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By H. P. Leighly, F. C. Perkins

THERE have been several statements in the literature about the difficulty of producing single crystals of high-purity (99.99pct) by the strain-anneal method. Consequently, investigators tend to employ low-purity aluminum for their single-crystal experiments, or else resort to the Bridgman or other techniques which depend on solidification for the production of single crystals. The following paragraphs describe a solid-state method for the manufacture of single crystals of high-purity aluminum which should provide crystals with greater perfection than those formed by solidification. The starting material for this method of producing single crystals was secured from the Aluminum Corp. of America and has a purity of 99.99 pct, the balance being trace amounts of impurities. Specimens approximately 1 by 4 in. are sheared from sheet having a nominal 0.050 in. thickness. The specimens are given a preliminary anneal at 640°C for approximately 3 hr in order to remove fabrication strains and to produce an average grain size of about 1/4-in. diam. The specimens are then etched in Tucker's etchant (45 pct HC1, 15 pct HNO3, 15 pct HF and 25 pct H2O) to remove the oxide film. Critical strain is applied by wrapping each specimen about a 1 3/4 in. round and subsequently straightening it against a flat surface. The high-purity aluminum sheet is sufficiently soft that this operation can be accomplished by ordinary finger pressure. The specimens are immediately annealed again at 640°C for 3 hr and reetched for examination. Ordinarily, considerable growth of certain of the grains will have occurred, and occasionally a single crystal will be produced on the first attempt. The procedure of alternately straining, annealing and etching is repeated until the majority of a batch of specimens contains usable crystal sizes. Typical examples are illustrated in Fig. 1. The greatest changes in crystal sizes are produced in the initial treatments. As the average crystal sizes get coarser in the later treatments, the sever- ity of the strain must be increased in order to produce grain boundary- migration. This increase in severity is effected by decreasing the diameter of the round used for straining (to 1 1/2 in., for example) and/or wrapping the specimens about the round twice, with opposite faces in contact with the round, before flattening. Usually the strain treatments described are not severe enough to produce nucleation in coarse grain high-purity aluminum. The growth of grains occurs by strain-induced grain-boundary migration. It has been observed that the grain boundaries move most readily during the first hour or so of each annealing treatment and that the rate of movement decreases with extended holding times at temperature. Prolonged annealing treatments are therefore not usually beneficial. Similarly, the rate of growth of each crystal appears to depend upon the orientation of the crystal with relation to those of its neighbors. Frequently island grains are formed after the initial heat treatment as the result of slow grain-boundary migration. These sometime become stationary during later heat treatments. Twin orientation interfaces are frequently developed during annealing. These imperfections can usually be removed by increasing the severity of strain to produce actual nucleation of new grains of more favorable orientation at the imperfection interfaces. The largest single crystals produced in our laboratory by the above method measured 4 by 1 by 0.050 in. Examination of Laue back-reflection patterns from a limited area of the specimens, gave no evidence of polygonization. Probably there is some indication of polygonization in the original grain area provided a more sensitive technique is used for detection. Experiments to produce wider specimens were less successful, possibly because wider sheets increase the complexity of the strains induced by deformation and promote widespread nucleation. Grain boundary migration occurs preferentially in a direction parallel to the longitudinal axis of the specimen. The choice of specimen geometry with respect to the rolling direction of the sheet appears to be immaterial in regard to the production of single crystals.

Jan 1, 1961

By William Rawles

THIS report is the first of a series planned by The Mineral Inquiry, organized by the American Institute of Mining and Metallurgical Engineers to make factual studies of the world's mineral resources in their political and international relations. The efforts of The Inquiry are directed toward filling certain notable gaps in available information, without duplication of many other investigations touching this field which are being conducted by other organizations, public and private. Much of its work is indirect-suggesting topics for study by other individuals and organizations and aiding in their planning and correlation. The present report is designed to show the nationality of the commercial control of mineral resources, in addition to the geographic distribution of production by nation-in other words, the overlapping of political and commercial control. Detailed accuracy cannot be claimed for the figures presented. For some companies division of ownership by nationality has been very difficult to ascertain, as many companies are reluctant to dis-close the extent of their holdings in other corporations, and the impossi-bility of tracing all stock ownership is obvious. Also there are frequent changes in the distribution of stock control. The percentages given rep¬resent only the participation that has been identified definitely, even though it is known in some cases with fair certainty that larger interests exist, as, for instance, American participation in foreign chromite companies. In bringing together these figures we have had the cordial co-operation of the United States Bureau of Mines, the United States Geological Survey, the Mineral Division of the Bureau of Foreign and Domestic Commerce, the Brookings Institution, and of many specialists connected with the mineral industries covered. The report does not cover the entire list of minerals. Coal, although it is, one of the most important minerals, was omitted because not more than one or two per cent of the world's production comes from mines that are owned by companies foreign to the countries where the coal is produced. Others, such as gold, are omitted because sufficient data have not yet been accumulated. It is hoped that some of these may be covered in subsequent reports. It is not our purpose here to discuss the significance of the figures sub-mitted, but only to point out the general nature of the problems on which they have a bearing.

Jan 1, 1933

OF no less importance nor less terrifying to consider than the marvelous effects of guns are those produced with fire by powder in underground mines. These are truly not only similar to fearful natural earthquakes, but it can perhaps be said that these made by art surpass the wrath of the earth with greater effect. For if the latter shakes it happens that it causes the things on the surface to shake and sometimes to fall into ruins, but the former not only shakes but always functions and destroys-surely a marvelous effect which is almost incomprehensible, and if experience did not demonstrate it, it could scarcely be believed. Who would say that the mountains, things of such great hardness, would yield to men, easily opening their bowels? Likewise, one who had not seen it would say that it was impossible for men to have a way of administering at will fearful and destructive thunderbolts which are of such a kind that, although men make them, they cannot protect themselves against them; indeed they cannot call themselves safe from the evilness of gunpowder even in mountains composed of very hard stones or in budded structures. For, as is seen, there is no seemingly impregnable fortress that does not yield when guns are brought near it. If it happens, indeed, that guns can- not be brought near to some place because of the harshness of the site,

Jan 1, 1942

By F. Claisse, R. Angers

Self-diffusion in iron has been measured during rapid a-r transformations using a variant of the Kryukou and Zhukhovitskii diffusion method. The study was performed by thermally cycling iron foils (1 to 6 cpm) through the transformation (=910°C). Some foils have been subjected to over 1000 cycles and some have spent more than 15 pct of their total diffusion time in the process of transformation. The experimental results show that the a-r transformation has no measurable effect on self-diffusion in iron. The study is completed by a quantitative analysis of mechanisms which can affect the diffusion rate during the transformation. The analysis confirms the experimental results. SINCE diffusion is an important factor in many solid-state transformations, it is of interest to study how it is affected by the stresses generated during these transformations. Clinard and Sherby1'2 were the first to make a study along these lines. They measured diffusion coefficients in Fe-FeCoV couples subjected to slow thermal cycling (1.5 cph) through the a-r transformation range. They found an enhancement of diffusion by a factor of about two. The purpose of the present paper is to report measurements of the self-diffusion coefficient of iron during much more rapid thermal cyclings (1 to 6 cpm) through the a-r transformation (-910°C). These more rapid cyclings produce higher strain rates during the transformation and should emphasize any possible influence of transformation upon diffusion. EXPERIMENTAL Iron foils, 25 to 35 µ thick, were cold-rolled from 99.92 pct pure iron and annealed in pure helium for 2 hr at 870°C; the resulting grain diameter was about 150 µ. Specimens 0.5 by 8 cm were cut from the foils and I7e55 was vapor deposited on one of their surfaces. A 38 gage alumel-chrome1 thermocouple was spot welded in the middle of one of the specimen long edges, Fig. 1. Two 38 gage chrome1 wires were also spot welded along the same edge on each side of the thermocouple; they were placed 2.5 cm apart and used for electrical resistance measurements. In order to prevent twisting and crumpling, the specimens were pinched between two quartz plates 0.1 by 1 by 7 cm and the assembly was close fitted into a 1 cm ID quartz tube. Four holes were drilled through the tube to let the 38 gage wires out: these were connected to the recording equipment by means of extension wires. 20-gage nickel wires fixed at both ends of the specimens were used to thermally cycle the foils by Joule heating. The above described device was placed in a 2.7 cm ID quartz tube which in turn was placed in a tubular furnace. Either a pure helium atmosphere or circulating hydrogen was used during the experiments. Specimens were subjected to thermal cycles between a minimum temperature To and a maximum temperature Tm at rates ranging from 1 to 6 cpm. This was obtained by maintaining the furnace at a constant temperature near the minimum temperature To and periodically passing an electric current through the specimen. Cooling was achieved by heat losses to the surroundings. The forms and periods of cycles were varied from one specimen to another; however, each specimen was subjected to one type of cycle only. The temperature and electrical resistance variations of the specimens were recorded as a function of time. The temperature curves were used for diffusion calculations while the electrical resistance curves were used to monitor the transformation and to determine its starting point and its approximate duration. Diffusion was measured by the method developed by Kryukov and zhukhovitskii3 and modified by Angers and Claisse.4,5 In this method a metallic foil is coated on one side with a radioactive isotope and the activity is measured periodically on both sides during the diffusion anneal. The following equation then holds: where: I1 Activity on the surface on which the deposit is made. I, Activity on the opposite surface. t Diffusion time. B Constant. D Diffusion coefficient. d Foil thickness including the deposit. G(t) A function of time; it is a second order correction term which is given graphically in Refs. 4 and 5. The diffusion coefficient D is found by plotting ln[(Il - I2)/(I1 + I,)] -G(t) against t; the resulting slope m leads to an accurate calculation of D through Eq. [2]. The effect of the a-r transformation on diffusion is expressed by the ratio DT/DU where:

Jan 1, 1970

By Benjamin L. Miller

THE essential differences expressed by the different speakers participating in this symposium concern merely the relative emphasis placed on the subjects that are commonly included under the term "geophysics" and the branches of science that form the basis for investigations in this field. In order to appreciate the present situation it may be profitable to briefly refer to a few historical matters. One can find almost countless descriptions of geological phenomena long antedating the introduction of the title of "geology," which has been credited to Richard de Bury in the fourteenth century. Interpretations, when they were offered, were generally pure speculation. Only toward the close of the eighteenth century do we find theories developed as the result of observations and tested by additional observations. It is difficult to select and give proper credit to the individual who was particularly responsible for turning geology into a distinctly observational science. William Smith, who has been called the "Father of English Geology," certainly represents the period when observation was the only method used. As he traveled through the British Isles, "sometimes 10,000 miles in a year," he was continually making notes of his observations. Geikie says: "His plain, solid, matter of fact intellect never branched into theory or speculation, but occupied itself wholly in the observation of facts." William Smith, with others of his time, definitely laid firmly the foundations on which modern geology has been built. Field and laboratory observations can no longer be said to constitute the sole basis for geologic contributions but we have not laid aside the methods of Smith and his followers. It is folly to underestimate the fundamental value of the observational part of geology in the present. The objection to purely observational geology is that it is mainly qualitative and not quantitative, general and not specific. No one can deny this charge and probably there are few who do not welcome every method or process whereby we can put aside generalities for definite established values. Physics is the science that has particularly come to the aid of the geologist in this respect. CONTRIBUTIONS OF PHYSICS It is not the intent of the writer to enumerate or to evaluate all of the contributions to geologic advance in the field of physics. A few only are used for the purpose of illustration. When Clarence King, Director of the United States Geological Exploration of the Fortieth Parallel, invited Ferdinand Zirkel to study 2500 thin sections of rocks collected from the western United States, the use of the microscope came into general use. Zirkel's report was published in 1876. He was not the first to use transmitted light for microscopic rock determination, some work having been done by Henry Clifton Sorby and others some years earlier, but he was the first to put into general use this method. We may well claim that this

Jan 1, 1941

By L. L. Wyman

THE resultant embrittlement caused by the exposure of oxygen-bearing copper when hot and exposed to reducing gases has been the subject of many studies.1 Little attention, however, has been given to the possible embrittling effects due to atmospheres or conditions that under some circumstances might be the source of a reducing gas. At rather infrequent intervals there occur reports of copper becoming embrittled during normal annealing cycles in commercial steam-atmos-hered furnaces such as customarily are used for this operation. As might be expected, several other factors exist-such as oil, dirt on the wire, or in the furnace, or metallic surface contacts that might produce reducing gases and be the source of the trouble. However, in consider-ation of the statement made by Ruder,2 it would seem that under some conditions steam itself might prove to be the source of trouble. A consideration of the amount of the dissociation of water vapor up to temperatures of the melting point of copper shows that' the amount of hydrogen that could come from this source is far too minute to account for any embrittlement. What such information does not tell is what will happen at the surface of copper when subjected to steam at elevated temperatures, for entirely different conditions may persist, which would account for Ruder's observation. Furthermore, there are no data as to what might happen at the surfaces of other materials present, the result-ant of which might affect the condition of the copper present. For this reason, it was decided to make a series of experiments com-parable to those previously conducted by the writer,1 which would clarify the effect of the steam on copper, and in copper in the presence of steel.

Jan 1, 1940

By T. L. Joseph

It is a distinct privilege to participate in this meeting convened to honor the memory of Henry Marion Howe, a distinguished scientist and metallurgist. Many have added to our rapidly growing fund of metallurgical knowledge but few have made the unique contribution of formulating basic concepts essential to an over-all comprehensive view of the subject of metallography. Of those previously selected to deliver this lecture, several have added a personal touch to their discourse because they were able to refer to their associations with Dr. Howe. It was not my good fortune to know him or to enjoy his inspiring influence. Like most of you, my contact has been with his published works, which are outstanding in that they provide lucid, detailed expositions of the nature and behavior of metals and alloys. His deep understanding and clarity of expression have greatly accelerated our progress in metallography and in the use of metals. The degree to which a man's thinking, experimentation and writing contribute toward an understanding of basic laws and phenomena determines whether his life's work is of transitory or permanent value. This occasion appropriately recognizes the fundamental importance of Dr. Howe's pioneer work in the field of metallurgy.. On two former occasions, gray iron was selected as a subject for discussion. The fact that the production of pig iron has not been discussed before does not reflect any lack of interest on the part of Dr. Howe or former lecturers in the process that underlies the production of steel. Although Dr. Howe's work in his later years centered around metallography, his earlier publications show a considerable interest in the production of iron and steel. He recognized that in the ascending spiral of metallurgical advancement we are not winding a single thread but are weaving a complex fabric. Specific evidence of his interest in the production of pig iron may be found in his book' on The Metallography of Cast Iron and Steel. In explaining why blast furnaces have been in constant use for about 600 years, he says: "The process is economical because it utilizes with extraordinary completeness the calorific power of the coke due to the thorough transfer of heat from the gaseous products of combustion to the charge." This emphasis on heat transfer, overlooked in many more extended and more recent discussions of the blast-furnace process, illustrates Professor Howe's ability to see the essentials. Other distinct advantages of the blast furnace, such as the removal of- much of the sulphur and practically all of the oxygen, were mentioned. It was also stated that although the blastfurnace process is complex in nature, its outward form is comparatively simple, thus permitting large-scale production at small labor costs. All who contemplate the production of metallic iron from its ores by any other process might well consider the

Jan 1, 1947

By T. L. Joseph

It is a distinct privilege to participate in this meeting convened to honor the memory of Henry Marion Howe, a distinguished scientist and metallurgist. Many have added to our rapidly growing fund of metallurgical knowledge but few have made the unique contribution of formulating basic concepts essential to an over-all comprehensive view of the subject of metallography. Of those previously selected to deliver this lecture, several have added a personal touch to their discourse because they were able to refer to their associations with Dr. Howe. It was not my good fortune to know him or to enjoy his inspiring influence. Like most of you, my contact has been with his published works, which are outstanding in that they provide lucid, detailed expositions of the nature and behavior of metals and alloys. His deep understanding and clarity of expression have greatly accelerated our progress in metallography and in the use of metals. The degree to which a man's thinking, experimentation and writing contribute toward an understanding of basic laws and phenomena determines whether his life's work is of transitory or permanent value. This occasion appropriately recognizes the fundamental importance of Dr. Howe's pioneer work in the field of metallurgy.. On two former occasions, gray iron was selected as a subject for discussion. The fact that the production of pig iron has not been discussed before does not reflect any lack of interest on the part of Dr. Howe or former lecturers in the process that underlies the production of steel. Although Dr. Howe's work in his later years centered around metallography, his earlier publications show a considerable interest in the production of iron and steel. He recognized that in the ascending spiral of metallurgical advancement we are not winding a single thread but are weaving a complex fabric. Specific evidence of his interest in the production of pig iron may be found in his book' on The Metallography of Cast Iron and Steel. In explaining why blast furnaces have been in constant use for about 600 years, he says: "The process is economical because it utilizes with extraordinary completeness the calorific power of the coke due to the thorough transfer of heat from the gaseous products of combustion to the charge." This emphasis on heat transfer, overlooked in many more extended and more recent discussions of the blast-furnace process, illustrates Professor Howe's ability to see the essentials. Other distinct advantages of the blast furnace, such as the removal of- much of the sulphur and practically all of the oxygen, were mentioned. It was also stated that although the blastfurnace process is complex in nature, its outward form is comparatively simple, thus permitting large-scale production at small labor costs. All who contemplate the production of metallic iron from its ores by any other process might well consider the

Jan 1, 1947

By M. H. Caron

D. C. Ralston—The fact that none of the organizations that have worked on these ammoniacal leaching processes have contributed discussion of Mr. Caron's papers today is a matter of some disappointment. Adaptations, modifications and improvements have been made by several organizations or individuals and to complete the record I want to document a number of them. The Nicaro Nickel Co. operated a Government owned plant at Nicaro, Oriente, Cuba, during the past war. A report on the project was written for Reconstruction Finance Corp. and is in the document file collected by the Office of Technical Services, Commerce Department and filed with the Library of Congress, where it can be consulted or bibliofilm or photostat copies obtained by asking for copies of PB 97271. Nicaro Nickel Co. has obtained a series of U.S. Patents, my list (probably incomplete) of which bears the following numbers: 2,400,098; 2,400,114; 2,400,115; 2,400,461; 2,400,612; 2,458,902 and 2,473,795. International Nickel Co. has also studied the problem and U.S. Patent 2,478,942 shows that some of the complications involving occasional low extractions have been unraveled. Forward, Samis, and Kudryk, of the University of British Columbia, have also published a study of copper-nickel sulphide concentrate.' Others are interested and it is evident that this type of hydrometallurgy is likely to find a happy application in the not-too-far distant future. Caron's two papers practically amount to a summation of his life's work on the important subject of nickeliferous iron ores and the American Institute of Mining and Metallurgical Engineers is fortunate to have been chosen the medium of publication. M. Rey—The ammonia leaching process has been the subject of certain studies in New Caledonia, but at the present time, the conditions are not very favorable to its adoption. The process is a combination of a thermal and a hydrometallurgical process. As a result, the first costs and the operative costs are rather high. To counteract this unfavorable situation, it would be necessary to make a very high extraction. But unfortunately, the process is delicate and in spite of all of Caron's valuable work, there are still many unknown factors. It is difficult to obtain regularly a high extraction, exceeding 75 to 80 pct. It would be interesting to have the opinion of Inter-national Nickel on the process and to know what the Dutch are doing in Celebes. M. H. Caron (author's reply)—I am quite familiar with the different types of nickel and cobalt ores as found on New Caledonia, and it may be pointed out that the Celebes ores are quite the same in their properties. Their behavior when treating the ores by the ammonia-leaching process is also alike and in my opinion, there is no reason why a high extraction of the New Caledonian ores could not be obtained if the process is properly applied. For the sake of completeness I may add that one of my patents has not been discussed in the papers. This patent deals particularly with the treatment of serpentine nickel ores. (Netherlands No. 62693 40a, French No. 965.786 April 21. 1948. and Cuban No. 13.625 Jan. 1950.)

Jan 1, 1951

By T. J. Whalen, S. M. Kaufman

Surface-tension measurements for liquid Fe-C-Co and Fe-C-Ni alloys were performed by the sesszle-drop technique at 1350o and 1425°C. Cobalt was shown to he more effective than nickel in lowering the surface tension of Fe-C alloys A minimum value for surface tension of 1640 dynes per cm was found in the Fe-C-Co system at a concentration of 1.5 pet C and 12pet Co. Analysis of these measurements in terms of adsorption and desorption behavior indicated that cobalt and nickel lower surface tension in Fe-C alloys by replacing carbon at the liquid-vapor interface. Comparison of results to date for Fe-C liquid alloys has shown that most substitutional-type elements having about the same atomic diameter as iron also have relatively the same influence on surface tension when present in dilute amounts. It has been shown previously that surface-adsorption behavior in liquid Fe-C ternary alloys is related to the manner in which the ternary addition affects the activity of carbon in the bulk solution.' Certain ternary additions, such as chromium, tending to decrease carbon activity cause adsorption of carbon and chromium to the liquid-vapor interface. Additions, such as silicon, increase the carbon activity, resulting in a desorption of carbon and an adsorption of silicon. Both cases were shown to cause a decrease in surface tension due to adsorption. It is the object of this paper, as part of the writers' continuing interest in the effect of alloying additions on the surface tension of Fe-C alloys, to present and discuss surface-tension data on solutions in the ternary systems Fe-C-Co and Fe-C-Ni. Available activity measurements for these systems in the solid state indicate a strong increase in carbon activity when either nickel or cobalt is added to Fe-C alloys.2, 3 EXPERIMENTAL PROCEDURE The alloy compositions used are shown in Table I. These alloys were prepared by vacuum melting in stabilized zirconia crucibles and then vacuum casting into cold-steel molds. The nominal analyses for the alloys used in this investigation are given in Table I. Surface tensions and densities were measured by the sessile-drop method4,5 in conjunction with the tables of Bashforth and bdams.' Specimens were prepared by slicing 1/4-in. cubes from the center of the vacuum-cast ingots and grinding the edges of these cubes until their shapes approximated spheres with flat bottoms. Proper handling techniques, including an acetone rinse immediately before use, assured minimum contamination from sources extraneous to the actual melting. For each experimental run a sample was placed on a BeO plaque and positioned and leveled inside a vacuum induction heating apparatus. The sample and plaque arrangement sat inside a molybdenum tube which acted as the susceptor. Diagrams of this apparatus may be found in the literature.= After heating to temperatures just above the liquidus at pressures of the order of 10-4 to 10- 5 mm Hg, photographs of the drop profile were made using its natural thermal radiation as a light source. Some measurements were made with partial pressures (-1 cm Hg) of a mixture of H2 and He gases. The H2-He atmospheres proved to be necessary at higher nickel contents to retard excessive vaporization losses. Chemical analysis for carbon and the ternary addition was performed for each alloy sample after completion of the experimental run.

Jan 1, 1964

By Walter Miller

A surprising development during the year was the continued high demand for petroleum products and the high level of crude oil charges to the stills. Generally speaking, the petroleum industry during 1946 succeeded in producing a greater quantity of crude oil and petroleum products than in any of the war years, and considerably exceeded the production of any prewar year. Daily crude still charges averaged between 4,700,000 and 4,800,000 bbl per day for 1946 and about equaled the 1945 record, although most pessimistic 1945 guesses, predictions, or fears ranged, for 1946, from only 3,900,000 to 4,400,000 bbl per day. In spite of the high crude charge to the stills, total stock of crude oil was higher at the end of the year by some 7,000,000 to 8,000,000 bbl. A similar story holds regarding stocks of the principal refined products. Gasoline on hand at year's end was two to three million barrels lower, and was considered low for the expected demand during the coming high consuming season, while stocks of light and heavy fuel oils, although some higher than a year previous, hardly reached a comfortable level. The trend in gasoline of high octane number, which has resulted in a marked rise in. the antiknock quality by the end of 1945 (five or six numbers higher than during the war and one number higher than the prewar quality of civilian motor gasoline of 1941) was abruptly arrested by an acute shortage of metallic lead for manufacturing tetraethyl lead. Government action in the form of lead price control, rationing, and the setting of octane ceiling specifications to conform to the reduced ethyl lead compound available were enforced until abrogated at the end of the year. It will be interesting to see how rapidly the octane levels will resume the rising trend, as more metallic lead slowly becomes available for making greater quantities of ethyl lead compound. As octane quality rises over present levels the disadvantage of the refiner without catalytic cracking equipment will increase. Gasoline made by catalytic cracking, without addition of ethyl lead, approximates 77 octane by the official ASTM Motor Method test, compared with 66 for gasoline generally similar in volatility made by the older thermal cracking operation. Catalytic gasoline shows an even greater improvement in the Research octane number, the comparison being roughly 86 Research versus 71 Research octane for the thermal cracked product. This higher differential in Research octane is credited by many, although not universally so, as contributing to better road performance, and consequently resulting in a more desirable product marketwise. In some parts of the country a premium of roughly one fourth cent per gallon is now being paid for gasoline with higher Research octane made possible by including catalytic cracked product in the final blends. If such price differentials in favor of catalytic gaso-

Jan 1, 1947

By Walter Miller

A surprising development during the year was the continued high demand for petroleum products and the high level of crude oil charges to the stills. Generally speaking, the petroleum industry during 1946 succeeded in producing a greater quantity of crude oil and petroleum products than in any of the war years, and considerably exceeded the production of any prewar year. Daily crude still charges averaged between 4,700,000 and 4,800,000 bbl per day for 1946 and about equaled the 1945 record, although most pessimistic 1945 guesses, predictions, or fears ranged, for 1946, from only 3,900,000 to 4,400,000 bbl per day. In spite of the high crude charge to the stills, total stock of crude oil was higher at the end of the year by some 7,000,000 to 8,000,000 bbl. A similar story holds regarding stocks of the principal refined products. Gasoline on hand at year's end was two to three million barrels lower, and was considered low for the expected demand during the coming high consuming season, while stocks of light and heavy fuel oils, although some higher than a year previous, hardly reached a comfortable level. The trend in gasoline of high octane number, which has resulted in a marked rise in. the antiknock quality by the end of 1945 (five or six numbers higher than during the war and one number higher than the prewar quality of civilian motor gasoline of 1941) was abruptly arrested by an acute shortage of metallic lead for manufacturing tetraethyl lead. Government action in the form of lead price control, rationing, and the setting of octane ceiling specifications to conform to the reduced ethyl lead compound available were enforced until abrogated at the end of the year. It will be interesting to see how rapidly the octane levels will resume the rising trend, as more metallic lead slowly becomes available for making greater quantities of ethyl lead compound. As octane quality rises over present levels the disadvantage of the refiner without catalytic cracking equipment will increase. Gasoline made by catalytic cracking, without addition of ethyl lead, approximates 77 octane by the official ASTM Motor Method test, compared with 66 for gasoline generally similar in volatility made by the older thermal cracking operation. Catalytic gasoline shows an even greater improvement in the Research octane number, the comparison being roughly 86 Research versus 71 Research octane for the thermal cracked product. This higher differential in Research octane is credited by many, although not universally so, as contributing to better road performance, and consequently resulting in a more desirable product marketwise. In some parts of the country a premium of roughly one fourth cent per gallon is now being paid for gasoline with higher Research octane made possible by including catalytic cracked product in the final blends. If such price differentials in favor of catalytic gaso-

Jan 1, 1947

By Kenneth Cotingham

Many factors joined in reducing drilling activity in Ohio in 1942. Conservation Order M-68 was important, but other things, such as operators and members of drilling crews joining the armed services and going into war plants, had an important part. The reduction in number of completions was considerable. In 1941, the total of wells drilled was 1561 but in 1942 the total was 1008. The total initial daily open flow discovered by the 701 gas wells drilled in 1941 was 492,000 M cu. ft., whereas the open flow of the 471 gas wells completed in 1942 was 314,488 M cu. ft. The total initial daily production of the 333 oil wells drilled in 1941 was 10,300 bbl., and in 1942 the 181 oil wells had a total daily initial of 7570 bbl. The average daily initial per gas well therefore was somewhat less in 1942 when compared with the preceding year, but the initial per ail well increased about 36 per cent over 1941. General Activity The total depth of the 652 oil and gas wells drilled in 1942 was 1,597,000 ft. The most active county was Perry, where 63 oil wells were drilled, most of them in Clayton township. In Morgan County. where 43 gas wells were drilled, the greatest activity was in York and Marion townships. Medina County was third in number of wells drilled, although of the total of 33 gas wells in the county, 26 were in the new Hinckley township pool. The total initial open flow of these 26 wells was 39,202 M CU. ft., and was considerably larger than from any other single area. Muskingum was an active county, particularly Washington and Wayne townships, in each of which seven gas wells were drilled, and Blue Rock and Harrison townships, in each of which five gas wells were drilled.

Jan 1, 1943

By Kenneth Cotingham

Many factors joined in reducing drilling activity in Ohio in 1942. Conservation Order M-68 was important, but other things, such as operators and members of drilling crews joining the armed services and going into war plants, had an important part. The reduction in number of completions was considerable. In 1941, the total of wells drilled was 1561 but in 1942 the total was 1008. The total initial daily open flow discovered by the 701 gas wells drilled in 1941 was 492,000 M cu. ft., whereas the open flow of the 471 gas wells completed in 1942 was 314,488 M cu. ft. The total initial daily production of the 333 oil wells drilled in 1941 was 10,300 bbl., and in 1942 the 181 oil wells had a total daily initial of 7570 bbl. The average daily initial per gas well therefore was somewhat less in 1942 when compared with the preceding year, but the initial per ail well increased about 36 per cent over 1941. General Activity The total depth of the 652 oil and gas wells drilled in 1942 was 1,597,000 ft. The most active county was Perry, where 63 oil wells were drilled, most of them in Clayton township. In Morgan County. where 43 gas wells were drilled, the greatest activity was in York and Marion townships. Medina County was third in number of wells drilled, although of the total of 33 gas wells in the county, 26 were in the new Hinckley township pool. The total initial open flow of these 26 wells was 39,202 M CU. ft., and was considerably larger than from any other single area. Muskingum was an active county, particularly Washington and Wayne townships, in each of which seven gas wells were drilled, and Blue Rock and Harrison townships, in each of which five gas wells were drilled.

Jan 1, 1943

By Jr. Ensign C. O., J. W. Trammell

The two principal methods of room-and-pillar mining practiced at White Pine make it important to predict variations in the thickness and rock types of a stratum called the upper sandstone. In full column mining, the nearly barren upper sandstone occurs between two ore horizons (called upper shale and parting shale, respectively), and is mined as a part of the ore column. In general, full column mining is not practiced where excessive upper sandstone thickness causes full column ore grade to be substantially lower than parting shale ore. In parting shale mining, the upper sandstone forms the mine roof. Difficulty in predicting upper sandstone character arose because the extent and directions of its variations were not apparent in the property's diamond drilling, in which holes are spaced on 1000-ft centers. A study of sedimentary features, undertaken to improve the predictability of trends in the upper sandstone, led to an interpretation of the sedimentary environment in which the sandstone was deposited. Ripple marks, mud cracks, and cross-bedding, as well as other, less well known features, such as channel casts, flute casts, and current crescent casts, were mapped or recorded. These data, coupled with the knowledge of regional facies changes gained from studying drill core, show that the upper sandstone was deposited by a series of streams flowing northeastward over the underlying parting shale. Deposition of the lowermost bed of the upper sandstone, near the ancient shoreline, was locally preceded by erosion of the parting shale, and the greatest thicknesses of sandstone are found in channels scoured out of the parting shale. Awareness of the rather strong linear trends in the upper sandstone makes it possible to project continuous areas of thick upper sandstone through apparently isolated "highs" in the upper sandstone thickness contour map, which is based on drill-hole information. Since local exceptions to general stratigraphic trends exist, a method was also needed for esti- mating, in detail, the thickness and degree of shali-ness of upper sandstone forming the roof in active parting shale mining areas. Because locally the parting shale was thinned by erosion during the deposition of upper sandstone, parting shale thickness is inversely proportional to upper sandstone thickness. Utilizing information taken from short drill holes into the roof, curves were constructed for the correlation of parting shale thickness (measurable in the mine) with the upper sandstone total thickness, as well as the thickness of its basal member. The White Pine mine is situated in Ontonagon County, approximately 6 miles south of Lake Superior, in the Upper Peninsula of Michigan (Fig. 1). The orebody mined by White Pine Copper Co. occurs in the lowermost 20 to 25 ft of the Nonesuch formation, a series of middle- to upper-Keweenawan shales, siltstones, and sandstones. This paper discusses the solution of problems in ore grade control and mine planning arising from the presence of an essentially barren sandstone stratum within the orebody. THE OREBODY AND MINING TYPES A brief description of the orebody and mining methods is necessary to show how the upper sandstone affects mine planning and grade control. In the mine, the cupriferous zone of the Nonesuch shale is divided into three major portions, as shown in Fig. 2. Lying conformably on top of the Copper Harbor formation (or "lower sandstone") is the lower part of the orebody, the parting shale. The parting shale is overlain by the upper sandstone. On top of the upper sandstone, the basal portion (8 ft) of the upper shale is quite similar to the parting shale. Both the upper shale and parting shale are divided into a number of smaller stratigraphic units, each having a characteristic copper content, as shown by the histogram of Fig. 2. Other authors1'3 have dealt in detail with the stratigraphy and mineralogy of the orebody. However, in this article, we are concerned with the major subdivisions only, and it will suffice to note the low copper content of the upper sandstone, shown in Fig. 2. At present, two types of room-and-pillar openings are created in the orebody. In one type, called parting

Jan 1, 1964

By S. A. Bradford

Internal-oxide precipitates in decarburized a iron alloys were studied by microscopic and X-ray methods. Diffusion of oxygen is primarily trans-granular, although large amounts of manganese or PhosPhorus cause preferred grain boundary dimsion at temperatures below 1450OF. Transgvanular internal oxidation follows the parabolic rate law with an apparent activation energy of 60 kcal per g-atom for decarburized rimmed steel and around 50 kcal per g-atom for higher alloy contents. The internal oxide is (Fe,Mn)0. Evidence was found for a miscibility gap in the FeO-MnO system. UNTIL very recently, the internal oxidation of metals was studied primarily as a scientific curiosity or, in a few cases, as a means of strengthening alloys by precipitation hardening. However, with the recent development of low-carbon enameling sheet steel, internal oxidation has become a problem of practical importance to the steel industry. For example, in 1961 it was reported1 that internal oxidation of steel can occur during decar-burization by open-coil annealing and will reduce the notch ductility of the sheet unless the process is carefully controlled. The present study was therefore undertaken to learn more about the rates and mechanism of oxygen diffusion and oxide formation in iron alloys. BACKGROUND The process of internal oxidation has been well-defined in the literature:',' oxygen dissolves in an alloy, diffuses inward from the surface of the metal, and reacts to form a precipitate with the alloying element that will provide the most stable oxide. he growth of the finely divided so-called subscale, i.e., the internal-oxidation zone, depends on the diffusion rates of both the oxygen and the reactive element.4 Investigators have generally found that increasing the temperature increases the size of the oxide particles, the rate of subscale growth, and the tendency to transgranular diffusion. With very few exceptions, the square of the thickness of the internal oxide layer is directly proportional to the reaction time. Given two conditions easily satisfied for iron systems— a) an oxygen solubility much less than the concentration of the alloying metal and b) an oxygen-diffusion rate to the oxide boundary much faster than that of the alloying element—then the general expression developed by Rhines and co-workers5 for the parabolic growth rate of the internal-oxide zone can be simplified to the following form: where Co and CM are, respectively, the solubility of oxygen and the concentration of the alloying element, DO is the diffusion coefficient of oxygen, O/M is the weight ratio of oxygen to metal in the precipitated oxide, and x is the thickness of the internal-oxide zone after an annealing time t. Both the oxygen solubility and diffusion coefficient can be approximately expressed as functions of temperature by Arrhenius-type equations: in which H and Q are, respectively, the heat of solution and the activation energy of diffusion. Consequently, the apparent activation energies calculated from Arrhenius plots are the sum of the heat of solution of oxygen in iron and the activation energy for diffusion of oxygen. The data, if not the interpretation, of Schenck et al.8 bear out the fact that oxygen diffuses in the atomic form. The general rate law for atomic diffusion is: the reaction rate being proportional to the square root of the pressure at low pressures. Benard and Moreau8 studied both the surface oxidation of Fe-Ni alloys and the gradual penetration of oxygen into the metal. They observed that oxide particles first form along grain boundaries and then grow to form continuous films that eventually envelop the grains. The parabolic rate law does not usually apply in these cases, especially at the higher temperatures. The oxide formed is wustite which gradually transforms into Fe3O4 and finally into Kennedy and coauthors8 examined Fe-Ni alloys with 26, 75, and 84 pct Ni oxidized at 800°C and

Jan 1, 1964

By D. L. Martin

The study of cobalt-platinum alloys has been of interest since they represent a class of permanent-magnet material in which the disorder-to-order transformation plays a controlling role. The magnetic properties of alloys in the range 40 to 60 at. pct have been found to be greatly influenced by composition and heat-treatment. The peak properties of 4700 coercive force and 9,000,000 gauss-oersteds energy product were obtained by controlled cooling and aging. These high values combined with ductility and machin-ability give the alloys useful characteristics although their high cost limits their application. THE cobalt-platinum alloys have been of interest in the study of permanent-magnet materials ever since the discovery by Jellinghaus that they had unusually high coerceive-force values.' The high coercive force was associated by Jellinghaus with the disorder-order reaction which occurred in these alloys. This was later verified by Gebhardt and Koster in a detailed study.2 An investigation of the structure, mechanism, and kinetics of the disorder-order transformation and resulting property changes in cobalt-platinum alloys has been in progress for some years. Certain phases of this study related to equilibrium rela- tions, and to the mechanism and kinetics of the ordering reaction have been published previously.3-5 In this paper, the results of the processing and heat-treatment studies on 40 to 60 at. pct CO alloys are presented. The magnetic properties have been found to be influenced greatly by the composition, by the cooling rate from the disordering treatment, and the final ordering time and temperature. Coercive force values, Hc, of 4700 oersteds and energy values, (BH)m, approaching 9,000,000 gauss-oersteds have been obtained by controlled cooling and ordering. PROCESSING OF THE ALLOYS The composition range of interest for permanent-magnet properties centers around the equiatomic composition Copt. In this region the alloys are dis-

Jan 1, 1959

By M. E. Wadsworth, C. H. Pitt

Nickel corrosion in sulfuric acid solutions at elevated temperatures and oxygen wer-pressures was imestigated. Weight loss was 1inear with time and varied directly with oxygen concentration. Independent variation of the possible active species in solution indicated that the undissociated sulfuric acid molecule plays an important part in the corrosion mechanism. The rate determining step was considered to be the adsorption of oxygen on a site containing adsorbed H2SO4. THE tendency for a metal to go into solution depends on a number of factors some of which are: 1) the position of the metal in the electrochemical series; 2) the type and concentration of corroding species in solution; 3) the concentration of oxygen in solution; 4) the type of film formed at the liquid-metal interface; and 5) the physical state of the metal. The corrosion of a metal in an aqueous solution may be considered to be a heterogeneous reaction that occurs at the liquid-metal interface. The reaction is generally considered to occur as a result of electrochemical potential differences within the system. Little work has been published in the literature concerning the corrosion of pure nickel. A great deal has been publistled dealing with the experimental and theoretical aspects of the over-all corrosion process. Evans,1 Uhlig,' and recently Todt 3 and Tomashoff,4 have published books which review the results of experiments which have been conducted on corrosion, and have developed some of the basic ideas of the more widely accepted theories of corrosion. Friend5 states that. nickel does not readily discharge hydrogen from any of the common nonoxidiz-ing acids and that a supply of some oxidizing agent is necessary for appreciable rates of corrosion. He further notes that at temperatures between atmospheric and close to boiling, corrosion rates tend to vary with concentration, temperature, and aeration in acid concentrations up to 25 pct. Whitman and Russel6 studied the effect of dissolved oxygen on a number of metals in acid solutions and found that oxygen accelerates the rate of corrosion of nickel in sulfuric acid. Flowers and Kelley7 in studying the action of dissolved CO, on electroplated nickel postulated that nickel dissolves as NiHCO3 in the presence of CO, and air. It was found that oxygen was necessary for corrosion to take place and that the rate increased with increasing amounts of oxygen in solution. Flowers and Kelley attributed the oxygen effect to cathodic depolarization. MacGillavry, Rosenbaum, and wensson' determined metal solution potentials of nickel in various electrolytes. They found that nickel has no tendency to corrode in alkaline solutions in the presence or absence of air. In acid solutions in the presence of air, metal solution potential increases in the order of 1/2 v were observed. This increase was attributed to probable chemisorption of oxygen on the nickel surface and the corrosion mechanism suggested was the interaction of H+ ions with the nickel oxide formed at the surface. Delahay9 observed the reduction of oxygen on various metals. A polarograph was used to measure the course of the reaction. With some metals hydrogen peroxide was produced as an intermediate compound. However, nickel was not considered to be a hdrogen peroxide producer. Van Rysselberghe 10,11 and associates attributed the accelerating effect of carbon dioxide on the corrosion process to the presence of percarbonic acid produced in solution reacting with the hydrogen peroxide. The percarbonic acid can be reduced at less negative potentials than hydrogen peroxide and as a result accelerates the reaction. EXPERIMENTAL Since a complete description of the apparatus used can be obtained elsewhere,12'13 no attempt will be made here to describe the equipment other than to note that it consisted essentially of an autoclave unit from which samples could be withdrawn periodically without disturbing the interior state of the autoclave. A titanium autoclave liner was used to protect the autoclave from the solution.

Jan 1, 1961

By J. K. Gustafson

Since prehistoric times, gold has been sought for its beauty and its unusual physical and chemical properties. Early in the dawn of civilization it became the ultimate unit of value, and for at least 6000 years it has been used to barter for other commodities. It has been prospected for, treasured and made into works of art and personal adornment. From time to time, it has even been the object of conquest. Because of its predominant role as a basis for money in recent centuries, economists have come to think of gold solely in these terms. Gold, however, has physical and chemical properties that make it one of the most useful metals in the modern world. It is the most ductile metal known. An ounce of it can be drawn into a continuous wire over 35 miles long. It is also so malleable that an ounce of it can be beaten into films 0.00001 in. thick covering 68 sq ft of surface. It has a density of 19.3 and is so heavy that 1 cu ft of it weighs more than half a ton. Gold is nonmagnetic and has a high electric conductivity that is only slightly less than that of silver and copper. Gold is so inert to all the chemicals found in nature that gold coins and jewelry buried beneath the soil or at the bottom of the sea for thousands of years appear to be as bright and perfect as when they were first immersed. Finally, gold has an extremely high reflectivity of both light and infrared rays.

Jan 1, 1971

By B. P. Mulcahy

When the phrase "selection of coal for carbonization" is used, there is always the implied continuance of thought "to make good coke.'' The reason for this, of course, lies in the fact that, in almost all instances, when coal is carbonized coke is the principal product. Under certain conditions the yield of gas may also be a factor, but even here it must be secondary to the coke yield, for in every instance coke represents the largest single product of the process. The importance of coke to the byproduct industry has been considerably enhanced during the past 20 years because of the continuously decreasing financial returns of all the by-products. This fact will account, in part, for the rebirth of interest and investigation in the carbonization process during the past 10 years. Many papers have been written on this subject, with naturally divergent thoughts because of the diversity of interests, but in each instance the common aim was the same—the making of better coke. Scope of Investigation In perusing this literature, the writer was struck with the constantly recurring imposed condition of asking for better coke, but with the distinct unwillingness to make any concession to temperature of carbonization. When there is a high demand for coke, the only means by which the industry can increase the quantity is to shorten the coking time by an increase in temperature, or to increase the quantity of low-volatile coal, or both; and since in many instances the percentage of low-volatile coal can be increased only in small quantities, because of factors to be discussed later, the big increase must come from shortening the coking time. When this is done most of the improvement accomplished by the selection of the coals in the mixture is lost. It is not felt necessary in this paper to discuss the advantages of minimum ash and sulphur and other materials in coal. The value of minimum contents of these materials in coke is well established. When the use of coals high in these contents is dictated, the selection of coals, as we will consider it here, cannot apply to full advantage. The scope of this paper, then, will be to discuss the factors of inherent coal characteristics and operating procedures that influence coke quality, for they are fundamentally related and both must be considered if we are to attain our objective of better coke. A study of either must embrace a study of both simultaneously. To properly evaluate the influence of the coal and to help in the selection, we must first be able to appraise the coke, and interpret fairly the influence of the process in all of its aspects. Appraisal of Coke To refer simply to the quality of coke gives no indication of what is meant, for the term is too general in its implication. An analysis of a coke is divided usually

Jan 1, 1944