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By G. A. Parks, C. Kovacs

The xanthate flotation of chrysocolla can be improved by preheating the ore to 500° to 600°C. Addition of water vapor reduces the preheating temperature required. The temperature range of flotation improvement correlates well with the range over which dehydroxylation occurs. This observation is consistent with changes in the structure and properties of the mineral as detected by measurement of solubility, D.T.A., T.G.A., X-ray diffraction, and infrared absorption and with recently proposed explanations of chrysocolla flotation. A brief experiment by one of the authors several years ago showed that exposure of chrysocolla to high temperature water vapor resulted in increased recovery by subsequent xanthate flotation. Recently renewed interest in flotation and thermal properties of chrysocolla1-5 prompted further study of this effect and more detailed reporting.6 This paper explores the response of pure chrysocolla recovery in Hallimond tube flotation tests to the time and temperature of exposure and to changes in the water vapor pressure. Brief attention is paid to the effects of such treatment on accessory minerals. A single experiment with flotation of chrysocolla from an ore is reported. MATERIALS Chysocolla from Inspiration, Gila County, Ariz. was crushed in a porcelain mortar, cleaned of visible and magnetic impurities, and screened to obtain -48 +65 mesh (Tyler) material for flotation test work. The clean material contained 28.5% Cu and was identified as chrysocolla by comparison of X-ray diffraction, D.T.A., and infrared absorption data with that reported for similar materials by others.4,5,7 Samples of malachite and chalcopyrite, prepared in a similar way, were also identified by X-ray diffraction. The sources of these materials are unknown. A sample of chysocolla-bearing oxidized copper ore from Pima, Ariz. was crushed and dry ground for thermal activation and subsequent flotation. PROCEDURES Activation: The apparatus used for exposure of materials to high temperature water vapor is illustrated in Fig. 1. The furnace temperature was controlled to ±5°C Water vapor pressure was controlled by pre-saturating a nitrogen carrier stream with water in an adjustable thermostatted saturator (multiple bubbler). A water manometer and capillary orifice flow meter were used to measure nitrogen flow rates for activation and for subsequent Hallimond tube tests. Gas flow rate and temperature were adjusted prior to introduction of samples. Exposure time was measured from the moment of introduction of the sample to the furnace, hence includes an initial drop below the control temperature. After heating, the samples were removed from the furnace and stored at room temperature in air. Representative samples of activated materials were examined by X-ray diffraction and infrared absorption.

Jan 1, 1967

By A. H. Grobe, F. N. Rhines

AT elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible' and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscale forma¬tion) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detail5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the I-b and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 4o alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. EXPERIMENTAL PROCEDURE Silver.-The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942

By Robert C. Linares

Cubic zinc sulfide has been grown from molten salt solutions substantially below the hexagonal-cubic phase transition of 1020°C. Crystals free of birefringence have been grown from molten lead chloride at temperatures from 500° to 800°C. Factors affecting the optical transmission and the birefringence are discussed. CUBIC zinc sulfide is of interest for electrooptic devices and as an optical coating material. However, it cannot readily be produced as large crystals which are free of birefringence. The birefringence arises from the fact that the cubic ZnS is usually grown as the high-temperature hexagonal phase and is transformed to the lower cubic phase by annealing.' This results in stacking faults, stress, and birefringence. A requirement for the growth of cubic ZnS is that it be grown below the phase transition of 1020°C.2 Crystals of cubic ZnS have been grown below 1020°C by the hydrothermal,3 flux,4 and vapor transport5 techniques. However, these all appear to have limitations in size or quality of material produced. It was felt that a new flux method might have a good chance of overcoming some of the previous problems. Mita6 reported the growth of hexagonal ZnS from molten NaCl and wilke7 reported the growth of iron sulfides from molten lead chloride solution, indicating that molten chlorides make good solvents for sulfides. An investigation of a number of possible molten chlorides as solvents showed that molten PbCl2 has an appreciable solubility for zinc sulfide and that crystals can be grown at temperatures from 500° to 800°C. EXPERIMENTAL Crystal growth was performed in open or sealed Vycor or fused silica tubes, in an argon atmosphere or vacuum. There were no deleterious effects due to using vacuum; however, a sealed essentially isothermal system must be used to prevent vapor transport mechanisms from dominating. This will be discussed later in detail. Noble metal containers were not usable as they were severely attacked by these melts. The materials used were: reagent-grade PbC12, reagent-grade ZnS, optical-coating-grade ZnS, and Irtran 2 (ZnS). Crystal growth was accomplished by both slow cooling techniques and gradient growth techniques. In the slow cooling techniques, 15 g of ZnS and 100 g of PbCl2 were used. The components were placed in the silica tube, heated at 800°C for 2 hr, and then slowly cooled (l° to 10° C per hr) to 500°C. The furnace was constructed so that the tube could be inverted, thus allowing the liquid to drain off the crystals at the end of the run. The gradient runs were made by placing the above mixtures in a silica tube at 550° to 600°c, Fig. 1. A temperature gradient was maintained such that the floating mass of undissolved sulfide was 10° to 50°C warmer than the bottom of the tube. Growth occurred on spontaneously nucleated sites at the cooler bottom. RESULTS When using high cooling rates (5° to 10°C per hr), crystals form in thin sheets perpendicular to the {111} face. Crystals 5 by 5 by 1.2 mm, Fig. 2, have been ob-

Jan 1, 1969

By G. Gabra

The kinetics of acidified thiourea leaching of pyrite concentrate was investigated at temperature ranging form 20 °C to a 60 °C. The effect of various parameters on the dissolution rates are discussed. The gold extraction was found to be zero and first orders with respect to Fe (111) and thiourea concentration, respectively. The order of the reaction with respect to sulfuric acid was found to be zero. The activation energy was determined from the Arrhenius plot as 2,039 kcal mole -1 (for a freshly prepared acidic solution containing Fe (111) as the oxidant and at 800 rpm stirring speed. This relatively low activation energy value suggests that the gold extraction is controlled by a-physical phenomenon. Under optimum conditions, more than 90% of gold has been dissolved in about 30 min. and 95% in 60 min. Attempt to recover gold from thiourea solution using active carbon is also discussed.

Jan 1, 1984

By Jean L. Leroy

The Lead Smelting works of Metallurgie Hoboken S.A. are located on the banks of the river Scheldt a few miles South of Antwerp. Lead refining began at Hoboken in 1687, when it was restricted mainly to desilverizing lead bullion from Central America. Since then, various changes have been made to develop the works into a comprehensive and integrated custom smelter and refinery. Multiple hearth roasting furnaces, down-draft sinter machines and blast furnaces of standard design are used for the treatment of "complex" lead ores and secondary materials. A lead refinery based on the Harris process, with Parkes desilverizing followed by vacuum dezincing and Kroll Betterton debismuthizing was commissioned in 1967. Facilities for the recovery of precious metals, bismuth, antimony, arsenic and sulfuric acid are available. Special problems arise from the presence of large quantities of copper in the materials treated.

Jan 1, 1970

By C. R. Kuzell

Although furnaces constructed of refractory brick have been operated for many decades, there has always been an unfulfilled desire by the operators for a less arduous and more satisfactory method of patching weak spots and burned-out zones in order to postpone and to effectively extend the termination of a furnace campaign. Not only has this desire frequently arisen when small spots have approached incipient failure while the furnace structure as a whole was still in good condition, but also when larger areas showed signs of needing replacement. The available methods have been arduous, sometimes dangerous, inefficient with respect to the life of new refractory material used, and nearly always have necessitated interruption of the continuity of the furnace operations and therefore reduction in furnace production during the period of time required for the repair work. Most of these older methods have involved the replacement of masonry by refractory shapes in the weakened areas. Many attempts have been made to develop a method of patching the burned-out areas by spraying granular refractory material upon old surfaces. While some success has been attained in attempts to renew the grooved, corroded side walls and fettling, and the edges of hearths, there have been no known successful applications of the spraying method in patching the underside of arches of operating furnaces. The method developed recently at the Clarkdale smelter of the United Verde Branch of Phelps Dodge Corporation, at Clarkdale, Aria., and described in this paper, has been found to be not only convenient and successful with respect to patching vertical or inclined surfaces, but has met with a marked degree of success in patching the parts of furnace arches that are exposed to flame, the successful result being obtained without interruption or interference with the continuity of furnace operations. It may be described as a method of renewing the interior refractory surfaces of operating furnaces by pneumatic spraying of an aqueous suspension of finely divided. particles of refractory material. It has been used

Jan 1, 1944

By H. L. B. Gould, Jr. Wenny D. H.

TO date there has been but limited interest in alloys of 80 to 95 pct Co and Fe with or without other additions. In 1932, S. R. Williams' reported practically zero magnetostriction for the 90 pct Co-10 pct Fe alloy. This same composition was used for pole pieces to control the magnetic field in magnetrons operating at high temperatures.' In 1947, a 90 pct Co, 9.5 pct Fe, and 0.5 pct Mn composition was investigated3 for use in ballast lamps because of its high temperature coefficient of resistance. Recently, as part of a survey of ductile and malleable magnetic alloys capable of being processed to thin gages for possible applications in memory devices, the high Co-Fe alloys have been re-examined to determine their fabricating and magnetic characteristics. Alloys from 80 up to 95 pct Co and Fe with and without additions such as vanadium were prepared. In general these all had excellent ductility and malleability. Wire was drawn to thin gages without difficulty and fine hard-drawn wires flattened to 2) The phenomenon may have potential in estimating the carbon content of molybdenum. A given solution-treating temperature and cooling rate could perhaps be calibrated so that the area fraction of surface covered by carbide could be interpreted in terms of carbon concentration. By segregating to the surface, a big "magnification" of the carbon content is obtained, which should make the method cheap, direct, and sensitive and, therefore, perhaps of interest to the molybdenum industry. This work was conducted at Battelle Memorial Institute. Financial support by the Aeronautical Systems Division, United States Air Force, under Contract No. AF 33(657)-7376, is gratefully acknowledged, and the writer is thankful for the experimental assistance of Miss Marjorie Cantin. ribbon without splitting. Similarly, strip was cold-rolled as much as 99.75 pct reduction to a 0.25 mil thickness without intermediate anneals. Samples of round and flat wire and foil, in the severely cold-worked and annealed states, were checked for magnetic characteristics. The alloys exhibited widely divergent magnetic characteristics depending on the processing and heat-treating procedures used in preparing the samples. Direct-current hysteresis loops showing the different magnetic characteristics of 90 pct Co, 9.5 pct Fe, and 0.5 pct Mn alloys are shown in Figs. 1 to 8 inclusive, while Figs. 9 and 10 show the loops for an alloy of 82 pct Co, 11.75 pct Fe, 5.6 pct V, and 0.65 pct Mn. Figs. 1 and 2 show the high remanence and exceedingly square-loop characteristics of the hard-drawn wire and ribbon roll flattened therefrom. With the change in processing from roll flattening to flattening by drawing through flat diamond dies the resultant change in texture is accompanied by the drastic change in the shape of the loop as shown in Fig. 3. This skewed loop on annealing reverts to a more normal loop as shown in Fig. 8. The most unique loops are obtained with flat rolled strip. These are shown in Figs. 4 and 5. In the case of the hard-rolled material, Fig. 4, there is little change in induction until the magnetizing force reaches 50 oe. From 50 to 60 oe there is a sharp increase in induction to over 15,000 gauss, which for all practical purposes is saturation. The induction remains at a constant value while the magnetizing force decreases to 40 oe. At this point the

Jan 1, 1965

By J. David Lowell

For his contributions to the field of mining geology, a striking example being his brilliant inte.rpretation of the complex geologic history of the San Manuel District (Pinal County, Arizona) which resulted in the discovery of the Kalamazoo orebody, and for his lecture, "Copper Resources in 1970." On a low desert ridge six miles south of Cairo lie the remains of the world's earliest known mining town, Maadi of predynastic Egypt. Copper artifacts, including ingots and an ax head which was spoiled in casting, indicate that copper ore was smelted in Maadi, and radiocarbon dating has placed the activity at least as early as 3300 B.C. This is the oldest documented date for the use of smelted copper, the first industrial metal used by man. Copper was mined and smelted almost as early in Asia Minor and on the island of Cyprus, but the greatest development of the budding copper industry was in Egypt, where specific historical records show that about 10,000 tons of copper metal were produced in the period from 1850-1580 B.C. Contrast this production of 35 tons per year with the present world production of about 7 million tpy. Evolution of the Copper Industry The copper ore mined by the ancients was high grade, and the copper produced was expensive. The copper industry began with narrow high-grade veins, but has evolved to the point where massive earth-moving equipment can be operated in huge, low-grade open pits. Indian pits dug before 3000 B.C. in the Lake Superior district were in ore which averaged 15% Cu. His- torical research done by Arthur Brant has shown that copper cost in the Middle East in 1840 B.C. in terms of 1970 labor dollars was about $25 per lb. The copper mined in northern Europe in 1540 in the time of Georgius Agricola averaged about 8% Cu, and the cost in 1970 labor dollars was about $10 per lb. Average ore grade had dropped to about 6% Cu in 1890, and the cost of copper in the U.S. in 1970 dollars was about 45¢ per lb. Butte, Mont., was a good example of the efficiently operated vein mines of this time. In 1906, Daniel Jackling made a dramatic entrance into the copper scene with the Bingham Canyon open-pit copper mine and proved that more profit was possible mining 2% porphyry copper ore on a

Jan 1, 1971

By A. Gatti

A dispersion of AI2O3 was produced within chromium by the hydrogen reduction of a solid solution of Cr2U3-A1203. The yesulting powder. was compacted, extruded, and the material tested in tension at various temperatures and in creep at 1800°F. The material is ductile above 1200°F and is at least twice as strong as electrolytic chvomium at all temperatures. Its creep resistance, rupture strength, and ductility at 1800°F warrant further work to improve its Low -temperatutre properties. BECAUSE of its high melting point and excellent corrosion resistance, chromium has long been considered as a base for high-temperature alloys. Most chromium base alloys, however, are extremely brittle at low temperatures. Elements such as nickel and iron lower the melting point of chromium and thereby limit its high-temperature usefulness. Chromium-alumina materials made by othersl, 2 have shown good high-temperature creep resistance but poor ductility and thermal shock resistance. Pure ductile chromium3 is weak at high temperatures and reverts to a brittle state if exposed to nitrogenous atmospheres. In sintered aluminum powder (SAP)4 and internally oxidized alloys of silver, copper, and nickel, fine dispersions of oxide phases can control hardness, recrystallization, and yield stress. The possibility of formation of a ductile, high-strength material by precipitating dispersions of alumina in a chromium matrix appears worthy of investigation. MATERIAL Powder Production—Chromium oxide and alumina in amounts to produce a final alloy of Cr + 16 pct AI2O3 by weight were colloid milled, filtered, dried and high fired for 16 hr at 1600°C in air. The resulting solid solution of oxides was ball-milled to a fine powder and the chromium oxide reduced to chromium by heating in pure dry hydrogen for 64 hr at 1400°C. Final Materials Produced by Powder Metallurgy Techniques—-Chromium powder, containing a disper-sion of alumina, was pressed into 1 1/8-in. diam slugs at 25 tons per sq in. and sintered 16 hr at 1400° C in pure dry hydrogen. The sintered slugs were encased in a stainless steel can, 2 in. in diam, and extruded at 1200° C through a 1/2-in. die. The 16 to 1 extrusion ratio produced a final chromium-alumina rod 1/4 in. in diam about 30 in. long. Samples of the rod were plunge-ground to small rupture bars of 0.82-in. gage length with a 0.01-sq-in. cross section. RESULTS Microstructure Studies—Fig. 1 is the microstruc-ture of the material in the as-sintered condition while Fig. 2 is the microstructure of the material as-extruded. Comparison of the as-sintered and as-extruded micrographs show the redistribution and realignment of the alumina inclusions by the extrusion

Jan 1, 1961

By J. F. Kemp

Introduction The Bulletin of the Institute for March, 1911, is chiefly devoted to papers upon the iron ores of northeastern Cuba. At that time information about the new developments in the peculiar brown hematites of the region was becoming widely circulated and interest was especially keen. For some years exploration had been conducted with pits and trenches and so great an area had been shown to contain ore in the Mayari, Moa, and Cubitas or San Felipe districts, that the reserves conveniently situated for the consumption of American furnaces were estimated as quite two billions of tons. In the subjoined footnote will be found a list of the principal papers of special interest which have already been published.1 The further remark may, however, be made that the

Jan 2, 1915

By R. M. Fowler, H. L. Hamner

DURING the last 25 years, there appeared in the literature a number of papers describing equipment and operating techniques for the determination of total oxygen in iron and steel. In the early papers, comparatively little attention was paid to side reactions that occur when iron is saturated with carbon at a high temperature in a high vacuum. As more experience was gained with the new method, the limitations appeared. Metals, with a boiling point lower than iron, distilled out of the crucible, condensed in the cooler part of the furnace, and subsequently reacted with carbon monoxide to form oxides and carbon. Aluminum, manganese, and the alkaline earth metals proved troublesome in this respect. Modifications have been devised to overcome the difficulties due to aluminum and manganese, while the alkaline earth metals are not of too much concern as yet to the steel chemist. The reactions of sulphur have received less attention, although it is generally recognized that some carbon disulphide is probably formed. Liquid air traps have been used in some cases to prevent any carbon disulphide from entering the analytical train. Sulphur was not a particular problem at the Union Carbide and Carbon Research Laboratories until the analysis of the irons of higher than usual sulphur contents became necessary. In order to describe the procedure developed for such irons, it will be necessary to first describe the type of vacuum-fusion equipment employed because the operation of vacuum-fusion equipment is an art to a considerable extent. At the Laboratories, vacuum-fusion equipment has been in daily operation since about 1930. Over the years, the evolution of this apparatus has been governed by the versatility required to analyze a wide variety of materials. Since all types of materials from high purity metals to slags are analyzed and, since seldom more than a few samples of one type are analyzed in succession, the apparatus was designed for accuracy and flexibility rather than for speed. A general view of the equipment is shown in Fig. 1, while Fig. 2 shows the relationship of the various parts. In Fig. 2, A is a vertical double-glazed 24X27/8 in. OD silica tube heated with a 20 kva mercury-arc high frequency generator. The tube is closed with a water-cooled brass head attached with de Khotinsky cement. A turret cap fits on this head and is sealed with a 1/8x3 in. "0" ring. The head contains a sight glass and two 8 in. horizontal glass tubes, for sample storage, cemented in with de Khotinsky cement. B is a four-stage Gaede mercury diffusion pump connected to the water-cooled head with a 11/2 in. copper tube through a flange with an "0" ring. The output of the vacuum pump feeds into an automatic Toepler F pump which compresses the gas sample over mercury in the measuring burettes, G and H. There are bypasses in this line for a McLeod gage C and a Piranni gage D, a manometer E, and for initial pumping out of the system with a Cenco Megavac backing-up pump. The reduction crucible shown in Fig. 3 is machined of Tungar Bulb quality (A.G.K.T.E.-2) graphite. The sample is guided into the crucible with the graphite funnel depicted on this figure. The arrangement of the crucible, radiation screens, etc. in the furnace is as follows: A 1 15/16x61/2 in. Alundum thimble, porosity RA-84, with two 1/8 in. holes near the top and opposite each other which take a pair of special tongs used for lowering it in place, is prepared. A 3/4 in. layer of powdered graphite is placed in this Alundum thimble, and the graphite crucible containing 20 g of ingot iron and 0.5 g of carbon is carefully centered on this bed of graphite powder and graphite powder is packed around it to the top of the graphite cru-

Jan 1, 1953

By A. H. Grobe, F. N. Rhines

AT elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible' and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver Norbury2 and Leroux and Raub3 have reported internal oxidation (subscale formation) in alloys of silver with 2, 7 5, and 30 per cent of copper The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver' Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detail 5,6 The present research confirms this anticipation The oxidation of a series of 20 dilute alloys of silver has been studied metallographically, some types of subscale not encountered among the copper alloys have been found Instances of internal oxidation in alloys of most of the metals of the I-b and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation, i e , they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them In a study of 4o alloys of these white metals only a few cases of internal oxidation have been found The probable reasons for this difference in behavior will be discussed presently EXPERIMENTAL PROCEDURE Silver -The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99 993 per cent Ag)* and the purest avail-

Jan 1, 1942

By Paul Foote

The temperature of a material may be ascertained by measurement of the intensity of the radiant energy it emits. This measurement may refer to the radiation of all wave lengths emitted by the material, or, if the material is glowing, the measurement may refer to the visible light emitted, or to the radiation in n very restricted portion of the visible spectrum. In general, the intensity of radiation depends not alone upon the temperature of the source, but, also upon its nature. Thus, glowing carbon appears to the eye about three times as bright as glowing platinum, at the same temperature. This is technically expressed by saying that the emissive power or emissivity of carbon is about three times that of platinum. A material having the highest theoretically possible emissivity is known as a "black body;" it is customary to assign a numerical value of 1 to the emissivity of a black body. A black body is experimentally realized by uniformly heating a hollow enclosure and observing the radiation coming from a small opening in the wall. The intensity of radiation emitted from this opening depends only on the temperature of the walls, and not on the material of which they are constructed. If E is the emissivity of any non-transparent material and R is its reflection coefficient, it can be shown that E + R, = 1. If a material having an emissivity of, say, 0.40, and hence a reflection coefficient of 0.60, is placed inside a black body it becomes indistinguishable from its Surroundings, because the total intensity of radiation leaving the material is the same as that emitted by the black body. While the material actually emits only 40 per cent of the intensity of a black body at the same temperature, 60 per cent. of the radiation falling upon it from the walls of the enclosure is reflected. However, if the material is removed from the black body and placed in the open air, the reflected intensity is no longer present and the object appears but 40 per cent. as bright as a black body at the same temperature.

Jan 8, 1919

By F. E. Rizzo, L. R. Bidwell, D. F. Frank

THE poor high-temperature oxidation resistance of the refractory metals becomes an important problem as higher operating temperatures are sought. A meaningful analysis of their oxidation behavior requires a knowledge of the phases that can appear during oxidation as well as their relative stability. Although several extensive investigations have been carried out to obtain this information for the W-0 system,1-10 serious inconsistencies still remain. First, the standard free energies of formation (AG°) determined in recent studies which used the solid electrolyte galvanic cell technique6,7,9 differ significantly from those obtained primarily from gas equilibration measurements.1,3,4,10 The disagreement is especially large for the highest oxides. These data have been used to predict the decomposition temperatures of WO2. 72 and WO2.90.1 A considerable extrapolation is required, resulting in a large uncertainty in the decomposition temperatures. Second, Bousquet and perachon3 have presented convincing evidence, ob- tained by gas equilibration measurements, in support of the long-contested existence of W30. Phillips and chang,ll on the other hand, were not able to observe this phase under similar experimental conditions. The purposes of this work, which is part of a continuing investigation of the W-Mo system, were to resolve the discrepancies between the AGO measured by gas equilibration and solid electrolyte galvanic cell techniques, to extend the latter measurements to lower temperatures, to redetermine the WO2.72 and WO2.90 decomposition temperatures, and to apply the more sensitive electromotive-force method to the question of the existence of W3O. I) EXPERIMENTAL PROCEDURE The measurement of ?G° of reaction by the use of calcia-stabilized zirconia solid electrolyte galvanic cells has been described previously.12 The method is based on the measurement of the difference in chemical potential of oxygen between an electrode containing the two oxides of interest and a reference electrode of known oxygen activity. Two different types of cell holders were used in this study. The first type of apparatus has been described earlier." It consisted of two solid electrodes separated by a disc of electrolyte. Both electrodes were exposed to the same stream of purified helium. With this design a gaseous transport of oxygen between the two electrodes is possible. The second type of apparatus, which has also been described earlier,14 effectively separated the two electrode atmospheres. It utilized a closed-end impervious, calcia-stabilized zirconia tube that was open to the atmosphere. The tube served as an electrolyte for the cell and provided a means for separating the anode compartment, which was held under a static vacuum, from an air reference cathode. The cells and reactions of interest are described in Table I. High-purity tungsten metal was obtained from the Fansteel Metallurgical Corp. and the Allied Chemical Corp. Table II contains an analysis of each material. WO3 was prepared by oxidizing the metal in air at approximately 600°C in high-purity recrystallized alumina boats and by the dehydration of reagent-grade tungstic acid in alundum boats. The two methods of preparing WO3 resulted in slightly different purities.

Jan 1, 1968

By F. Paredes, W. R. Holman, R. W. Crawford

The diffusion coefficient for hydrogen in the ß titanium alloy containing 13 pct V, 11 pct CY, and 3 pct A1 was measured over the temperature range 20° to 500°C. Results fit the expression: D= 1.58 x lgs exp-------==-----) cm2,sec THE diffusion coefficient for hydrogen in the metastable ß-phase titanium alloy containing 13 pct V, 11 pct Cr, and 3 pct A1 was measured as part of an investigation of the effects of hydrogen on the mechanical properties of titanium alloys. Several theories on the mechanisms of hydrogen embrittle-ment include diffusion of hydrogen at ambient temperature as an important step in the embrittling process.'-5 In hydrogen-contaminated a-ß titanium alloys, it has been postulated that the rate-controlling step may be the rate at which hydrogen diffuses from the ß phase to stress- or strain-nucleated brittle hydride platelets at the a-ß interface.' However, embrittlement of the all-ß alloy investigated in this work may proceed by a different mechanism, since this alloy can be embrittled without the formation of detectable hydride platelets.6 Troiano has suggested that in this case the mechanism of delayed failure or embrittlement is similar to that proposed for high-strength steel, i.e., repeated crack initiation caused by a decrease in bonding energy as hydrogen diffuses to points of high tri-axial stress at the root of a notch. In both types of alloy the rate of embrittlement is believed to be controlled by diffusion of hydrogen in the ß phase. Accurate hydrogen-diffusion data in the vicinity of room temperature should therefore be of some assistance in understanding the mechanisms of embrittlement in these two classes of titanium alloys. Diffusion of hydrogen in pure titanium has been studied by Wasilewski and Kehl7 at temperatures above 500°C. Their measurements on diffusion in the ß phase were extended below the ß-a transformation temperature (882°C) to approximately 600°C. This was possible because of the 8 stabilizing effect of hydrogen. No results at lower temperatures have been published and there are no data in the literature on hydrogen diffusion in the ß -phase alloy used in this program. Hydrogen diffusion in metals is generally investigated by measuring the rate of transport of hydrogen past a solid-gas interface, i.e., by absorption, permeation, or degassing-rate measurements. These methods produce accurate diffusion data when bulk diffusion is the rate-determining step in the over-all process. However, at the lower temperatures of interest in hydrogen-embrittlement studies or under conditions where surface films are present, the measured rates may be surface-controlled and the calculated diffusion coefficients will be in error. Surface effects were eliminated in the present work by using a modification of the common welded-couple technique m which two bars with uniform but different compositions are joined before the diffusion anneal." The same type of step change in the initial concentration vs distance curve was produced by electrolytically hydrogenating thin-strip specimens which had been electrically insulated over half of their length. Concentration vs distance curves were determined, after appropriate diffusion-annealing treatments, by vacuum-extraction analyses of transverse samples sheared from the strips. Diffusion coefficients were calculated by the methods of Grube.M This technique was feasible because of the large concentrations of hydrogen which can be charged into p -phase alloys without the formation of hydrides15'16 and because of the extremely low degassing rates observed when hydrogenated titanium alloys are heated in air. EXPERIMENTAL WORK The diffusion couples were cut from a 0.022-in.-thick mi ll-annealed sheet.* Strips 8 in. long by 1/2

Jan 1, 1965

By Sidney H. Haughton

WHEN the white pioneers of the eighteenth and nineteenth centuries advanced from the coastal settlements of southern Africa into the interior of the subcontinent, they found it inhabited, more or less sparsely, by brown or black peoples mainly of pastoral habits but equipped with a fighting spirit and certain fighting weapons. Some of the tribes were smiths, others were miners and metallurgists; all used fuel, either industrially or domestically. Some of that fuel was wood, some cattle dung, and in some places the natives mined outcrop coal. Coal was first discovered by Europeans in Natal about 1840. After proper deliberation and after allowing due time for a consideration of all the implications, the Natal Government decided in 1881 (40 years after) to import an English expert to investigate and report on the discovery. Things then moved rapidly, and in what to a geologist is the remarkably short space of eight years, Natal collieries were producing at the rate of nearly 30,000 long tons per annum or 100 long tons per working day!

Jan 1, 1945

By R. W. Hertzberg, F. D. Lemkey, J. A. Ford

The technique of unidirectional solidification has been applied to the A1-AI3Ni and A1-CuAl2 ezltectic alloy systems; the controlled microstructure of A1-A3Ni consists of parallel A13Ni whiskers emhedded in an aluminum matrix while the Al-CuAl2, system solidifies as parallel alternate lamellae of aluminm and CuAl2. Mechanical tests (tension and flexure) have shown that the particle-matrix interface bond formed during unidirectional solidification allowes for efficient load transfer from the matrix to the reinforcing phase. Strength and fracture characterstics of the alloys were studied as a function of phase orientation; the tensile strength of controlled Al-Al3Ni samples was 43,000 psi (three times greater than that of as-cast specime~s). The strength of the Al-CIA2, cutectic was studied as a function of lamellae-flexure stress-axis orientation using a microbend apparatus. A twofold increase in outer fiber stress was observed as the lamellae were rotated from a position of no reinforcing (perpendicular to the stress axis) to one of maximum reinforcing (parallel to the stress axis), The brittle reinforcing constituent in each alloy (A13Ni and CuAl2) was observed to he the nucleating phase for fracture. It is to be concluded from this investigation that unidirectionally solidified eutectic alloys have a potential use as reinforcing coniposite) materials. In a recent review article, Chadwick1 has described the work of many investigators in the area of controlled solidification of binary eutectic alloys. Thus far, more than twenty eutectic alloys have been unidirectionally solidified to produce structures consisting of two phases in the form of alternating lamellae or as whiskers embedded within a continuous matrix; in either case, the phases are aligned parallel to the growth direction. In particular, Kraft and Albright2 have shown that the Al-CuA1, eutectic alloy exhibits a lamellar microstruc- ture as a result of unidirectional solidification while Lemkey, Hertzberg, and Ford3 have studied the A13Ni whisker-aluminum matrix morphology in the A1-A13Ni system. Whether these alloys could exhibit reinforcing behavior would have to depend upon the strength and volume fraction of the reinforcing phase (AI3Ni and CuA12) and the nature of the bond between the reinforcing phase and the matrix. Hertzberg and Kraft4 have shown that the interface bond between chromium whiskers and a copper matrix in unidirectionally solidified Cu-Cr is particularly good while Lemkey and Kraft5 have reported chromium-whisker tensile strengths in excess of 1,000,000 psi. However, with the chromium volume fraction being less than 2 pct, no reinforcing behavior was displayed by the Cu-Cr alloy.6 In view of the encouraging results concerning the good interfacial bond and high strength of the reinforcing phase in the Cu-Cr system and preliminary mechanical test data reported by Lemkey et al.3 for the A1-A13Ni system, the A1-CuA1, and A1-A13Ni eutectic alloys containing 50 and 10 vol pct, respectively, of the reinforcing phase give promise of possessing mechanical reinforcing behavior. Based on this premise, the objective of the investigation was to study the strength and fracture behavior exhibited by these anisotropic microstructures. EXPERIMENTAL PROCEDURE Controlled Solidification Procedure. An extensive description of the technique of unidirectional solidification has been presented elsewhere.' However, the pertinent details for each eutectic system studied are discussed below. Al-A13Ni System. Several master heats of this alloy were prepared by vacuum-induction melting in an A12O3crucible and casting in SiO2 mold or by induction melting in alumina crucibles under argon. The initial heats were prepared from 99.99 pct A1 and 99.99+ pct Ni, while later heats used 99.999+ pct A1 and 99.99+ pct Ni. Specimens of these master heats were unidirectionally solidified using induction and resistance heating sources and argon atmospheres at growth rates from 1.1 to 28.7 cm per hr. The thermal gradients in the liquid were controlled in the range of 26" to 36°C per cm for these runs. Al-CuA12 System. The master heat and controlled

Jan 1, 1965

This paper "On Coal" was published in three issues of The Western Gleaner in 1814. Name of author is not given. This magazine was started by Cramer, Spear & Eichbaum, in Pittsburgh, Pa., in December 1813, and ran for about two years. Copies are very rare, and this one is made from an original in the Darlington Library, University of Pittsburgh. This is almost certainly the first general article on coal published west of the Allegheny Mountains, and one of the earliest in this country. ON COAL Its Natural History-Mining of Coal-Phenomena occasioned by Fire-damp-Method of Coking-Distillation of Tar from Pit-coal-Gas-light-Coal, a Manure I. NATURAL HISTORY OF COAL There are few productions of nature which present to the philosopher a wider field of investigation than pit-coal. A substance highly inflammable is found in the deep recesses of the earth, sometimes loaded with numerous superincumbent strata of hard rock, and extending frequently along with these strata through a vast expanse of territory. Though metals may be said to be inflammable substances, as they combine more or less rapidly with oxygen when placed under particular circumstances, yet the character of rapid combustion with disengagement of light and heat, seems to belong. principally to such substances as are derived either from the animal or vegetable kingdom. That this is probably the case with regard to coal we are further induced to believe, by the remarkable circumstance, that the chemical analysis of this natural production yields especially, though in various proportions, those materials which constitute essentially the vegetable. And if any thing was wanting to confirm, us in that opinion we might trace in a number of fossile substances the gradual transition of the vegetable into the state of mineral coal. This fact is so intimately connected with the natural history of coal, that we cannot think it superfluous to give it some farther development. Among the great number of principles which the chemist is capable of tracing in the vegetable kingdom, the presence of extract, resin and fibre seem to form the characteristical marks of plants.-If vegetable matter be boiled in water, and the water, after having been strained and filtered, be exposed for some time to the open air, a flocculent precipitate takes `place from every part of the liquor; which soon subsides to the bottom of the vessel containing it. This is the extract; altered, indeed, by exposure, and now no longer soluble in water, a change which is supposed to depend on the absorption of oxygen; and if, by any means the proportion of oxygen be increased, the extract gradually becomes of a darker color, blackens, and approaches to the state of charred wood.

Jan 1, 1942

By Walter Mueller

Transition in the underground coal industry, begun with the passage of the Federal Coal Mine Health and Safety Act of 1969, should be completed midway in the 1972-80 period. Surprisingly, many of the far reaching effects of this act have been, for the most part, beneficial to the industry from the standpoint of health, safety and basic operating standards. Production has dwindled, but the next few years will see production declines level out. Average declines of approximately 27% have been recorded since passage of the 1969 act, with costs increasing an average of $1.50 per ton throughout the industry. Nationwide averages presently are in the range of 14 tons per man-shift, and by 1980 this may be further reduced to a 10-ton per man-shift average for the industry. But in spite of the many temporary set-backs affecting the industry, the marketing opportunities are clearly visible. Due primarily to the energy squeeze facing the U.S. over the near term, the 'underground coal operator is and will be enjoying unusual leverage in selling his product.

Jan 10, 1972

By W. P. Lass

Discussion of the paper of W. P. LASS, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 103, July, 1915, pp. 1443 to 1447. ROBERT M. KEENEY, Somersville, Conn. (communication to the Secretary *).-There is not only a possibility of improvement in present methods of treatment of the byproducts of refining in the cyanide plant by the use of the electric furnace, but also in melting and refining of gold precipitate. This interesting paper by Mr. Lass shows an electric furnace in successful operation in a large plant for the treatment of by-products. Electric melting of cyanide precipitate is a cheaper form of treatment in many cases than any of the combustion methods now used because of the high cost of oil, coke or coal in many camps, while on the other hand electric power may be had cheaply, especially in a place where there is possibility of development of high-head hydro-electric plants for power purposes. Also, if the oil-fired tilting furnace is used for direct melting of the precipitate, as is the case at many small mills, a great saving in cost is made by the use of the electric furnace because of the high crucible cost in melting with the tilting furnace. A study of this paper indicates the cost of the operation approximately. Consider all the fluxes to be turned in as byproducts and coke at $18 per ton.

Jan 12, 1915