Search Documents

By J. P. Dunlop

The fact is not.ablc though probably little known that thc Unitcd Statcls is the only nation obtaining and distributing through its Govcrn-ment burcaus any data pertaining to waste metals and drosses. Some foreign goverrlnlents do issuc reports relating to rnine or smelter production of prirrlar~ metals, but none gives in scope and detail t'he information published now by the U. S. Bureau of Mines and formerly by the U. S. Geological Survey; and this is despite the fact that the funds annually allotted for those purposes are insignificant in comparison with allotments for the preparation of data relating to other industries of like importance. The earliest data on the production of metals from secondary sources in the United States were contained in a press bulletin issued by the U. S. Geological Survey on Jan. 4, 1909. The information published was that for thc year 1907 obtained ant1 compiled by C. E. Siebenthal, who was one of the first to visualize the growing importance of the scrap-letal indust,ry. Thc Nationd Conscrvation Commission had emphasized its opinion that the known domestic supply of certain kinds of the morc important irietals was being rapidly marketed and that while there was no immediate cause for concern it was best to conserve such resources. Not only had there been a lanlentable lack of any data regarding the quantity of scrap inetals available or used but also gross carelessness and indifference in the segregation, collection, and effective use of scrap material. Siebenthal realized that even approximately correct statistics of recoveries from the more important base-metal scrap and drosses wcrc nearly as essential t,o both producers and consumers as the stat'istics of the output of primary metals. There were not then nor are there now sufficient funds for complete collection of data, nor was it considered the province of the Geological Survey t'o do more than determine approximately the recovery of secondary metals for use in supplementing those given for the primary metals. Undoubtedly the first bulletins issued did not give the full output, for it takes time to establish contacts for an inquiry covering so

By W. H. Yarroll Discussion by W. A. Griffith

W. A. Griffith (Head, Research Department, Phelps Dodge Corp., Morenci, Ariz.) - It is gratifying to see the increasingly common use of classical statistical procedures by metallurgical researchers. Mr. Yarroll has given excellent illustrations of the utility of multiple correlation analysis of complex metallurgical data. Our experience in applying these procedures to historical plant operating data has differed, however, from that which he suggests. The uninitiated frequently assume that the volumi-

Jan 1, 1969

By M. N. Brodie, John Chapman

INTRODUCTION - DEFINITION & HISTORICAL PERSPECTIVE While this symposium is concerned with comminution which, by definition, relates to all stages of size reduction of an ore body to a form suitable for mineral separation, the electrical drive aspect of the grinding section will receive most attention in contrast to the crushing, screening and materials handling elements of the process. The reason for this is that today's large mills, thirty feet diameter and upwards, present mechanical and electrical problems which require a degree of sophistication in their solution not previously required. The ability to satisfy these demands, so far as electrical technology is concerned, largely results from the development of semi-conductor devices. These can now handle typical electrical distribution power levels within remarkably s m all volumes and with high efficiency when compared with the motor-generator sets, mercury arc rectifiers, rotating amplifiers, magnetic amplifiers and vacuum tubes which were commonly used to provide speed and torque controls as recently as the early nineteen-sixties. The hardware available to the electrical engineer has changed dramatically whereby even the simplest control system formerly using hard-wired relays is now superseded by the program m able logic controller with its computer-like memory containing the sequence of operation, in other words, the software. Reverting now to the mineral process itself, it is assumed that the ore body has been mined using explosives and is delivered to the concentrating plant in its 'run of mine' form. The problem becomes one of reducing the material to a size which will permit an acceptable recovery of the mineral with the most economical use of energy. The size of 'run of mine' material will range from about minus five feet for high tonnage open pit operations to minus two feet for the smaller underground mine. The final reduction in size may range from minus ten mesh to minus two hundred mesh (exceptionally as fine as minus six hundred mesh) depending upon the concentration method and dissemination of the mineral values within the ore. There is no single circuit that satisfies all applications, but the pattern of metallurgical equipment use shown in Table 1 appears discernable from current practice, in general terms.

Jan 1, 1982

By Ivan Simon, R. K. McConnell

Anticipating the availability of tiltmeters suitable for use in boreholes, this article proposes a method of using one or more of these meters to determine in situ stress distribution before and after mining operations. Several ways of using relief techniques to measure in situ stresses in rocks have been developed. These techniques, summarized by Merrill,1 involve measuring deformations which take place when a specimen of rock is wholly or partially isolated from the stress field in the surrounding rock. Measurements of rock deformation caused by stress relief from mining operations can, in principle, also be used to estimate in situ stress distributions. Müller2 has mentioned experiments being carried on in Austria with a "deformation indicator" to determine the tilting of holes drilled before a mine opening is made. Similar work using borehole extensometers has been reported by Potts? and Duvall4 has called attention to the possible use of tiltmeters in making these measurements. Considerable attention is now being paid to the use of tiltmeters in detecting rock deformation associated with fault movements, earthquakes, earth tides, etc. The instruments used for these measurements have usually been of the mercury tube, water tube, or quartz fiber type, but because of their large size, and/or fragile nature, such instruments would not be suitable for use in mining stress measurements. Recent instrumentation developments, however, give promise that rugged, sensitive tiltmeters small enough for use in boreholes may soon be available.' In anticipation of these developments, this article presents a number of calculations of the possibility of using one or more tiltmeters emplaced in a drill hole prior to mining operations to determine the in situ stress distribution both before and after a mining operation. Consider point p (x, z) near a tunnel of radius a

Jan 1, 1969

By R. G. Aspden, D. A. Colling

THE {120}(001) texture has been reported in near 50 pct Ni-Fe alloys <0.004 in. thick1,2 and in copper 0.014 in. thick.3 This texture is one of two types of secondary recrystallization textures observed to replace a cube texture matrix and is desirable in Fe-Ni alloys because of its unique magnetic characteristics.1,2 However, the conditions for and mechanism of the {120}(001) formation are not well understood.3 During an investigation of the influence of alloying elements on the magnetic characteristics of 49 pct Ni-Fe alloys with a sheet thickness of 0.014 in., we have observed the growth of {120}(001) secondaries when strong deoxidizers such as aluminum and calcium were present. It is believed that this observation in unique and provides additional insight with regard to the mechanism for {120}(001) texture formation. Three alloys were prepared with electrolytic iron and nickel and contained a nominal 49 wt pct Ni. Alloy A was a straight binary Fe-Ni alloy, whereas intentional additions of 0.013 wt pct Ca to alloy B and of 0.59 wt pct A1 to alloy C were made. Ingots were forged at 1100 C, hot-rolled to 0.150 in. gage, pickled, and cold-rolled to 0.014 in. Standard U-shaped magnetic test specimens were punched, deburred, sprayed with MgO, and annealed in ~50°C dew point hydrogen. Textures were identified with the aid of etch pits, the

Jan 1, 1970

"Located in Madison River Canyon, about 14 miles by road from Norris, Mont. Built in 1907 by Madison River Power Co.DAM: Rock filled wooden crib structure, 183 ft. long, 34 ft. high or 44 ft. to top of flashboards.SPILLWAY: 140 ft. long, equipped with flashboards 10 ft. high.PIPE: One 10-foot and one 12-foot wood-stave pipe, 7,515 feet long.PRESSURE: One pressure chamber, 32 ft. high, 30 ft. wide and 81 ft.CHAMBER: long, built of concrete.PENSTOCKS: 4 9-foot steel penstocks about 200 ft. long, one for each wheel.WATER WHEELS: 4 double horizontal, center discharge, Sampson special 44-inch turbines, 3,600 h-p., at 100 ft. head. Speed 300 r. p. m„ direct connected to generators.GENERATORS: 4 G. E., W. C., 2,250 k-w., 4,000 volts, 300 r. p. m., 3 phase, 60 cycles, alternators, with exciters mounted on same shaft.TRANSFORMERS: 12 G. E., W. C., 900 k-w., 60 cycles. High tension voltage 23,100, 34,650, 46,200; low tension voltage 4,000, 3,800, 3,600. Now operating at 46,200, delta connected. They can be connected Y for 40,000, 60,000 or 80,000.OPERATION: This is the principal plant of the whole system and carries most of the load."

Jan 1, 1913

By A Andersen

DURING an investigation of the copper-rich portion of the copper-silicon-iron system as part of an extensive research program on P.M.G. alloys, which was begun in 1937 in the research laboratory of the Phelps Dodge Corporation, it became apparent that the binary copper-silicon system below 7 per cent Si needed revision, therefore an investiga-tion was undertaken. Both X-ray methods and microscopic technique were employed. Despite the many investigations that have the clarification of this sys-tem as their object, no two successive reports on the system have agreed in placement of the alpha-phase solubility limit, and uncertainty about the secondary phase first to appear has been voiced several times.3,4,5 It was therefore not surprising, when T. Isawa&apos;s6 and M. Okamoto&apos;s7 works were reported at the time we were finishing up our experimental work, to find essential disagreement between their results and ours. But when C. S. Smith&apos;s latest work on the copper-silicon system8 was published just as we were finishing our laboratory report, it was indeed gratifying to find that the latter&apos;s diagram and ours checked in all essen-tial features, except the temperature of the peritectic line above 830° C. Many attempts were made to retain the beta phase during the present investigation, but none was successful. Isawa,6 however, reports that he has been able to obtain X-ray photograms of the beta phase. The structure, he states, is body-centered cubic with a lattice constant of 2.848 A.. at 7.2 per cent Si. Okamoto7 and Smith8 both use the designation Kappa for the hexag-onal phase, and to avoid confusion this designation will be adhered to in the present paper.

Jan 1, 1939

ARTHUR H. STORRS, Scranton, Pa.-I would like to ask whether this same process is applicable to bituminous coal? FELLS A. VOGEL, New York, N. Y.-This Dutch process is applicable to bituminous or any other kind of coal. The Berwind Fuel Co. has had a plant in operation, in Superior, Wis., for about 2 years, using the Dutch process, and it has made a very satisfactory briquette, using Pocahontas coal. There is just one item in Mr. Frey&apos;s paper I would like to discuss; that is, the matter of cost. Mr. Frey figures a total cost of $3.35, based on the use of 7 per cent. of oil. Of course, the price of oil has advanced seriously within the last year or two, and any possible reduction in the percentage of oil required in the manufacture of briquettes is very important. I believe that Mr. Frey will agree that very good briquettes can be made with considerably less than 7 per cent. of oil; in fact, actual experience has shown that it can be clone with less than 5 per cent. The only possible effects of a low percentage of oil, particularly in anthracite briquettes, are that the briquette might not burn so freely, and that it might not be quite so hard. Briquettes made by the Lehigh Coal & Navigation Co., using 7 per cent. of binder, are extremely tough. Those briquettes have been handled in one of the local yards in Brooklyn, chuting them from railroad cars into boats and digging them out by grab buckets, and the losses average less than 2 per cent. This compares very favorably with domestic anthracite coal, with which the losses from breakage amount to between 7 and 10 per cent.

Jan 4, 1918

By AIME

Burton J. Westman-Besides decreasing the diamond size, there appear to be two other approaches open to overcome excessive diamond loss and, more particularly, the rapid diamond polish that took place in this quartz-feldspar rock. First, however, a short discussion of the diamond characteristics should be made in order to discuss the situation more clearly. The West African diamonds which we can assume were used. for this drilling have two disadvantages when drilling hard, exceptionally fine-grained rocks. These are rapid polishing and, if .the bit isn&apos;t "drilled in" carefully, a tendency to damage, resulting in excessive diamond loss. The normal wear resistance of any diamond is inversely proportional to the compressive strength of the diamond, therefore only the highest grade, of diamonds free from insipient fractures should be employed. Using upwards of 90 diamonds per carat instead of the20 to 30 per carat not only decreases the total projected area of the cutting points but increases the stress per point which, in turn, causes greater depth of penetration into the rock. Considering this depth of penetration, therefore, suggests an approach other than increasing the, number of diamonds per carat and that is to decrease the actual number of diamond points (also the carat weight per bit) so that the penetrating force on an individual diamond is increased. This penetration increases the chipping or rock shearing action.

Jan 1, 1950

Coal Transport Via Pipe Line Claimed Feasible Moving coal via pipe line is a project proposed by the U. S. Bureau of Mines. A pipe line 100 miles long capable of transporting 5000 tons of coal a day with water could be built for about $10 million. The cost of moving the coal 100 miles would be between $1.28 and $2.01 a ton.

Jan 9, 1951

By C. W. Merrill

The price records of seven representative mineral commodities for the 68-year period 1890 through 1957 have been compiled and analyzed for significant trends. When these records are reduced to real prices in terms of dollars of constant purchasing power or to the purchasing power of industrial wages at average rates, a substantial overall fall in prices is revealed. This downtrend contradicts the widely held concept that heavy drafts on a mineral resource must lead to scarcity, reflected in rising prices. Three metals (aluminum, copper, and pig iron), two fuels (bituminous coal and petroleum), and two nonmetals (sulfur and cement) have been chosen because of their pre-eminence in their respective categories, their significance in an industrial economy, and the ready availability of their price records. It might be added that these seven commodities were selected before any price figures were compiled; none was selected or rejected to substantiate any preconceived notions as to price trends. The overall importance of the seven is demonstrated by the fact that, taken together, they composed over three-fourths of the value of all minerals produced in the U. S. in 1957. The first step in the analysis was to reduce the price records to a basis for significant comparisons. Two such comparisons have been made: 1) The quantities of each of the commodities that could have been purchased for an average hour&apos;s wage in each year, and 2) the unit price of each commodity through the years in terms of deflated dollars. These data are set forth in the accompanying table and two charts. The quantities of the mineral commodity purchasable with the average wage for one hour&apos;s work in all manufacturing industries through 1926 were based on annual average prices and on average annual wage rates determined by Paul H. Douglas and published in his "Real Wages in the United States, 1890-1926." The series was extended through 1957 by the Bureau of Labor Statistics, U. S. Department of Labor. Calculations based on these data show that the average worker could have purchased 1.28 lb of copper with his hourly wage in 1890, whereas his hourly wage would have purchased 8.11 lb in 1957, an increase of 633 pct in the 68-year period. An average hour&apos;s wage would have bought 10.85 gal of petroleum in 1890, compared with 33.04 gal in 1957. Even more spectacular is the increase in sulfur, of which 25.25 lb could have been purchased with the 1904 average hourly wage; 223.08 lb were purchasable with the wage in 1957—an increase of 883 pct. Comparable price data for sulfur are not available for years earlier than 1904. For every commodity, the calculations show an improvement in the wage earner&apos;s purchasing power in 1957 compared with the early years. Measuring purchasing power in terms of wages does not give an entirely fair picture of the availability of a commodity in an economy. When the efficiency of an economy changes and the balance shifts among such elements as raw-material production, manufacturing, and service trade, the economic significance of an hour&apos;s work changes. Partly to meet such criticism, but mostly to present another interesting measure of the response of minerals to changing market conditions, a second set of calculations has been made to deflate unit prices for the seven commodities into terms of 1954 dollars. To accomplish this adjustment to a common 1954 parity, the Gross National Product Price Deflator, developed by the Office of Business Economics, U. S. Department of Commerce, was used. Although the results of these calculations are not as striking as those based on labor&apos;s increasing purchasing power, nevertheless the declines outweigh the rises in the prices of the mineral commodities. In terms of these deflated prices, aluminum and sulfur are much cheaper today than in the early years; copper was substantially cheaper in 1957 than in 1890; pig iron and petroleum are little changed; and only bituminous coal and cement have increased substantially. Strangely, the two mineral commodities with the strongest reserve positions are the two to exhibit rising real prices. Now this apparent overall downtrend in prices has taken place during a period of almost fantastic increase in the demand for mineral products. The value of minerals consumed in the world during the period greatly exceeds all mineral consumption up to 1890. A stage has been reached in the U.S. in which 95 pct of the energy used is of mineral origin and in which machines, structures, roadways, communication facilities, and most other elements in the industrial economy are primarily of mineral origin. Even agricultural fertility is maintained, in large measure, by mineral fertilizers. A series published in Minerals Yearbook shows that the value of U. S. mineral products has risen from $615 million in 1890 to $18,000 million in 1957, a 29-fold increase. Even in deflated dollars, the increase has been eightfold, while population has expanded less than threefold. Not only are demands of the industrial nations— the U. S., countries of Western Europe, and Japan— increasing at rapid rates, but those countries with agrarian economies are calling themselves underdeveloped and clamoring to industrialize. The ever-expanding mineral requirements in the U. S. and throughout the world show no abatement. Mineral reserves frequently have been described as wasting assets. Much concern has been shown for future users, who have been pictured as finding themselves on a plundered planet. Conservationists have viewed the future with alarm and have demanded legislation and regulations to reduce the drain on mineral reserves.

Jan 1, 1960

By H. J. Denning, M. W. Brabbins, A. K. Isaac

The quality of a coalface floor is the essential element that enables powered supports to generate their designed loads in control of coalface strata. The paper introduces a technique for the appraisal of coalface foundation stability. A criterion of support efficiency, viz., the support pressure increase/strata convergence, is included in case study data obtained from investigations in the South Wales Coalfield, U.K.

Jan 1, 1984

By Eugene McAuliffe

THE last obtainable figures of the value of the coal mining investment are those contained in the U. S. Census Reports, from data gathered in 1919. The values shown therein and set forth below cover lands and equipment and do not include distribution and marketing facilities. The working capital necessary to meet pay rolls to purchase material and supplies and workmen&apos;s compensation insurance are likewise excluded.

Jan 1, 1926

While the production of this state has not realized the early hopes that this coal would replace eastern coal on the Pacific Coast, it has been steady though small. Nearly all of the tonnages given are from Goodyear&apos;s, The Coal Mines of the Western Coast of the U. s., a carefully com- piled and accurate account of the development of the industry along the Pacific. [ ]

Jan 1, 1942

By Rodolfo V. de la Cruz

The accurate assessment of the in situ deformability of rock masses is very important in the de and construction of underground openings for mining and geotechnical engineering applications. This paper presents a method and device for determining the in situ deformability of rock masses by relating the borehole jack load to the diametral displacements at a number of orientations around the borehole wall. The method called mu1tiple measurement method include the steps in which: a) diametral displacement sensors are installed at different orientations around the borehole to measure the changes in length of various diameters of the borehole; b) a uniaxial load is applied on two opposed octants of the borehole wall, and; c) using elastic theory and assuming a reasonable value for the Poisson&apos;s Ratio of the rock mass, the in situ deformability of the surrounding rock materials is determined from the measured diametral displacements and applied unidirectional load. The multiple measurement method has a significant advantage over existing methods since it provides several independent data in a single test from which to calculate the in situ deformability of the rock mass. The multiple data provide a check and counter check on the reliability and accuracy of the various measurements. The multiple data would also provide a means of quantifying the degree of fissuring on the borehole wall. Information on the degree of fissuring is very important in numerical modeling of rock masses.

Jan 1, 1984

By Northcutt Ely, Charles F. Wheatley

This chapter deals with the systems of laws by which governments regulate the exploration for and production of the minerals within their jurisdictions. It is a summary, restricted by necessary space limitations, of material assembled by the author for a forthcoming publication of the United States Bureau of Mines, "Summary of Mining and Petroleum Laws of the World." (Information Circular, 1959.) The present study is organized in three parts, dealing with (1) the historical background of these legal systems, (2) laws of the United States, and (3) laws of other countries of the world. The reader&apos;s attention is invited to the acknowledgments at the end of the chapter, which inadequately express the appreciation due those who have assisted in the collection of this material. Part I. Historical Development of Major Western Systems of Land Tenancy with Respect to the Ownership and Control of Minerals The use of metals in primitive societies was largely confined to the manufacture of weapons for self-preservation. The ruler&apos;s control over copper, then brass, then iron, was essential to maintenance of his own ascendancy at home and his group&apos;s position against neighbors who had access to similar metals. Ancient societies were thus characterized by the ruling group&apos;s ownership of minerals and metals. The Egyptian civilization, which emerged in the fourth millenium B.C. upon the agricultural subjugation of the lower valley of the Nile, was responsible for extensive development of the upper valley as a source of mineral wealth. The production of gold during the height of that civilization has been estimated at $30,000,000 per year, thus equaling the early placers of California and Australia. The mines of Egypt were the property of the Pharaohs and were controlled at their direction. Greek mining developed a different scheme of land tenancy which more closely resembled modem concepts. Development of mineral resources was

Jan 1, 1959

By H. I. Aaronson, H. A. Domian, G. M. Pound

Zener&apos;s two-parameter theory of the y a reaction in Fe-X alloys is extended to encornpass austenite-stabilizing as well as fewite-stabilizing elements, and is then cottzbitzed with statistical thermodynamic theories of Fe-C alloys to permit development of a ther-modynamic description of the proeutectoid fewite reaction in Fe-C-X alloys. Equilibrium tielines are calculated for tile a + y rep&apos;on from experimental data and frort extrapolations of the y/y +a equilibrium surface. Sectzovs of the y/y + 0 surface are calculaled for the tzetastable sstuation LYL u-kich alloyrtg eleitzents do not partition betzseen azrstenite andfer-rite. The finding that the metastable y/a + y curves Lie close to their equilibriuwz counterparts when X = Si, .Vo, Co, Al, and Cu but well below them when X = A/ln or Ari pr-elides a thermodunamic explanation for the expcri1?7e?ztally obserted absence of partition during the proeutec toid ferrite reartlon in the fortner alloys and for the occurrence of partition at hzgher ternperatures in the latter alloys. Cotarison ofno- patitzoa free-energy changes and y/y i a curr,es in Fe-C-X alloys with the equilibrium 11al1es of these quantities in Fe-C alloys furnishes additional qualitative insight into the irqluence of allojling elements upon the kinetics of the proeutectoicl ferrite reaction. THE introduction of a substitutional alloying element, X, appreciably complicates calculation of the thermodynamics of the formation of proeutectoid ferrite from austenite. As noted in the preceding paper,&apos; the positional entropy of the interstitial species is the principal component of the free energy of an interstitial solid solution with which theory has so far been able to deal. One would expect, however, that other components of the free energy of this type of solid solution may be significantly altered by the addition of a substitutional alloying element. Even if the assumptions are made, by analogy to the case of Fe-C alloys,&apos; that changes in the positional entropy of carbon represent a significant part of the thermodynamic effects of an alloying element, and that the remaining effects can be taken into account by fitting the equations developed on this basis to experimental data on Fe-C-X phase diagrams or on the activities of carbon in alloyed austenite and ferrite, the experimental information available on either of these quantities is not yet sufficiently accurate or extensive, respectively, to make such an approach useful. An attempt made by Zener on the former basis to explain the effects of alloying elements on the thermodynamics of Fe-C alloys in terms of a temperature-independent "free-energy change" (actually enthalpy hane&apos;) required to transfer 1 mole of an alloying element from austenite to ferrite, in which the "free-energy change" was determined by fitting the theoretical relationships developed to Fe-C-X phase diagrams, thus proved inadequate in part because of deficiencies in the available ternary-phase-diagram data.= Other difficulties of a more fundamental nature, however, also indicated the desirability of a different approach to the problem.3y4y6 zener6 subsequently proposed that the free-energy change associated with y — a transformation in pure iron can be decomposed into magnetic and nonmagnetic components. Alloying elements were assumed to affect those components separately. One parameter was used to describe the quantitative effect exerted on each component. These parameters were evaluated from Ms (martensite-start) temperature data and from other experimental information usually either readily available or measurable with acceptable accuracy. Zener applied this treatment only to the calculation of Fe-X phase diagrams in which X is a ferrite-stabilizing element. In the present study, this treatment is extended to include austenite-stabilizing elements, and then combined with treatments previously considered for Fe-C alloys1 to permit calculation of the thermodynamic quantities of interest in the austenite - proeutectoid ferrite transformation in Fe-C-X alloys, where a number of representative, and commonly used alloying elements are chosen for X, including Si, Mn, Co, Mo, Al, Cr, and Cu. The results are used to explain important features of the partition of alloying elements between austenite and proeutectoid ferrite, as reported in a companion paper7 on the basis of electron-probe analysis, and to provide some additional understanding of the influence of alloying elements upon the kinetics of nucleation and growth of proeutectoid ferrite. Portions of this treatment6 have been clarified in the course of a review by Kaufman and Cohen.3 The consolidated summary of these developments with which this section is begun provides a basis for further clarification of the treatment, from which extension to include austenite- as well as ferrite-stabilizing elements is a natural consequence. The division of the free-energy change associated with the 7 - a transformation in pure iron, into two independent components is formally stated as:

Jan 1, 1967

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

The oxidation characteristics of hafnium and zirconiunr diboride were measured between 1200 and 2200&apos;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:&apos;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&apos;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 R. W. Smith, R. W. Lai

Very recently there has been a quickening of research effort in the field of silicate mineral flotation, particularly as regards the flotation of beryl.&apos; These studies have already contributed much to the understanding of both anionic and cat-ionic flotation of silicates. Of particular interest concerning anionic flotation has been the work done on heavy metal activation of silicates by M. C. Fuerstenau and co-workers.4,7 In addition. in the paper by Fuerstenau, Rice, Somasundaran and Fuerstenau7 attention was paid to low pH anionic flotation of beryl in the absence of activators. This subject was also covered in the papers by Avotins,3

Jan 1, 1967

By D. Turnbull, J. C. Fisher

ACCORDING to the "reaction-path" modell,2 of martensite nucleation, the shear angle of the embryonic martensite plate must be treated as a variable, and included in any calculation of nucleus critical size. Also, as can be deduced from this model, the interfacial free energy between austenite and martensite does not reach its final value until the shear is completed. It is zero for zero shear angle. However, in order to account for the kinetics of the martensite transformation, some sort of interfacial energy barrier appears to be necessary even with the reaction-path model, for otherwise the volume and the energy of formation of the critical size nucleus both collapse to zero.3 Cohen independently suggested that surface energy could be incorporated into the reaction-path model, with the overall free energy of a martensite embryo being a function of its volume and shear angle.&apos; It is possible to estimate the energy associated with the formation of a critical-size martensite nucleus starting with the reaction-path model and including a surface free-energy barrier. As the dependence of interfacial free energy upon shear angle is unknown, a simple type of dependence will be assumed, with the belief that the true dependence would not lead to appreciably different results. Consider the work required to form a lenticular martensite plate with radius r, thickness t, and shear angle 8. There are three contributions; one being the interfacial free energy, one being the free energy change in the martensite plate, and one being the free energy increase in the surrounding austenite. The interfacial free energy u is assumed to depend upon the shear angle 0 according to the relationship s=s0(?/?0)n [1] where 8, is the equilibrium shear angle and n is an exponent that may lie in the range 0 n 2. The work required to form the interfaces of a martensite plate then is W. = 2pr² s0(?/?0)n [2] The free energy change per unit volume of martensite is composed of two parts, one the ordinary volume free energy ?f1. which is negative, and the other the elastic strain energy G?m²/2, where G is the shear modulus and 7, the shear strain relative to the martensite structure. This expression for the strain energy is valid only when the shear strain ym, is sufficiently small that the martensite is within its linear elastic range. There is no doubt that ym, lies beyond the linear elastic range for embryos that are considerably subcritical. However, for critical nuclei it will be shown that ym, is 1.5 pct or less, within the linear elastic range of martensite. For embryos of nearly critical size, then, the strain energy of the martensite is correctly given by G?m²/2. The shear strain in the martensite is ym, = 8, — 8, and the work required to form the strained martensite is Wm --= (pr²t/2) [?fv + G(?O - ?)²/2] [3] The free energy change in the austenite is entirely that due to elastic distortion. The elastic strain is not uniformly distributed in the austenite, being large near the martensite plate and small elsewhere. Approximately, however, the energy corresponds to a uniform shear strain ya= (?t/2)/r [4] throughout the volume 4pr³/3 surrounding the plate. The work required to strain the surrounding austenite then is Wa = (4pr³/3) (G?a²/2) = (G?²/6) prt² [51 For simplicity, the same shear modulus G is assumed for each structure. The total free energy for forming a plate then is W = W3 + Wm + Wa. = 2pr² s0 (?/p?0)n + (pr²t/2) [?fr+G(?0-?)²/2] + (G?²6) prt2 [6] This expression is correct for nuclei and for embryos of nearly critical size, where, as will be shown, the strain energy in the martensite is correctly given by the expression G (? — ?)². Having W as a function of r, t, and 8, as in Eq. 6, there is a saddle-point where W has a stationary value, W subsequently decreasing indefinitely as the nucleus volume increases along the reaction path. The stationary value of W is the energy of the critical nucleus. The critical nucleus has radius, thickness, and shear angle such that ?W/?r - awlat: = ?W/?p? = 0. Performing these differentiations and calculating the critical nucleus energy, W* = [8192p(G?/6)²;s/27 ?fv4] [7] where a= (?/?0)3n+1[l +G(8"-8)&apos;/2af.]&apos; [7a] and where 8 is to be determined from the equation (1 + 3n/4) + G8(6O - (9)/[Af. +G(6>o-6>)72] = 0 [8] For ?f, near —200 cal per mol or —10" ergs per cc, and 8, near 1/6, as for iron-base alloys, Eq. 8 gives ?0 - ? ~ - (4 + 3n) ?f1./4G0O [9] as the difference between the equilibrium shear angle and the actual shear angle for a critical nu-

Jan 1, 1954