted to the analysis of carbon-14 marked flotation reagents by Chang, de Bruyn, and Bloecher. nalytica1 method and procedures have been described in detail by Bloecher.' Contact angles were measured by the captive-bubble technique." The mineral specimens were carefully selected to avoid cracks and inclusions of other minerals. All specimens were mounted in plastic and polished to produce a smooth surface. The final polishing and contact-angle measuring

Jan 1, 1955

A. G. Cockbain—The paper by Burlingame, Bitsianes and Joseph is of great interest in extending the work done on high grade sinters, particularly that of Hessle, and the development and application to them of the technique of McBriar, Johnson, Andrews and Davies on ironstone sinters. In this laboratory the work of McBriar et al. has also been continued and extended to cover high grade sinters, and a sectioning technique similar to that used by McBriar et al. was attempted on sinter cakes made in the laboratory sinter unit, using magnetite concentrates (containing 64 pct Fe). In these experiments no attempt was made to flush out the products of combustion with nitrogen before cooling. It was considered that free air penetration would occur on only a limited scale with the size of sinter cake made (14 in. sq x 12 in. deep). Chemical analyses of the zones showed generally similar features of those described by Burlingame et al. and especially the FeO rich region at and just behind the flame front, i.e. zones of ignition and combustion. This seems to indicate that the nitrogen atmosphere does not materially affect the states of oxidation in the sinter cake or at least that special care is not required unless the sinter cake is small. Burlingame et al. consider that FeO present has some significant part to play in the mechanism of sintering. This view does not find favor with the author. The reduction of iron oxides in the presence of red hot coke is a well known phenomenon, whether conducted in an atmosphere of nitrogen or in a crucible in air, and in view of the presence of some carbon in the hot sinter, especially just at the ignition zone, cessation of the progress of the flame front will in no way affect the reduction of iron oxides near hot coke. Even in a nitrogen atmosphere some CO and CO, will be generated by reduction and by continual oxidation and reduction of CO as the transfer agent, the oxidation state of the iron oxides can be lowered quite rupidly so long as free carbon exists with enough heat. Knowing the composition of the gas at the flame front (obtainable by probes), it would be possible to calculate the static oxidation state of Fe2O3/Fe3O2 in equilibrium with it and hence obtain a check on the chemical analyses to see if in fact direct reduction of the Fe2O3/Fe2O1 to FeO has taken place. Have the authors attempted this? It appears to this writer that what is required is some means of reducing rapidly the heat content of the ignition zone and immediately behind, and at the same time insuring no oxidation by the air. In ironstone sinters the difficulty of oxidation state of the iron did not arise on account of the very large slag bulk. However, in high grade sinters knowledge of this, and also the mechanism whereby high oxidation states can be obtained in the final sinter, is of great interest. R. D. Burlingame (author's reply)—The question has been raised as to whether the high FeO content found in high-fuel sinters is due to actual reduction at the advancing flame front or due to unavoidable direct reduction during the quenching period. For such direct reduction to have taken place in the freshly-formed sinter, a considerable amount of solid carbon would have had to escape combustion and be available throughout the hot sinter zone during the quenching period. A simple stoichiometric calculation with the limited data available indicates that a zone of freshly-formed sinter over 2 in. wide must have averaged roughly 2 pct C to accomplish the amount of reduction found. Furthermore, the presence of this amount of carbon would indicate that the fuel in the charge had not burned over a narrow front but over a zone at least 2 in. thick. In contrast to such a condition, the data of the present investigation indicate that the combustion of fuel is confined mainly to a narrow front in which high temperatures and reducing conditions favor. the formation of excess ferrous iron.

Jan 1, 1959

By G. R. Belton, Y. K. Rao

A galvanic cell, using liquid MgCl2 or MgC12-CaC12 mixtures as the electrolyte, has been used to determine activities in Mg-A1 liquid alloys between 700' and 880°C. The incovporation of a chlorine electrode in the cell also allowed measurements to be made of the standard free energy of formation of MgCl2(l). The results are shown to be in good agreement with thermo-chetrlical values from the literature, and this is taken as evidence that the small, known solubility of magnesium in iMgCl2 introduces no significant error in galcanic cell measurements. Within experimental error, the activity coefficients and relative partial molar enthalpies at 800°C are shown to be represented by the following "subregular" solution equations: logy~~ =-0.68(1 -xMgj3 log yAL =-1.02(1 - XMf + 0.68(1 - XMf H.M = -4400(1 - %)3 / cal Mg 7Ag' HZ =-6600(1 - xA1)' + 4400(1 - XMf cal SCHNEIDER and toll' have used a transpiration technique to measure the vapor pressures of magnesium over Mg-A1 alloys between 544" and 594°C. amsstad,' however, has since suggested that the extrapolation to zero flow rate, used by these authors in interpreting their apparent pressure vs flow rate data, gives unreliable results. Rogers, Tomlinson, and Richardson,3 in interpreting the results of solution equilibria between Mg-A1 alloys and liquid MgC12, also considered the measurements of Schneider and Stoll to be unreliable and preferred to derive activities for the alloys from the earlier boiling point determinations of ~eit~ebel~ and the partial molar heats recommended by Kubaschewski and ~atterall.~ These latter heats were based substantially on the early calorimetric work of Kawa-kami but, unfortunately, his work on other systems has sometimes been found to be inaccurate.7 Rogers et al., in the above-mentioned paper,3 tentatively concluded that the most likely species responsible for the limited solubility (0.3 mole pct at 800°C) of magnesium in MgC12 were Mg° (neutral) and Mg2++. Two more recent studies8,9 have supported Mg2++ as the soluble species. In the present study, activities in Mg-A1 alloys have been determined by means of a galvanic cell involving liquid MgCl2 or MgC12CaCl, mixtures as the electrolyte. Since the reactive nature of magnesium precluded simple Faraday yield experiments, a chlorine electrode was incorporated in the cell in order that the performance of the cell could be checked by measurements of the heat and free energy of formation of MgC12. This procedure was considered necessary since it has been suggested1' that the solubility of a metal in a molten salt might introduce electronic conductivity; also, previous determinations of the standard electrode potential for MgC12 differed by as much as 70 mv11-13 EXPERIMENTAL Materials. Analyses of the materials used in preparing the alloys and the electrolyte mixtures are presented in Table I. The alloys were prepared by induction melting weighed amounts of the metals in a graphite crucible held under an argon atmosphere. Pure anhydrous magnesium chloride was prepared by heating the mixture MgCl, . 6H20 +NH4C1(1:1) to 650°C, followed by melting under dry argon. The melting point of the dry MgC12 was found by differential thermal analysis to be 714.8oC, which compares well with the accepted value of 714C.14 This agreement was taken to be an indication of the high purity of the dried salt. Table I. Compositions of Materials, wt pn Impurity Mg Al MgCI2 CaCI, Ba - - 0.005 Ca - - 0.010 Cu 0.02 0.02 Fe - 0.10 0.001 0.010 Pb 0.01 - 0.001 0.005 Mn 0.15 0.001 Si - 0.10 Sr - - 0.005 MBSO* - 0.040 ARGON TUNGSTEN CHLORINE LEAD—411 11 II ALUMINA 'A I / ave GRAPHITE on irA~_ ( ^"l ROD MAGNESIUM S>ILICA~^ /, OR ALLOY-. I /A] ___________ -«^- _ ELECTROLYTE I y FRITTED DISCS Fig. l—Arrangement of chlorine and metal electrodes in electrolytic cell.

Jan 1, 1970

By P. K. Hopke, A. Hubbard, K. H. Leong, J. J. Stukel, K. Nourmohammadi

INTRODUCTION In order to understand the transport and deposition of radon daughters in mine atmospheres, it is necessary to know the variation in the attachment of the daughter atoms to particles as a function of particle size, composition, number density, relative humidity, temperature, and radon concentration, the free gaseous diffusion coefficients of the daughters, and the variation in the mass transfer of the activity, both free and attached to particles, to mine surfaces as a function of particle size distribution, surface roughness of the mine walls, and the flow conditions. If all of these parameters are known in a model system, it should be possible to understand the transport and fate of the airborne radioactivity in real mines under certain well-defined flow conditions. There have been a number of recent investigations of the attachment of radon decay products to particles 1-4, but there are still a number of unanswered questions regarding the process. However, it is clear that for most real mine atmospheres, the vast majority of the activity is attached to particles. The size distributions for the activity-bearing airborne particles have been studied 5,6, and it has been found that most of the activity resides on particles with diameters in the range of 0.05 µm to 0.3 µm with an average mass median diameter between 0.1 and 0.2 µm. The behavior of the unattached radon daughter species has also been recently studied[ 7], and many of the previous problems regarding the value of the diffusion coefficient for Po-218 have been resolved. A major problem in the understanding of the airborne transport of radioactivity in mines is the lack of detailed knowledge of mass tranfer to and fluid flow over rough walls under fully developed turbulent flow conditions. This paper will report the progress on a project that is designed to obtained that information. MATHEMATICAL MODEL DEVELOPMENT Deposition of particles on smooth surfaces in turbulent flow has been extensively studied. A comprehensive review of these results has been prepared by Sehmel 8. There has not been such a comprehensive study of particle deposition on rough walls under such flow conditions. In recent years, only a single model has been proposed to explain such deposition 9,10 and in both of these papers the flow structure in the rough walled pipe was not taken fully into account. As part of the work being conducted on this project, a more complete model was outlined in a previous report [11]. The basic theory will be reviewed to provide a context for the flow measurements to be reported. The flux of particle deposited on the walls of a pipe in a turbulent flow is derived from the one dimensional form of Fick's law as given by [N = Dpdpp/dr (1) where N is the flux of particles deposited per unit area per unit time, D is the total eddy diffusivity of the particles, p is the airborne concentration of particles, and pr is the distance measured from the center of the pipe. The rate of deposition is best expressed by a deposition velocity Vp = NIP pb (2) where P b is the mean particle concentration in the sulk flow. The shear radius, V/ut and the shear velocity, u , are used to calculate a nondimensional distance, and velocity, respectively, where v is the kinematic viscosity of the fluid. The nondimensional form of equation 1 is given by Vd = DP dpp(3) V dr+ where Pp = Pp/ Ppb(4) By integrating equation 3 from the rough wall stopping distance, S , to the center of the pipe, the deposition velocity can be obtained. In order to make this calculation, it is necessary to have accurate descriptions for the particle eddy diffusivity, stopping distance, and shear velocity in order to insure that the influence of the flow structure has been properly accounted for. The shear velocity can be determined experimentally from the shear stress evaluated at the wall, Tw, and the fluid density, ut =VT w/p = ub V f/2 (5) where ub is the mean bulk axial velocity. The wall shear stress for a given pressure drop, dP/dL, and hydraulic diameter, Dh, is]

Jan 1, 1981

By Edward Hanrahan

September 1981 I'm here today to report on a revolution -- a revolution in the way the Federal Government looks at energy. I'm not talking about a simple change in the relative emphasis on sources -- such as more recognition for coal and nuclear power, with less rhetoric about "soft- technology." Nor am I describing a mere change in focus -- from the demand side to the supply side. And I am not referring exclusively to our obvious goal of budget cuts. No, I'm here to discuss a fundamental change in Federal direction -- one that started as soon as President Reagan was inaugurated, and one that is articulated in the National Energy Policy Plan he sent to Congress in July. That brief policy document was backed up by three volumes of supporting data; but I think I can catch it's flavor for you in just three phrases: * First, various energy forms complete with each other and complement one another. * Second, fair competition among them (which includes honest pricing) will give us the best "energy mix." • And, finally there may be ligitimate arguments about where Federal responsibility in regard to energy spills over into Federal interference; but it's about time we drew the distinction -- and eliminated the latter. This Administration's national energy policy is quite different from any we have had in recent years. It is tuned to human nature and changing times. We are seeking the best practical solutions in the energy -a lot better than the ones we have been offered before, but still something less than perfection. One way we do that is by counting on a fully informed public to guide it's own destiny. And, instead of treating energy as an isolated entity, we recognize it as part of the overall economy. The President's Program for Economic Recovery is as much a factor in energy policy as the specific actions of the Department of Energy. One striking difference from the past energy policy 1s that this policy plan does not say: "In 1985 we will -produce so many hundreds of millions of tons of coal: . . . or . . . "By the end of this century the Nation will be deriving X percent of it's electricity from wind generators." Unfortunately, targets like these are what many people have come to expect from the Federal Government -- and what they think of as energy policy, whether the figures hold up in the long run or not. But . . . think about it! Nether the Department of Energy nor any other part of the Federal Government produces coal, or mines uranium, or manufactures solar collectors. There are only a few sections of the country where the Federal Government generates and sells electricity. So it does not take any great insight to recognize that the amount of energy we will produce or consume as a Nation In the future depends on many factors beyond direct government action. And those future totals cannot be predicted precisely, anyway -- by the Government or by anybody else. According to our way of thinking, the choices should be up to the people. When the free market works within a healthy economy, individuals express their preferences in the marketplace -- adjusting the balance of all energy factors continually in a way that no computer could be programmed to reflect perfectly. So, instead of having the Government issue a rigid set of numerical goals, our main concern simply is that there be enough energy. We want the Nation itself to decide how much that should be, what form it should take, and how that energy should reach consumers. The marketplace decides. Considering the recent past, this is indeed a revolutionary idea. It has some pitfalls, and we won't reach this ideal of free choice overnight. But that is where we are headed. And I'll offer some evidence in a few minutes that the policy has already started working. First, let me give you some of it's highlights: 1) Nobody who appreciates the philosophical underpinnings of this Administration will be surprised that the energy policy shows faith In domestic energy production and the supply side of the economy; but it also recognizes the important role of energy conservation -- the wise and efficient use of energy resources.

Jan 1, 1982

By Byoung Whie Lee

In order to investigate the change in surface energy as a function of cold work ad environment, the contact angles between a liquid and the surface of elec-tropolislzed aluminum with various degrees of cold work were measured. Specinlens cut from aluminum rod (99.99 pct Al) were annealed at 600°C for 24 hr and then cold compressed parallel to the drawing di-rectzon of the rod in increments of approximately 10 pcl from 0 to 70 pct. The sections, taken transversely to the drawing direction, were mechanically and electro chemically polished. Contact angles between the sessile drop of distilled water, glycerin, and glycol and the specimen surface were measured optically. The differences in interfacial energy were calculated from the contact angle data. The effects of chemical washing and surface roughness of the specimen on the contact angle were also studied. The liquid contact angle was a linear function of the degree of cold working (D) ad changed markedly with differed liquids. THE plastic deformation of polycrystalline metals induces a preferred orientation in crystal structure. A preferred orientation changes the atomic density of a metal surface. This change in surface atomic density brings about the changes in surface interactions of the metals."' Also, the plastic deformation of metals raises the internal energy by increasing the stored energy.' Consequently, the total Helmholtz free energy of the metal increases and, in turn, the surface free energy of the metal. In order to study the effect of plastic deformation on solid surface phenomena, the liquid contact angle of a sessile drop made on cold compressed and elec-trochemically polished aluminum was measured. The preferred orientation in aluminum, due to uniaxial compression, is known to be [110] direction parallel to the compression axis. However, this description is only a first approximation of a rather complex orientation. In actuality, half the crystallites are more than 10 deg from this orientation, regardless of the amount of compression." For randomly oriented fcc crystals, the average surface atomic density can be calculated as follows: The number of atoms in a unit volume is 4/a3, where a is a lattice constant. Hence, the number of atoms per unit surface area is about (4/a3)2/3 = 2.52/a2 However, when the preferred orientation took place along [110] direction, the surface atomic density is as follows: The area of (110) plane of a unit cell, considering ridges and valleys, is BYOUNG WHlE LEE, Member AIME, is Research Metallurgist, Atomic Energy Research Institute of the Republic of Korea, Seoul, Korea. Manuscript submitted May 29, 1968. IMD 2 x J2- a x Ga = 6a2 Since this plane contains 4 atoms, the surface atomic density is 4i6a2 = 2.3/a2 Upon changing from random to preferred orientations, the surface atomic density decreases about 10 pct. The increase in the stored energy and the change in surface atomic density due to plastic deformation would certainly alter the surface tension of a metal. EXPERIMENT High purity aluminum rod of 6-mm diam (99.99 pct Al, obtained from Johnson, Matthey & Co., Ltd, London, England) was cut into sections approximately 1 cm long. The transverse cross section was mechanically polished. Then, the specimens were annealed in air at 600°C for 24 hr. Thus, eight annealed specimens were uniaxially compressed at room temperature from 0 to 70 pct of cold working with an increment of 10 pct. The extent of cold working was determined by the percentage of reduction in axial length to the original length. The specimens were further polished mechanically and, then, electrochemically with the Modern Battelle Type 1 electropolishing solution with a current density of 0.3 to 0.4 amp per sq cm and an electrode potential of 8 to 12 v at the solution temperature of 78" to 82°C for approxirr~ately 5 min. The Modern Whlte Diffusing Screen \t/ --------------- re Goniometer for Mercury Lamp ^-^ Sessile Drop ¦=• Condenser c=> Microscope l_*~_i bJ Mlcromster Filer with Protmcter Fig. 1—Schematic diagram of apparatus set-up for liquid contact angle measurement.

Jan 1, 1970

T.B.King (Depaytment of Metallurgy, Massachusetts Institute of Technology)— A valuable contribution of the authors is in the factual information which they have been able to gather; this type of information is quite difficult to obtain. In many respects, however, it would have been better if they had not subsequently embarked on a discussion of the chemistry of the converter process. It seems inconceivable that the authors do not refer to the papers of Schuhmann and his associates14 which have set the thermodynamic foundation for the whole copper smelting operation. In addition, a very useful review on the physical chemistry of copper smelting by Ruddle 5 appeared as long ago as 1953. An examination of this literature would have convinced the authors that there is no cause to be surprised at a correlation between the magnetic content and the silica content of converter slags, though they rightly point out that one should distinguish between the total magnetite content of the slag and the amount of magnetite which may be considered to be in solution. It is not true that the lowest melting converter slag is that corresponding to the eutectic between ferrous oxide and silica. The simplest slag system which can be considered is a three-component system, since both ferric and ferrous iron are present. As Schuhmann, Powell, and Michal have shown, there are lower melting compositions than this eutectic in the ternary system. The most unfortunate impression given by this paper is that the driving force for chemical reaction is determined by the heat of reaction: of course the entropy change must be taken into account. It would have been more correct to list, in Table VI, values for free energies of formation. Nor can it be said that the data in Table VI represent the "best available data." They do not corregtond with any of the recent, acknowledged sources. F. E. Lathe and L. Hodnett(author's reply)— We are pleased that Dr. King finds the factual information in our uawer of some interest. Dr. King suggests that it would have been better if our analysis and discussion of the data had been omitted, largely because our list of references is so. incomplete. If he will carefully read our introduction, he will see that the questionnaire was sent out in the hope of obtaining data which would throw light on certain questions relating to the use of converter refractories. We did not attempt (nor would the AIME have published!) a complete review of the literature on copper converting, as Dr. King has apparently assumed, nor indeed a complete analysis of the data submitted, but tried only to find a sound basis for the choice of refractories, taking into consideration common variations in converter practice. We hope our paper indicates that, by raising the silica content of the converter slag and operating at a higher temperature, the normal circulating load of magnetite can be greatly reduced, and the whole reverberatory-converter operation improved to a major degree, with resultant important savings. Under such operating conditions, chrome-magnesite brick may be expected to stand up better than those of straight magnesite. Regardless of the choice as between these brick types, however, we find the cost of converter refractories to be so low in comparison with other converter costs as to justify operation under the more severe conditions suggested. Valuable as are the papers by Schuhmann and associates and the book by Ruddle, we make no apology for omitting reference to them, nor for using heats of reaction without mention of entropy changes or free energies of formation. Our primary object was to interest the practicing copper metallurgist, with whose language we may claim to be fairly familiar; we think it would have been unwise to include the highly theoretical phases of the subject which Dr. King suggests. The interest shown in our preliminary paper presented at the New York meeting in 1956, and the trends in practice whtat we have observed since that time, suggest that we did not wholly miss the target. In conclusion, we sincerely hope that Professors King and Schuhmann will independently review the data obtained in our questionnaire and submit a paper giving their own recommendations as to the choice of refractories and the particular converter operating conditions which will result in the lowest overall cost of copper smelting and converting.

Jan 1, 1960

By E. A. Gulbransen, K. F. Andrew

THIS paper. will present the results of our studies on the kinetics of the gas phase reactions of co-lumbium and tantalum with O2, N2 and H2. Studies on zirconium and titanium have been previously reported.9,11 Due to their high melting points and their many excellent physical and chemical properties, colurn-bium and tantalum have been finding their places as useful metals in science and industry. Chemically the metals are very inert to gas and liquid phase corrosion at room temperature. However, at moderate temperatures of 250°C and higher the metals react readily with oxygen and hydrogen. It is of interest to study the gas phase reactions of these metals for the following reasons: (1) to compare the rates of the several reactions with those of other metals and to correlate the rate data with theory and structure predictions, (2) to add basic information on the practical difficulties of the reduction, refining and working of columbium and tantalum, (3) to anticipate new uses for the metals and (4) to understand the role that the metals play as components in high temperature alloys. Literature Survey A number of papers exist in the literature on the gas phase reactions of columbium and tantalum with O2, N2 and H2; however, only fragmentary data have been reported on the kinetics of these reactions. Although the free energy of formation of the oxide Ta2O520at 25°C has been determined and some thermodynamic work has been reported on columbium and its oxides, the data are not sufficient to make equilibria calculations at elevated temperatures. Oxidation: 1. Kinetics: The rate of oxidation of columbium and tantalum has been studied by McAdam and Geil23 using the interference color method. Tantalum is reported to oxidize more slowly than columbium, zirconium and iron. The amounts of oxidation of columbium after 20 hr in air for several temperatures are reported by the Fansteel Metallurgical Corporation.36 Columbium starts to oxidize in air at about 200°C. The oxide is said to be adherent and prevents further oxidation until the temperature is raised. Columbium is reported not to become brittle on heating in air for short periods like tantalum because the oxide film prevents further reaction. The columbium oxides dissolve into the metal when heated in a vacuum at temperatures between red heat and 1200°C. Above 1200°C the oxides are reported to evaporate. Columbium, in the oxide free state, is an active getter in vacuum tubes. 2. Preparation and Structure: G. Grube, O. Kuba-schewski and K. Zwiauer15 have studied the decomposition of Cb2O5 in argon. They find that CbO2 is formed slowly at 1150° and rapidly at 1300°C. Cb2O5 can be reduced to CbO2 by moist H2. The reduction of this dioxide to the lower oxides is rapid. By varying conditions CbO2, Cb2O3, CbO and Cb2O can be formed. CbO2, CbO and Cb2O have independent lattices while Cb2O3 is a stoichiometric mixture of CbO and CbO2. In a later paper O. Kuba-schewski" has shown that CbO is cubic and that CbO2 has a rutile type of lattice. The most exhaustive work on the oxides of columbium is that of G. Brauer.8 The number and constitution of the solid phases in the binary system Cb-O were investigated by the preparative, analytical and X ray methods. He indicates that only the oxides Cb2O5, CbO2 and CbO exist with limited regions of homogeneity. The solid oxide Cb,O, exists

Jan 1, 1951