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By Charles D. Hoyt

T IME studies and cost accounting were combined to increase the efficiency of the overall mining method and thereby reduce costs at the Titania mine of the National Lead Co. in southern Norway about 70 miles southeast of Stavanger. From these studies a more effective drilling system was developed, standards were adopted for setting base pay rates, shrinkage stoping was abandoned for open stoping, a new mechanical loading chute was adopted, and the loading and haulage system was changed. Ore minerals at the Titania mine are ilmenite and magnetite; gangue minerals are plagioclase and hyperstene with accessory minerals of biotite, pyrite, chalcopyrite, and spinel. The average content of the ore is 17 pct TiO2 and from 20 to 25 pct iron. The ilmenite crystals contain microscopic lamels of hematite, making it impossible to obtain a high TiO2 content in the concentrate. An ilmenite concentrate with 44 pct TiO2 and 36 pct Fe, and a magnetite concen-

Jan 9, 1950

By Harold R. Wampler, John L. Bolles, Adrian J. Broderick

Phelps Dodge's 60,000 tpd Morenci Concentrator has been in operation since 1942. The integrating of process control applications into the concentrator began in 1972. A process control system is presently on-line controlling 30 primary grinding circuits and all reagent additions. The system consists of a centralized control room process control Computer, on-stream X-ray analyzer, on-stream particle size analyzers and an operator interface. This paper describes the process control system's development, control concepts and its influence on the concentrator performance.

Jan 1, 1978

By Arthur F. Colombo

The selective - deslime - flotation process developed by the Federal Bureau of Mines as part of its goal of maintaining an adequate supply of minerals to meet national economic and strategic needs is described. The operating parameters for the selective flocculation - cationic flotation of oxidized taconites from the western Mesabi range in Minnesota are discussed. Data from the operation of a 410 kg/hr (900 lb/hr) pilot plant employing reclaimed water are summarized for 2 types of oxidized taconites.

Jan 1, 1979

By A. S. Richardson

THE conditions that make necessary the mechanical ventilation of the Butte mines of the Anaconda Copper Mining Co. are due to a number of causes, all of which are incidental to the depth at which mining operations are now carried on. The main object to be accomplished, of course, is the reduction of the temperature and humidity of the air in the working places. Ventilation fans, both surface and underground, have been used for many years, but increasing depth has made the problem much more difficult. Further improvement in both ventilation equipment and methods, therefore, became necessary; and it is the purpose of this paper to describe the work planned and done under the improvement program. The mines of the district have been frequently described in various technical publications, so a description is unnecessary here. From a mine-ventilation viewpoint, compared with coal-mine ventilation systems, the problem is complicated by the fact that the workings to be ventilated are situated on a large number of steeply dipping veins which frequently intersect and are faulted, and also by the fact that the extent, or existence, of orebodies is not definitely known in advance of actual development work. For these reasons ventilation work cannot be planned in advance of actual operations, nor can such regular systems of ventilation as are used in working the more uniform and continuous bodies of coal be developed. When operations are conducted at a normal rate, about 10,000 miners are employed on two shifts, so that about 5000 men will be underground at one time. But as ventilation is necessary to reduce high temperature and humidity due, mainly, to natural causes, the quantity of air per man per minute is not a governing consideration in determining ventilation requirements. Most important among the numerous sources of heat and humidity in the mines are : heat generated during decay of mine timber; heat and humidity given off by mine rock and water; heat generated by oxidation of sulfide minerals; heat given off by electrical equipment; heat generated by mine fires (in certain localities).

Jan 2, 1922

By C. W. Mac Gregor

THE observation of the flow layers, or Lüders' lines, produced in mild steel when it is stressed into the plastic range often provides considerable useful information for the study of the fundamental mechanism of the plastic flow of metals. It is a commonly observed fact that as soon as the upper yield point in a mild-steel tensile-test bar is passed, an unstable condition develops in the equilibrium, the load on the testing machine drops and if the surface of the bar contains a thin mill scale, the latter begins to flake off rapidly along certain "lines." These "lines" are in reality traces of wedge-shaped flow layers and are formed by the inter-section of the surface of slip and the surface of the bar. The average plane of the flow layer itself has been found by various experimenters to be inclined at an angle of approximately 45° to the axis of the test bar. In a body of more complicated shape stressed in possibly a different man-ner, the tangent planes to the flow layers at each point seem in many cases to be inclined at an angle of about 45° to the principal stress direc-tions at the point. As examples of the latter may be mentioned the logarithmic spirals obtained when a rivet hole is punched in a thin plate, or when a tube is subjected to internal pressure only, etc. Hence if the flow layers are observed from an experiment, the shear-stress trajectories -the curves indicating the directions of the maximum shearing stresses in the body-may then be approximately determined. Since the latter curves form an orthogonal family inclined at 45° to the principal stress directions, the family of principal stress trajectories, or the curves indicating the directions of the principal stresses, may be thus obtained. Although the discontinuous type of stress-strain curve at the yield point is commonly observed with test bars of mild steel, more recent experiments have shown that this is by no means the only material exhibiting this interesting phenomenon. A similar effect has been observed in zinc and cadmium crystals, by Becker and Orowan;1 in duralumin and other aluminum alloys, by Dawidenkow, 2 Elm,3 Fell, and others; in copper and copper-alloy crystals, by Elam;5 in brass by Elam;5 in brass wires by deForest;6 in higher carbon steels, tungsten steel, and

Jan 1, 1939

By J. M. Callow

THE results obtained by pneumatic flotation throughout the country on all classes of ore, and. the tonnage now being treated by this particular method, speak for themselves. Its advantages over the so-called agitation process are now established by facts and data from practice. The comparative efficiency of a rapidly revolving paddle, as a means for aerating an ore pulp, and of a cycloidal or turbine blower for the same purpose, would seem to be so obvious as to leave no room for discussion. Practitioners in this art are to be congratulated on the acquisition of the valuable literary contributions that have recently been made on the theory of. flotation by Messrs. Ralston, Van Arsdale, Taggart and Beach, and others, and the very valuable and able articles, by Messrs. Laist and Wiggin on "Flotation Concentration at Anaconda, Mont.," by, Dr. Rudolf Gahl- on the "History of Flotation at Inspiration," and by David Cole on "The Advent of Flotation in the Morenci District." It is not within the province of this article to attempt an answer to the various issues raised in regard to the theory, or to defend the one advanced by me a year ago. But since discussion usually benefits the profession, a reply will be made to some of the statements made by the last-named writers. COMPARATIVE SENSITIVENESS AND ATTENDANCE Concerning 'the article, "Flotation Concentration at Anaconda, Mont.," by Laist and Wiggin, a little explanation is in order. It should be stated that; with the exception of about 24 days at the end of the testing 'period, the Callow experimental plant at Anaconda was not run under my direction. This perhaps accounts for some of the conclusions drawn on page 562 of the descriptive paper. The conclusion that the use of acid seems to be of considerable advantage, calls, for some comment. While the tests conducted by the Anaconda Copper Co. do show acid to be, of considerable benefit, this is a consequence of using acid sludge as a flotation agent. My belief has always been that the Anaconda

Jan 2, 1917

By A. G. Weber, R. L. Ledbetter, A. L. Hicks

A procedure which makes use of both analog and digital computers has been developed for predicting the pressure-production behavior. of water-drive reservoirs. The electric analyzer is used for matching the past pressure and production history of the reservoir and inferring the physical characteristies of the aquifer. When the history has been matched, a .set of base curves called influence functionce" are derived and the future behavior of the reservoir is calculated from these curves. INTRODUCTION Electric analog methods are particularly well-suited for complex water-drive problems. Like all other methods of analyzing water-drive reservoirs, however, analog methods are subject to certain limitations. One of the more obvious and serious of these results from inaccurate or insufficient knowledge about physical characteristics of the reservoir and aquifer. However, it is not insurmountable because the unknown characteristics can usually be inferred from the reservoir's previous behavior. Simons and Spain have shown that even with scant reservoir data and limited production history, electric analyzer studies can provide useful and reliable results. Aside from this limitation on analyzer predictions, the main disadvantage has been lack of a technique for keeping predictions abreast of latest production forecasts. Pressure behavior of a reservoir depends on the rate at which fluid is withdrawn; it is therefore necessary to specify the future withdrawal schedule before the future pressure behavior can be calculated. Conventionally, the electric analyzer predicts pressure behavior for a specific production schedule. If this schedule is abandoned in favor of some new one, as is frequently the case, either the study must be rerun or results adjusted in some manner. The usual procedure is to predict pressures for several different forecasts covering a wide range of production rates. Pressures for specific rates other than those studied can then be approximated by interpolating between the analyzer predicted curves. However, reliability of this type of prediction is doubtful. This paper describes a technique for predicting future behavior of water-drive reservoirs that retains all advantages of electric analyzer analysis and eliminates the main disadvantage. That is, the analyzer is used conventionally to infer unknown reservoir parameters from the pressure history, but not to predict the future behavior directly. Instead, a derived set of base curves, called influence l'unctions, can be used to calculate future behavior for any production schedule.

By R. M. Sellwood

The No. 4 I.S.F. Smelter Complex at the Avonmouth Works of Imperial Smelting Corporation (N.S.C.) Limited commenced operation at the beginning of 1968. The furnace rating is 120,000 tons zinc and 40,000 tons lead per annum. Zinc and lead concentrates are unloaded onto a 1,000 tons per hour capacity conveyor belt and automatically weighed and sampled before receipt into a 48,000 ton capacity raw material store. Distribution is by a reversible boom stacker into 16 x 3,000 ton bays and recovery is by a front end loader. Materials are fed to 16 proportioning bins for feeding via continuous weigh feeders to a 132 square metre effective updraught area sinter machine with a material flow rate of 240 tons per hour over the machine. The required quantity of output lump sinter at up to 800ºC is fed to 2 x 600 ton storage bins on the I.S.F. plant. By-product SO2 rich gas is fed to a conventional wet gas single stream acid plant rated at 600 tons per day utilizing a dry N.T.P. gas volume of 100,000 cubic metres per hour. The hot sinter and preheated coke (800ºC) are automatically neighed and charged to a 27.3m2 shaft area I.S.F. fitted with 2 x 5.5 m. wide lead splash condensers. Grade 4 zinc is tapped and transferred to the zinc refinery. Conventional type lead bullion and slag are tapped from the bottom of the furnace through a separation forehearth. The refinery consists of 6 lead and 3 cadmium columns to produce some 52,000 tons per annum of S.H.G. metal. S.H.G. metal and Grade 4 metal is cast into various shapes as required.

Jan 1, 1970

By A. E. J. Engel

INDUSTRIAL talcs and ground soapstones both include earth materials of different chemical and mineral compositions. In general, the industrial talcs are composed of silicates that contain appreciable amounts of magnesia. Generally talc, the mineral, is a predominant or at least common constituent. Talc, the mineral, is a hydrous magnesium silicate, with a suggested theoretical formula H2Mg3 (SiO3)4 or H2O.3MgO.4SiO2, which postulates 63.5 pct SiO2, 31.7 pct MgO, and 4.8 pct H20.11 Actually different single grains or leaves of pure talc have variations in water content ranging from 3.5 pct to more than 7 pct, as well as slight differences in the proportions of MgO and Si02.16 Only a very small percentage of the ground industrial talcs produced in the United States approaches the composition given above (see Table 1). The purer talcs invariably occur as alteration products of magnesium carbonate rocks. Some of these relatively pure talcs include compact, massive types largely mined in California, which are designated as steatite.38,58 In general, steatites cannot contain in excess of 1.5 pct CaO, 1.5 pct combined FeO and Fe203, and 4 pct A1203. The less pure varieties of massive talc and mixtures of magnesian silicates are commonly called soapstones, or merely talc. Many industrial earth products classified as talc or as soapstone contain a variety of minerals, especially serpentine (H4Mg,Si2O9), chlorites (hydrous magnesium, iron, aluminum silicates), tremolite (Ca2Mg5H2[SiO3]8), anthophyllite ([MgCa]SiO3), diopside (CaMg[SiO3]2), and quartz (SiO2). The carbonates calcite (CaC03), dolomite (CaMg[CO3]2), and magnesite (MgCO3) are also present in some industrial talcs and soapstones. Some of these minerals, as well as sulphides, sulphates, and iron and manganese oxides, if present at all or in excess of minute amounts, may alter the composition of the industrial talc sufficiently to restrict materially its use or to lower or destroy its value. These factors are discussed in a subsequent section of this chapter.

Jan 1, 1949

By L. E. Wemple

Previous to 1915, zinc refining had not become a general practice among the zinc smelters in the United States. Such refining as had been carried on was confined chiefly to remelting very high-leaded zinc, such as third-draw metal from the retort furnaces, and slab dross, and hard spelter from galvanizing pots. In this remelting operation, the lead and iron were settled out and the refined spelter obtained graded fifth class, ie., Prime Western. Owing to the presence of lead in most zinc ores, the bulk of the spelter produced by direct smelting is of this Prime Western grade. Careful selection of ores of low lead content gave purer grades of spelter, z.e., Brass Special and Intermediate; and smelters which could secure ores carrying practically no lead produced high-grade spelter. Thus, in general, the grade of spelter produced by any smelter was predetermined by the purity of the ore it could obtain. The needs of the warring nations of Europe for enormous quantities of cartridge and other high-grade brass resulted in such a demand for the purer grades of spelter that the available supply of lead-free and low-lead ores could not produce the quantity required. Prime Western grades went begging, so to speak, while high grades sold at times from 5 to 15 c. per pound over the Prime Western market. The great demand, coupled with the wide market margin, which permitted the inherent costs and losses, resulted in the conversion of the lower grades into higher grades by processes of refining. These conditions also accentuated the development and size of the electrolytic plants, which were being worked out at the time this increased demand for pure grade of metal occurred. The electrolytic process, where available, produces a higher grade of spelter from impure ores than does the fire process; a large portion of those impurities in the ore, which by the distillation process would be carried into the spelter, are removed in the leaching of the ores and the purification of the solutions. The refining process, adopted at a number of smelters for the purpose of converting low-grade spelter into grades suitable for bras4 was that of redistillation.

Jan 1, 1918

By R. E. Boni, G. Derge

SURFACE tensions of molten silicates are of metallurgical importance for many reasons. From a knowledge of their values, an insight into the problem of liquid slag structure can be gained. Also, such problems as separation of slag from metal, slag penetration of refractories, spreading of enamel coats on metals, bonding of cutting wheels, adsorption of gases, frothing of slags, and homogen-ization of slags are related to the surface tensions of the silicates. Because of the absence of a correlated review of the work that has been conducted in this field, the following survey is presented. It is not a complete summary of all the surface tension studies of silicates but only a review of the literature which is pertinent to metallurgical applications and research. Liquid Surface Tension The surface of a liquid differs from the interior in that its particles (ions, atoms, or molecules) are not

Jan 1, 1957

By Frank R. Van Horn

It is customary to ascribe two general modes of occurrence to natural gas, namely, shale gas which, as the name indicates, is found in shale, and reservoir gas, which occurs in sandstone, conglomerate and dolomitic limestone. Both of these types are found in the Cleveland district. The shale gas has been produced on a small scale for a long period of years, probably dating back as far as 1883. Shale gas is a low-pressure gas, small in volume with variable pressure, and is limited to no definite horizon. It is generally independent of oil, may last for a long time, and is not dependent to any great extent on the structure of the rocks. There are many such wells in the district which range from 400 to 1,840 ft. in depth, although most have been completed at about 800 ft. This indicates that the wells pass through the Cleveland and Chagrin shales into the Huron or Portage shale of the Upper Devonian. During the last 2 years great interest has developed in a deeper-seated reservoir gas. What is commonly called reservoir gas is generally a high-pressure gas occurring in large volume at a definite horizon. Oil may, or may not, be associated with the gas, and in most regions in which reservoir gas is found, the geological structure is of great importance. This type of gas occurs in all large fields such as those of West Virginia which have been supplying Cleveland until the recent discovery of local gas at great depths in commercial amounts. Historical Outline The oldest well producing reservoir gas in the district was drilled in 1886 in Newburg for what was then known as the Cleveland Rolling Mill Co. This well was 3,000 ft. deep, and was thought to have reached the "Clinton" formation. Two "sands" showing small amounts of oil were recorded in the Niagara limestone at depths of 2,658 and 2,686 ft. This is about the horizon of the so-called Newburg sand which has proved to be of some importance as a source of gas and oil by recent drilling operations. The rock pressure was reported to be 400 to 500 lb. per square inch, but since the volume was only 14,000 to 16,000 cu. ft. daily, the well was not only considered unsuccessful but was thought to prove the absence of high-pressure gas in commercial quantities in the Cleveland district.

Jan 1, 1917

By Norman L. Wimmler, H. G. Iverson, S. Ricker, P. E. Oscarson, S. H. Lorain

THIS paper has been prepared with the principal objective of recording the results of the Bureau of Mines exploration of five major clay deposits in the Western Region. It is based mainly on data contained in unpublished Bureau of Mines reports. Acknowledgment is made to the Federal Geological Survey for its cooperative work with the Bureau of Mines, to the various State geological and mining departments, and other State and local agencies. CLAY EXPLORATION BY THE BUREAU OF MINES Much has been written and published on clays and clay deposits relating to their refractory, ceramic, and other qualities but such literature is lacking in analyses of the available alumina content of the clays and provides little indication of their possibilities as a source of alumina. With this new objective in view, a great many of the known clay deposits were reexamined and new ones discovered. The Bureau of Mines made preliminary examination of numerous areas in the western United States. Five of those most favorably indicated were systematically drilled, and in each a large amount of high-alumina clay has been found. These five major projects are Molalla and Hobart Butte, in western Oregon; Cowlitz-Castle Rock, in southwestern Washington; Lone, in California; and the Olson-Troy area in Idaho (Fig. I). Preliminary scout drilling was done in the Stockton deposit at Coeur d'Alene, Idaho; the Whiteware deposit near Lewistown, Mont.; and 13 areas in the Spokane or eastern Washington region, where the most favorably indicated area, known as the Excelsior, is now being drilled more systematically. Preliminary drilling was undertaken in numerous areas adjacent to the major deposits and others more remote. As a result, large additional clay possibilities were found. THE CLAY DEPOSITS The clay deposits under consideration are of the sedimentary or transported types, parts of which have been altered further by the agencies of weathering, ground water, or hydrothermal action. There are extensive deposits of residual clays in northern Idaho and in eastern Washington, but they have been found to be low in the available alumina and to contain much free quartz, mica, and unaltered feldspar. To be of value, they must first be subjected to beneficiation to remove these gangue minerals. The sedimentary clays have been derived largely from the decomposition, erosion, and transportation of granites, gneisses, schists, and basalts. At Molalla, some

Jan 1, 1944

By O. P. Chisholm

Dross emerges from the blast furnace either with the lead through a lead well or by tapping from a forehearth or settler, but until a dozen years or so ago few dross reverberatories were used in western lead smelters because it was the usual procedure to circulate the dross from the drossing lead kettles back to the blast furnace. It was quite customary for lead smelters to produce matte in their blast furnaces, as this was the form in which copper could be collected, concentrated if necessary, and shipped to the copper smelters for further treatment. The main prerequisites for good matte formation arc., of course, a more or less definite amount of copper on the charge and sufficient sulphur. Such troublesome impurities as arsenic and antimony were ignored, in so far as possible, although they contaminated the bullion and thereby increased refinery costs. At the same time stocks of blastfurnace speiss containing gold, silver, lead and copper in addition to iron, arsenic and antimony, were being accumulated for want of a market to absorb them. As the dross was being fed back to the furnaces as rapidly as it was being produced, arsenic and antimony tended to build up until the arsenic could effect a combination with copper and iron and an alliance with lead, and the antimony a combination with copper and an alliancc with lead. Sulphur, being the most active agent in taking up the copper, left little of that element for the arsenic and antimony, so that on the whole a somewhat unsatisfactory metallurgy resulted. During this same period, certain lead plants were beginning to encounter trouble with zinc due to the replacement of crude ores of lot zinc content by concentrates containing high percentages of lead and zinc in sulphide form, the blast-furnace slags resulting from the smelting of such concentrates being characterized by a decidedly increased zinc content. It was soon realized that zinc plus sulphur was "poison" to a lead blast furnace and steps were taken to reduce the sulphur content,. At this stage some plants found that any substantial matte fall was out.

Jan 1, 1937

By St. John, JOHN Ancel

AT THE New York meeting of the Institute of Metals Division in February, 1927, Jeffries and Tarasov presented a paper on Tungsten and Thoria,1 in which the experimental facts were interpreted in accordance with the prevailing point of view that the thorium is present as the oxide, thoria. In discussing that paper the writer of this article stated that his own investigations, which had been unavailable to Messrs. Jeffries and Tarasov, showed that the so-called "thoriated" tungsten filament failed to disclose any sign of the oxide when subjected to X-ray diffraction analysis, but did give plenty of evidence of the presence of metallic thorium and, in certain cases, of a material believed to bean alloy of tungsten in thorium. Since these results were completely at variance with the results reported in the paper under discussion and with other papers which had preceded it from time to time in the past, it was felt that further discussion should be withheld until the new evidence could be presented adequately. Arrangements were therefore made to present that evidence at this meeting. MATERIAL EXAMINED The material examined was high-emission filament such as is used in radio tubes, supposed to contain about 0.75 per cent. thoria. The actual analysis was not stated.

Jan 1, 1927

By Archer E. Wheeler, Milo W. Krejci

The Boston & Montana Reduction Works at Great Falls, Mont., was formerly the reduction works of the Boston & Montana Consolidated Copper & Silver Mining Co., and continued as the reduction plant for the independent company until June 1, 1910, when the consolidation of a large number of the operating companies of Butte was effected. It then became merged in the Anaconda Copper Mining Co. as the Boston & Montana Reduction Department of the Anaconda Copper Mining Co. The history of copper converting at this plant, while not covering the entire period of the commercial use of the process in this country, does cover by far the larger part of it, and as the operation of and appliances for the process have undergone many changes during the time, it may, perhaps, be of some interest to put the record of these changes into permanent form. The plan followed in the preparation of this paper has been to give first a brief chronological record of the principal events and changes and then, even at the risk of some repetitions, to give more detaild accounts of some of these changes under separate headings. The headings for the complete paper are as follows: 1. General. Chronological Review. 10. Development of Different Classes 2. Mechanical Manipulation. of Converters After Class I. 3. Casting of Finished Copper. 11. Basic Lining. 4. Tamping of Linings. 12. Number and Size of Tuyeres. 5. Early Acid Linings. 13. Cast Copper Tuyeres. 6. Acid Linings With the Use of Ore. 14. Efficiency of Air. 7. Introduction of Flux Through the 15. Size of Converter Mouth. Tuyeres. 16. Height of Converter. 8. Bottom Blast. 17. Summary. 9. Disposal of Converter Slag, General Chronological Review. Ground was broken for the general concentrating and smelting plant in the spring of 1,891. The first departments to start operations were the concentrator in March, 1892, and the Brückner roasting and reverbera-tory smelting departments in April, 1892. The converter department

Jan 1, 1914

By Orlando Romig

PART I-PREPARATION OP METALLIC SINGLE CRYSTALS WITH ESPECIAL REFERENCE TO SINGLE CRYSTALS OP ZINC? As metals and alloys are composed, of, an aggregate of allotriomorphic crystals or grains, each possessing an individual orientation, the physical characteristics of a metal or an alloy are closely related to the properties of the individual crystals. The preparation and study of single metallic crystals are, therefore, matters of considerable importance. The advent of the X-ray spectrograph as a valuable metallurgical tool has magnified the importance of this subject, because the interpretation of some X-ray spectrographs is difficult unless single crystals are used in these studies. PREVIOUS WORK The first paper, as far as the writer knows, on the behavior or preparation of single crystals of metals is by Baker.1 He describes the behavior of extruded wires of sodium and potassium. These wires, when pulled in tension, instead of I showing the usual conical fracture common to most metals, had a chisel-shaped fracture when they were broken. I and II, Fig. 1, have a similar fracture. Baker checked his results by preparing single crystal wires from molten sodium and potassium and observing their properties. He prepared the wires by filling glass tubes, under oil, with the molten metal. The surfaces of the strained wires showed slip bands of remarkable clearness of which photographs are shown in his paper. He concluded that these wires were single crystals and "that the portions of the metal brought into play are cubes. Such cubes, when placed so that a plane through 'two opposite edges was parallel to the axis of the wire, would allow of lateral contraction by faces gliding over one another in one direction only and not in the direction at right angles."

Jan 1, 1927

By Larry Kaufman, Joan B. Berkowitz-Mattuck, Edward V. Claugherty

The oxidation characteristics of hafnium and zirconiunr diboride were measured between 1200 and 2200'K by a thermal- conductivity method which continuously ttzeasures the rate of reaction of oxygen with the diboride and by a metallographic air oridation method zuhich provides a measure of the total arr7ount of bovide conuerted to oxide for a given time interval. The oxidized specimens obtained from the tl~eritaal-coi~ductitrity method were also examined by quantitatire metal-lographic procedares. The significant results obtained in this investigation reveal that metal-rich compositions of lzafi~iutil diboride proride the most oxidation-resistatzt material up to 2000°K; hafnium diboride is tmre oxidation- resistant titan zirconium diboride at all tempevatures examined; the morphology of the oxide formed on H/B2 and Llie temperature coefficient qi. the oxidation rate constants change at the temperature of ttze monoclinic to tetragonal phase transition] in HfO2; the oxidation of neither HfB2 nor ZrB2, results iN catastrophic Jazlure at lorc. oxygen pressures; and pvefevetztial gvaLti boundary oxidation was not obsevued for either HfBi or ZYB, A comprehensive study of the high-temperature characteristics of refractory transition-metal di-borides is currently in progress. This program has included investigation of the physical, thermal, and thermodynamic properties of TiB2, ZrB2, HfB2, NbB2, and TaB2. In addition, aspects of the synthesis and fabrication of such materials have been studied. In view of the diverse nature of this research, a number of other laboratories have actively participated and contributed specific capabilities for analysis and characterization of these materials. As a consequence, an extensive description of the relevant properties of these compounds has emerged which is central in evaluating their high-temperature (1200" to 2500°K) performance. To date, information on thermodynamic stability, specific heat, and vaporization characteristics,1 hot hardness and electrical resistivity,1, 3 therma1 expansion:'4 and thermal conductivity 1, 5 has been presented. This information has been generated on materials of the highest purity (98.5 to 99.9 wt pct Me + B) and density currently available. Samples fabricated by zone melting6 and high-pressure hot pressing"3'7 techniques have been used to generate suitable specimens for all of the aforementioned studies. dation characteristics of the most oxidation-resistant of these materials, hafnium and zirconium diboride, is presented and a description of the synthesis and the experimental procedures used to prepare and characterize specimens is given. The high-temperature range under consideration (1200" to 2200°K) and the known dependence of oxidation characteristics on sample chemistry, density, and oxidation conditions required a close coupling of the synthesis, fabrication, and evaluation procedures.8 This was accomplished by continual surveillance of chemical composition of starting materials before and after specimen fabrication and by evaluation of density, phase constitution, and microstructural features prior to and after oxidation exposure. I) PROCUREMENT AND CHARACTERIZATION OF STARTING MATERIALS In view of the current state of the art in fabricating refractory boride materials, the methods used in preparing samples for the present study are given in detail as follows: starting materials were purchased in high-purity powder form and fabricated by high-pressure hot pressing into 0.40 by 1.00 in. bars from which oxidation specimens were obtained. The hafnium diboride used in this study was purchased from Wah Chang Corp.; the zirconium diboride from U.S. Borax and Chemical Co. These powders were routinely characterized by quantitative chemical analyses for metal, boron, carbon, oxygen, nitrogen, and iron, by qualitative emission-spectrographic analysis for trace impurities, by X-ray procedures for extraneous phase identification, and by powder densitometry for comparison with X-ray (theoretical) density. Hafnium and zirconium metal and elemental boron were also purchased as high-purity powders and characterized for impurities by emission-spectrographic analyses. The hafnium diboride was procured in three shipments which were designated as HfBl.g7(1), HfB1.88(2A), and HfB2.12(2). The indicated stoichiometry is based on the atomic ratio of total boron to total hafnium; the number in parentheses identifies the shipment number. Shipment 1 was 5 1b, shipment 2A, 1 1b, and shipment 2, 8 1b. The zirconium diboride was procured as a 20-1b shipment and designated as ZrB1.89(1). A small quantity of purified zirconium diboride was also supplied and designated ZrB1, 9(P). The averaged results for chemical analyses which were generally performed according to the procedures set forth in the compilation by KrieGe9 are presented in Table I. Qualitative spectrographic analyses indicated that Ca, Cr, Ti, Si, Zr (in H~B~), and A1 were present at levels between 0.01 and 0.10 wt pct. Other metallic elements were found to be less than 0.01 wt pct. Since it is virtually impossible to purchase these materials in the desired quantities (5 to 20 lb) as single-phase compounds it is necessary to obtain

Jan 1, 1968

By L. N. Brown

The use of sheet and strip metal has increascd rapidly during the last few years and manufacturers have been called upon for an ever-increasing tonnage, better drawing quality, and better surface. The automobile industry is probably the most insistent in striving for a better product and a desire to reduce costs. Confronted by these demands, the mills have directed their efforts toward the delivery of material. Their personnel has been occupied largely with the problems incident to production, as any increase forced the use of new sources of raw material with their problems. These problems, combined with those met in the daily routine, have demanded immediate attention, with the result that the standardizing of heat treatments, quality, or temper, etc., have been neglected. Considerable work in standardizing has been done by many companies, but no acceptable method has been developed. The following method, therefore, is given with the hope that some method that can be accepted by the manufacturers and users may be developed. The problem of selecting a material with such properties that the losses in processing are a minimum is interesting and difficult. A description of the properties required is likewise difficult, largely because of loose terms. Another handicap is the number of methods of testing which have not been standardized and concerning which little information is available. In the selection of drawing or forming stock, it is advisable to eliminate as many variables as possible; consequently the method of testing the material is of the utmost importance. The method should be rapid and comparatively easy of application, as it is more important that a large percentage of the stock be tested with reasonable accuracy than that

Jan 1, 1923

By J. L. Huitt, B. B. McGlothlin, J. J. Day

Laboratory tests were made with pure minerals and actual reservoir rock samples to study the effects of hydrothermal (steam m hot water) treatments on reservoir rock properties. These tests showed that hydro-thermal treatment of many reservoir rocks can result in significant rock softening. The softening was attributed primarily to the partial destruction of dolomite and kaolinite and the synthesis of montmorillonite in the presence of excess silica. In many cases, the softening was great enough to cause considerable healing of propped fractures; therefore, a serious reduction in welt productivity could result. In other tests it was found that the addition of ammonia to a hydrothermal treating fluid in a concentration as low as 0.013 Ib/lb of water not only could prevent rock softening but could cause rock hardening. The results of X-ray diflraction analyses of rock samples showed that when ammonia was added to the treating fluid, ammonium-mica and analcite were formed instead of montmorillonite. No significant permeability damage was observed in the sandstones that were subjected to the ammonia-hydro-thermal environment; in some sandstones, permeabifity improvements resulted. INTRODUCTION As the use of steam or hot water becomes more prevalent in well stimulation methods. the need for information on the effects of such treatments on reservoir rock properties becomes increasingly apparent. Several works have been published on high-temperature changes in rock properties,',' but these are more applicable to in situ combustion operations than to steam or hot water injection processes. The mineralogical literature contains many publications which report on the changes occurring with various pure minerals in hydrothermal systems. A review of this literature denotes the ease with which entirely new, crystalline mineral phases can be synthesized from other minerals in hydrothermal environments at temperatures, pressures and residence times typical of those encountered in oilfield thermal recovery or stimulation processes. Discussions of many of these experiments are given by Deer et al. Grim,' Roy et al., Zen\ and Hawkins.' One of the most significant of these pure mineral studies is the hydrothermal synthesis work of Levinson and Vian" in which montmorillonite was synthesized from naturally occurring minerals; i.e., kaolinite, quartz and carbonate minerals (particularly dolomite). These reactions occurred at 575F in only 2 days and at 300F in 5 days. These results may be applicable to petroleum reservoir rocks since the minerals studied were those which are commonly found in sandstones. Furthermore, the environmental conditions imposed in the studies were very similar to those involved in thermal stimulation of petroleum reservoirs, e.g., steam or hot water injection. Other studies have suggested that weak rocks could be hardened by "electrochemical induration", a process in which an electric current is applied to a clay-containing rock body. These tests can be regarded as hydrothermal treatments since they were conducted in some instances with aqueous solutions and since clay temperatures during the electrical treatment reached a maximum of about 100C. Although a number of studies of the reaction of pure minerals have been reported, very little has been published on the reactions of petroleum rock-hydrothermal systems. No work has been reported on preventing the more detrimental rock changes in rock softening which might occur during the injection of steam or hot water into reservoirs. The studies described in this paper were conducted to provide such information. EXPERIMENTAL APPROACH The laboratory tests included studies of the effect of hydrothermal treatment on core samples from several different reservoirs. The hydrothermal treatments (simulated steam treatments) were conducted with distilled water at 575F, for the most part, for periods of 2 to 6 days. This temperature level was selected because it represented that temperature which would probably prevail in several cases under consideration for steam injection projects. The core samples, as well as the pure mineral samples, were contained in high-pressure stainless steel, autoclave-type pressure vessels. The effects of the hydrothermal treatments were evaluated by measuring the penetrometer hardness, formation rock embedment strength and permeabilities of the core samples before and after the treatments (Fig. 1)'" In addition, the mineralogical changes in the specimens were studied by X-ray diffraction. Concomitant with the core sample studies, the mineralogical changes were studied in greater detail by conducting hydrothermal synthesis experiments with pure minerals at similar temperature levels and residence times. For the most part, samples of finely-crushed pure dolomite.