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By Richard Akerman

(Translated by FREDERICK PRIME, JR., Professor of Metallurgy in Lafayette College, Easton, Pa.) [THE attention now being paid both in this country and Europe to the greatest economy in the working of the blast furnace, and the eagerness with which all thoughtful men in the iron business look for any new information which will tend to throw light on this sub¬ject, is a quite sufficient excuse for presenting this paper to the Amer¬ican Institute of Mining Engineers.] I. It must be borne in mind that when two bodies unite to form a chemical compound, heat is almost always evolved. In order to

Jan 1, 1873

By E. A. Gulbransen, J. W. Hickman

IN a previous paper1 the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300° to 700°C. except for copper, where the range selected was 100° to 500°C. The results of these studies were presented in graphical form as existence diagram, of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviations in lattice parameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: I The existence diagrams of various alloys. [2.] The effect of the structure of the [ying] metal on the existence diagram of Iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body- centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K42B1 Nichrome V, Hipernik, Inconel, Stellite " 21," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1946

By Edward H. Robie

MANY engineers currently are working harder than usual, in part because of the demands being made upon them for increased production in the war effort, and in part because engineers are in short supply so that there is more to do for those who are available. In some instances the question has come up as to what additional payment, if any, should properly be made for overtime work, and to what extent is such payment legally permitted under the rules of the Salary Stabilization Board. Most engineers employed in an executive, administrative, or outside salesman capacity are not paid for overtime. They are paid for doing a job instead of for the hours they put in, and are free to do all the unpaid home work they feel they should do after dinner, as well as to do a bit of thinking and worrying during wakeful hours in bed. But engineers employed in a strictly professional capacity normally have standard office hours. Some employers pay for overtime and some don't. Their practice as it existed on Jan. 25, 1951 may be continued. In the absence of such practice at that time, the Salary Stabilization Board says that the engineer may now receive additional compensation up to his straight-time rate for an extended work week. No formal approval of the Board is required. "A professional engineer," in the mind of the Board, "is a person employed in a professional capacity, who, by reason of his special knowledge of the mathematical and physical sciences and the principles and methods of engineering analysis and design, acquired by professional education and practical experience, is qualified to practice engineering." Inducted Engineers A letter from a young man just inducted into the service and fearful that his engineering training is not going to be utilized reached us last week from Fort Riley, Kan. The AIME, cooperating with the other Founder Societies, is doing what it can, through the Engineering Manpower Commission, to see that engineers are not being wasted in the military establishment. So we passed this young man's letter along to T. A. Marshall Jr., executive secretary of that Commission. Mr. Marshall tells us that the normal procedure now being followed by the Army in handling Selective Service inductees is to have them first complete 16 weeks of basic training before assignment to specialized categories. During that time they are classified. If one has an engineering degree he should be classified as scientific and engineering personnel at the end of the basic training period. He should then be transferred to a technical detachment and assigned an MOS (Military Occupational Specialties) reflecting his education. If a young man is looking for a commission, it might be added that the current policy in the Army is to transfer to OCS (Officer Candidate School) applicants for commissions in the infantry only. The local unit commander can give information on this point, based upon the aptitude shown in tests. In view of the current shortage of engineers, it is believed that a young man should seriously consider remaining in enlisted status unless he can obtain a commission in a branch of the service that can make full use of his technical skills. His work may thus be more to his liking even if his uniform is not. New York or Atlantic City? In which place is it preferable to hold the annual meeting of a professional society like the AIME-New York or Atlantic City? That is, a winter meeting. The American Society of Mechanical Engineers has held its recent meetings at Atlantic City, with increasing attendance and satisfaction. The American Institute of Chemical Engineers chose Atlantic City for its recent December annual meeting. Only twice has the AIME ever met in this famous seashore resort: in 1898 and 1904. Chief advantages of going to Atlantic City over New York are that technical sessions are better attended, there being little else to do there in Winter; the cost to members is less, and hotel facilities are better adapted to a large meeting. As to cost, take a banquet, for instance. The Chalfonte-Haddon Hall, which caters especially to winter conventions, charges about $7 for a banquet dinner of standard quality. A similar dinner at the Statler in New York would cost about $8.50, and about $10.50 at the Waldorf-Astoria. (The charge for tickets is somewhat greater than this because of the cost of music, programs, flowers, and other incidentals.) Rooms, too, are somewhat less at Atlantic City, two in a room being accommodated for about $7 per day each, compared with $7 to $10 at a headquarters hotel in New York. On the other hand, AIME headquarters is put to some extra expense for staff travel, food and lodging, and members living in New York and environs are forced to pay a hotel bill. New York, of course, has more varied amusements to offer, plenty of big stores, and the glamour of a big city. The choice may be discussed at the forthcoming meeting in New York. In the meantime if any reader cares to express an opinion one way or the other we shall be glad to hear it. College Scholarships Most parents of children in the later stages of high school find it necessary to give some consideration to the cost of a college education. Although salaries have increased substantially it seems that the cost of the necessities of life, such as food, housing, and maintaining the family automobile, have gone up even more, so the problem of financing the children's education is as acute as ever. Many overlook the possibility of scholarships, or feel that only a student at or near the top of his class has a chance to get one. As a matter of fact, close to 150,000 scholarships and more than 15,000 fellowships, worth some $42,000,000, are available in 1200 American colleges and universities. Those who are interested should send 55¢ to the Superintendent of Documents, Government Printing Office, Washington 25, D. C. for a 248-page publication just issued by the U. S. Office of Education, entitled "Scholarships and Fellowships Available at Institutions of Higher Education."

Jan 1, 1952

By Walter F. Gries

AN ounce of prevention is worth A a pound of cure' is an old proverb that has sometimes been forgotten in programs having to do with the health of workmen. Realization of the truth of this maxim is increasing, however, and today the iron-mining industry, with which I am particularly concerned, is becoming more alive to the prevention of illness and the conservation of health, thus decreasing the need for treatment after diagnosis has established its necessity. The healthy workman is the happy, efficient workman, and new programs tending to make him more health-minded are being put into operation. Preventive medicine is less costly than corrective medicine, to say nothing of the better results obtained. Periodic physical examinations, with close follow-up attention when required, have reduced the time lost because of illness, workmen's compensation costs, and group-insurance benefits for nonindustrial disabilities.

Jan 1, 1939

By B. Chalmers, L. Bäckerud

The growth temperature of dendrite tips has been measured in a binary alloy system, Al-Cu, as a function of rate of formation of solid phase. Metallographic examination has rerealed the dendritic structure dereloped during different stages of the freezing process and factors influencing the undercooling, such as solute buildup, surface tension, and kinetic effects, have been estimated. Practical implications of the results are discussed. THE development of a dendritic growth pattern during the solidification of metals and alloys has an influence at least equal to that of grain size on the properties of the casting or ingot being produced. and consequently much interest has been devoted to the study of this phenomenon. A review of the knowledge gathered up to 1964 has been given by Chalmers.' Among recent publications in the area the works of Jackson et al 2 and Flemings and his coworkers3,4 are of special interest. This work is an experimental study of the factors which influence the development of a dendritic pattern during the solidification of a typical binary alloy system, A1-Cu, when there is no heat source in the liquid. This means that the temperature and the temperature gradient are controlled by the heat extraction from and latent heat evolved by the growing crystals. EXPERIMENTAL PROCEDURE Samples were prepared from a master alloy made up of aluminum, 99.995 pct, and copper. 99.99 pct, of the concentrations given below and of sufficient size to fill cylindrical graphite molds of 35 mm ID and 35 mm height. Bottom. wall. and lid of the graphite molds were all of 6 mm thickness, Fig. 1. Thin ceramic thermocouple shields could be introduced at different positions in the sample through holes in the lid. The assembly was heated in a small vertical resistance furnace to a suitable temperature. 700° to 720°C. which is well above the melting point of the sample. It was thereafter taken out of the furnace and chilled at selected rates, and the temperature changes in the sample were recorded. For high sensitivity in the temperature recordings, a reference thermocouple was held in a solidifying pure aluminum melt. which was very well insulated and therefore was at a constant temperature. 660°C, for nearly half an hour. The thermocouples were connected so that the difference voltage was fed into the recorder of which the most sensitive range was 1 mV. Temperature variations could be read to within 0.l°C. The thermocouples used were of the Chromel-Alumel type (28- or 38-gage wires) and the recorder a two-pen Moseley strip chart recorder. The different rates of chilling were obtained in the following way. a) The graphite crucible was wrapped in one or two layers of an insulating. feltlike material (Fiberfrax paper from the Carborundum Co.). The drop in temperature per unit time after complete solidification could thereby be varied from 8" to 18°C per min. This corresponds to a rate of heat extraction in the given samples from 0.08 to 0.17 cal cm-' sec-I. 6) The bare graphite mold was placed free on a piece of firebrick. The measured temperature drop was around 50°C per min (-0.5 cal cm-" ' sec- I). c) By blowing compressed air through a tube with many holes surrounding the mold in a ring shape. the rate of heat transfer could be raised to 150' to 200°C per min (-1.7 cal cm-3 sec- I). d) Cooling rates around 1000 C per mill (-9.4 cal cm-3 sec-l) were obtained by substituting the air in the device used in c by water. The range of cooling rates used in these experiments correspond to technical casting processes from slow solidification as obtained in sand molds to very rapid freezing which occurs in some continuous casting and welding processes. EXPERIMENTAL RESULTS The A1-Cu system was chosen for the experiments: the relevant part of the phase diagram is reproduced in Fig. 2. Observation of the Center Temperature. When a thermocouple is inserted in the center of the melt. the type of cooling curves obtained at slow solidification rates differs little from numerous published curves from similar systems. and the solidification pattern

Jan 1, 1970

By Arthur Phillips

THE normal method of preparing metallic alloys for commercial use involves the preparation of a melt containing the given components in the chosen proportions and allowing the homogeneous liquid mass to solidify in a mold of the desired form. The solidification is frequently accompanied by a segregation of the alloying elements in different parts of the casting. When the segregation is occasioned primarily by marked differences in density of the solid and liquid phases, it is termed "gravity" segregation. When the segregation conforms to a. selective freezing in harmony with the teachings of the equilibrium diagram of the alloy system-i.e., the lower melting phases are concentrated in the regions of the casting last to freeze-it is often referred to as " normal" segrega-tion. However, in many cases the lower-melting part of the system is concentrated in the parts of the casting first to freeze and the result in this case is termed "inverse" segregation. To complete the. terminology of the subject, normal segregation in a single phase is usually called "coring" and the word will be used in that sense in this paper. Inverse segregation, particularly when the liquid phase is exuded or sweated out on the surface of the casting, is sometimes called "location." Unfortunately, some ambiguity has arisen from the use of this term and it is perhaps advisable to confine its use to the dictionary definition; namely, "The separation of two phases by heat sufficient to melt one but not the other." The gravity and normal types of segregation are both well understood and to some extent are controllable by taking advantage of the most favorable cooling rate for a given casting condition. Inverse segregation has received considerable attention from several investigators- but none of the theories offered seem to account in a convincing way for the many examples of this type. The observations made in the present work on segregation in single crystals, and in some other castings, tend to support one theory of the mechanism of inverse segregation and definitely to

Jan 1, 1937

By Martial P. Corriveau

Almost everyone agrees that coal and oil shale are the only fossil fuel resources in which the United States is self-sufficient. Of the two, only coal has a technology sufficiently developed to be of intermediate term benefit. Since it takes at least 20 years to bring advanced technology into practice, it seems logical that the major focus on energy developments should be aimed at coal. Meanwhile, we need to trade-off between actions to meet our immediate needs and the various political regulations and social demands that are disrupting the coal industry and the industries dependent upon it. The largest single user of coal is the electric power generation industry. Over 300 million tons of coal are presently being consumed each year. In view of the 5-to 7-years lead time to bring in a base-load fossil-fuel fired generating station, our requirements for double this tonnage in 1980 are already well forecast; that is, if the coal companies are allowed to mine and the utilities are allowed to burn the coal.

Jan 2, 1974

By Sherwin Kelly

IN presenting this brief historical perspective, it is not my purpose to address myself to the geophysicists, to most of whom the story is already well known. My objective is to draw the attention of those who hold the belief that geophysics is something new, typically twentieth century, to the fact that fundamentally, whether it was known by the name of geo-physics or not, the science is an ancient and an honorable one. It began many centuries ago, and our modern civilization and its commerce owe a great debt to its founders, who today are likely to he overlooked and their names forgotten. The word "geophysics" means the physics of the earth, and is descriptive of a science that in many ways bears the same relationship to geology that astrophysics does to astronomy. When dealing with dis-tant stars or deeply buried rocks, the experimenter cannot reach them to obtain samples, which can be taken to his laboratory for study. He therefore exhibits the resourcefulness of Mahomet in the mountain episode, and makes the terrestrial globe or the cosmic universe his labora-tory, studying the effects of distant bodies on certain "fields of force"" which come to him across interstellar space, or through the rocks that make our earth. The application of these techniques of the physics laboratory to the study of the stars is the science of astrophysics, and to the investigation of the earth is geophysics. Yet the origin of the most valuable contribution to the world's trade and commerce ever made by geophysics remains lost in deep obscurity. Unknown even is the country wherein lived the unsung genius who invented the first geophysical instrument, the mariner's compass! Worse yet, it is not certain whether this invaluable guide of man had its begin-nings in Europe or in Asia. A Chinese legend tells of the Emperor Hwang-ti, who attacked his enemy Tchi-yeou on the plains of Tchou-lou in the year 2634 B.C., whereupon the latter magically raised such a fog that the Emperor could not pursue the retreating troops. Not to be outdone, the mighty ruler constructed a chariot that indicated the cardi-

Jan 1, 1938

By A. B. Bowman

The 1963 Jackling Award lecturer describes the founding of Banner Mining Co. and its trials and tribulations before becoming an established firm. Such aspects as geological description of Banner mining areas, history of exploration and production, areas of present interest to the company and research work conducted by the company are included. Several years ago a wealthy Chinese business friend of mine purchased an interest in a proposed oil well to be drilled a great distance from his home. A few months later it came in as a producer and proved to be a huge success and materially added to his resources. I asked him why a man of his wealth should be so lucky in a venture outside his sphere of knowledge when most people of modest means never seemed to get ahead. His answer was, "Fat Hoy takes a chance." Even though this was his answer, I knew from my association with him that there were other tempering considerations which Mr. Hoy applied before making up his mind to enter any transaction. First, he was a cautious individual. He was also a great believer in details and insisted on knowing everything possible about a situation, and finally, he was what we call a very solid individual with good basic instincts and judgment. This philosophy of Mr. Hoy may be applied to most any business but especially to those engaged in a search for natural resources such as mining where great risks are involved. This article concerns events in the history and growth of Banner Mining Co., with which I have been associated for 27 years in capacities from mine surveyor to vice president. Mr. Hoy's philosophy has played a significant role in the exploration projects of this company over the years, but what is more important, the officers, directors, and controlling interests in Banner have been aggressive in their search for ore reserves. THE BIRTH OF BANNER Banner Mining Company was incorporated in September 1935 by a group of Oklahoma and Texas oil men for the purpose of exploring and developing the Bonney-Manilla mines at Lordsburg, N.M. These properties had a history of intermittent production since the first ore discoveries as far back as 1870. Most of the production from the district has come from four mines, namely, the Eighty-Five, the Atwood, the Bonney-Manilla, and the Misers Chest. The last two are now owned by Banner Mining. The Eighty-Five mine operated between 1885 and 1931, and production totalled 1,494,287 tons averaging 0.11 oz of gold per ton, 1.23 oz of silver per ton, and 2.80% copper. The vein extended for a distance of about 3000 ft northeast and was mined to a depth of 1650 ft. The Atwood mine, adjoining the Eighty-Five mine, to date has been of lesser importance as a producer, but it has been operating for several years producing high silica flux ores for a smelter. Production totalled 352,828 tons up to January 1, 1962 From the Bonney-Manilla and Misers Chest mines, owned by Banner, production through 1961 totalled 2,006,343 tons with an average grade as mined of 0.0192 oz of gold per ton, 0.760 oz of silver per ton and 2.63% copper. Banner built a 150-tpd flotation mill in 1936 after almost a year of development on the 600 level of the Bonney mine. After less than one year's operation, it became apparent that the 150-tpd rate was not sufficient to make a reasonable profit due to the marginal grade ores. The low tenor of the ore, mainly chalco-pyrite in a highly siliceous gangue, made mandatory the close control of costs in order to make ends meet. A 300-tpd unit was added to the mill in 1937, and it is still the operating unit today. The clean sulfides presented no problems in milling. A metallurgist doing research on it at the time stated that the copper minerals seemed to have a built-in desire to float. Mill recovery of copper throughout the 27 years of operation has averaged 96.23%. A PERIOD OF FORCED GROWTH World War II brought many hardships to Banner. Labor and supply shortages caused drastic curtailment in development work. Rapidly rising costs far outdistanced any relief from pegged prices which we received from Government agencies. Finally, a branch of the Government asked us to stop all devel-

Jan 1, 1963

By Arne Bergholm

Australian rutile was chlorinated in the presence of CO or carbon. The chlorination velocity in CO was found to be strongly influenced by temperature and proportional to the CO concentration, but independent of the Cl, concentration. In the presence of carbon, the reaction velocity is much higher. The reactivity of the carbon and the distance between the carbon and the rutile surfaces are important variables. The reaction velocity is approximately proportional to the Cl, concentration and independent of the CO concentration of the surrounding atmosphere. Experiments with fluidized-bed chlorination of carbon-rutile mixtures indicate that the motion of the bed has little influence on the reaction velocity. At low temperatures, the chlorination velocity of dense tablets is much greater than that of TiO, coke mixtures suitable for fluidization. The reaction mechanism is discussed. In the industrial production of TiCl, rutile is chlorinated in the presence of carbon. Disregarding intermediate steps, the reaction may be expressed by the following equations: The ultimate object of this study was to find out whether the reaction velocity was higher in fluidized bed operation compared with chlorination of pelle-tized carbon-rutile mixtures. From a literature survey and preliminary experiments it was learned that some basic knowledge about the reaction mechanism was needed for a good experimental design. Therefore the following sets of experiments were carried out: 1) Studies on the reaction velocity in the chlorination of rutile with CO as the only reducing agent. 2) Chlorination of separate rutile-carbon tablets. 3) Chlorination of rutile-carbon tablets at different temperatures with various kinds of carbon, various grain sizes, and various tablet-making techniques. This series of experiments was carried out not only with pure chlorine but also with mixtures of chlorine with argon, CO and CO,. 4) Chlorination of rutile-carbon tablets made in a strictly standardized manner. 5) Chlorination of static-bed rutile-carbon mixtures. 6) Fluidized-bed chlorination of the same mixture. The experiments 4 to 6 formed the final and direct test of the main question: Static bed vs fluidized bedo. Although there are many patents and papers dealing with the general aspects of chlorination, only few experiments from which detailed information can be obtained have been reported in the literature. Pamfilov and coworkersl3 have studied chlorination of TiO, with CO or carbon as the reducing agent. They found that the weight decrease per hour at 600o to 800°C amounted to 11 to 14 pct with CO and 45 to 51 pct with carbon. They suggest that phosgene might be an intermediate in the chlorination of TiO,. Takimoto and Hattori have chlorinated reduced titanium oxide (TiO) and found a very high rate of TiC1, -production. They proved that the composition of the gas from the chlorination of rutile-carbon mixtures contained mainly CO. They reported for instance 74.7 pct CO, and 5.6 pct CO at 800°C at which temperature the Boudouard equilibrium composition is 12 pct CO and 88 pct CO. Seligman and Segerchano6 have studied the chlorination of TiO. They proved that Ti0 and chlorine react rather rapidly at temperatures as low as 300°C. Above 400°C, the reaction was complete. At 500°C the velocity of this reaction was much higher than was chlorination of TiO, + C. McTaggart,7 Nishimura, et al. and Wilskam have chlorinated mixtures of carbon and various kinds of rutile or beneficated ilmenite. Nishimura, et al. also report the results from reduction of TiO, with H2, CO, or carbon. At 900°C only 1 pct Ti O is formed in 2 hrs. At 1100°C 23.1 pct Ti, 0, was formed if elementary carbon was present. No carbide formation occurred below 1400°C. McIntosh and Cofferll have observed that the CO, content of the exit gases from chlorination of rutile and calcined petroleum coke is appreciably higher than found in the Boudouard equilibrium. At 900°C the ratio (CO, /CO + CO) is about 80 pct, whereas the equilibrium value is about 2 pct. W. E. Dunn12 has studied the chlorination rates of several TiO,-bearing minerals with CO + Cl, or COCl . Chlorinations were carried out either in a fluidized reactor or a fixed-bed reactor, both having a 30-mm diameter. The results obtained in both reactors were comparable. It was proved that benefi-ciated ilmenite (i.e., ilmenite from which the iron oxide had been removed by chlorination) was chlorinated 10 times faster thanrutile. Sore1 slag showed an intermediate rate. When phosgene is used, the

Jan 1, 1962

By George R. Ensminger, E. Heaton Hemingway

During the past year, the Watertown Arsenal has been interested in the occluded gas and oxide content of certain ordnance steels in order to determine, if possible, whether some of the peculiar failures in their physical properties might not be traced to these causes. For the purpose of best accomplishing a study of this nature, it was decided to heat the various samples of steel in a vacuum for definite periods of time at high temperatures and carefully examine the quantity and composition of the gases evolved. By the use of a fused quartz tube fitted with a water-cooled, ground-glass stopper, it was possible to maintain a vacuum at a temperature of 1000" C. for 10 hr. without perceptible leakage being evidenced as measured by a McLeod gage. The silica tube was connected with an evacuating system so constructed that the volatilized gases could be removed from time to time and a low vacuum of 0.0002 to 0.0010 mm. of mercury continuously maintained. At no time during the period of heating or in the removal of the gases did the evacuated system come in contact with rubber stoppers or any rubber connections, making contamination from such a source, impossible. In other words, the only volatile products that could be: obtained must necessarily have come from the steel itself or from the glass and fused quartz system or from the mercury used as a sealing agent. In the carlier experiments, the steel treated was in the form of turnings, but this practice was discarded because the weight's of the turnings before and after being heated were widely inconsistent,, even when taken from the same piece of steel. This discrepancy developed largely through variation in the amount of metal volatilized with the gases; this metal could always be seen in the form of a ring where it condensed in the cooler portion of the tube in either the amorphous or crystalline condition. Because of the frequency in occurrence and the variation in the manner of deposition, this material was roughly analyzed and found to consist for the most part of iron. At the same time two samples of steel that had been

Jan 1, 1922

By E. Heaton Hemingway, George R. Ensminger

During the past year, the Watertown Arsenal has been interested in the occluded gas and oxide content of certain ordnance steels in order to determine, if possible, whether some of the peculiar failures in their physical properties might not be traced to these causes. For the purpose of best accomplishing a study of this nature, it was decided to heat the various samples of steel in a vacuum for definite periods of time at high temperatures and carefully examine the quantity and composition of the gases evolved. By the use of a fused quartz tube fitted with a water-cooled, ground-glass stopper, it was possible to maintain a vacuum at a temperature of 1000" C. for 10 hr. without perceptible leakage being evidenced as measured by a McLeod gage. The silica tube was connected with an evacuating system so constructed that the volatilized gases could be removed from time to time and a low vacuum of 0.0002 to 0.0010 mm. of mercury continuously maintained. At no time during the period of heating or in the removal of the gases did the evacuated system come in contact with rubber stoppers or any rubber connections, making contamination from such a source, impossible. In other words, the only volatile products that could be: obtained must necessarily have come from the steel itself or from the glass and fused quartz system or from the mercury used as a sealing agent. In the carlier experiments, the steel treated was in the form of turnings, but this practice was discarded because the weight's of the turnings before and after being heated were widely inconsistent,, even when taken from the same piece of steel. This discrepancy developed largely through variation in the amount of metal volatilized with the gases; this metal could always be seen in the form of a ring where it condensed in the cooler portion of the tube in either the amorphous or crystalline condition. Because of the frequency in occurrence and the variation in the manner of deposition, this material was roughly analyzed and found to consist for the most part of iron. At the same time two samples of steel that had been

Jan 1, 1922

By F.B. Foley, S.P. Howell

Not infrequently, in the case of the failure of a metal structure, such as a bridge, tank, airplane, gun carriage, etc., a doubt arises whether the failure was due, among other causes, to the effect of an overburden or of an explosive maliciously or accidentally exploded in contact with it. As few means of discriminating between the effects of these causes have been known and these means were of a rough qualitative character, it was surprising to find in the record of an inquiry into the failure of a structure, the statement that, by observations on the Neumann bands in the structure, it was possible to determine the speed of breakage in the metal and to distinguish between a fracture caused by an explosion and one caused by an ordinary mechanical strain. Such a criterion, if well proved, was of value to the explosives experts of the Bureau of Minea, the Ordnance Department of the United States Army and the Bureau of Ordnance of the United States Navy, but search showed no record of it in the literature nor did any of the metallurgists and metallographers consulted know of any data on which such a criterion could be based having been assembled and critically studied. However, it was universally held that there was promise in the idea and that there exkted unique facilities at the Bureau of Mines Experiment Station at Pittsburgh for the preparation, under definitely known conditions, of material for study by metallographers, and that material of value might also be obtained from the proving grounds of the Army and Navy. Therefore, with the approval of the Director of the Bureau of Minea and the Chiefs of Ordnance of the War and Navy Departments, the Chairman of the Division of Engineering of the National Research Council, on April 12, 1919, appointed a Committee on the Investigation of Neumann Bands, which has since been engaged in this study and which, after some slight change in its personnel, consists now of the following: Dr. William Campbell, Advisory Metallurgist, Bureau of Ordnance, Navy Department. P. B. Foley, Metallurgist, Bureau of Mines. S. P. Howell, Explosives Engineer, Bureau of Mines. Comdr. 0. M. Hustvedt, U. S. N., Bureau of Ordnance, Navy Department. Dr. Charles E. Munroe, Chief Explosives Chemist, Bureau of Mines.

Jan 1, 1923

By S. P. Howell, F. B. Foley

Not infrequently, in the case of the failure of a metal structure, such as a bridge, tank, airplane, gun carriage, etc., a doubt arises whether the failure was due, among other causes, to the effect of an overburden or of an explosive maliciously or accidentally exploded in contact with it. As few means of discriminating between the effects of these causes have been known and these means were of a rough qualitative character, it was surprising to find in the record of an inquiry into the failure of a structure, the statement that, by observations on the Neumann bands in the structure, it was possible to determine the speed of breakage in the metal and to distinguish between a fracture caused by an explosion and one caused by an ordinary mechanical strain. Such a criterion, if well proved, was of value to the explosives experts of the Bureau of Minea, the Ordnance Department of the United States Army and the Bureau of Ordnance of the United States Navy, but search showed no record of it in the literature nor did any of the metallurgists and metallographers consulted know of any data on which such a criterion could be based having been assembled and critically studied. However, it was universally held that there was promise in the idea and that there exkted unique facilities at the Bureau of Mines Experiment Station at Pittsburgh for the preparation, under definitely known conditions, of material for study by metallographers, and that material of value might also be obtained from the proving grounds of the Army and Navy. Therefore, with the approval of the Director of the Bureau of Minea and the Chiefs of Ordnance of the War and Navy Departments, the Chairman of the Division of Engineering of the National Research Council, on April 12, 1919, appointed a Committee on the Investigation of Neumann Bands, which has since been engaged in this study and which, after some slight change in its personnel, consists now of the following: Dr. William Campbell, Advisory Metallurgist, Bureau of Ordnance, Navy Department. P. B. Foley, Metallurgist, Bureau of Mines. S. P. Howell, Explosives Engineer, Bureau of Mines. Comdr. 0. M. Hustvedt, U. S. N., Bureau of Ordnance, Navy Department. Dr. Charles E. Munroe, Chief Explosives Chemist, Bureau of Mines.

Jan 1, 1923

By M. S. Seltzer

High temperature steady-state creep rates have been determined jor lead sulfide single crystals whose defect concentrations were fixed by equilibration under controlled sulfur pressure. The activation energy of creep, Qc , for undoped lead sulfide, is a function 01 composilion, decreasing from 2.9 to 2.2 ev as the carrier concentration increases from 9 x 1016 to 8 1018 electrons cm-3 for lead excess crystals, and increasing from 1.7 to 2.3 ev as the concentration of holes increases from 4 x 1017 to 1 x 1018 cm-3 in sulfur excess material. For five different composilions, Qc for undoped and bismuth-doped crystals has been found to be equal to Qpb + Qs, the self-diffusion activation energies for lead and sulfur in PbS. It is well-established1 that high-temperature steady-state creep of pure metals is a diffusion-controlled process, where the activation energy of creep is equal, within experimental error, to the activation energy of self-diffusion. The relationship between the activation energy for steady-state creep and those for self-diffusion in binary compounds is more complicated, however, because two different diffusing species must be considered, and becayse the activation energies may be influenced by compositional variations and by foreign atom additions.2-4 In some cases experimentally determined creep activation energies are correlated with those for self-diffusion of the slower-moving species, but such agreement is by no means universal. Interpretation of experimental results is difficult because few investigations include measurements of creep rates and self-diffusion coefficients of both diffusing species on single crystals of similar composition and foreign atom concentration. The objective of this investigation, therefore, is to determine the influence of stoichiometric defects and foreign atoms on steady-state creep and self-diffusion for a well-characterized binary compound. Lead sulfide, a compound semiconductor which crystallizes in the NaC1-type structure, and whose homogeneity range includes compositions on either side of the 1:l atom ratio, was chosen for study in this investigation. The pressure-temperature-composition relations for PbS are available,5,3 and deviations from stoichiometry may be monitored by electrical measurements.7 Single-crystal specimens are available to allow observation of effects due to bulk phenomena without interference from grain-boundary effects. These crystals have been employed to determine steady-state creep rates under compressive stress for "pure" and bismuth-doped PbS as a function of sulfur pressure and temperature as well as crystal orientation and applied stress in order to establish the relationships between defect concentrations and creep rates. EXPERIMENTAL PROCEDURES Crystal Growth. Lead sulfide crystals, prepared by the Bridgman method, are grown in evacuated quartz crucibles, filled with almost equal atomic proportions of high-purity (99.999 pct) lead and sulfur, and heated to a temperature above the melting point of PbS (about 1127°C) so that the lead and sulfur react to form molten PbS. The crucible and melt are dropped through the hot zone of the crystal-growing furnace at the rate of 1 cm per hr. The maximum melting point of PbS is slightly on the lead-rich side of the 50:50 composition; hence crystals grown from a near stoichiometric melt are usually n-type semiconductors containing excess lead atoms. Typically the lead excess concentration in solid solution with the PbS is 3 x 1018 atoms cm-3. Crystals containing either 1/20 or 1/2 mole pct Bi2S3 were prepared by addition of the foreign atoms prior to crystal synthesis. Preparation of Specimens of Controlled Stoichiom-etry. Since it is difficult to grow crystals of desired composition, the process of crystal growth and control of stoichiometry are separated into two distinct operations. Equilibration of as-grown PbS to a desired composition is most easily accomplished by first annealing the n-type crystals under high sulfur pressure (about 1 atm) at temperatures above 700°C. This process serves to put excess lead precipitates into solution, yielding 0 -type crystals upon quenching to room temperature. Inter diffusion occurs readily in crystals so treated, and the methods described by Bloem may then be employed to obtain crystals of controlled stoi-chiometry. For the creep measurements made in this study, this involves heating crystals in mixtures of H2 and H2S The equilibrium constant for H2S is given by: Thus the sulfur partial pressure is obtained from knowledge of the H2/H2S ratio and Kh2S for the temperature in question. Fig. 1 shows the p-T-x diagram for PbS. It can be seen that, within the stability limits for single-phase lead sulfide, desired compositions may be obtained by equilibrating under a specified sulfur pressure and temperature. Characterization of Crystals. The principal methods for evaluating PbS crystals include measurement of electrical properties and mass-spectrographic analysis. The measured electrical parameters include Hall coefficient, conductivity type, and electrical resistivity Bloem7 has shown that there is a 1:l relation between the defect concentration and carrier concentration obtained. Hence, if the contribution to the carrier con-

Jan 1, 1968

By M. E. Straumanis, J. -P. Krumme

In basic ([KOH + KCl] with a total polarity of 2) or acidic (2N H2SO4) electrolytes and at anodic current densities of more thun 2 to 4 ma per sq cnz, n-type GaAs single crystals of lozo resistivity preferentially dissol~je forming etch tunnels with triangular or civc~ilay cross sections and of a width between 0.5 arid 5 p. These etch tunnels are oriented along any one of the four possible (111) directions of GaAs. However, their growth occurs only in one direction of a given (111) whick apparently is determined by the atomic sequence Ga —As (and not the rezlerse) in respect to an individual valence bridge in the crystal. It is concluded from comparison with the cubic lattice structure of GaAs that the etch tunnels represent macroscopic evidence for the tetrahedral bonds and their polar properties. If the anodic current density is increased the tunnel fomation results in the development of a fibrous surface layer consisting of GaAs. The latter separates frorn the substrate (in an anodic s~irface disintegration process) by the growth pressure of an As,0, filnz forming in the interior of the fibrous layer, 100 to 200 µ under the surface, at more than about 50 ma per sq cni. The fibrous GaAs film has the same crystallographic orientation as the substvate and represents a skeleton of the original crystal. Since the etch-tunnel density in a separated GaAs layer is about 108 c?n-', and the etch tunnels develop only along (111) in a given polar direction, it is assurraed tlmt the dislocations have no influence on the growth of these tunnels. ElECTROLYTIC treatment of smooth surfaces of poly- and single-crystalline GaAs at high anodic current densities causes the formation of porous surface layers.' This phenomenon suggests comparison with effects being observed with magnesium,' indium,, gallium,4 and aluminum5 and known as "anodic disintegration". The purpose of the present paper is to explore and to explain the reasons for the formation of such surface layers on GaAs and, in particular, to investigate the influence of the lattice polarity of this III-V compound semiconductor in the (111) direction on the anodic dissolution behavior. GaAs SINGLE CRYSTALS For the experiments described below GaAs single crystals from the Monsanto Co., St. Louis, Mo., were used. Their impurity levels were below 1 ppm and their dopant levels between 1 and 100 ppm. They were grown in (111) using the Czochralski or the gradient-freeze technique. The crystals had n-type conductivity and electric resistivities between 1 and 5 ohm-cm. EXPERIMENTAL The GaAs single-crystal rods were cut perpendicularly to (111) into wafers of about 1 mm thickness using a wire-blade crystal slicer and an aqueous slurry of Sic or a diamond saw. The orientation of the faces of these wafers were checked by Laue back-reflection patterns. If there was a deviation from (111) the faces were abraded under a certain angle using grinding paper and distilled water. The damaged surface layer was removed from each crystal by chemical etching with a mixture of 1HF:1HNO3: 1H20 or 2HF:1HNO3:2HAc (glacial). {110) faces were obtained by mechanical cleavage, producing surfaces which did not require a further treatment. The GaAs wafers were mounted using "alligator" clamps instead of soldered electrical contacts.' Only the bare crystal surfaces were dipped into the electrolyte. The clamps were coated with insulating wax to prevent any contact with the electrolyte. The experiments were carried out in aqueous 2 N H2so4,' or in an aqueous solution of KOH and KCl1 (1 mole KOH + 1 mole KCl in 1000 cu cm solution). Anodic current densities up to several hundred ma per sq cm were applied for periods between 30 sec and 2 hr. For the purpose of investigating the initial steps of disintegration the anodic current density applied never exceeded 20 ma per sq cm. The films which partially separated from the anodic surfaces under high-field conditions were treated with KOH to further their detachment by dissolving the As2O3 formed. The washed and dried films were pasted to strips of filter paper, and Laue pictures were made. The back-reflection patterns obtained were compared with those of the original anode surface before and after anodic dissolution. Furthermore, space reciprocal lattices7 were constructed from asymmetric rotation crystal patternsa which permitted the determination of the crystallographic orientation of the detached films of the corrugated anodic surfaces. The disintegration products were identified from assymmetric powder patterns.8 The polarity of the {111) faces was determined by chemical etching with mixtures of 1HF:1H2O2(30 pct): 2H2O or 1HNO3:2H2O. Different patterns on each of two inverse (111) sides appeared.'-l8 The correlation of these patterns to the Ga{111) or the As(111) side has already been established by the use of light figures,18-20 by X-ray diffraction near the absorption edges of gallium and arsenic,'lmZ4 and by LEED measurements.25 The geometric structure of these surfaces and the interior of the anodically attacked crystals were observed and photographed with a high-power microscope using oil immersion objectives up to magnification of X1720.

Jan 1, 1968

By G. M. Ikeda, J. G. Sibakin

An investigation was carried out to determine the variables affecting the coiling temperature of strip in the 56-in. hot strip mill. After statistical treatment, equations have been derived to determine the temperature drop between mill and coiler for both full spray (top and bottom) and top spray only practices. The individual influences of each variable in the temperature drop were derived for both practices. Limitations of the present practices were shown and adjustments in cooling for increased rolling speeds were suggested. A method of estimating the required number of sprays, their spacing, pressure, etc., to achieve a desired temperature drop is developed. MAXIMUM finishing temperature of a hot strip mill is mainly determined by the rolling speed, gage, and the temperature of the bar entering the mill. This finishing temperature may be limited by the maximum admissible coiling temperature in cases when either the cooling facilities on the runout table are not adequate or, more generally, when the cooling capacity of the runout table and the production capacity of the continuous mill are out of balance. Some time ago, the balance between these two factors was not considered detrimental to production. Recently, a new drafting schedule was introduced which increased the production rate, the entry temperature, and hence the finishing temperature. Thus, the restriction of the maximum specified coiling temperature became an important factor for many of the thicker gages. An investigation of the factors determining the coiling temperature may be, therefore, of considerable importance. A brief description of the available equipment will be a useful illustration of the techniques and methods used for this investigation. The 56 in. continuous hot strip mill is composed of six 4-high stands each containing two 221/2-in. diam work rolls and two 45-in. diam back-up rolls. Either of the last two stands can be used as the finishing stand. Which stand is used is dependent on the total percentage of reduction to be taken over the whole train, i.e., on the entry thickness and the final gage. The characteristics of these last two stands are given in Table I. Table I. Operational Characteristics of Nos. 5 and 6 Stands No. .5 NO. 6 Maximum voltage GOO 600 Power, hp 30(10 W00 I normal, kilonmp 4.35 3.73 Rpm of motor and rolls ISO 15 0 ITS to 300 Spettl ot strip, fpm 333 6 to 376T.2 103) to 2062 The speed of the finishing stand varies with the amount of reduction, strip width, and the exit gage. Finishing speeds in general use for varying gages are shown in Table 11. These speeds may change with an increase or decrease in the entry temperature of the strip. Even though the maximum speed of No. 6 stand is shown as 2062 fpm, this has so far never been attained,

Jan 1, 1957

By Reginald E. Hore

Since the discovery of silver at Cobalt, Ontario, in August, 1903, more than 100,000,000 oz. of silver have been produced by the mines in the Nipissing district, and there is reason to believe that at least as much more will be produced in the nex five years. The estimated value of the aggregate output o ore to the end of 1910 is $48,327,280. The ore yielded 93,977,833, oz. of silver and was mined at a net profit of abou $16,000,000. For 1910 the production was 30,558,825 oz., valued at $15,436,894, and yielding a profit of about $9,000.000. The details of the production of the Cobalt district for the years 1904 to 1909, inclusive, as reported by the Ontario Bureau of Mines, are given in Table I. The shipments from Cobalt are in the form of smelting-ore, concentrates from milling-ore, and bullion. The smelting-ore is largely high grade, averaging about 3,000 oz. per ton A smaller return is from what is called low-grade ore and which

Jan 1, 1912

By H. L. Talbot, A. J. Hall, R. S. Young

A method for the chemical differentiation of oxidized cobalt from sulphide cobalt in complex mine and concentrator products is of considerable interest to a number of mining companies throughout the world. At Rhokana Corporation, in Northern Rhodesia, for instance, cobalt is found chiefly in the sulphide form, as carrollite, but a cobalt oxide mineral also occurs irregularly underground, and relatively small quantities in the mill feed from time to time are difficult to detect visually at the concentrator. The oxide cobalt is not amenable to the sulphide flotation process used at Rhokana and nearly all of it passes into the tailing. The occasional period when high tailing losses occur with no appreciable change in the cobalt content of the mill feed has naturally been disturbing to the concentrator staff, who had no means of determining whether an influx of cobalt oxide ore or laxity on the part of the mill flotation operators as responsible for these results. A procedure for determining oxidized copper minerals, based on their solubility in dilute sulphuric acid saturated with SO2, has been used for many years in the copper industry. In the presence of cuprite the procedure fails, but otherwise it gives results quite satisfactory for control pur- poses. Empirical methods for determining oxidized forms of zinc and lead have been proposed, but they are generally unsatisfactory except in isolated cases of a very simple ore. No published procedure for determining oxidized forms of cobalt or siinilar elements has come to the authors'notice. Experimental Procedure There are obviously two alternatives in attacking a problem of this nature. One is to employ a solvent for oxide cobalt that will not dissolve cobalt sulphide. The other is to find a substance capable of oxidizing the cobalt sulphide to sulphate, which of course is water-soluble and can then be leached from the water-insoluble oxide cobalt. A representative sample of Rhokana cobalt oxide ore was secured, ground to minus 200-mesh, and carefully rolled to furnish a standard sample for this work. The analysis of this material gave the following percentages: Co, 0.55; Cu, 1.64; Fe, 2.98; S, 0.08; SiO2, 41.42; Al2o3, 11.20; CaO, 13.82; MgO, 3.80. As a source of cobalt sulphide a similar large sample of carrollite was prepared, analyzing Co, 23.36 per cent; Cu, 27.32; and S, 31.13. This sample of course was not pure carrollite, but was the best obtainable in quantities sufficient for a standard intended for considerable work. It was a pure sulphide sample, microscopic examination showing only carrollite, a little bornite, and gangue, with no visible sign of oxidized ore present. A wide variety of reagents as used in an effort to selectively dissolve oxide cobalt or to oxidize sulphide cobalt to

Jan 1, 1949

By J. W. Borough

THE electrical conductivity of pure copper is markedly decreased by small amounts of impurity in solution. The magnitude of this effect has been very carefully determined by numerous investigators who studied a wide variety of impurity elements. Much of this work is summarized in an excellent review by Pawlek and Reichel.' The case of zinc impurity in copper is an exception to the above in that there has been no well-documented study of the effect using high-purity starting materials. The values for the effect of zinc on conductivity, which are usually taken from unpublished work by Skowronki, indicate that zinc in low concentration has no effect whatever in lowering the conductivity of pure copper. This effect, if true, is unusual since it is generally known that even in lowest concentration, impurities exert an effect on conductivity which is proportional to the amount dissolved. It is more reasonable to suspect that in the original work on the effect of zinc some of the zinc was oxidized out of solution during specimen preparation. The following experi- and calculated d-spacings based on the unit cell dimensions of Baenziger et al. Since the single crystal studies of Baenziger et al. were limited to (hk0) and (hk 1) data, it was not possible to Compare all the intensities of the powder and single crystal patterns. However, the strongest reflections of both studies, the (321) reflection, agree very well when the appropriate multiplicity factor is used. Good agreement was also found in a number of other reflections of lesser intensity. Despite the precautions taken in annealing the U6Fe powder, an appreciable amount of UO, was detected in the powder pattern after heat treatment. The powder pattern reported by Groganoand Clews is given in Table I. Except for the 3.15A line, which is the strongest line of UO,, their pattern, as far as it goes, compares favoEably with the data from this study. Gordon and Kaufmann have reported a diffraction powder pattern purported to be U, Fe but it bears very little resemblance to the patterns of Table I. ments were carried out to redetermine the effect of zinc on conductivity using high-purity starting materials and processing conditions capable of producing oxygen-free alloys. Materials used in the experiment were ASR 99.999 pct Cu and Cumingo 99.999 pct Zn. Four 1 lb melts were prepared with identical procedure in argon atmosphere with crucibles made from Speer No. 580 graphite. The compositions were 0.0, 0.1, 0.3 and 1.0 pct Zn. Standard No. 14 wire (0.064 in. diam) was made from these melts as follows. The 1 pct Zn sample was first reduced 94 pct by cold swaging with five annealing treatments of 800o for 10 min in hydrogen between swagings, and then reduced 94 pct to the

Jan 1, 1962