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By W. T. Isbell

IN the Parkes process of lead refining, after desilverization has been completed by means of the addition of zinc, there remains in the lead from 0.5 to 0.6 pct zinc. At this stage in the refining operations virtually all impurities are reduced to refined lead specifications except zinc and antimony. All excess copper, nickel and cobalt have been removed by the zinc additions. The silver remaining should not exceed 0.1 oz per ton. It then remains only to remove the zinc and antimony in order to produce refined lead. At the Herculaneum plant of the St. Joseph Lead Co., practice formerly was to complete the refining by means of oxidation in a reverberatory furnace. This process consisted of heating the lead to 14000 to 1500°F and allowing it to come in contact with excess air passing over the surface of the lead and periodically agitating the bath of lead with air. This procedure not only resulted in the loss of zinc but of a considerable quantity of lead converted to the oxide in the form of dross and fume. The fume, collected in the baghouse, together with the dross was returned to the blast furnace, thus adding appreciably to the circulating load on the blast furnace and refinery. In addition, operation and maintenance of the reverberatory furnace was expensive and required the performance of disagreeably hot and somewhat hazardous work. The process of dezincing with high vacuum was developed at this plant as a substitute for the oxidation process and finally led to lower operating costs, the practical elimination of dross and fume and the direct production of metallic zinc, which is very suitable for re-use in the desilverization process. Essentially this process consists of subjecting the lead to high vacuum, in a kettle provided with means for heating, a bell-shaped member open at the lower end so constructed that it can be immersed in the molten lead, and means for evacuating the interior of the bell and for sealing an agitator. Metallic zinc is thus produced and collects on the upper cooled part of the bell member. This metallic zinc is periodically removed and re-used in the desilverization process. The process is quite simple. It is conducted at a low temperature, thus permitting the use of iron equipment, and shows a material saving in refining costs over the old method. EQUIPMENT AND ITS USES Dezincing Machine.-The equipment employed in this process consists of a dezincing machine, a steel kettle of 120 tons capacity, a vacuum system and equipment for handling the dezincing machine (Fig I). The dezincing machine consists of a compact assembly, suitable for handling with an overhead crane, consisting of a treating chamber and the agitating mechanism. Treating Chamber.-The treating cham¬ber is a bell-shaped shell (4), similar in shape to a hemispherical kettle with a lid

Jan 1, 1947

By Ronald C. Koo

SMALL additions of potassium, aluminum, and silicon as oxides (referred to as dope) to tungsten have been known for several decades to have a very large effect in raising the recrystallization temperature and altering the recrystallized grain morphology of heavily drawn wire. Previous investigations of this doping effect1 6 have led to various speculations but all failed to deduce unequivocally the physical state or the mechanistic influence of the dopant. Recently, walter7 has observed, by transmission electron microscopy, strings of "fine particles" in heavily rolled and annealed doped tungsten sheet and concluded that they were particles of mullite (Al6Si2013). His conclusion was inferred from the electron diffraction patterns of large particles ex-trated by carbon replication of fractured surfaces of slabs rolled from sintered ingots. That the strings of "fine particles" in heavily rolled and annealed sheet were also mullite was an assumption for which no evidence was presented. A similar investigation has been carried out in this laboratory over the past 2 years on a variety of tungsten wire: doped tungsten, and undoped tungsten, as well as 218 doped tungsten purchased from the Lamp Metals and Components Department of the G.E. Lamp Division. Although the electron microscope observations are similar to those reported by Walter, the writer has reached a different conclusion concerning the physical state of the dopant in annealed tungsten. The purpose of this communication is to present evidence that the strings of "fine particles" observed in transmission specimens are not mullite, but are voids. In the present investigation, tungsten wire, 0.88 mm in diam, was rolled into ribbon 0.2 mm by 125 µ thick. The ribbons were annealed in vacuo at a pressure of -1 x 10-5 Torr and then thinned electrolytically in a 2 pct KOH solution. Fig. 1 shows a typical transmissicjn electron micrograph of a sample annealed at 1700°C for 30 min which reveals rows of closely spaced voids having a light contrast (referred to as "fine particles" by Walter) aligned parallel to the working direction. Stereo micrographs (by D. Moon, Westinghouse Research and Development Center) have shown that these voids do not exist on the surfaces of the specimens as a result of thinning but are within the thin-foil specimens. The following experiments have been performed to verify that these are indeed voids. I) Effect of Annealing. Voids are absent in unannealed specimens and appear only after annealing. This behavior cannot be explained if they were solid particles such as mullite. Precipitation (in an unquenched specimen) upon annealing requires solute elements having decreasing solubilities with increasing temperature. Although the solubility of aluminum in tungsten does decrease with increasing temperature, precipitation requires a concentration in excess of 1.4 wt pct,8 which is at least two orders of magnitude higher than the aluminum content in doped tungsten. It is also unreasonable to assume that particles aligned in rows initially present in unannealed specimens were too

Jan 1, 1968

By P. Pietrokowsky

lntermediate phases in the binary metal alloy systems Ti-Zn, Ti-Hg, Zr-Zn, Zr-Cd, and Zr-Hg have been investigated by X-ray powder diffraction methods. Gamma-TiBHg and Zr3Hg have a beta tungsten structure; TiHg and ZrHg are analogous to ordered AuCu (L l0 type); delta-TixHg and ZrHg, are isomorphous with ordered AuCu,, (L l2 type); ZrZnz is face-centered cubic (C 15 type); TiZna crystallizes in a C 14 type structure; and Zrll-, occurs in cubic and tetragonal modifications in which a random distribution of atoms exists. Additional information for the intermediate phase TiZn, is presented. THE physical metallurgy of titanium and zir-conium when alloyed with elements in subgroup 11-B of the periodic table has received comparatively little attention in the literature. Laves and Wallbaum' reported the existence of several intermediate phases in the system Ti-Zn. They identified TiZn as a CsCl (B 2) structure and described TiZn, as an ordered Cu,Au (L 1, type) crystal structure. Gebhardt' investigated very limited zinc-rich regions in the systems Ti-Zn and Zr-Zn. Phase relationships in these partial constitution diagrams were deduced from the results of thermal analysis and metallography, X-ray results being inconclusive. The first zinc-rich intermediate phase in either system was not identified. More recently, Anderson, Boyle, and Ramsey" have had occasion to refer to a partial Ti-Zn phase diagram (unpublished data) covering the region 0 to 10 atomic pct Ti, wherein two intermediate phases corresponding approximately to TiZn,, and TiZn,, were indicated. The metals used in this investigation and typical analyses as determined by the suppliers are given in Table I. The iodide-process zirconium which was used was not hafnium free. Experimental Methods Alloy Preparation: The relative ease with which titanium and zirconium combine with other elements places extensive restrictions on the methods by which alloying can be achieved. The direct current electric arc melting procedure was found to be unsatisfactory for preparing these binary alloys and for this reason solid state diffusion methods were utilized. The iodide process titanium and zirconium rods were filed by hand. Fines were subjected to a magnetic separation and classified as to size as either finer than 200 mesh or coarser than 200 but finer than 80 mesh. Powder mixtures of various binary combinations of titanium and zirconium with zinc and cadmium were compacted in a 12 mm diameter die and then placed in Vycor or quartz vials which were evacuated and sealed. The mercury alloys were prepared in a similar manner; the proper weight of liquid mercury being placed in a vial with minus 200 mesh titanium or zirconium. These ampoules were then heat treated at various temperatures and times depending on the characteristics of the particular alloy system. Upon completion of the heat treatment the ampoules were cooled rapidly and the specimens weighed. The loss in weight varied from 1 to 3 pct (except as noted in the text) and for this reason the calculated compositions were accepted as a fair measure of the actual alloy compositions. X-Ray Dif raction Techniques: Powder diffraction experiments were conducted at room temperature with a 143.2 mm Debye-Scherrer X-ray camera in which the film was placed in the Straumanis arrangement. When copper radiation was used, a nickel filter was employed, and for the cobalt target a filter of iron oxide was used. In both cases, the /i? filter was placed between the X-ray target and the powder specimen which was mounted on a glass fiber. The lack of information based on optical metallography placed reliance on the results obtained from the X-ray experiments for determination of

Jan 1, 1955

By Charles L. Mantell, George Ferment

This investigation determined the jeasibility of current-potential curves as an analytical tool for monitoving manganese electroicinning solutions for metallic impurities. Nine metallic impurities were studied: trickel, cobalt, silver, copper, zinc, molybdenum, catlmiun magnesium, and sodium. The individual effect of each metallic irzplrl,iLy on the standard point-izatiorr was determined for a range of 'concentration. Not all of Ihe impurities affected the polarization curve; correlation between transition current and cotrcetztration of impurity. Molybdenum had an uncorrelated effect on the polarization curie. The effects of binary mixtures of impurities were studied to see if the transition current of the mixture could be predicted. Interactions occurred between impurities which prei'etzted the pvecliction the transition current of tile rrlisLitr.e by additive laws. The polarization curve was shown to be sensitive to metallic impurities which affect the current efficiency of a manganese cell. THE application of current-potential curves in manganese electrowinning is not new but played an important part in the conversion of an inoperative large-scale pilot plant into a continuous comnercial operation.1"" The effects of trace metallic impurities in manganese electrowinning solutions on cathode current-potential curves,5-19 specifically nine impurities (nickel, cobalt, silver, copper, zinc, molybdenum, cadmium, magnesium, and sodium) were studied for a range of concentrations. Cadmium, magnesium, and sodium had no effect. Nickel, cobalt, silver, copper, and zinc yielded a correlation between transition current and concentration of impurity: molybdenum had an uncorrelated effect. Binary mixtures of impurities were studied to de-termine if the transition current could be predicted from the values for the individual constituents. Interactions between impurities prevented the prediction of the transition current of the mixtures by an additive law. The polarization curve was shown to be sensitive to metallic impurities which affected the rurrent efficiency of a manganese cell. The electrowinning of manganese relies upon maintaining a high-purity electrolyte. Purification schemes were developed to remove all of the heavy metals, the magnesium and calcium. Concentration limits have been established for single impurities. With high-purity electrolytes, favorable cell efficiencies are consistently obtained; but with impure solutions there is a reduction in efficiency. With the rapid rise to commercial prominence of electrochemical processes, there has been a lag in developing rapid methods for determining whether an electrolyte is sufficiently pure for efficient electrolysis. The most sensitive test for impurities is the behavior of the electrochemical cell. Impure electrolytes will cause a serious reduction in cell efficiency, and in many cases metal deposition will be prevented or reversed. The effects of impurities are not usually evident until after long periods of electrolysis, resulting in a disruption of the process. A method which could predict the behavior of an electrolyte in terms of cell efficiency prior to reaching the commercial cell is needed. Van Arsdale and Maier," Allmand and Campbell,a1'22 and others attempted to develop an electrochemical process for manganese,"3"29 but all met with some degree of difficulty. Jacobs et a studied the effects of metallic impurities in manganese electrowinning. Plant methods were based on a 2-hr plating in a small electrolytic cell. The final method was based on a 24-hr plating run, performed in a relatively large test cell. Here, current efficiencies were calculated with and without impurities in the electrolyte, and the critical concentration was established as the maximum amount of impurity that the electrolyte could tolerate before there was a serious loss in efficiency. The amount of impurity that could be tolerated decreased as the plating time increased, indicating deposition of the impurity. This test duplicated the conditions of commercial practire, and was sensitive to impurities. Small amounts of impurities significantly affect the hydrogen overvoltage at a metal surface, increasing or decreasing it depending upon the nature of the impurity. ockris established the limit for the onset of poisoning at 10-l moles per liter. The effects of impurities were studied by potential-time curves at a constant current density. The technique did not lend itself to rapid analysis in that several hours were needed to establish stable potential-time curves. Serfass and coworkers3' developed calorimetric and spectrophotometric techniques for analyzing for trace impurities. Our method4'" is based on current-cathode potential curves produced by continuously changing the cell voltage at a programmed rate. Starting with a clean stainless-steel cathode, the cell voltage was initially adjusted to yield zero current: the program was then started and the current was plotted as a function of the cathode potential. Fig. 1 is a typical current-potential curve. In initial region A the hydrogen-evolution reaction predominates and the polarization curve

Jan 1, 1967

By AIME AIME

A JOINT meeting of the Canadian Institute of Mining and Metallurgy and the American Institute of Mining and Metallurgical Engineers was held at Spokane, Wash., and Cranbrook and Kimberley, B. C., on Oct. 13 to 16, 1926, with a total attendance at one or another or all of the meetings of about 300 members, ladies and guests. At the opening meeting, on Oct. 13, in the Davenport Hotel, Spokane, about 175 were present. The morning was occupied with addresses of welcome by M. H. Sullivan for the Columbia Section, who called on Mayor Charles A. Fleming, President John F. Davies for the Chamber of Commerce, and E. R. Hannibal, president of the Associated Engineers, each of whom heartily welcomed the visitors. Philip N. Moore, former president, and special representative of President Samuel A. Taylor, replied for the A.I.M.E., and Lewis Stockett, president, and Charles A. Banks, chairman, British Columbia Division, Canadian Institute of Mining and Metallurgy, and Henry M. Parks for the visiting A.I.M.E. sections, made appropriate responses on behalf of those they represented. The members and ladies had luncheon with the Associated Engineers. Philip N. Moore addressed the assembly on "The Opportunity of the Engineer"; an excerpt from his address appears on another page. At the afternoon meeting, with Lewis Stockett in the chair, Frank M. Smith was asked to make a brief statement of the proceedings of the Silver Producers Association in Denver. Supplementing his talk by placing a well-prepared statement on "Silver and the Plan of the Royal Commission on Indian Currency and Finance" in the hands of those present, he narrated what had been undertaken by the Silver Producers Association and what they hoped to accomplish.

Jan 1, 1926

By Philip Lindstrom

T he Radon mine is in the north end of the Big Indian mining district in San Juan County, Utah. Hecla Mining Co. operated the mine from early 1955 to early 1964 through an operating agreement with Federal Resources, Inc. Development consisted of a 3-compartment, 690-ft shaft, 4 main levels driven on the ore horizon and a haulage level below the ore. Evaluation of physical and economic factors showed that this flat-dipping ore occurrence could be mined by a low-cost coal mining method. The value of the deposit was high and unusual pre¬miums were possible by clean mining. Complete extraction without loss of ore pillars, minimum ore dilution and high production per man were obtained by longwall mining.

Jan 12, 1964

By Allan E. Martin, Harold M. Feder, Irving Johnson

The cadmium-uranium system was studied by thermal, metallographic, X-7-ay and sampling techniques; special emphasis was placed on the establishment of the liquidus lines, The single inter metallic phase, identified as the compound UCd11 melts peritectically at 473°C to form a-umnium and melt containing 2.5 wt pct uranium. The cadmium-rich eutectic (0.07 wt pct uranium) freezes at 320.6°C. Solid solubilities in uraizium and cadmium appear to be negligible. Between 473°C and 600°C the liquidus line is retograde. NO publication relating to the cadmium-uranium phase diagram was found in the literature. The establishment of this diagram was of considerable interest to us because of a possible application of the system to the pyrometallurgical reprocessing of nuclear fuels. Analysis of liquid samples, metallographic examination, thermal analysis, and X-ray diffraction analysis were used to establish the phase diagram from about 300° to 670°C. Particular emphasis was placed on the establishment of the liquidus lines. The same system was concurrently studied in this laboratory by the galvanic cell method.' Both studies benefited from a continual interchange of information. MATERIALS AND EXPERIMENTAL PROCEDURES Stick cadmium (99.95 pct Cd, American Smelting and Refining Co.) contained 140 ppm lead as the major impurity. Reactor grade uranium (99.9 pct U, National Lead Co.) was most often used in the form of 20-meshspheres. This form was particularly suitable because it does not oxidize as readily as finer powder. The liquidus lines were determined by chemical analysis of filtered samples of the saturated melts. The liquid sampling technique is described elsewhere2 alumina crucibles (Morganite Triangle RR), tantalum stirring rods, tantalum thermocouple protecthecadmiumtion tubes, Vycor or Pyrex sampling tubes, and grades 60 or 80 porous graphite filters were used. Uranium dissolves in liquid cadmium rather slowly. In order to achieve saturation of the melts it was necessary to modify the procedure of Ref. 2 by the use of more vigorous stirring and longer holding periods (at least 3 hr) at each sampling temperature. The samples were analyzed for uranium by spectro-photometry (dibenzoyl methane method) or by polar- ography. The analyses are estimated to be accurate to 2 pct. Thermal analysis was performed on alloys contained in Morganite alumina crucibles in helium atmospheres. Standard techniques were employed; heating and cooling rates were about 1°C per min. For the determination of the peritectic temperature, Cd-10 pct U charges were first held for at least 50 hr at temperatures in the range 435° to 460°C to form substantial amounts of the intermediate phase. For the determination of the effect of cadmium on the a-p transformation temperature of uranium, charges of Cd-25 pct U (-140+100 mesh uranium spheres) were first held near the transformation temperature, with stirring, to promote solution of cadmium in the solid uranium. The holding times and temperatures for these treatments were 18 hr at 680°C for the cooling run and 28 hr at 630°C for the heating run. Alloy specimens for X-ray diffraction and metallographic examination of the intermediate phase were prepared in sealed, helium-filled Vycor or Pyrex tubes. Ingots from solubility runs and thermal analysis experiments also were examined metallographically. Crystals of the intermediate phase were recovered from certain cadmium-rich alloys by selective dissolution of the matrix in 20 pct ammonium nitrate solution at room temperature. Temperatures were measured with calibrated Pt/Pt-10 pct Rh thermocouples to an estimated accuracy of 0.3°C. However, the depression of the freezing point of cadmium at the eutectic is estimated to be accurate to 0.05°C because a special calibration of the thermocouple was made in place in the equipment with pure cadmium just prior to the measurement. EXPERIMENTAL RESULTS The results of this study were used to construct the cadmium-uranium phase diagram shown in Fig. 1. This diagram is relatively simple; it is characterized by a single intermediate phase, 6 (UCd11), which decomposes peritectically, and which forms a eutectic system with cadmium. The solid solubilities in the terminal phases appear to be negligible. An unusual feature of the diagram is the retrograde slope of the liquidus line above the peritectic temperature. The Liquidus Lines. The liquidus lines above and below the peritectic temperature are based on three separate solubility experiments. The data are shown in Fig. 1 and are given in Table I. It is apparent from the figure that the solubility data obtained by the approach to saturation from higher temperatures fall on substantially the same lines as those obtained

Jan 1, 1962

By David W. James

DURING a recent investigation of the transition from a planar to a nonplanar solid/liquid interface for the systems H20-NH4F and 0-AIR,' an apparatus was developed which enabled the morphology of the ice-water interface to be examined during the transition. The slightly curved interface was viewed at a glancing angle with a Bausch and Lomb X30 stereomicro-scope. The interface was obliquely illuminated by a polarized light source. It was thus possible to differentiate between small projections or depressions at the interface, both by a shadowing effect and by the way in which they distorted the colored interference fringes across a particular crystal surface. Many attempts were made to photograph the various stages of interface breakdown. Unfortunately, the limited depth of focus of the microscope rendered the system unsuitable for photographic recording. Visual examination, however, was facilitated by continuous adjustment of the microscope focus control. The following observations of the interface transition were recorded for dilute solutions of ammonium fluoride in water. They are compared with iller's postulated morphologies shown in Fig. 1. i) The initial departure from planarity was characterized by the appearance of a large number of small depressions or "pores" in the interface. ii) The pores were arranged in wavy rows all lying roughly in the same direction within a particular grain. iii) The pores did not appear to form near to grain boundaries. iv) The pores appeared in certain grains before others. v) The transition from the pore structure to the elongated cell structure, Fig. l(d), was difficult to follow. It occurred quite rapidly and no truly irregular cell structure, Fig. l(c), was noticed. vi) The elongated cells gradually became more uniform in size and shape, with straight cell boundaries. They remained elongated, however, and no regular hexagonal cells were observed, cf. Fig. l(e). Several conclusions may be drawn from these observations. Firstly, the appearance of a poxed or, more accurately, a pore structure can be used as a criterion for the onset of constitutional supercooling. Care should, of course, be taken to distinguish between the true pore structure and artifacts caused by splashed-back liquid, particles of oxide, or inefficient decantation of liquid retained between cell boundaries, as described by Spittle et al? Secondly, and contrary to the suggestions of Tiller el l., it seems that interfacial perturbations are characterized not by curved projections but by small depressions or pores. A recent independent investigation by Biloni, Bolling, and cole5 reported in this issue indicates that the depressions might be explained in terms of dislocations intersecting the solid/liquid interface. It is possible that the dislocation concentration is reduced in the vicinity of grain boundaries. This would then explain the grain boundary depleted areas noted in (iii) above. This work was partially supported by the Air Force Office of Scientific Research, Contract No. AF 49-(638)-1029.

Jan 1, 1967

By W. C. Hagel

In 1952, Hauffe and pfeiffer1,2 reported that parabolic rates of nickel oxidation are decreased by factors of two and four at 1100° and 1000°C, respectively, when Li2O vapor is present. Hauffe 's3 explanation was that monovalent lithium enters the crystal lattice of p-type NiO to decrease cation-vacancy concentration and, hence, diffusion of Ni2+ ions across the growing oxide. After first succeeding in adding lithium directly to molten nickel, the purpose of this investigation was to determine whether alloyed lithium is a more effective oxidation inhibitor than the external vapor. Seven 650-g heats were prepared by melting carbonyl nickel inductively under 1 atm of argon. Various amounts of lithium were added by dropping small chunks into the melt. Only about 10-pct recovery was achieved with the remainder lost by spattering and volatilization. Nominal and actual

Jan 1, 1965

By E. A. Farrell

A comprehensive survey is made of the status of the asbestos industry as it relates to marketing the product. Included are descriptions of the various types of asbestos and the grading and classification systems used. The uses of asbestos, distribution practices, and types of ore bodies are all related to marketing. World production, the producers and their capacities and world consumption for 1966-67 are summarized and statistical data are included. Asbestos is a general term describing a family of fibrous minerals of the serpentine and amphibole mineral groups. Asbestos has a long history going back to the time of the Egyptians, when it was used as a lamp wick. The commercial mining of asbestos started in Canada, Russia, and Africa in the 1800's, and the first asbestos products were made in Italy and Russia. The five main types of asbestos are: chrysotile, accounting for 95% of the total mined, amosite, crocido-lite, anthophyllite, and tremolite. Canada, Russia, and Africa are the major producers of asbestos. The commercial utility of asbestos was at first based on the heat resistance of the fibrous mineral in the form of packing, at the start of the industrial revolution. Its current utility is based more on its ability to reinforce binders such as portland cement, rubber, and plastics. Its inertness to the chemical nature of most binders is unique. Most important is its ability to maintain its reinforcing utility when the product is exposed to weather and soil conditions as in asbestos cement boards and pipe, and heat, pressure, and chemical exposure as in brake linings and gaskets and packings. The mineral asbestos is also unique because its fibrous form permits it to be spun and woven to cloth or formed into paper. Many asbestos applications are critical to national defense and at the present time, there are no satisfactory substitutes. Grading and Classification Canadian chrysotile asbestos fiber is graded and priced by length since basically the longer the fiber the higher the utility. The Canadian asbestos industry does not, however, classify the fiber by direct length measurement, but by a dry screening test. The method is called the Quebec Standard Screen (QS) test. One pound of fiber is mechanically shaken in four vertically stacked sieve boxes. The relative proportions remaining on the sieves defines the grade. The longer the fiber, the larger is the amount that stays on the top coarse screens and the less on the lower, finer mesh screens. Other tests can be used to further define the length distribution of fiber such as the wet screen Bauer McNett and the Suter Webb Comb (3 group only). The Canadian grading system divides the milled fibers into 5 main groups: group 3, 4, 5, 6, and 7, with 3 group being the longest, and 7 the shortest. Each group is further divided to subgrades, identified in each group by the letters A to Z, with "A" the longest and "Z" the shortest. See Appendix 1 for the Canadian QS classification system. The Russians also use the QS test on chrysotile. The Africans classify their chrysotile into grades similar to Canadian. The African crocidolite and amosite, however, are classified into actual length groups such as l to 2 in. and 2 to 3 in. Amosite and crocidolite are generally longer than chrysotile but also more brittle. Milled asbestos is not composed of staple length fibers like fiber glass or cotton, but of a mixture or blend of fibers ranging from long to short. Milled asbestos has a fiber length distribution similar to the particle size distribution of a powder. For example, the longest group 3 chrysotile grades have a high percentage of the longest fibers (1/2 to 3/4 in.) and low percentage of short fibers (0.003 in.). The figures in Table 1 give the approximate length distribution of the longest, middle, and shortest groups. A second and further method of classifying fiber is the degree to which the fiber bundles are separated to form a larger number of smaller diameter bundles. This property is normally described as the degree of fiberization, openness or surface area. Air permeability tests are used to measure surface area. Asbestos pro-

Jan 1, 1971

By R. Schuhmann

Available thermodynamic data applicable to copper smelting systems are collected and tabulated, and the important gaps are pointed out. A few examples are given of estimations which can be made from the available data. An experimental research program is proposed to supply the thermodynamic data that appear most essential to better quantitative understanding of the chemistry of copper smelting. The proposed program is designed also to shed specific light on the practical problems of slag losses and magnetite behavior. OPPER smelting, from flotation concentrates to V-/ blister copper, is conspicuous among the large scale chemical processes which are conducted with only relatively incomplete knowledge of the physical chemistry involved. For example, no common metallurgy text explains adequately why copper enters the matte phase while iron enters only to the extent that sulphur is left over after satisfying the copper. Explaining this important phenomenon as a manifestation of the greater affinity of sulphur for copper than for iron is unsound because the affinities of copper and iron for sulphur are about the same at smelting temperatures. As will be shown, other affinities are really decisive in the relatively clear-cut separation of copper in the matte. In contrast, thermodynamic studies have contributed much to our understanding of copper refining, zinc oxide reduction, magnesium production, steelmaking, etc. For each of these processes, the important reactions are clearly recognized, and fair to good quantitative values of the free-energy changes and equilibrium constants are available. Such data have proved to be of constantly increasing practical value in process development and improvement. Work in other fields has furnished much thermodynamic data applicable to copper smelting systems. In fact, several promising starts have been made in applying such data to specific smelting problems. Kelleyl made an appraisal of the possibilities of recovering elementary sulphur from low grade matte. His calculations and compilations of thermodynamic data have represented the starting point for much of the work in this field, including the present survey. Huang and Hayward2 nd Aksoy3 used thermodynamic methods in the study of copper losses in reverberatory slags. Peretti4 used thermodynamic data in explaining the chemistry of converting. The recent publications of Darken and Gurry"." and of Darken,' dealing with the iron-oxygen and iron-silicon-oxygen systems, respectively, present equilibrium data that are applicable to copper smelting systems. Also additional data were reported recently on the affinity of sulphur for copper, manganese, and iron8 and on the sulphur pressures of iron-sulphur melts." The survey presented in this paper was made as the basis for planning an experimental program on the thermodynamics of copper smelting. Few researches on the chemistry of copper smelting have been reported in recent years, so that a reappraisal and coordination of old and new data are essential if further work is to take the directions of maximum value. The experimental program is now in progress, and the plan of attack is outlined at the end of this paper. Progressive Oxidation and Desulphurization of Copper-bearing Liquid Phases: The chemical activities of sulphur and oxygen are two of the most important thermodynamic yardsticks to be applied to copper smelting processes. Virtually the entire smelting and refining sequence involves a series of systems characterized by decreasing sulphur activity and increasing oxygen activity. In this section, therefore, an attempt is made to define and explain these activities in terms of equilibrium partial pressures of SO2, s2, and O,. Also, estimates of these quantities are presented, the estimates being based largely on calculations presented in a later section of this paper. The sequence of steps from raw flotation concentrate to fully oxidized copper ready for poling involves progressive and controlled oxidation. Iron is oxidized and enters the slag. Sulphur is oxidized and leaves in the gas. Table I summarizes several important features of this oxidation and desulphurization sequence, starting at the beginning of the matte blow in the converter. The top line gives in order the principal smelting and refining stages up to fully oxidized copper, plus the additional step, not used commercially, of oxidizing all the way to Cu,O. In the second line are shown the principal copper-bearing liquid phases which characterize the process. Through most of the sequence the copper

Jan 1, 1951

By W. R. Ingalls

THE propaganda in favor of the adoption of the metric system of weights and measures in the United States is founded upon the idea of compulsory adoption. There can be no argument about this, for the metric system has been legal, by Act of Congress, in the United States since 1866. Nobody ought to oppose an educational movement, and if pro-metric activities were confined to that there might be no reason to gainsay them. I do not propose to enter into any discussion of 'the relative merits of the metric and the English systems of weights and measures. The simple case is that the metric system not having made much headway in the United States after more than 50 years of legality, 'it is now aimed to force it upon the people by legislative compulsion. The main arguments in favor of such compulsory adoption are that it would- simplify the education of our children and would promote our foreign trade, for the reason that more countries of the world, with which we do business, use the metric system than the English system. I am going to disregard,' in this contribution, the first of these arguments, for it is largely conjectural." Not so with the other, which is specific, and being so its speciousness can be, proved. It is true that the metric system is used by more countries of the world than the, English system. It is commonly stated that of the Indo-European nations only the United States, Great Britain, and her colonies, and Russia have failed to adopt it. However, if with "colonies" we equate Canada, Australia, New Zealand, Tasmania and South Africa, we have a longer list of non-metric countries, and it comprises not only the most populous, but also the most industrial nations of the world.

Jan 1, 1921

By D. W. Akins

The case history of a combination gas and water flood instituted early in the life of a field is described. It was recognized from the beginning that recovery would be low, under normal production methods, from the several separate, thin beds of porous limestone which had such poor native permeability that the wells would not produce without acidizing. It is thought that the combination flood gives excellent recovery efficiencies for this type of reservoir. The chief function of the gas flood now is to maintain bottom hole pressure in that part of the reservoir which will not be affected by the water injection program until later. Present estimates are that ultimate recovery will be approximately double the recovery expected under the original solution gas drive mechanism. Wide (80-acre) spacing has enhanced the economics of the over-all field program by the elimination of more than $5,000,000 worth of unnecessary wells. INTRODUCTION The Haynesville Pettit Field was discovered in November, 1941, with the completion of T. L. James Co.'s Callie Akin No. 1, located in the W 1/2 of the NE 1/4 Section 27-23N-8W, Claiborne Parish, La., at an approximate depth of 5,300 ft. The center of the field is about two miles north and a mile west of the town of Haynesville, La. A total of 189 producing wells have been drilled on 14,500 acres. An additional nine dry holes were drilled. The Louisiana-Arkansas state line divides the field so that 34 wells are in Arkansas and 155 are in Louisiana. Governmental sections are divided equally to contain eight production units making 80-acre spacing where the sections are regular. Along the state line in Louisiana there is an irregular tier of sections, each of which contains approximately 456 acres. When divided equally into eight production units the spacing is 57 acres per well for these three and a fraction productive sections. All Haynesville Pettit wells are identified by their section number followed by their position in the section as determined by numbering the production units counterclockwise beginning in the upper right corner of the section. All of the producing wells in the field except two are unit-ized and operated by the Haynesville Operators Committee. These two wells are located in the extreme northern part of the field in Arkansas. Efforts to bring them into the Unit are being continued. The Pettit operators organized the Haynesville Operators Committee and the field became a unit operation May 1: 1944. GEOLOGY The Pettit is Lower Cretaceous in age and is defined as the uppermost porosity in the Sligo formation. The unitized area known as the Haynesville Pettit Field is composed of two separate zones of porosity approximately 40 ft apart and without connection between the two, except in wells. These zones are known as the Upper Pettit and the Lower Pettit. The Upper Pettit is separated into two sections throughout most of its area by a relatively thin but quite impervious shale streak. These are called the "A" and "B" sections of the Upper Pettit. All of these lenticular zones are composed of coquina limestone and a small percentage of normal oolites. The large

Jan 1, 1951

By D. W. Akins

The case history of a combination gas and water flood instituted early in the life of a field is described. It was recognized from the beginning that recovery would be low, under normal production methods, from the several separate, thin beds of porous limestone which had such poor native permeability that the wells would not produce without acidizing. It is thought that the combination flood gives excellent recovery efficiencies for this type of reservoir. The chief function of the gas flood now is to maintain bottom hole pressure in that part of the reservoir which will not be affected by the water injection program until later. Present estimates are that ultimate recovery will be approximately double the recovery expected under the original solution gas drive mechanism. Wide (80-acre) spacing has enhanced the economics of the over-all field program by the elimination of more than $5,000,000 worth of unnecessary wells. INTRODUCTION The Haynesville Pettit Field was discovered in November, 1941, with the completion of T. L. James Co.'s Callie Akin No. 1, located in the W 1/2 of the NE 1/4 Section 27-23N-8W, Claiborne Parish, La., at an approximate depth of 5,300 ft. The center of the field is about two miles north and a mile west of the town of Haynesville, La. A total of 189 producing wells have been drilled on 14,500 acres. An additional nine dry holes were drilled. The Louisiana-Arkansas state line divides the field so that 34 wells are in Arkansas and 155 are in Louisiana. Governmental sections are divided equally to contain eight production units making 80-acre spacing where the sections are regular. Along the state line in Louisiana there is an irregular tier of sections, each of which contains approximately 456 acres. When divided equally into eight production units the spacing is 57 acres per well for these three and a fraction productive sections. All Haynesville Pettit wells are identified by their section number followed by their position in the section as determined by numbering the production units counterclockwise beginning in the upper right corner of the section. All of the producing wells in the field except two are unit-ized and operated by the Haynesville Operators Committee. These two wells are located in the extreme northern part of the field in Arkansas. Efforts to bring them into the Unit are being continued. The Pettit operators organized the Haynesville Operators Committee and the field became a unit operation May 1: 1944. GEOLOGY The Pettit is Lower Cretaceous in age and is defined as the uppermost porosity in the Sligo formation. The unitized area known as the Haynesville Pettit Field is composed of two separate zones of porosity approximately 40 ft apart and without connection between the two, except in wells. These zones are known as the Upper Pettit and the Lower Pettit. The Upper Pettit is separated into two sections throughout most of its area by a relatively thin but quite impervious shale streak. These are called the "A" and "B" sections of the Upper Pettit. All of these lenticular zones are composed of coquina limestone and a small percentage of normal oolites. The large

Jan 1, 1951

By Richard L. Gordon, Charles J. Johnson

Electric power demand doubles about every ten years, and because of the associated burgeoning fuel requirements, power stations absorb over half of the coal output in the United States. Throughout the 1960's, demand for coal utilized to generate electricity grew at an average annual rate of 6.5% but coal producers held back greater expansion because they expected nuclear plants to proliferate faster than they actually did. Even so, the growth rate is expected to continue at the 1960's rate until at least 1976. The continuation of the 6.5% growth rate beyond 1976, however, will require additional orders for coal-fired plants during the early 1970's. In fact, plants consuming a total of 130 million tons of coal must be ordered in the next few years. If the requisite plants materialize, total 1980 coal output for electrical power generation will be approximately 600 million tons.

Jan 1, 1971

By E. J. Wasp, N. T. Cowper, R. A. Davis, W. F. McDermott

On October 26, 1967, the world's first long distance iron ore slurry line was put into service by Savage River Mines. The commissioning of this $5 million installation climaxed three years of development, testing, and construction. The mine and concentrator are located approximately 30 miles from the town of Waratah in a rugged semi-mountainous terrain. The open pit mine will produce approximately 5 million long tons a year of crude ore, which is ground in autogenous mills, separated magnetically, thickened and prepared for the pipeline. The 53-mile pipeline transports the 2,250,000 tons of concentrate north to Port Latta. The Port Latta facilities include the receiving, storage and thickening equipment for the slurry as well as filtering, balling and pelletizing equipment to produce the 2,250,000 tons of high grade iron ore pellets. Five vertical shaft furnaces are used for pelletizing.

Jan 1, 1969

By D. C. Bard

THESE notes are based on the megascopic study of a suite of 2,400 specimens of minerals and ores from the Butte mines, combined with field observations at intervals over a period of several years. The estimate of average vein composition is based on field acquaintance with the veins. It is probably correct in its broader proportions, and should be of use for comparison. Chemical and Mineral Composition of Butte Sulphide Vein. Matter. Per Cent. Oxygen 43.00-Quartz, rhodonite, rhodochrosite, barite, calcite, and hübnerite. Silicon 36.00-Quartz, rhodonite, and willemite (very rare). Sulphur 5.00-Sulphides of. iron, zinc, copper, lead,. and sulphates of barium and rarely calcium. Iron 5.00-Ferric sulphides (pyrite, bornite, chalcopyrite), also in sphalerite, tetrahedrite, and rarely hematite and siderite. Manganese, . . . . 2.00-Rhodonite, rhodochrosite, and hübnerite. Zinc, . . . . 1.00-Spha erite, very rare wurtzite and willemite, and tetrahedrite and tennantite.

Jan 8, 1913

By W. F. Dietrich

Mineral fillers are relatively inert chemically under the conditions of use but have physical properties* that modify those of the materials • The properties. uses, and other data on 15 classes of important *The pro listed in the second edition of Industrial Minerals and Rocks.l A third edition of this reference is in preparation. in which they are incorporated. The mineral fillers considered in this article are asbestos, barite, clays, diatomite, crushed limestone, limestone whiting and lime, mica, silica, talc and soapstone, and pyrophyllite. Slate and stone, other than limestone and its derivatives, are excluded because, even though used in large quantities, they are exceptionally low-cost materials generally produced close to the area where they are used. Carbon black is excluded because it is manufactured from natural gas and more than 90 pct of the output is used in rubber; hence the factors for estimating requirements are easily evaluated. OVERALL GROWTH FACTORS Table I gives the population, retail sales, and value added by manufactures in the U. S. and in the eleven western states in 1954. These data are rough guides to the proportionate part of total U. S. markets for products containing mineral fillers that may be expected in a given area. For example, the population of the eight Mountain states in 1954 was 3.6 pct, and retail sales in these states were 3.8 pct of the U. S. total, but the value added by manufactures was only 1.3 pct of the U. S. total. On the other hand, the three Pacific Coast states, with 10.3 pct of the total population, had 12.0 pct of the retail sales and produced 9.6 pct of the value added by manufactures. On an industry-by-industry basis the correlation between the three guideposts will not be as close as shown in the 1954 data for the Pacific Coast states, but in the long-term view the continuing rapid population growth in the western states is certain to result in expanded industrial production at an even more accelerated pace, which will shorten the gap between local consumption and production in most major groups of manufactured consumer goods. Of course, there will always remain favorable areas for production of specific products. Such special situations must be individually analyzed. Fig. 1 compares the population trends in the U. S., the western states, and California with Real Gross National Product from 1910 to 1957, with forecasts to 1970. It is estimated' that the U. S. Real Gross National Product, as measured by the value of goods and

Jan 1, 1960

By Felix G. Berra, David H. Orr

The first large scale application of radio remote control equipment to standard gage railroad trains has been achieved at the Morenci mine of Phelps Dodge Corp. at Morenci, Ariz. Twenty or more ore and waste haulage trains are remote control operated at any one time, each with a one-man crew. Reduction of train crews from two men to one man has materially lowered the total cost of train operation. Elimination of brakemen has also resulted in an improvement in train efficiency brought about by a shortening of train haulage cycle times.

Jan 4, 1965

By David V. Ragone, James A. Craig, Richard E. Balzhiser

The Gibbs free energies of formation of UC2 and UC were measured by equilibrating two-phase mixtures of UC2 + C and UC, + UC with liquid bismuth. The measured equilibrium concentrations of uranium in the bismuth combined with available activity coefficient information yielded uranium activities in these two-phase regions. Measurements on UC2 were performed over the range 1015 to 1160 K and on UC over the range 1115° to 1165°K. The values obtained for UC2 are in excellent agveement with values determined using combustton calorimetry and low-temperature heat capacity measurements. The UC values are in fair agreement with the calorimetric values, differing by about 10 pct from the calorimetric determination. MUCH interest has been shown in the uranium carbides in recent years because of their potential as nuclear fuels. As nuclear reactor operating temperatures have been raised to increase thermal efficiency, new fuels have been required. The uranium carbides are of interest because of their high melting points, >2000°C, high thermal conductivity, and resistance to irradiation damage. The manufacture and use of uranium carbides are aided by a knowledge of their stability and reactivity under various conditions. In this regard the thermo-chemical properties of the carbides, i.e., heat capacity, heat of formation, free energy of formation, and so forth, are particularly important. A great amount of work has recently been done on the thermodynamics of the U-C system. Unfortunately, however, there has not been good agreement among the various investigations. This study of the free energies of formation of uranium monocarbide and uranium di-carbide in the temperature region 1100°-1200° K was undertaken to help clarify the situation. It should be noted that in the temperature range of this investigation, 1100°- 1200° K, the thermodynam-ically stable phase in equilibrium with graphite is U2C3, not UC2, Fig. 1. However, U2C3 is reported to be stable only under extremely low oxygen and nitrogen pressure. Although UC2 is metastable below 150O°C, it exists under most experimental conditions. It should also be noted that "UC," never exists as UC2 but with compositions near UC1.9. However, "UC2" will be used to designate the dicarbide phase except when the stoi-chiometry is necessary for clarity. METHOD The approach taken in this study of the free energies of formation of UC and UC2 was to determine the thermo- dynamic activities of uranium in the two-phase regions UC, + C and UC + UC, by equilibrating the two-phase mixtures with the liquid bismuth. When a mixture of solid UC2 + C is brought to equilibrium with liquid bismuth, the reaction that occurs is: Neither carbon nor UC, could be detected as dissolved material in the bismuth. The standard free energy for this reaction may be written: In the two-phase region UC, + C, Fig. 1, the thermo-dynamic activities of UC2 and carbon are unity. The activity of uranium in this region was determined by measuring the concentration of uranium in a liquid bismuth melt in equilibrium with the two-phase mixture. This concentration was then used in conjunction with the activity coefficient data of uranium in bismuth reported by Tien et al.' to determine the activity of uranium in the two-phase region, UC, + C. All of the quantities in Eq. [2] were then known, and the AG; (uc,) was evaluated. UC + UC2. For the studies involving UC + UC,, the reaction taking place when the two-phase mixture is brought to equilibrium with liquid bismuth is: The standard free-energy change for this reaction is given by:

Jan 1, 1969