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By Gustav S. Preller, A. M. Gaudin

Fox the past 20 years it has been generally accepted that the flotation process is made possible as a result of the action of certain chemical substances on the surface of the mineral particles. In fact, it has been suspected, but never demonstrated, that this action produces on the mineral particles a layer of chemosorbed ions that is of the order of magnitude of a monolayer; that is, of a layer one ion deep. It is the purpose of this paper to present certain initial results on the relationship of mineral surface area and collecting-agent requirements. Up to about eight years ago, all considerations involving the surface area of finely divided solids were-limited by the fact that there was not in existence any general method for determining the extent of such surfaces, especially on mixed materials. However, the method invented by Brunauer, Emmett and Teller1 has changed the situation by providing a general procedure (BET method). This procedure has already been applied to mineral dressing problems2 -4 and has now received confirmation as to accuracy by an entirely independent method.5 This confirmatory or "absolute" method uses a very tedious calorimetric procedure and is not suitable for routine determinations; but still another method6 now is available to relate the results obtained by the BET method to those obtained calorimetrically. This Harkins-Jura method has the advantage that it does not require an assumption concerning the parking area per molecule of adsorbate (nitrogen). In the original work by Brunauer, Emmett and Teller the parking area per nitrogen molecule was calculated to be either 13.8Å2. or 16.2Å2. according as the nitrogen was assumed to be closely packed as in crystalline nitrogen or loosely packed as in liquid nitrogen. The initial experimental work from this laboratory2 supported the 13.8Å2. figure; that work was done on glass spheres of measurable geometric area and it was based on the assumption that the glass spheres were truly smooth; any deviation from this assumption would, of course, have made the calculated parking area higher. Harkins and Jura's results suggest that the parking area is not the same for all substrata; furthermore, the average of the 87 measurements cited indicates a "preferred" parking area for the nitrogen molecule of about 15.2Å2., with extreme values at 13.7 and 16.9Å2. The average of 21 determinations made in connection with this study' gave a parking area of 14.3 ± 0.27Å2. In view of this result and of the Harkins and Jura

Jan 1, 1946

By J. A. Faucher

The mining industry has undergone significant technological advances in metallurgical process methods in recent years. The 1000 tpd concentrator of St. Lawrence Colum-bium Metals Corp. portrays the continuing effort made by the industry to achieve economical concentration of new and difficult ores. During the active search for sources of uranium in the early fifties, radioactive minerals were found in the Oka district near Montreal. The compatatively small quantities of uranium which were found occurred in association with widespread columbium (niobium) mineralization which included perovskite, a calcium titanate containing roughly 40% Cb2O5; niocalite, a silicate containing some 20% Cb2O5; and pyrochlore, a calcium niobate containing 45 -70% Cb2O5 as well as fluorine and some water. An idealized formula for one type of pyrochlore is: A typical chemical analysis of pyrochlore is shown in Table I. An important feature of this analysis is the lack of tin, lead, sulphur and P2O5 which conforms with the requirements of most consumers. In general the cerium content varies with sodium content and any increase in Ta2O5 lowers the Cb2O5 content of the concentrate. However, Ta2O5 rarely exceeds 0.5%. The carbonatite host rock of the columbium mineralization has the average mineral composition shown in Table 11. In Table 11, the term "diopside" is used to cover all silicates except mica which is shown separately because of the problems involved with its separation during the concentration process. In some ore zones, small quantities of rare earth minerals, such as monazite are present.

Jan 1, 1964

By G. Donald Emigh

Nothing is more important to life-plant and animal-than phosphate. Its compounds are essential to the energy functions of all living systems and for the formation of bones and teeth. Animals get their phosphate from eating plants and other animals, or domestically from feed supplements. Plants get their phosphates from the soil. Man's most important use of phosphate is for fertilizer; approximately 95% of the world's phosphate rock production is consumed by fertilizers. Most of the balance is processed in electric furnaces into elemental phosphorus, the important raw material for making industrial phosphates. Recovery of uranium from phosphates has been possible but not widely used. However, recent significant developments have generated interest in such recovery in the US and elsewhere. Phosphate occurs in all igneous and sedimentary rocks, and in all fresh and salt water. However, economical recovery is limited to deposits where natural concentration of the phosphate mineral has occurred. Occasionally natural concentration is great enough that the material can be used as mined; generally, however, the ore is low grade_ and must be concentrated. Phosphate rock is produced in 31 countries. Fig. 1 shows the location of major phosphate rock producers as well as some of the known phosphate deposits not yet in production. In the last decade the world phosphate industry has experienced steady growth. World production rose from 98 Mt of phosphate rock in 1973 to 140 Mt in 1982. Fig. 2 shows the growth curve of rock production and graphically illustrates the almost straight-line rise since 1945 in both US and world production. Table 1 gives the breakdown, by countries, of world rock production, 1974 through 1979. Table 2 shows US rock production by producing areas. Definitions of Terms Used in the Phosphate Industry Phosphate Rock: Commonly called rock in sedimentary deposits and apatite in igneous deposits. Those expressions generally include any mined, or mined and beneficiated, fluorine-containing calcium phosphate used as the raw material for the next stage of manufacturing. The average phosphate content in rocks is 0.1 to 0.2% P2O5, as documented by McKelvey (1973). About 200 minerals contain more than 1 % P2O5. However, the important mineral in igneous rocks is fluorapatite, [Ca5 (PO4),3 F], containing about 42% P205 and 3.8% F2; in sedimentary rocks the important mineral is francolite, a carbonate fluorapatite containing up to 2% molecular CO2. Both are in the apatite family of minerals. Most phosphate rock, whether beneficiated or not, is a fine-grained material. The expression phosphate rock has no relation to its phosphate content. For example, phosphate rock from Idaho used in the production of phosphorus may contain about 24% P205, whereas rock from Morocco may contain 36.6% P2O5. Phosphorite: A deposit of phosphate directly or indirectly of sedimentary origin, which is of economic interest. Grade of Phosphate Rock: The calcium phosphate content of phosphate rock is expressed in different world areas by one of the following terms: BPL (bone phosphate of lime) TPL (triphosphate of lime) P2O5 (phosphorus pentoxide) P (phosphorus-not commonly used) An illustration of relationship is: 80% BPL = 80% TPL = 36.6% P5O2 = 16% P

Jan 1, 1983

By R. Dugdale, F. Habashi

Studies on hand-picked samples of chrysocolla from Arizona showed that heating in an inert atmosphere enhances greatly copper extraction by ammoniacal-ammonium carbonate solutions. Heating in hydrogen improves the extraction of copper even further and maximum extraction by ammoniacal-ammonium carbonate and by sodium cyanide solutions is achieved for samples heated at 350°C. Heating in SO2 atmosphere results in the simultaneous formation of CuSO4 and Cu2O; maximum reaction rate is also achieved at 350°C. At temperatures higher than 350°C, CuCO4 starts to decompose. Chrysocolla heated above 600°C either in argon, H2, or SO2, is rendered less amenable to leaching, supposedly due to the formation of insoluble copper silicates.

Jan 1, 1974

By Dodge, C. E.

ONE of the first mining areas to be developed in Arizona was that in the district centering about Clifton and Morenci. Traces of metals were first noticed by Henry Clifton on an expedition in 1864. Definite copper outcroppings were also reported in the following year by General J. H. Carleton when he led his troops into the district on an Indian raid. Actual mining operations were started in the early seventies. and the first smelter was finished in 1873. Two adequately financed companies acquired most of the property, and both commenced production about 1882. These were the Arizona Copper Co.. owned by a group of Scotch investors, and the Detroit Copper Mining Co., afterwards purchased by the firm of Phelps, Dodge & Co. Later the Shannon Copper Co. acquired and operated a number of claims in the northern part of the district. These three companies all operated underground, mines independently for many years.

Jan 1, 1942

By A. W. Sommer, H. H. Kellogg

It is shown that SO3-O2 mixtures react with sphalerite at an appreciable rate ill the temperature range of 361° to 527°C to fornz ZnSO4. The rate of reaction follows a parabolle lax. Oxygen, or O2-SO2 mixtures, have a negligible effect on sphalcrite in the same temperatuee range. PRACTICAL roasting of sphalerite is usually performed at 800°C or higher. The calcine is composed of zinc oxide unless the roaster atmosphere contains relatively large amounts of SO2 and the temperature is held to 800oC or lower, in which case zinc sul-fate may also form. Ong, Wadsworth, and assell' have made a careful kinetic study of sphalerite oxidation under these "normal conditions" and have concluded that the rate of the reaction is controlled by the decomposition of an activated complex adsorbed on the sphalerite surface. They found the rate of oxidation to be small at 700°C. Extrapolation of their data to 400°C would indicate an almost negligible rate at this temperature. In our work sphalerite was reacted with air, mixtures of SO2, O2, and N2, and mixtures of SO3, O2, and N2 in the temperature range 361o to 527OC. Negligible rates of oxidation were found, except for the gas mixtures containing SOs. With this latter gas, the oxidation of finely divided sphalerite was fairly rapid and zinc sulfate was the product. Based on the limited evidence available, the rate of sphalerite oxidation by SO3 is postulated to be controlled by gaseous diffusion through pores or cracks in the zinc-sulfate coating. This evidence for the direct reaction of sphalerite and SO, at low temperature may prove of importance to the understanding of zinc-sulfate formation in the dust-collecting equipment usually associated with zinc roasters. The roaster gas carries off fine dust, much of which may be unreacted sphalerite. The temperature in dust-collecting equipment drops from the roaster temperature (about 800°C) through the range of temperature we studied, to ambient temperature. Such dusts are known to contain far larger amounts of zinc sulfate than the primary calcine. It has been assumed in the past that this sulfate is formed by reaction of ZnO dust with SO3 (or SO, plus 0,) in the partly cooled gases. Our work shows that an alternative possibility exists—the direct reaction of SO3 with ZnS dust. EXPERIMENTAL Reaction rates for sphalerite at 350° to 600°C are relatively small so that it was necessary to use finely divided material with a relatively large surface area in order to obtain measureable amounts of reaction. In the preliminary experiments, pure mineral sphalerite, ground to pass a 325-mesh sieve, and chemically precipitated ZnS (in the form of an impalpable powder) were used. In the quantitative rate experiments the ground mineral sphalerite was processed in an Infrasizer to obtain a product with particle size between 9 and 18 µ. The analysis of this material was 66.7 pct Zn, 0.09 pct Fe, and 32.7 pct S (theoretical sphalerite is 67.1 pct Zn, 32.9 pct S). The sized powder was carefully mixed and divided into l-g samples. The apparatus used for the quantitative rate measurements is shown in Fig. 1. For the preliminary experiments the following change was made: The external catalyst furnace (B, C)* was not used. *Letters refer to Fig._______1 .___- Rather, when catalysis of the SO2 + O2 reaction was desired, the glass beads in basket M were replaced by vanadium-oxide pellets. Procedure—A l-g sample of ZnS was placed on a shallow stainless-steel tray, I, and spread evenly to a depth of about 1mm. The tray was placed in the reaction assembly and the assembly inserted in the cold furnace. The furnace tube was flushed with dry argon and then heated to the desired reaction temperature. The temperature was controlled to ±0.5oC. Gas mixtures (O2 + N2 or O2 + SO2) were prepared from tank gases by means of a mixing device identical to that employed by Darken and Gurry.2 The total flow rate of gas was 205 ml per min to point A of Fig. 1. The accuracy of the individual and

Jan 1, 1960

By W. H. Porter, M. E. Wadsworth, J. R. Lewis, K. L. Leiter

The oxidation of Cu2S in oxygen and the sulfating of Cu2O in oxygen-sulfur dioxide atmospheres was carried out under a variety of conditions. The oxidation of Cu2S was found to be retarded by entrapment of SO, and O2, which stabilized internal sulfates for long periods of time. The course of the reaction was followed by measuring weight changes and also by SO, evolution. Sulfating of Cu2O was a maximum at ratios of SO, to O2 approximating maximum SO, production. At elevated temperatures SO, was found to increase the rate of oxidation of Cu2 O to CuO even though sulfates did not form. All sulfating reactions followed the parabolic rate law indicating diffusion. MANY studies of the roasting of copper sulfides have been reported in recent years. Diev et al.1 investigated the roasting of chalcocite (Cu2S) in air, and oxygen enriched air. Lewis et al.2 also studied the oxidation of natural and synthetic chalcocite in air and oxygen atmospheres and their studies indicated that the maximum formation of water soluble sulfates occurred at approximately 450oC. Ashcroft3 reported that oxide production during the roasting of chalcocite resulted only from secondary decomposition of sulfates which were formed as primary products. peretti4 refuted this claim by showing that a layer of Cu2O appeared directly adjacent to the Cu2S during roasting of cylindrical briquettes of cupric sulfide, CuS. The linear advance of the Cu2S-Cu2O interface was used as a measure of the kinetics of the roasting reaction. The reactions proposed were: 2 CuS—Cu2S + 1/2 S2 [4-1] 1/2 S2 + O24 SO2 [4-2] cuzs +3/2 O2 4 Cu2O + SO2 [4-3] cu2o + 1/2 O2—2 cuo [4-4] At temperatures above 663oC, CuO was the only final solid phase reported. Below 663" C increasing amounts of sulfate were found mixed with the CuO. McCabe and Morgan5 investigated the roasting of discs of synthetic chalcocite and reported the following sequence of products beginning at the sulfide surface: Cu2O, a mixture of Cu2O and CuSO4, Cum,, CuO . CuSO4, and CuO. The principal reactions were reported to be: Cu2S + 3/2 O2-Cu2O + SO2 [5-1] CU2O + 2 SO2 + 3/2 O2—2 CUSO4 [5-21 2 CUSO4— CUO . cum, + SO3 [ 5-31 cuo . cuso4—-2 cuo + SO, [ 5-41 Eq.15-11 supports the claim of Peretti, Eq. [4-31, that CuzO is formed directly from Cu2S rather than as a secondary product from a sulfate as suggested by Ashcroft. On the other hand CuO was found to form as a secondary product from the decomposition of copper sulfate and basic copper sulfate, Eqs. [5-31 and [5-41. The formation of sulfates was explained by McCabe and morgan5 to be a direct reaction of Cu2O with 0, and SO, or SO, at distinct regions in which the partial pressures of each were such as to form the sulfate. Thornhill and pidgeon6 roasted both natural and synthetic chalcocite grains in air at temperatures between 420" and 550° C. They found a dense primary oxidation layer in contact with the sulfide. A secondary layer of porous oxidation products was found to expand with roasting time. The oxide products were leached away and the remaining core was studied by X-ray diffraction. The X-ray patterns showed an increased conversion of chalcocite to digenite with time. Digenite,7 a defect structure of cuprous sulfide, occurs naturally as Cu,-,S where x = 0.12 to 0.45, with an average analysis of Cu, ,S. The mechanism of digenite formation was proposed as: Cu2S + oxygen—Cu1-8S + 0.1 Cu2O [6-1] Cuj.eS + oxygen—0.9 Cu2S + SO2 [6-2] It is apparent from the above studies that the oxidation of Cu2S, ultimately ending in CuO, may be divided into ihree general stages (all of which may occur simultaneously): 1) primary oxidation to Cu2O; 2) secondary sulfate formation; and 3) sulfate decomposition. Consequently reactions of O2 and SO, with Cu20 constitute important aspects of the roasting of chalcocite. Virtually no studies have been made regarding sulfating reactions involving Cu,O. Mills and Evans8 noted the effect of sulfur dioxide on the oxidation of copper at low temperatures and low SO, partial pressures. They reported a measurable increase in the oxidation rate of copper when SO2, was present. Interest in the Cu2O-CuO-0, system has been limited predominantly to misciblllty studies and determinations of heats of formation by

Jan 1, 1961

By Arnt Solbu, Jomar Thonstad

The reaction between CO, and aluminum in cryolite-alumina melts in contact with aluminum has been studied by passing CO2 over the melt. In unstirred melts a homogeneous reaction between dissolved metal and dissolved CO2 was observed. In stirred melts in which convection was induced by bubbling argon through the melt, the dissolved metal apparently reacted mainly with gaseous CO2. The rate of formation of CO increased slightly with increasing depth of the melt, and it did not depend on whether CO2 was passed over or bubbled through the melt. The rate of formation of CO increased with increasing area of the metal/melt interface and with the application of anodic current to the metal. It is concluded that the dissolution of metal into the melt is the rate-determining reaction. THE current efficiency in aluminum electrolysis is determined by the rate of the recombination reaction between the anode gas and the metal: 2A1 + 3CO2—A12O3 + 3CO [1] as originally stated by Pearson and waddington.1 The occurrence of this reaction in cryolite-alumina melts in contact with aluminum was first verified experimentally by Schadinger.2 Thonstad3 has shown that the reaction may proceed further to give free carbon: 2A1 + 3CO— A12O3 + 3C [2] Normally only a few percent of the CO formed undergoes such reduction. The mechanism of these reactions has not yet been clarified. Aluminum, as well as CO,, is soluble in the melt. The solubility of aluminum in cryolite-alumina melts at around 1000°C corresponds to 75 x 10- 6 mole A1 per cu cm,4 while that of CO2 is only 3 x 10-6 mole CO, per cu cm.5 Taking into account the stoichiometry of Reaction [I], the ratio between dissolved aluminum and dissolved CO2 available for the reaction in a saturated melt is about 40. Therefore, as will be shown in the following, the reaction probably mainly occurs between gaseous COa and dissolved aluminum. The dissolved aluminum presumably consists of subvalent ions of aluminum and sodium.4'6 Since the interpretation of the present results is not dependent upon the nature of this solution, the dissolved metal will be designated solely as Al+ in the following. The reaction can then be divided into four steps: A) dissolution of metal, e.g., 2A1 + Al3 — 3A1+ [3] B) diffusion of dissolved metal through a boundary layer; C) transport of dissolved metal through the bulk of the melt; D) Reaction [1]. If dissolved CO, takes part in the reaction, three additional steps embodying the dissolution and transport of CO2 must be added. schadinger2 observed, when bubbling CO2 through the melt, that the rate of formation of CO (in the following designated rfco) did not depend on the distance from the metal surface. The results also indicate that the rate of bubbling did not affect the rfco. When passing CO, over the melt, Revazyan7 found that the loss of metal did not depend on the depth of the melt above the metal or on the flow rate of CO2, and concluded that Step A is rate-determining. In an unstirred melt, however, Gjerstad and welch8 found that the rfCo decreased with increasing depth of the melt, indicating that step C was rate-determining. It thus appears that the rate control of the process depends on the experimental conditions, particularly on the convection. In the present measurements the reaction has been studied in unstirred as well as in stirred melts. EXPERIMENTAL AND RESULTS The experiments were carried out at 1000°C in a Kanthal furnace with a 10-cm uniform temperature zone (±0.l°C). The melts were made up of "super purity" aluminum (99.998 pct), hand-picked natural cryolite, and reagent-grade alumina. In experiments where alumina crucibles were used, the alumina content in the melt was close to saturation (13.5 wt pct9); otherwise it was 4 wt pct. Pure Co2 (99.85 pct) was passed over the melt, and the exit gas was analyzed for CO2 and CO by the conventional absorption method.3 From the weighed amount of CO (as CO2) the rfco was calculated as the number of moles of CO formed per min per sq cm of the surface area of the melt. The amount of carbon formed by Reaction [2] was not determined. As already indicated the rfco is much higher than the rfC, by Reaction [2]. Since the rfC probably is proportional to the rfco, the measured rfco should then the proportional to, but slightly lower than, the total rate of Reactions [I] and 121. In general the scatter of results obtained in duplicate measurements was ±5 to 10 pct, while within a given run a precision of ±3 to 5 pct was obtained. The various crucible assemblies that were used will be described below. Measurements in Unstirred Melts. When carrying out aluminum electrolysis in small alumina crucibles. Tuset10 observed that after solidification the lower part of the electrolyte was gray and contained free metal, while the upper part near the anode was white and contained no metal. One may test for the presence of free metal by treating with dilute hydrochlorid acid.

Jan 1, 1969

E. Windsor Richards, London, England:—In reading this paper the most interesting point to me mas the question of the maximum percentage of phosphorus allowable in the steel rail. Mr. Colby said, and we will all agree with him, that the engineer knew, and even a steel-rail maker grants that phosphorus is the most undesirable constituent of steel. We in England have been for a long time considering a specification for the supply of steel rails. This matter has been taken up by the Institution of Civil Engineers, the Mechanical Engineers, the Iron and Steel Institute, the Institute of Naval Architects, and the Electrical Engineers. Committees have been formed,and the whole matter has received most careful attention. They arrived at last at an analysis which I will read: " The carbon is to be from 0.35 to 0.5 per cent.; the manganese from 0.7 to 1.0 per cent.; the silicon, not to exceed 0.10 per cent.; phosphorus, 0.07; and sulphur, 0.07 per cent." As to the phosphorus, which is the most important point of all in the analysis, we have for many years, and indeed until very lately, always agreed to supply steel which would not contain above 0.06 per cent. of phosphorus. Iron-ores are not quite as good now as they were formerly, and the manufacturers at the meetings of the committees referred to, tried to obtain an increase in the allowance of phosphorus. They asked the Sub-committee to agree to 0.08 per cent. of phosphorus. They tried all they possibly could to obtain that; but they failed. English engineers in Great George Street and all over England, representing the important Associa tions I have mentioned, would only agree to 0.07 per cent. and that is the maximum allowance of phosphorus. Mr. Colby is an able advocate, but with all his ability he would not have been able to persuade the English engineers to agree to 0.08 per cent.

Jan 1, 1907

By M. A. Rigdon, R. E. Grace

The dissociation of cupric oxide to cuprous oxide and oxygen was studied with a microbalmce technique at 700" to 750°C. In this temperature range the dissociation pressure of the reaction 2CuO= Cu2O + 1/2 O2 was: The theory of near-equilibriwm reaction rates predicts a linear relationship between reaction rate and the Gibbs free-energy change for small values of AF/RT. This correlation is found to be valid for AF/RT = -0.1 or approximately 200 cal per mole away from equilibrium. THE theory of reaction rates near equilibrium as developed from classical thermodynamics suggests a small range of linear behavior between the overall reaction rate and the free-energy change accompanying the process. The extent of this linear correlation is generally unknown, even to the order of magnitude. The idea of linearity is also found in the formal mathematics of coupled transport phenomena, e.g., chemical diffusion, thermal diffusion, thermoelectricity, and so forth. The linear array of forces and fluxes which leads to various main and cross coefficients is predicated upon linearity between reaction rates and the bulk thermodynamics which govern the process. The general case in reaction kinetics is well-known: the magnitude of the free-energy change does not cor- relate with observed reaction kinetics, irrespective of whether the process occurs by diffusion or chemical reaction or both. The real need is to investigate specific reaction paths near equilibrium in order to learn of the limitations in attempting to correlate reaction rates and thermodynamics. It is the main purpose of this paper to examine the dissociation kinetics of cupric oxide under conditions of known driving force where the dissociation process is likely to occur by chemical reaction. A secondary objective is to obtain equilibrium data for the CuO-Cu20-O2 system. In a prior paper Edmiston and race' investigated reduction kinetics of wustite in H2-H2O gas mixtures. The present study was carried out in oxygen according to the following reaction:

Jan 1, 1969

By H. A. Lequear, J. D. Lubahn

A sudden change from one constant strain rate to another during a tensile test causes an unusual transient in aluminum alloy 61ST. A sudden change from one constant stress to another during a creep test does not produce an unusual transient in this material. A specially devised test shows that the nature of the previous steady-state conditions, which the sudden change disturbs, is one of the factors affecting the transient behavior. Some of the observations may be explained in terms of strain aging. USUALLY a sudden change during a tensile test from one constant strain rate to another causes a small, abrupt vertical shift from one stress-strain curve to another, parallel one. This behavior is apparently characteristic of all metals at very low temperatures and of many metals for wide ranges of temperature. It is illustrated in Fig. 1 for some early data on 61ST tested at — 195oC, and in Fig. 2 for some recent data on copper at room temperature. The greater accuracy of the results of Fig. 2 over previous ones' is due to the equipment shown in Fig. 3. Three levers apply the bulk of the load, while the changes in the small remainder load are indicated sensitively by a low capacity load scale. Refs. 2 and 3 describe the recording equipment. A test like those in Figs. 1 and 2 provides the information necessary to determine the rate sensitizrity, n,4 of the metal. ( a log s ) ? log s n = ------------------------ ----------------------------= ( a logs e, ? log e logS2-logS1 log S2/S1 log i2 — log e1 log e2/e1 where S equals stress: e is logarithmic strain or natural logarithm of (final gage length/initial gage length);" i is strain rate or de/dt: and n is rate sensitivity, rate of change of log stress with log strain rate at a given strain, or (a log S/a log i),. Normally, the rate sensitivity, n, is positive, which means that an increase in stress causes an increase in rate. However, certain exceptions, attributed to strain aging,5 have been observed. Fig. 2 indicates how rate sensitivity values are derived from the measurements. Table I summarizes the rate sensitivity values derivable from Fig. 1. In contrast to the behavior of copper in Fig. 2, the aluminum alloy 61ST, which strain ages when tested near room temperature, exhibits an unusual transient when the strain rate is suddenly changed,' as shown in Fig. 4. Initially, there is a comparatively sudden vertical shift of the stress-strain curve in a direction corresponding to the rate change, but then the curve gradually shifts back again. The initial shift is not as sudden as might be expected, because the testing machine is unable to achieve the impressed rate change instantaneously, as illustrated in Fig. 2. The behavior shown in Fig. 4 will be referred to as a tensile transient, the word tensile implying that the behavior was observed in a tension type of test. The corresponding test, where the strain rate is maintained constant except for the sudden change, will be called a tensile transient test. A creep transient, by contrast, will be defined as a temporarily abnormal behavior in a creep transient test, where there is a sudden change from one constant load to another.' In Fig. 4, a naive look at the gradually decreasing and then increasing load after a sudden rate incre-

Jan 1, 1957

By W. Mckewan, W. M. Fassell

The oxidation rates of copper have been determined at temperatures from 600" to 900°C in oxygen from 14.7 to 400 psi total oxygen pressure. The oxidation rate of copper is unchanged by oxygen pressures within the range studied. The observed data extend Feit-knecht's conclusion concerning the pressure independence of copper from atmospheric pressure to 400 psi. All samples studied in the above-mentioned temperature and pressure range have both Cu2O and CuO present in the oxide film. NUMEROUS papers have been published on the oxidation of copper, some of which have noted the effect of oxygen pressure on the oxidation rate of copper. It must be noted, however, that no data on the oxidation rates of copper at pressure in excess of 1 atm have been reported in the literature. (Le Chatelier¹ reported that a black oxide of silver was formed at 300°C and 15 atm pressure.) This is likewise true for the other metals. This investigation was initiated to obtain experimental oxidation rate constants for pure metals at elevated temperatures and high oxygen pressure. Copper was selected as the first metal since probably more reliable data are available on its oxidation rates and related physical and chemical properties than for any other metal or alloy. As a general summary, the following conclusions appear well established for the oxidation of copper: 1—The oxide coating consists of Cu2O with a superficial coating of CuO providing the ambient oxygen pressure exceeds the equilibrium pressure for the coexistence of Cu2O and CuO.² The following sequence of phases is then Cu/Cu2O/CuO/O2 (gas). The Cu2O consists of large crystals that have no relation to the orientation of the metal crystals, except for a very thin layer adjacent to the metal." The CuO consists of very fine crystals randomly oriented. If the oxygen pressure is below the equilibrium pressure for the coexistence of Cu2O and CuO, the coating consists of Cu,O only. 2—The rate-determining factor in the parabolic oxidation of copper is the diffusion of Cu+ ions through the Cu,O layer.4,6,7 The Cu+ ions are accompanied by electrons to maintain electrical neutrality. The mechanism of the reaction at the Cu2O/CuO interface and the method of growth of the CuO is in some doubt. 3—On copper, there are three reported pressure effects: (a) At pressures below 0.3 mm Hg oxygen pressure, the oxidation rate increases directly with pressure.', ' .Vxygen starvation at the surface may account for this effect. (b) At oxygen pressures from 0.3 to 63 mm, the oxidation rate increases as the 7th root of the oxygen pressure providing the temperature is such that only Cu2O is present in the film. (c) At pressures from above the equilibrium pressure for the coexistence of Cu2O and CuO (varies with temperature) to atmospheric pressure, the oxidation rate is independent of the oxygen pressure.' Equipment In order to determine the oxidation rates of metals in an oxidizing atmosphere at pressures up to 400 psi, the equipment is somewhat different than for low pressure work as is shown in Figs. 1 and 2. A Leeds and Northrup Micromax recording controller (A) is used to control the temperature of the Ni-chrome furnace winding in conjunction with a Micromax electric drive unit. The drive unit adjusts a 20 amp Variac (variable transformer) to control the power input into the Nichrome furnace winding. Due to the "self heating" of the sample by oxidation, frequently encountered in oxidation rate studies, it is essential that the sample temperature be measured independently. This is done by means of a series of six chromel-alumel calibrated thermocouples located spirally around the oxidizing metal sample. Each thermocouple is partially shielded from the direct radiation of the furnace wall by

Jan 1, 1954

By J. W. Downey, R. A. Morris, M. V. Nevitt

An experimental survey has determined the occurrence of Ti2 Ni-type phases in binary and ternary alloys of Ti, Zr, or Hf with first, second, or third long-period transition metals and also in ternary systems in which 0 is the third component. The existence of eleven previously unreported isomorphs is cited and some approximate phase boundaries are given. Lattice parameters are reported for the new phases. The periodic table relationships involved in the occurrence of the phase are discussed. A previous paper' reported the occurrence of a group of Ti2Ni-type phases (structure-type E93) containing Zr in combination with Rh, Ir, and Pt, and Hf in combination with Rh, Pd, Ir, and Pt, and cited evidence to show that all of the Zr phases and the Hf-Pd phase are not binary phases but occur only when 0 is present. More recently one of the present authors found that in the ternary systems of Ti and 0 with Cr, Mn, Fe, Co, and Ni the occurrence of the Ti2Ni-type phase could be correlated qualitatively with valency electron concentration, and that the role of 0 appeared to be that of an electron acceptor.' This paper describes the results of a broader investigation of the occurrence of Ti2Ni-type phases in binary and ternary systems containing Ti, Zr, or Hf. EXPERIMENTAL PROCEDURE Alloys were prepared by arc melting. The purity of the metals Zr, Rh, Hf, Ir, Pd, and Pt was given in the previous paper.' The additional materials used for this work were metals with a minimum purity of 99.9 pct and reagent grade ZrO2, TiO2, Cr2O3, and NiO. Chemical analysis of several alloys in each system indicated good agreement between intended compositions and cast-button compositions. For the heat treatment precautions were taken to avoid oxygen contamination. The specimens were wrapped in Mo foil and sealed in fused quartz tubes at a room temperature pressure of 1 x mm of Hg. These capsules were then annealed in a vacuum furnace at an external pressure of 5 X mm of Hg. Since the major constituent in most of the alloys studied was the brittle Ti2Ni-type phase, Debye-Scherrer patterns with sharp lines could be obtained with powder crushed from the annealed solid samples without being reannealed. Metallographic, X-ray diffraction, and density determination techniques previously described1, 2 were used. RESULTS AND DISCUSSION Zr-Rh-O, Zr-Ir-Oand Zr-Pt-O Systems-Figs. 1 through 3 show the approximate boundaries of the Ti2Ni-type phase fields at the temperatures indicated in the ternary systems Zr-Rh-O, Zr-Ir-O and Zr-Pt-0. In each isothermal section the Ti2Ni-type phase field is labeled E and the unidentified binary phase found in the previous work' is labeled ?. The dotted lines, which are not phase boundaries, correspond to the composition (Zr2 B)1-xOx. In each system the Ti2Ni-type phase field is displaced to the high-Zr side of this composition line. However, the departures from Zr2B stoichiometry for the metal components are not as high as Zr3B, as was inferred from the previous work. Lattice parameters of the Ti2Ni-type phases in the alloys shown as triangular data points in Figs. 1 through 3 are given in Table IA. The probable compositions of the Ti2Ni-type phases have been estimated from the isothermal sections. Although there are a few exceptions that probably result from uncertainties in phase boundary location and from the effect of variation of oxygen content, the generalization can be

Jan 1, 1961

D. J. DEMOREST,* Washington, D. C. (written discussion ?).-This paper is a real contribution to technical science; it will make it' easier to think accurately about the inner workings of a blast furnace. I was rather surprised to read that the authors regarded as a new discovery the idea that a molten mixture of CaO, A1203, and Si02 is a molten solution of the compounds of these oxides rather than of the oxides in each other. Surely no. chemist with an active respect for the known facts of chemical affinity could believe that these oxides could be melted together without forming compounds, and that these compounds would then dissolve in one another. This work does, however, help to establish what it was supposed must be true. I think it is worth while, in the light of the work of the Geophysics Laboratory, this work of the Bureau of Mines, and that of previous investigators, to visualize what happens as a charge passes down through a blast furnace, thinking especially of the slag-forming materials. These are chiefly kaolin (Al203.2SiO2.2H2O), quartz, and limestone. These substances do not undergo much change until the limestone decomposes at about the middle of the furnace, whereupon the chemical affinities of CaO and SiO2 must begin to he active; especially if there is any amorphous Si02 present. This forms CaSiO3, and the SiO2, CaSi02 and Al2-032SiO2 then come together to form the binary and ternary eutectics so well located by the work of the Geophysics Laboratory. No matter how much lime has been charged into the furnace, the formation of this eutectic will start it about the same height in the furnace and the gangue will start to get pasty at the same height. If the charge is such that the

Jan 4, 1918

By Edward Saibel

THE object of this study is to investigate the effect of prior tensile strain on the fracture stress of a metal. This is done in a theoretical manner starting from the point of view developed by the author in his thermodynamic theory of the fracture of metals. The results are compared with experimental findings and a rational interpretation is given to work that shows the variation of fracture stress with prior tensile strain. THEORY OF FRACTURE In the thermodynamic theory of the fracture of metals developed earlier,1 it was shown that a critical strain energy per unit volume exists. This is characteristic of the material and may be calculated from basic thermodynamic data. When the area under the flow curve reaches this characteristic value, fracture occurs. The general criterion for fracture is expressed in the form u ± uo = JLm?AV/V [1] where Lm, is the latent heat of melting of the unit volume, ?V/V is the ratio of the change in volume of the unit volume to the original unit volume on passing from the solid to the liquid state, [uo] is an initial energy density, and J is a conversion factor, which changes energy from heat to mechanical units. As a first approximation, it will be assumed that the stress-strain curve is the straight line that extends from the point of maximum load onward, extrapolated back to the axis of zero strain, for example, line AC of Fig. 1. If the point of intersection of the straight line with the axis of zero strain is represented by so, and the slope of the straight line is p, the analytic form of the flow curve is [s = s + pd [2]] and the strain energy per unit volume evaluated from [JvdS] becomes (vsod + pd2/ 2). When this latter term reaches the critical value JLm?V/V (designated hereafter by M), it is assumed that fracture occurs. This leads to the following expression for the fracture stress: [s1 = \/C r.2 + 2Mp [31] The strain at fracture may be calculated from Eqs 2 and 3. It is assumed in this paper that the initial energy density is either zero or that it may be neglected. Furthermore, the complicated states of stress and of strain existing in the necked region of the tensile specimen after "necking" has occurred will also be neglected for the present, so that average conditions will be assumed to prevail. FLOW AND FRACTURE CURVES Ludwig2 attributed to materials two fundamental properties: (I) a resistance to flow and (2) a resistance to fracture. He reasoned that at each instant the

Jan 1, 1947

By E. C. Truesdale, W. K. Waring

The Research,Division of The New Jersey Zinc Company (of Pa.) has conducted, over a period of years, numerous tests of the reducibility of various zinc ores and the reactivity of various kids of coal, using a number of different experimental methods. Most of these tests have involved the reduction of mixtures of ore and coal. In such cases the following simultaneous reactions are believed to be mainly responsible for the production of zinc, as was shown by Bodenstein' some years ago: ZnO + CO = Zn + CO2 [i] C + COj = 2CO [2] Each of these reactions is dependent upon the other for the supply of CO and COz, respectively, and the over-all rate of formation of zinc vapor will be determined by the slower of these two reactions. An analogous pair of reactions sometimes of importance is: ZnO + He = Zn + HZO 13] C + Hz0 = CO + He U3 While it is possible to obtain an indication of the relative reducibility of various ores, or of a fine versus a coarse Ore, by testing them with a given coal, and while coal reactivities may be measured in a corresponding manner, a more direct determination of relative reaction rates is possible by carrying out the desired reactions, such as I and 2, separately and under reproducible conditions. It is one purpose of this paper to present some of the results that have been obtained by the latter method. C. G. Maier2 discusses the relative rates of reactions I and 2 and concludes that while at relatively low temperatures reaction I is faster than reaction 2, this difference becomes less with increasing temperatures, although at smelting temperatures reaction is still the faster. He also says (p. 48), "At temperatures . . . be- -tween 1100' and 1300°C., . . . the zinc oxide reduction reaction is intrinsically more rapid than its physical limitations; that is, it is limited by gas diffusion rates.'' In the course of numerous reactivity tests involving the separate use of reactions and I and 2, we have obtained data that show by direct experiment, we believe for the first time, the correctness of Maier's statements concerning these reactions. We also include data on the relative rate of reaction 3, involving reduction by hydrogen. Finally, some interesting results obtained by carrying out the reduction of ' a zinc ore-coal briquet in streaming atmospheres of nitrogen, carbon monoxide and hydrogen, respectively, are presented.*

Jan 1, 1944

By A. J. Shaler, H. Udin, J. Wulff

In the study of the sintering of meta powders, we have come to the conclusion in this laboratory that further progress requires a more basic understanding of the operating mechanisms. This is emphasized in detail by Shaler. He has shown that a knowledge of the exact value of the surface tension is imperative for a solution of the kinetics of sintering. This force plays a principal role in causing the density of compacts to increase.2 Furthermore, a knowledge of the surface tension of solids is also applicable to other aspects of physical metallurgy. C. S. Smith3 points out the relation between surface and interfacial tension and their function in determining the microstructure and resulting properties of polycrystal-line and polyphase alloys. This paper describes one group of results of an experimental program designed for the study of the surface tension in solid metals. As a by-product of this work, considerable information has been obtained on the rate and nature of the flow of a metal at temperatures approaching the melting point and under extremely low stresses, a field of mechanical behavior heretofore scarcely touched by metallurgists. The importance of this additional information to students of powder metallurgy need not be stressed. Theoretical Considerations Interfacial tension arises from the condition that an excess of energy exists at the interface between two phases. Gibbs proves that this energy is a partial function of the interfacial area; thus: ?F/?s = ? where ?F/?s is the rate of change of free energy of the system with changing surface area, at constant temperature, pressure and composition, and ? is the interfacial tension, or interfacial free energy per unit area. If one of the phases is the pure liquid or solid, and the other the vapor of the substance, ? may properly be termed "surface tension," and is a characteristic of the solid or liquid. The attempt of a body to lower its free energy by decreasing its surface gives rise to a force in the surface which is numerically equal in terms of unit length to the free energy per unit area of the surface. Thus ? may be expressed either in erg-cm-² or in dyne-cm-1. Similarly, surface tension may be determined either by a thermo-dynamic measurement of the surface energy or by a mechanical measurement of the surface force. We have chosen the latter approach. Tammann and Boehme4 determined the surface tension of gold by measuring the amount of shrinkage or extension of thin weighted foil at various temperatures and interpolating to zero strain. The method is of questionable accuracy because of the tendency of foil to form minute tears when heated under tension. Their assumption of F = 2W?, where W is the width of the foil, is unsound, as the foil can decrease its surface area by transverse as well as by longitudinal shrinkage. Although their experimentation was meticulous, the paper does not include details of the sample configuration required for recalculating ? on a correct basis, even if such a calculation were possible. In the experimental procedure chosen here, a series of small weights of increasing magnitude are suspended from a series of line copper wires of uniform cross-section. This array is brought to a temperature at which creep is appreciable under extremely small stress. If the weight overbalances the contracting force of surface tension, the wire stretches; otherwise, it shrinks. The magnitude of the strain is determined by the amount of unbalance, so a plot of strain vs. load should cross the zero strain axis at w = F?. If balance is visualized as a thermodynamic equilibrium, the critical load is readily calculated. At constant temperature, an infinitesimal change in surface energy should be equal to the work done on or by the weight: ds = wdl [A] For a cylinder, s = 2pr2 + 2prl [2] If the volume remains constant, r = vV/pl [31 s = 2vpl+2V/l [4] ds = vpv/l - 2V/l²) dl [5] Substituting [5] into [I] gives for the equilibrium load, w = ?(z/rV- 2V/12) [6] and, again expressing V in terms of r and l, w = pr?(1 - 2r/l [7] Here the end-effect term, 2r/l, is neglected for thin wires in subsequent work. Eq 7 can be confirmed by means of a stress analysis. If the x-axis is chosen along the wire, then the stress is 2pr? - w pr² pr2 [8] A cylinder of diameter dis equivalent to a sphere of radius r, insofar as radial surface tension effects are concerned.³ Thus xv = 2?/d = ?/r = sz [9] For the case of zero strain in the x direction, the strain will also be zero in the y and z directions. Since the wire is under hydrostatic stress, Eq 8 and 9 are

Jan 1, 1950

By S. H. Cathcart

Price, production and drilling operations exceeded any year since 1930. A top price for crude of $2.55 was maintained from May 1 to November 6 and increased activity about coincides with that period. The average crude price for the year was: Bradford, $2.46; Kane-Butler, $2.34; Southwest Pennsylvania, $2.13. Production for the year exceeded 15 million barrels, an increase of about 2 million barrels over 1933. That this increase was more than justified by market demand is indicated by a reduction of 892,000 bbl. in stocks for the year. Two classes of data appear on Table 1, which are differentiated by footnote references. Where possible the .figures were obtained from individuals and companies that, from long acquaintance and varied contacts, are most capable of supplying an estimate where an estimate is necessary. The remaining data represent a rather careful compilation from all available published records (see p. 378). Drilling operations and production as summarized by the Oil City Derrick are as shown on Table 2.

Jan 1, 1935

?AARONSON, ALFRED E, .Vice-Pres, Mid-Co Petroleum Co , Mid-Co Bldg, Tulsa, Okla '18 ABADIE, EMILE R, Min Engr - Box 927, Porterville, Cal '76 ||ABADILLA, QuiRiCo A, Student, Colorado School of Mines, Golden, Colo. '20 ABBOTT, CLARENCE E, Gen'l Supt, Iron Mines Div, Tenn Coal, Iron & R R Co , 1405 Minnesota Ave, Bessemer, Ala. '04 ABBOTT, Louis BENJAMIN, Chief Engr, Consolidation Coal Co-, Elkhorn Div, Jenkins, Ky '15 ABBOTT, ROBERT R Met. Engr, Peerless Motor Car Co, Cleveland, Ohio. '12 ABE, ASAKA Fujita Min Co, Dojima, Osaka, Japan '14 ABEEL, GEORGE H, JR, Cons Min Engr, 633 St Paul Ave, Los Angeles, Cal '18 ABEL, ALBERT E, Mgr., Pittsburgh Dist, Valley Mould & Iron Corpn, 28th St & R R Ave, Pittsburgh, Pa '19 ABEL, W D, Min. Engr. 3897 Sacramento St , San Francisco, Cal. '19 ABELL, 0 J, Pres & Treas, Abell-Howe Co, 332 South Michigan Ave, Chicago, Ill '19 ABERNATHY, G E Willow Springs, Mo '20 ABEY, HIROSHI, Min & Met Engr, Arakawa Mine, Mitsubishi Co, Senpoku-gun, Akitaken, Japan '17

Jan 1, 1923

By C. Y. Cheng

THE purpose of this note is to show that the dislocation mechanism controlling the creep of Fe-4 pet Si alloy1 may equally account for the behavior of a-Fe2 over the same temperature range. A recent study of the creep behavior of a-Fe has been made by Ishida et al.2 Their results were in agreement with the mechanism of nonconservative motion of jogged screw dislocations over the entire range of temperatures investigated, from 480° to 1045°K. However, the observed creep rate was much higher than that which could be accounted for by the above model unless the authors assumed that pipe diffusion became significant below 775°K. More recently, Cheng et al.1 inves-gated the creep of Fe-4 pet Si alloy over about the same temperature range and found that the results could be correlated fairly well with a dislocation climb mechanism as represented by Eq. [l]. Proceeding as shown previously,1 if creep is controlled by a single climb mechanism, at intermediate stresses, the shear creep rate, y, can be represented by where n and K are material constants {K is independent of the temperature but dependent on the structure, that is, K decreases during the primary stage and reaches a steady-state value over the secondary stage of creep), t is the applied shear stress, G is the shear modulus, gc is the free energy of activation for creep (usually equal to that for self-diffusion, gd), and RT has the usual meaning. By solving for y, the apparent activation energy for creep, Q which can be determined experimentally, is given by where hc is the enthalpy of activation for creep which usually is also equal to that for self-diffusion, h^. By using Eq. [2], the data in Fig. 2 of Ref. 2 can be re-plotted as shown in Fig. 1. By comparing the two figures, it is seen that the slight increase in the apparent activation for creep over Region II, as noted in Fig. 2 of Ref. 2, is due to the influence of temperature on the shear modulus rather than of the stress on the

Jan 1, 1969