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By Frederick N. Rhines, William A. Anderson

The investigations of Wymanl have demonstrated that copper deoxidized with several of the commonly used agents that confer immunily to ordinary hydrogen em-brittlement can still be embrittled if it is annealed alternately under oxidizing and reducing conditions. During the oxidizing cycle, oxygen diffuses into the copper and frequently deposits a subscale composed of the oxide of the residual deoxidizing agent. Upon subsequent reduction with hot hydrogen, the copper becomes ruptured along the grain boundaries to a depth sharply limited by the previous penetration of oxygen as delineated by the inner boundary of the subscale. Obviously the sensitivity to this kind of hydrogen embrittlement is engendered by the introduction of oxygen during the oxidizing anneal, but beyond this the mechanism of the process, and hence the controlling factors, remain obscure. There are several possibilities: (I) oxygen dissolved in the copper matrix of the subscale may, upon cooling prior to the hydrogen anneal, precipitate as cuprous oxide which is subsequently reduced by hydrogen as in the familiar case of hydrogen embrittlement; (2) oxygen in solid solution in copper may itself confer susceptibility to embrittlement by hydrogen; (3) the normally refractory oxides such as those of aluminum, silicon and titanium may themselves be reduced by hydrogen when in contact with copper; or (4) the precipitated oxides of the subscale may be complex compounds such, perhaps, as SiO2.Cu2O, which are partially reduced by hydrogen. These possibilities have been examined, and it has been concluded that the first three and possibly the fourth are operative collectively or individually under more or less predictable conditions. Effect OF Precipitated Cuprous Oxide and Dissolved Oxygen The literature provides no definite proof that oxygen in solid solution in copper can confer susceptibility to hydrogen embrittlement; indeed, the research of Leiter2 seemed to indicate the opposite—that to produce the effect, cuprous oxide must be present in massive form and in a more or less continuous network along the grain boundaries. To test this point, pure copper has been annealed in hydrogen under conditions designed to ensure the presence in various samples of: (I) precipitated cuprous oxide, (2) dissolved oxygen only, and (3) no oxygen in any form. Very pure copper" said to contain no oxygen and no spectro-scopically detectable traces of any other element (that is, no individual detectable impurity in quantity greater than 0.0001 per cent) was used. Strips of this material cold.-rolled 75 per cent to 1/8 in. in thickness were subjected to the following treatments, the results of which are noted:

Jan 1, 1941

By Wen H. Su

Multiple seam mining and its associated problems are very serious in Southern West Virginia where poor planning or lack of knowledge in seam interaction often results in complete loss of coal properties. Several measures have been proposed to alleviate the interaction problems under various multiple seam conditions, but few of them are specific in terms of mining plan. Two parallel approaches are adopted for this paper. One is field investigation which consists mainly of mine site visits and gathering of data. The other is the two-dimensional finite element simulation of mine workings using the data gathered as input. Two typical cases which represent the past and present multiple seam mining practice in West Virginia were investigated. Much attention is focused on the interaction problems experienced and the important parameters controlling interaction. Several key parameters controlling interaction in multiple seam mining were analyzed. Proper mining plans, by which the interaction problems can be minimized, are proposed for the individual cases after a better understanding of the interaction mechanism was realized through finite element analyses.

Jan 1, 1984

By F. A. Forward, J. Halpern

A new process for extracting uranium from ores with carbonate solutions is described. Leaching is carried out under oxygen pressure to ensure that all the uranium is converted to the soluble hexavalent state. By this method), alkaline leaching can be used successfully to treat a greater variety of ores, including pitchblende ores, than has been possible in the past. The advantages of carbonate leaching over conventional acid leaching processes are enhanced further by a new method which has been developed for recovering uranium from basic leach solutions. This is achieved by reducing the uranium to the tetravalent state with hydrogen in the presence of a suitable catalyst. A high grade uranium oxide product is precipitated directly from the leach solutions. Vanadium oxide also can be precipitated by this method. The chemistry of the leaching and precipitation reactions are discussed, and laboratory results are presented which illustrate the applicability of the process and describe the variables affecting leaching and precipitation rates, recoveries, and reagent consumption. THE extractive metallurgy of uranium is influenced by a number of special considerations which generally do not arise in connection with the treatment of the more common base metal ores. Perhaps foremost among these is the very low uranium content of most of the ores which are encountered today, usually only a few tenths of one percent. A further difficulty is presented by the fact that the uranium often occurs in such a form that it cannot be concentrated efficiently by gravity or flotation methods. In these and other important respects, there is evident some degree of parallelism between the extractive metallurgy of uranium and that of gold and, as in the latter case, it has generally been found that uranium ores can best be treated directly by selective leaching methods. It is readily evident that this parallel does not extend to the chemical properties of the two metals. Unlike gold, which is easily reduced to metallic form, uranium is highly reactive. It tends to occur as oxides, silicates, or salts. Two ores are of predominant importance as commercial sources of this metal: pitchblende which contains uranium as the oxide, U3O51 and carnotite in which the uranium is present as a complex salt with vanadium, K2O-2UCV3V2O5-3H2O. These ores may vary widely in respect to the nature of their gangue constituents. Some are largely siliceous in composition, while others consist mainly of calcite. Sometimes substantial amounts of pyrite or of organic materials are present and these may lead to specific problems in treating the ore. Further complications may be introduced by the presence of other metal values such as gold, copper, cobalt, or vanadium whose re- covery has to be considered along with that of the uranium, or whose separation from uranium presents particular difficulty. In general, there are two main processes for recovering uranium in common use today.'.2 One of these employs an acid solution such as dilute sulphuric acid to extract the uranium from the ore. A suitable oxidizing agent such as MnO, or NaNO, is sometimes added if the uranium in the ore is in a partially reduced state. The uranium dissolves as a uranyl sulphate salt and can be precipitated subsequently by neutralization or other suitable treatment of the solution. The second process employs an alkaline leaching solution, usually containing sodium carbonate. The uranium, which must be in the hexavalent state, is dissolved as a complex uranyl tricarbonate salt, and then is precipitated either by neutralizing the solution with acid or by adding an excess of sodium hydroxide. The latter method has the advantage of permitting the solutions to be recycled, since the carbonate is not destroyed. This is essential if the process is to be economical, particularly with low grade ores. With each of these processes, there are associated a number of advantages and disadvantages and the choice between using acid or carbonate leaching is generally determined by the nature of the ore to be treated. In the past, more ores appear to have been amenable to acid leaching than to carbonate leaching and the former process correspondingly has found wider application. With most ores, acid leaching has been found to operate fairly efficiently and to yield high recoveries. One of the main disadvantages has been that large amounts of impurities, such as iron and aluminum, sometimes are taken into solution along with the uranium. This may give rise to a high reagent consumption and to difficulties in separating a pure uranium product. Excessive reagent consumption in the acid leach process also may result

Jan 1, 1955

SUGGESTIONS that existing schools give instruction bearing on the mineral industry, or that schools for that purpose should be established in the United States, began to be made early, and it would require too much space to catalogue them all. Some of the more important may be mentioned to indicate their general character. In the "advertisement to such parents as have now (or expect to have) children prepared to be educated in the College of New York," which appeared in the New York Mercury of June 3, 1754, Samuel Johnson, the first president of King's College, the predecessor of Columbia, said that it was the "design of this college to instruct and perfect the youth," among other things, "in the arts of Numbering and Measuring of Surveying, and Navigation and Geography. . . . and in the Air, Water and Earth around us, and the various kinds of Meteors, Stones, Mines and Minerals, Plants and Animals; and in the knowledge of all Nature in the Heavens above us, and of everything useful for the Comfort, Convenience and the Elegance of Life . . . " Though the concept that natural science should be used to enlarge the bounds of human life was thus implicit at Columbia from the , very beginning (John Stevens graduated from it in 1768, James Renwick in 1807, Horatio Allen in 1833, and A. W. Craven in 1899), it was only during the period of Renwick's professorship of Natural and Experimental Philosophy and Chemistry (1830- 1853) that much attention was given to applied science.* Among the Austin papers, published by the American Historical Association,~ there is a draft in Stephen F. Austin's handwriting of a proposed memorial from the legislature of , Missouri to Congress, not only urging "the propriety and utility * See chapter 4 for early interest in this subject in Philadelphia.

Jan 1, 1941

By Robert E. Hochscheid

The subject article appears in the February, 1978, edition of Mining Engineering, and on page 190 carries the statement, "As most operators know, in a Water-Only cyclone, ability to adjust the vortex finder is quite important due to the sensitivity of this type of operations to variance in feed conditions and having to take them apart to make this adjustment is always a nuisance." Our experience as a manufacturer and supplier of Water Only cyclones does not agree with the above statement, and we offer the following brief discussion. Our company finds that the sensitivity of the Water-Only cyclone is a function of the fineness of the coal being washed, with the sensitivity to vortex finder length being greatest for coals coarser than 3/4-in. and virtually insensitive to raw coal finer than 1 mm. For coals finer than 1 mm, we find that we can use the shortest standard vortex finder in either our 10- or 15- in. Water Only cyclone without exception. For coals 5/8-in. x 1 mm ceramic vortex finders of fixed length have been satisfactory in all cases following an initial testing period in which the length was determined. Coals coarser that 5/8-in. are more sensitive to the vortex finder length, and two installations handling coals coarser than 1-in. continued to experiment with vortex finders of various lengths long after the initial startup period. For coals of all sizes, final adjustment of product quality has been achieved by determining the optimum size of apex orifice, which is accessible and readily changed, if necessary. Comments above assume no unusual change in the coal being washed or the required quality of clean coal.

Jan 1, 1979

By R. L. Wiegel

The two questions considered in this study are: (1) what similarity is there in the liberation of magnetite from various iron formations, and (2) how is this liberation affected by the size reduction technique employed. Twelve sample suites were obtained from commercial concentrators processing magnetite iron formation in the United States, Canada, and Australia. These samples have grades in the range 15 to 45% magnetite iron and approximate mineral grain sizes o f 50 to 2000 microns. Efforts were directed at measuring the liberation characteristics of the samples obtained from the concentrators primary grinding mills. The Davis tube, a laboratory magnetic separator, was used to concentrate individual size fractions of the size reduction product to determine liberation data. These liberation data were compared with relationships calculated from a highly idealized mathematical model of liberation in a binary mineral system. The results of these comparisons have been encouraging for nine or ten of the twelve samples tested. This leads to the conclusion that for most commercial iron formations, at least with conventional rod mill size reduction, it is possible to quantitatively characterize liberation with two parameters: an effective mineral grain size and ore grade. Limited laboratory size reduction tests as well as one of two sets of liberation data from commercial primary autogenous grinding lend some support to the contention that autogenous grinding can affect mineral liberation.

Jan 1, 1976

By Harold B. Fell

MANY oil producers are in disagreement with the idea held by some that an increase in the price of crude oil would be unlikely to stimulate much production and that we will be obliged to draw upon foreign sources of petroleum to supplement our domestic production as the years go by. Supporting our con trary opinion are numerous facts and figures. The most recent official estimate of the maximum efficient rate of production from the oil wells of the United States is 5,271,000 bbl per day. The Economics Advisory Committee of the Interstate Oil Compact Commission estimates, assuming certain supplies from imports and from natural gasoline and benzol, that crude oil require-

Jan 1, 1947

By AIME AIME

ON Thursday, Oct. 9, oil men from far and wide gathered at Beaumont, Texas to participate in a three-day celebration of the fortieth anniversary of the completion of the famous Lucas gusher well at Spindletop field just south of Beaumont, and to pay tribute to Anthony F. Lucas, for whom the Lucas Medal of the A.I.M.E. is named. In the afternoon the gathered host drove to the site of the discovery well to dedicate a 58-ft. granite monu¬ment erected on the spot where the original derrick stood. Representatives of the A.I.M.E. took a prominent part in the dedication ceremonies, giving the two principal addresses of the afternoon's program. Everette DeGolyer, past President, paid a personal tribute to Capt. Lucas, as a pioneer producer, an engineer, and a friend and well wisher of all young engineers. He gave a splendid picture of the useful and full life of Capt. Lucas who always took a great interest in the activities of the Petroleum Division of the Institute, from its inception to the time of his death.

Jan 1, 1941

By Frederick A. Mumpton

For more than 200 years zeolites have been familiar minerals to geologists and mining engineers as minor, but ubiquitous constituents in vugs and fractures of most basalt and traprock formations. More than 35 different species have been recognized including several, such as chabazite, erionite, mordenite, and faujasite, whose adsorption properties rival those of many synthetic molecular sieves. Igneous occurrences of this type have never been mined on a commercial scale; they are generally small and low grade, and they commonly contain as many as four zeolite minerals, along with small quantities of calcite, quartz, and other silicate minerals. Their economic beneficiation to monomineralic zeolite products has also not been achieved and, for the most part, industrial applications of zeolites have relied primarily on synthetic molecular sieves that were crystallized from hydrous aluminosilicate gels. During the middle 1950s, when Union Carbide Corp. and other groups were developing processes and markets for their fledgling synthetic zeolite businesses, natural zeolites

Jan 1, 1975

By R. S. Dean

BLUE HEAT PHENOMENA IN constructing a theory of the flow and hardening of metals, we necessarily make use of such phenomena as seem to be, universally observed in metals. It is, therefore, a matter of. concern to the constructors of such mnemonic systems if one or two of the group classified as metals show anomalous behavior. Such egregious phenomena are observed in pure or nearly-pure iron in the reaction of its mechanical properties to low-temperature annealing after cold work and to increased temperature of testing. In short it has been generally observed that iron," as an outstanding exception among metals, increases its hardness and strength by low-temperature annealing. after cold work,1 and also by increase of testing temperature to the range of 150° to 300° C. The investigation here recorded was made then with the object of ascertaining if similar phenomena were observed in high purity iron and, if not, to the presence of which impurities these phenomena could be traced.

Jan 1, 1929

By AIME AIME

THE paper by C. H., Lieb on the "Economics of Oil-Producing Practice" (June issue, M. & M.) contains much food for thought. The engineers should be gratified that an executive with Mr. Lieb's. responsibility should recognize their standing in the industry. Yet after giving them that recognition, he proceeds to spur them on to greater accomplishments by pointing out that their job is only partly done and in some instances poorly done. The operating policies in this paper when applied to new pools with flowing wells are sound. Neither do I take exception to their application to pumping wells. But I do wish to comment on what lie says about price when applied to the many more wells that are approaching abandonment that is, the small producing wells. Mr. Lieb states in effect that higher prices would be detrimental from the long range viewpoint. I doubt that the present prices of crude will provide an ample return from the hundreds of thousands of small wells that have possibilities of substantial recovery by means of water-flooding, repressuring with gas, and air drive. Probably expenditure for experimental work can he justified, but at this time it must usually be considered as experimental. Recently I visited a property where it was estimated that $250,000 would be spent on a 160-acre tract for flooding purposes. The rate of r e t n r n and amount of profit at today's prices are uncertain. It can be argued that if this type of recovery is not economic with crude at $1 then it can he delayed as it is now possible to secure economically an ample supply of crude from our flush fields. But these old fields still retain large quantities of crude in a dormant state, and should not he abandoned per-

Jan 1, 1936

By Charles E. Packard

Many coal producers have been faced recently with the problem of arranging their production facilities to accommodate recent trends in the transportation of their product. Each operator is normally faced with a different problem requiring a system to meet his specific needs. It may be that he would be required to load a seven or eight thousand ton integral train each day which would naturally call for a large storage pile, high loading rate, accomplished in a minimum of time On the other hand, it may be that he is faced with furnishing coal to make up one-half of a unit train that is to be assembled twice a week. Whether the problem is large or small, many considerations must be given to each specific problem to be certain that the proper scheme is applied. The operator actually has several choices as to what type of storage and loading facilities he may consider. The storage pile, for instance, may be open type, conical in shape, kidney-shaped, or long and wedge-shaped. It may also be enclosed by steel or concrete

Jan 8, 1964

By C. H. Wilson, J. J. Jakosky

In recent years geophysical prospecting methods have become well established as important steps in economically initiating new mining ventures in the field of base-metal exploration, placer mining and water-supply problems. The value of these methods as applied to these problems has been greatly increased by new and improved instruments, and a greater degree of skill in laboratory and interpretative technique. Considerable success has been attained, with subsequent drilling checking the predicted depths within 1 to 5 per cent, on problems requiring information on thickness of fill material, depth to and contour of bedrock, extent and yardage of gravels to be mined, and location of hydrostatic water table. In these applications the geophysical work gives data comparable to drilling, and at a cost of about one-fiftieth that of drilling. Discussion of several surveys with accompanying illustrations showing geophysical methods applicable to both simple and complicated placer problems are contained in the paper. The electrical instruments for measuring electromagnetic field strength and surface potentials are described, and their use, coupled with that of other geophysical instruments in modern field procedure, is noted.:

Jan 1, 1934

EDUCATION is a business; and, if the consumer is satisfied with the product, no one has any grounds for complaint. "Pretty well satisfied" about slims up the attitude of the mining industry toward the young graduates presently entering the field. Yet, with amazing regularity the controversy over the five-year curriculum recurs in educational circles. The educational mills grind out their products, some higher grade than others, depending on individual proclivity. The cycle continues almost without interruption. Arthur Taggart, however, takes his bowie knife to some of the sturdiest limbs of the tree of knowledge in his article on engineering education on page 770 of this issue. As all who know him might suspect, the pruning is not restrained. With one swing of the knife, such practically-labeled courses as Mine Design are stricken from the tree and transplanted to the field of Graduate Education. Emphasis on the basic sciences and the study of man through courses in history, economics, and literature are recommended to constitute an undergraduate curriculum. Such courses show the least depreciation and therefore give the student the most for his money. Partial justification for this dramatic departure from tradition is explained by the increasing number of companies giving training courses. Why make the student pay for what he can get paid for learning after graduation, the author argues. Other leading educators espouse this doctrine. Dean S. C. Hollister of Cornell, for the Committee on Adequacy and Standards of Engineering Education, recommended to ECPD in 1951 that emphasis be placed on the basic sciences. "Sifting back through the curriculum, it seems clear that instruction in the basic sciences, if taught in a manner such that knowledge of them makes available working tools, contributes the most sustaining part of the curriculum", reported the committee. Note that he would utilize practical problems from the fields of engineering in teaching the sciences. In our opinion the important thing to learn in college is how to think the engineering approach. Recitation on traditional solutions of classic problems sharpens the memory, not the ingenuity of the student. The engineering schools of the nation recognize the advantage of great emphasis on fundamentals, and the inclusion of cultural courses in the curriculum. However, industry presently requires graduates to have a substantial knowledge of the tools of the trade upon graduation. This means that the colleges are forced to pare to the bone to encompass the required studies in the time allotted. In addition, there is the limitation of student money. College educators also claim that entering freshmen are often improperly prepared in such subjects as writing and mathematics. These considerations make it difficult for the critic of the engineering graduate to make any headway with the educators. Actually with the mounting problems imposed by lower grade and more complex ores, a new breed of engineers is needed. The impetus for this new product must come from industry. If there was a concerted effort from industry for an improved type of engineer, the colleges would modify their aims to meet the demand for the kind of individual desired.

Jan 1, 1952

By C. MeCulloch

A NOVEL practice in the bituminous coal industry is the accelerated method of burning coal to ash used in the laboratory of the Fidelity washery of the United Electric Coal Companies, Du Quoin, Ill. Development of this method has supplanted the tedious float-and-sink process for plant control at this plant. In normal operation the plant operators have available within thirty minutes the accurate ash percentage of the coal loaded in the railroad cars and can therefore make adjustments to maintain a practically uniform quality of washed coal, regardless of the variations in washery feed.

Jan 1, 1937

By H. W. McQuaid

IT IS usually assumed that chemical specifications are sufficient for steel to be used for case carburizing, and if the steel analyzes within the ordinary limits specified for steel for this purpose, no difficulty traceable to the steel used should be encountered in obtaining satisfactory results in the case carburizing and hardening. Much work has been done to determine the effect of various alloying elements on the rate of carbon penetration, etc. but, to our knowledge, little if anything has been published in regard to the effect of the quality of the steel on the final results in the hardening of case-carburized steel parts. The writers believe that the structure of the case both before and after quenching is greatly affected by the actual condition of the steel itself as made, and that for good results in the case-carburizing and hardening departments, the steel should be of the best possible quality as regards non-metallic impurities. It is the purpose of this paper to prove that the presence of excess dissolved oxides in the steel, as made in the melting furnace, affects permanently the results obtained in carburizing and hardening and that it is possible that the presence of dissolved oxide can result in total unfitness of low-carbon steel for, case hardening purposes. When races and rolls for roller bearings are made from a low-carbon steel, case carburized and hardened, it is of primary importance that the results of this treatment be of the highest quality. It is necessary, therefore, that in the case-carburizing work each detail be rigorously checked to avoid any defects which would cause the loss of much time and material. The case carburizing with which this paper deals was done in under-fired oil furnaces. The temperature of each furnace is controlled by means of a platinum platinum-rhodium thermocouple, in connection with a potentiometer indicator and potentiometer recorder. The temperature of each furnace is registered every 15 min. by an operator, who is continually checked by the automatic recorders.

Jan 2, 1922

By P. R. Swann, J. G. Parr

Quenched structures were studied in alloys containing up to 12.5 pct cobalt. The subsequent decomposition of a 10 pct cobalt retained-ß phase alloy was investigated using metallographic and X-ray diffraction methods. Hardness measurements also were made during the decomposition process. Precipitation of Ti2Co is by nucleation and growth; and an activation energy of 50,000 cal per mole was determined. The values of the coefficient ß suggest that the precipitate is pearlitic at temperatures between 450 and 475°C, and spheroidal between 500 and 525°C. THIS paper describes part of a series of invesligations into phase transformations in binary alloys of titanium with transition elements. The general approach is similar to that taken in work on titanium-iron and titanium-nickel alloys.' Previous investigators'' have established the titanium-rich end of the titanium-cobalt phase diagram, reproduced in Fig. 1. Orrell and Fontana' showed that alloys containing more than about 6 pct" cobalt quenched from the ß range, produced 100 pcl retained-p phase. The isothermal decomposition of alloys containing between 0.8 pct Co and 15.5 pct CO was investigated by the same workers in the temperature range 650 to 1000°C. They reported that these alloys transformed into a or Ti,Co depending on the cobalt content, but no quantitative data were given. In the work to be described a series of alloys containing 0.8 pct Co to 12.5 pct Co was examined in the quenched condition. The 10 pct Co alloy (the lowest cobalt content to retain 100 pct ß on quenching) was selected for further work on the tempering kinetics of the ß decomposition. Experimental Procedure Since our own melting equipment was not installed at the outset of this work, the Physical Metallurgy Division of the Department of Mines and Technical Surveys (Ottawa, Canada) prepared the alloys. These were made of Japanese sponge, (which when melted had a value of 103 DPH, using a 1-kg load), and electrolytically prepared cobalt. The al- loys, made up to contain 0.8, 1.6, 3.3, 5.8, 8.3, 10.0 and 12.5 pct Co, were homogenized by swaging into rods at 900°C. Filings were taken from the rods, and any iron chips from the file were separated magnetically. Size fractions of both plus and minus 200 mesh (about 75p) were shown by their constitution, after annealing just below the eutectoid temperature, to contain the same cobalt content. Consequently, it was permissible to use the —200-mesh fraction, knowing it to be representative of the rod composition. Quenching in argon was carried out in a newly designed furnace, whose features include (1) an Inconel furnace tube, (2) a positive pressure of argon maintained at all times in the furnace—even when a sample is removed or inserted. The furnace is shown in Fig. 2 and is described in the Appendix. The tempering processes were carried out on powder samples sealed in evacuated quartz capsules. Since the highest tempering temperature was 525OC, no protection against reaction with the quartz was necessary. (Tests were made on filings of iodide titanium and showed no hardness increase after equivalent heat-treatments.) A thermocouple was attached to the capsule, which was heated to the

Jan 1, 1959

By D. F. Stoneburner

The thermoelectric power and electrical conductivity of a series of liquid alloys of thallium were determined in order to study the relation of chemical bonding to semiconduction in liquids. The results indicate metallic behavior for the alloys of thallium with arsenic, antimony, and bismuth, while the sulfides, selenides, and tellurides indicate semiconduction. The results are compared with the Properties of the same alloys in the solid state. This work supports the observation that long-range order is not a necessary requirement for semiconduction. PREVIOUS work1,5 has shown that some sulfides and oxides behave as semiconductors in the liquid state. Although the band theory has been of great help in understanding the properties of solid semiconductors, its quantitative application to liquids is difficult. The very existence of liquid electronic semiconductors shows that ascribing the discrete structure of the energy spectrum to strict lattice periodicity, or long-range order, is not always satisfactory. Rather, the short-range order determines the structure of energy levels and the width of the forbidden gap and, consequently, the concentration of free holes and electrons. This is borne out by the analysis of data accumulated by Regel and coworkers.6 The similarity of electronic structure of liquid and solid phases of certain liquid metals was pointed out by Knight et a1.,7 who examined nuclear resonance in solid and liquid Li, Na, Rb, Cs, Mg, Al, Ga, Sn, and Bi. They found noticeable changes in the electronic structure upon melting only in the cases of bismuth and gallium. They concluded that "a liquid metal possesses a band structure which is very like that of the solid, provided the short-range structure is not altered during melting." In semiconductors in which the near-neighbor arrangement remains the same on fusion, the material would be expected to retain its semiconducting properties. The quantum theory of semiconductors, with its band structure of energy levels, is linked exclusively to long-range order. Furthermore, it has limited usefulness in predicting new semiconductors. Many sulfide8-12 have made comparisons of properties on the basis of crystal structure or the position in the periodic table, both methods involving the same factors as chemical bonding. Mooser and Pearson8"10 have pointed out that crystal structure depends on chemical bonding, and that this bonding is a property of the atoms themselves. As the periodic arrangement of the atoms offers an easy comparison of such factors as atomic weight and number of valence electrons it provides clues to expected similarities of bonding for various elements or groups of elements. This approach has led Mooser and Pearson to formulate their valence-bond theory of semiconduction, in which they define a semiconducting bond. These authors state that "semiconductivity is the result of the presence in a solid of predominantly covalent bonds. These lead, through the process of electron sharing, to completely filled s and p orbi-tals in the valence shells of all atoms of elemental semiconductors while in semiconducting compounds only one atom of any two bonded together need acquire closed s and p orbitals. The presence of empty 'metallic' orbitals in some atoms of a compound does not destroy the semiconductivity provided that these atoms are not bonded together; it may, however, give rise to pivoting resonance in

Jan 1, 1965

By D. W. Fuerstenau

Recently R. J. Charles1 showed that comminution of brittle or semi-brittle materials in batch operations is described more appropriately by a variable energy relationship than by the specific relationships proposed by Rittinger,2 Kick,3 and Bond.' That is, the value of n in the empirical differential operation which applies to crushing and grinding (Eq. 1) is variable. Independently, Holmes' developed an identical generalized equaton for size reduction. The experimental data of Charles and Holmes show that the value of n is determined by the material and the comminuting machine and is constant for a given combination of these two conditions. The general objective of the present article is to extend the Charles-Holmes concepts to continuous ball milling. The specific objective is to analyze the operation of a vibratory ball mill dry-grinding chromite in a continuous open circuit and to develop an equation for the comminution of chromite in this mill. Basic Principles: In a batch mill the length of time during which the material is ground is a direct measure of the energy expended on the material, except possibly for exceedingly fine grinding. However, in a continuous operation, the fraction of the total expended energy which is useful for grinding will vary according to feed rate and amount of material in the mill. If the amount of material within a continuously operating vibratory mill is low enough so that only part of the expended energy is used for grinding, the extent of size reduction at constant power input must depend upon the length of time the material is retained within the mill, namely, upon retention time. The following analysis pertains to a continuous mill operating under these conditions. The empirical differential equation that applies to the comminution of brittle materials is:" dE = -Cdx/x" [1] where dE is an infinitesimal energy expenditure, C a constant, dx an infinitesimal size change, x the particle size, and n a constant. For continuous grinding in an open circuit at constant power input, P, Eq. 1 must be written as (dtr)P = -C dx/x" [la] where dt, is an infinitesimal time during which a particle of size x is in the mill, and C' is a constant. A ground product never consists of particles of single size but always comprises a distribution of sizes. In comminution, the expenditure of energy causes a lateral shift in the size distribution.', ' " The general objective of any engineering study of comminution is to correlate the magnitude of this size distribution shift with the energy expended, the ultimate aim being to cause the greatest shift with the least amount of expended energy. Although a number of criteria can be used to measure this shift, Schuhmann's size modulus has been found convenient.' Mathematically, the Schuhmann size distribution can be expressed as follows:" y = l00(x/k) [2] or in differential form: dy = [F- xa-' dx ] K, where y is percentage of material finer than size x, a is a constant that determines weight distribution among particles of various sizes, and k the size modulus that denotes the theoretically maximum-sized particle in any size distribution. By considering the energy required to reduce an element of weight of material, dy, from size x, to size x, the element of time during which the material must remain in the mill at at power will be (dt..).= J'-Cax!(dy) [3] Summing up all the elements of weight from zero to 100 for a product that conforms to the Schuhmann size distribution yields C C f Cdx,\( 100«x°-'dx\

Jan 1, 1960

By H. C. Rogers, B. W. Roberts

Vanadium foils and wires, either cold-worked or recrystallized, show a ductile-brittle-ductile fracture sequence with temperature. At about 150°C the hydrogenated vanadium wires are found to be ductile. At room temperature the wires show brittle fracture, and at liquid nitrogen temperature the wires are again ductile, although to a lesser extent than found at 150°C. Hydrogenated cold-rolled vanadium foils have been found to fracture in unusually straight lines along the [100] texture directions. The hydrogen content required to show this [loo] texture fracture is limited to a few atomic percent in range. Hydrogen content above this range causes fracture to occur in random directions. PRELIMINARY experiments with hydrogenated vanadium foils indicated that the embrittling effect of the hydrogen on the vanadium, which was severe at room temperature, was reduced at both lower and higher temperatures. In order to investigate more quantitatively the ductility changes with temperature, vanadium wires were tested in tension at three temperatures. The reduction of area was measured and the fractures examined. Specimen Preparation—The material used was kindly supplied by A. U. Seyboltl in the form of M-in. rod. The nominal analysis was: 99.2 pct V assay, 0.2 pct C, 0.01 pct Si, 0.01 pct Fe, 0.015 pct Ca, 0.02 pct O,, 0.01 pct N2, and 0.003 pct H,. The specimens were 0.035-in. diam wires. These were prepared by cold-swaging the supplied rod to the final diameter without intermediate anneal. They were finished with long-bearing dies. The surface was then given a light polishing with 0 emery paper and degreased in trichlorethylene. An X-ray check indicated that the cold-swaged wire had a fairly strong [110] fiber texture. The wires were then recrystallized in vacuum in continuously pumped quartz tubes at two temperatures to give two different grain sizes. One group of wires was given 45 min at 800°C; another, 60 min at 1000°C. The microstructures in Fig. 1 show the wires after they have been electropolished and elec-troetched in 10 pct HCI. After the 800°C anneal, the vanadium grains had a diameter of 1 to 2p and there appeared to be a tendency to elongation in the longitudinal direction. However, the latter may be an etching effect. After the 1000°C anneal, the grains appeared to be equi-axed, but there was a very large spread in grain size, probably due to some impurity segregation in the wire, Fig. 1, right. The grain diameters varied between the limits of 1 to 150p. The small particles shown particularly clearly in Fig. 1, left, are also visible on the polished surface of all samples before etching and are undoubtedly carbides and nitrides of vanadium. An X-ray check indicated these annealed wires had a strong [110} recrystallization fiber texture. The hydrogenation was carried out in an iron retort with dry hydrogen flowing through it, the retort and contents being heated in a tube furnace with a hydrogen atmosphere. The hydrogenation temperature was approximately 500°C. The hydro-genation times chosen were approximately those which would be just enough to cause the vanadium to be brittle at room temperature and thus allow the greatest chance for ductility to occur at the other two temperatures. Part of the fine grained specimens were hydrogenated for 21/2 min at 490°C. Part of the coarse grained specimens were hydro-genated for 11/2 min at 515°C.

Jan 1, 1957