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INSTITUTE MEDALS AND PRIZES ASIDE from the John Fritz Medal, in which the Institute participates through its representation on the John Fritz Medal Board, the Institute itself has four awards it may make annually, as fol¬lows. the Robert W. Hunt Medal and Prize, the J. E. Johnson, Jr., Award, the James Douglas Medal, and the William Lawrence Saun¬ders Medal. ROBERT W. HUNT MEDAL AND PRIZE The partners of Robert W. Hunt established a fund which was presented to the Institute at a fitting ceremony-on May 27, 1920, to establish an annual medal and a sum of money to be awarded under the following rules 1 The award shall consist of two prizes first of a gold medal, second of a sum of money, a certificate to accompany each prize The money prize shall not be awarded to a member over 40 years of age, but under unusual circumstances, both prizes may be allotted to one person provided that he is not over 40 years of age In general it will be understood that the Committee shall award the money prize to the younger men, rather than the medal 2 The awards shall be made not oftener than once a year to that person or persons contributing to the Institute the best original paper or papers on iron and steel The scope of the term "iron and steel" shall be determined by the sub-committee considering the awards In general, papers dealing with the practical side of the subject have preference over those dealing with the theoretical side in recognition of the fact that Captain Hunt's main contributions to the industry have been in the improvement of production and quality of material

Jan 1, 1923

By E. T. Dumble

In the Bosquejo Geoldgico de Mexico, published in 1897 by the Secretaria de Fomento as Nos. 4, 5 and 6 of the Boletin del Institute Geologico de Mexico, the Director, Jose C. Aguilera, after a detailed account of the geological observations made by himself and his assistants on their several trips through the various districts of the Republic, gives in Part 2 a synopsis of the geology of Mexico, describing . al1 the formations recognized, the rocks comprised in them, their geographical distribution, disturbances, principal eruptions and economic features, as explanatory of the Geological Map of Mexico. In Part 3 Prof. Ordonez describes many of the interesting eruptive rocks of Mexico." This work brings together in a very satisfactory way about all of the published results of geological investigations in Mexico; and although the determinations of the authors with reference to some of the sedimentary deposits are very different from those of other writers, they seem to be based upon good paleontological grounds in each instance. From the map and the text of this paper it appears that the condition of knowledge in regard to the geology of the State of Sonora, at the time of its publication, was about as follows: The western portion of the State, lying between the coast line of the Gulf of California and the foot-hills of the Sierra Madre mountains, is largely Quaternary, interrupted by areas of Azoic rocks and of later eruptives, with two or three limited exposures of limestones of the Cretaceous; while the eastern or

Jan 1, 1900

By SME

A regular feature of the December issue is the abstracts of graduate theses in the mineral industry field presented during the preceding year. The following abstracts were submitted for this second article in the series.

Jan 1, 1976

E. M. BROHL. It seems as though the physicists in this crowd in the case of the cartridge cases have been a little in advance of the chemists in the crowd. What I am curious about here, and the way this appears to me, without too much study, is that in season cracking we get an atomic distortion so that both by sound means and by magnetic means we are finding a reluctance of the atomic planetary system to line up in accordance with the so-called good metal. The point that is brought up, or rather that has not been brought up-and I think perhaps we could think of that from the chemical point of view-is that this season cracking as I am used to the stress-corrosion cracking, appears to act much as though it were copper oxide. You remember when YOU take copper oxide films in which we again use this distortion of the atomic system to allow currents to pass selectively in one direction only, we get results almost identical with what we saw on the oscillograph report. In other words, on the one section of this season cracking we had a trace of one phase and if you notice on the sections three and four of the numbered oscillograph trace we had what appears 180 deg. out of phase.

Jan 1, 1945

By C. E. Agnew

THE Eastern district, composed of New Jersey and eastern Pennsyl-vania, with its native ores, was the cradle of the iron industry of the United States. The district attained and held the leadership in produc-tion of pig iron for over 100 years, from pre-Revolutionary days to approximately 1875. The first shipment of Lake hematite ore was made in 1853. It was a small shipment, transported by a sailing vessel and a canal barge, but it was the beginning of the end of the supremacy of the Eastern district, although at that time the ore was supposed to be too rich to be successfully smelted with the block coal then in use at western furnaces. The iron made from the first shipment of Lake ore was worked into nails by the Sharon Iron Co., at Sharon, Pa. The writer's great-grandfather, David Agnew, and his brother, John P., Agnew, owners and-operators of the Sharpsville furnace, Sharpsville, Pa., worked the shipment through a furnace. Because of this, the writer feels some satisfaction in having been one of a group that solved the problem of making profitable an operation using Eastern district ores exclusively. With the development of Lake mines, and the production and use of coke, the Middle West district gradually assumed the position of leader-ship in production; because, even though the ores were transported 1000 miles by water and rail, its cost figure on pig iron was better than that of the eastern producer whose furnace was next to his mine. Such a cost figure was possible because the ore was naturally rich in iron and reduced easily. It was possible to carry a heavy burden on the furnace, which resulted in large tonnage and low coke per ton of iron. This paper is in no sense a technical one. The purpose is to show that with the proper physical preparation of the Eastern magnetites they will reduce as easily as the Lake hematites, and because of the high iron concentration give the Eastern producer just as much advantage as formally he was at a disadvantage in comparison with the Middle West producer.

Jan 1, 1938

By W. H. Meyer

During the seventeen years Fairchild has been making aerial surveys and aerial photographic equipment many changes and improvements have been made in the equipment and in the technique of using it. Aerial photographic operations have been developed from the crude methods and apparatus of wartime to a science upon which exact engineering calculations can be based. In the early days there was no airplane specially designed to meet aerial photographic requirements. One type of camera was used in all types of operations. Projects were made to conform to the products we could make and deliver. Obviously this entailed definite limitations. We now have airplanes designed specially for aerial photographic operations in accordance with the conditions encountered in actual service experience. We have cameras for every photographic purpose and our laboratory technique and equipment have been developed to the point where it is possible to make contour maps from vertical aerial photographs with contour intervals as close as five feet. Therefore, the selection of equipment now can be made in accordance with the time at our disposal, the justifiable cost, the scale desired, and the general requirements of the client. This does not mean, however, that arbitrary deliveries can be set for aerial photographic products. The factors in each project vary and each job must be considered in accordance with the factors involved. This accounts for the fact that products of aerial surveys may readily vary from $1.25 to $200 a square mile. Sherman M. Fairchild became interested in the design of a radically different aerial camera during the war. At its close he was about ready to demonstrate his design to the War Department. By 1920, he was able to bring out his first completed model. It had a number of radical features, one of which was the first dependable high-speed between-the-lens shutter, which makes for accuracy in aerial photographic work. Another feature was the use of metal throughout, eliminating the wooden parts that had been employed in wartime cameras. Another feature was the interchangeability of parts.

Jan 1, 1937

By Wilson B. Emery

The Hidden Dome gas field, situated in Washakie County, Wyoming, was discovered Sept. 26, 1917. Subsequently five additional gas wells were completed and a large reserve was developed. For a number of years this field completely supplied the domestic market at Basin and Greybull, as well as the refinery at the latter town, and it is still supplying gas in small amounts to this market. Production is obtained from the sands of the Frontier formation at depths ranging from 1000 to 1500 ft. The original rock pressure was 725 Ib. and initial production ranged from 4,000,000 to 28,000,000 cu. ft. per day per well. Porosity of the sand, determined from the size of the productive area and the amount of gas recovered, is over 18 per cent. Area and Management It is estimated that the productive area is about 640 acres. Its outline is indicated on Fig. 5, on which are also shown the locations of holes drilled on the structure and the area of unit operation. The unit area is owned by the Ohio Oil Co. and development and operation have been by this company. No productive well has been completed outside this area. The entire area was Government land filed on under the placer mining law. Results of Unit Operation With six producing wells, or an average of one to each 160 acres, the pool is completely developed. Location of the wells was made with respect to structural conditions plus the requirement that at least one well be drilled on each 160-acre placer claim. Perhaps a somewhat more uniform spacing of the wells might have been accomplished and one well eliminated, but it must be borne in mind that the holes, on account of their shallow depth, were not expensive and that the object was to develop as reliable a reserve as possible. There is no cause to suspect that these holes have not adequately drained the reservoir and there is every reason to think that any additional wells, which might have been drilled under diversified ownership and operation, would have been an economic waste. Unit operation by a competent company has not only resulted in the elimination of loss of gas through careless development and operation

Jan 1, 1930

HAVING shown you before how moulds of statues and also those of guns are constructed, I wish to tell you at present how, if you wish to cast them in bronze, you are further to prepare and arrange these moulds so that they may receive the melted mass of the metals in a friendly manner and without disturbance. I know that you understand that a real and intense heat has been intro-

Jan 1, 1942

By W. McA. Johnson

The work of J. E. Johnson, Jr., on the effect of small amounts of oxygen in cast iron in increasing its strength and resistance to shock, is of interest from the technical and scientific standpoints. The following exposition of the theory carries Mr. Johnson's explanation further and, in my opinion, will disclose certain related phenomena and perhaps shed further light on the subject. Some facts, so novel in character as to excite incredulity, have been accepted finally by many metallurgical authorities. One of these is that oxygen to the amount of 0.060 per cent. in cast iron gives it a breaking strength of 3,500 Ib. per square inch, compared with a breaking strength of 2,500 lb. per square inch in cast iron of the same composition with respect to elements other than oxygen, but having only 0.010 per cent, oxygen. The "oxygenated" cast iron, even if made in a coke furnace, has properties equivalent to the best charcoal pig iron. Mr. Johnson has also established the fact that the variations in combined carbon cannot account for the results. By microphotographic evidence he has shown that in oxygenated cast iron the graphite particles are dense and spherical, while in well-deoxidized cast iron the graphite particles are flaky and leaf-like. It is just a matter of common sense that iron of the latter structure is much weaker than the former. The analytical and microscopical work has been done with care and there is no doubt in my mind about the accuracy of the experimental results. In this paper then, we shall consider it as accepted that small amounts (0.060 per cent.) of oxygen increase the strength of cast iron by producing a structure in which the round and solid particles of graphite are surrounded firmly by a principal matrix of ferrite. The purpose of this paper is to show that the reason why the graphite particles are round is founded on the fact that the particles of any precipitate are made denser and harder by the presence of a reagent having a solvent action on the precipitate. This can be stated as a law, although I have never seen it so given in any textbook. Let us then, for purposes of illustration, give a concrete example and develop the theory of such mechanical and chemical actions as occur: It is well known that, by a soluble sulphate, a barium salt in solution is precipitated in a dense and easily filtered body when the solution is

Jan 1, 1916

By Walter Bonsack

THE CHAIRMAN.-This is the third and last session of the Institute of Metals Division's Symposium on Secondary Metals, and certainly the best of those that I have attended in the last few years. I would say that the increase in interest in secondary metals is quite noticeable by the steadily increasing attendance at these meetings. We have heard about the necessity of utilizing salvaged materials, but we still speak about them as low-grade, or down-graded materials. We still have the wrong perspective. We must willingly admit that these materials are valuable; we cannot go on using the choicest primary metals as morsels for our economic diet in a war of such unbelievable dimensions. This brings up the question-why are we so selective. The answer certainly is not that we know nothing else will do, but rather that we do not know what else will do. To be honest, we should admit our lack of knowledge concerning our complex alloys. Compared to the organic chemists, we metallurgists are very conservative, and the sooner we realize this and start to overcome it the better, because if we do not eliminate this difference, many customers of the metals business will go over to the plastics. If we take for example the development of aluminum alloys, you will see what I mean. From the binary aluminum alloys of 1920, we have progressed to ternary and quarternary alloys in the 1930's. We are only now beginning to use more complex alloys as we are forced to learn more about the effect of various elements on existing alloys. The effects of these elements should be studied now. They can be studied by two methods of approach. The usual method is to start from the base alloy and add various elements one by one in increasing amounts and study the resultant changes in properties. This is a tedious, long way. The other method which the smelters frequently use is to take the off-grade heats and study their characteristics. While the producer of primary alloys often has difficulties in alloying certain elements with the alloy under investigation, the smelter often finds them well alloyed in his raw materials and has no difficulties at all. Elements such as lead are difficult to alloy with aluminum and they tend to segregate severely. However, the amount which will remain alloyed in the metal is usually found in some "secondary" aluminum alloys. If one considers such concentration as the saturation, then by dilution with the same type of alloy, but free of such element, one can produce numerous intermediary alloys for investigation. In this fashion one is fairly certain to get uniformly spaced concentrations of the element under investigation. Similar cases probably exist with other metals. Nevertheless, the amount of work necessary to study all possible combinations is still tremendous. Necessity forces us now to utilize alloys which contain more elements than we are accustomed to. It is, therefore, necessary to study carefully the more complicated alloys. In secondary aluminum we are working and using the alloys which contain as many as 6 to 10 elements and we have learned over a period of several decades to balance

Jan 1, 1943

By G. E. Agar

The energy required for dry grinding of phosphate rock in ball and roller mills has been analyzed by the method suggested by Charles and others. The findings are not wholly in agreement with Charles' predictions; but, nevertheless, the method of analysis is shown to be sound. Some of the deviation is probably attributable to the characteristics of a dry grinding system. Many laboratory and pilot plant scale experiments have been made to determine the energy requirements for size reduction. This topic was recently reviewed by Agar and Brown' and it was apparent that very little if any data exists in the literature which permits one to apply the Charles 2-Holmes3 analysis to industrial size systems. More recently, the idea has been put forward that the postulate of comminution by impact used by Charles and others was not sufficient to explain size-reduction throughout the grinding operation. The opportunity exists in the grinding operations of International Minerals and Chemical Corp. (IMC) to analyze the energy-size relationship for dry grinding phosphate rock in both ball and roller mills. This situation arises because the mills are used for custom grinding and make products from 50% to 85% minus 200 mesh. BACKGROUND A correlation of particle size in a comminuted material with the energy expended in size reduction was proposed by charles2 to be of the form

Jan 1, 1965

By Edward Griffith

The anthracite industry, which produces about 50 million net tons of coal annually, has been talked of as being able to last for another century; but if the water record of the past century continues into the expected century, this expectation of many years production still to come out of the remaining reserves will not be attained. The industry will be a submerged one in fact as well as in name. A recorded forecast of what has since occurred appears on page 34 of the Mine Inspectors' reports of 1897: It should also be noticed that bodies of water had accumulated in parts of abandoned mines before duplicate surveys of the same were required by law; and as a result we have today to contend with bodies of water, the exact location and position of which are not correctly known. Since that date, 47 years ago, the implications of the foregoing comment have grown enormously. This is shown in Fig. I and in the following table showing flooded and partially flooded areas that have come into existence since the early 1930's in the northern anthracite field: Number of Year Flooded Areas 1932...................... 2 1933...................... 3 1934..................... 3 1935...................... 5 1936...................... 7 1937...................... 9 1938.................... 11 1939...................... 11 1940...................... 11 1941...................... 14 1942...................... 14 1944...................... 26 Similar conditions exist in other fields in the anthracite region. In the period between 1923 and 1940, abandonment of collieries in the southern field resulted in the flooding of approximately 60 sq. miles (30 per cent) of the field. The ahandonment of collieries in this field has imposed additional expense for pumping on the collieries still operating. This condition will be aggravated by the extension of developments and cause suspension of operations if economic conditions do not justify the assumption of additional pumping costs. During the years, the region's rainfall has not altered, but the quantity going inside the mines through breakages in the surface, brought about by extraction of the coal, has increased materially, as indicated by the ratio of tons of water pumped to tons of coal produced underground for one of the large companies in the northern anthracite field: Year Ratio 1920................. 8.4:1 1925.................. 10.6:I I930.................. II.4:I 1935................. 26.2:1 1940.................. 32.7: I 1942.................. 30.3:I The data in Table I shows the total amount of water pumped and its ratio to underground production for one of the large companies in the southern anthracite field, and shows a rapidly growing serious situation. Rainfall quickly affects the workings in all the fields. In mine inspection district 7 of the southern field the rainfall in 1935 was 92,083,000,000 gal. The total water pumped was 36,274,000,000 gal. (39.4 per cent of the rainfall). The operating mines

Jan 1, 1947

Recently the Colorado Engineering Council was formed "to coördinate the work of various technical, scientific, and engineering organizations, promote the welfare and professional standing of their members, and foster a more general recognition of the engineer in civic matters." The membership consists of local associations of members of the national engineering societies and other local engineering, scientific, or technical associations.

Jan 8, 1919

By T. O. Anderson, E. J. Stahl

Tests to increase knowledge concerning the process of hydraulic fracturing have been performed on three wells in the Allegheny field in western New York. The fracture orientation and its physical appearance at the well-bore was determined by impression packers run at appropriate times throughout the program. Fract~tre azi171uth and its dimensions thus determined were compared to the rock properties and treatment conditions. Logs to provide data concerning rock properties and to improve identification of vertical fractures were run before each step of the fracture treatment. Pressure osc~illu~iot~s were studied after each phase of tile treatments surface pressures during treatment. These measurements show that subsurface pressures exhibit many of the same characteristics as surface pressures during treatment of a well; however, transient pressures are dampened and deelayed in time at the bottom of the well when COmpared with surface pressures. Data obtained from this study provides a means to help locale and determine orientation of vertical fractures made in the open wellbore. Although these rests were performed in only one area, much of the information gained may be applied to fracturing programs in orher areas. INTRODUCTION In this study, various tests were made to provide data to better understand formation fracturing in situ. The reservoir studied is the Richburg oil sand which is a part of a series of predominantly grey sandstones and shales with occasional brown sandstone layers, known as the Caneadea unit of the Canadaway group of Upper Devonian age. Average physical characteristics of 12 cored wells in this area are 13-ft thick gross sand formation, 12-ft thick net sand. 1.7 md permeability, 11 percent porosity, 44 percent oil saturation (before secondary recovery) and 16 percent water saturation (before secondary recovery). This particular area of the Allegheny oil field was originally drilled prior to 1890. The first waterflood secondary recovery attempt was made in 1929. The present sustained waterflood development began in 1951 and is being carried out on a 4.5 to 5-acre spacing. Objectives of these tests were to (I) study fracture azimuth and dimension in relation to rock properties and treating conditions, (2) improve fracture identification techniques, (3) compare surface and subsurface pressure during all phases of treatment and (4) compare the periods of the fluid column oscillations occurring after each phase of treatment. Although the areas of investigation listed appear divergent in purpose, the program was designed primarily to increase knowledge of down-hole conditions leading to rock failure and extension of the fracture thus created. TEST PROCEDURES Wells upon which tests were conducted are designated as Wells 1 through 3. Well 2 was located 440 ft north of Well 1, and Well 3 was located approximately 880 ft west of Well 1. Wells 1 and 2 were completed with cable tools, while the producing interval of Well 3 was rotary cored using fresh water as the drilling fluid to obtain oriented cores. Tests were divided into separate phases on each well as the fracturing program progressed and consisted of measurements performed prior to treatment, during and after the formation breakdown operation. during fracture treatment and after treatment. To verify location and azimuth of the fracture created, and to obtain an impression of wellbore irregularities, a packer was used (Fig. 1). This packer was lowered on tubing into the wellbore opposite the interval under study and inflated in stages to allow the impression material to conform to the wall of the wellbore. A magnetic compass was attached to the tool for orientation reference. Impressions made prior to treatment showed no existing fractures in the wells under study. Impressions made after both formation breakdown and treatment pro-

Institute of Metals Division Ferrous and Nonferrous Physical Metallurgy Established as a Division April 26, 1918 (Bylaws published In the 1944 TRANSACTIONS Volume of the Division) A A SMITH, JR, Chairman E A ANDERSON, Past-Chairman F N RHINES, Senior Vice-Chairman W A DEAN, Vice-Chairman H A MALONEY, Treasurer ERNEST KIRKENDALL, Secretary 29 West 39th Street, New York 18, N Y Executive Committee R M BRICK 2 W A JOHNSON 1 H I DIXON 2 E W PALMER 1 M GENSAMER 2 J H SCAFF 3 J D HANAWALT 1 J D SULLIVAN 3

Jan 1, 1952

By H. M. Howe

On commencing the construction of the Orford Company's copper smelting works, at Bergen Point, N. J., I endeavored to convince our President, Mr. W. E. C. Eustis, by actual tests, that at the pressure of from 15 to 18 ounces per square inch, employed by us in smelting, less power was consumed in delivering a unit of blast by a Baker blower than by a fan blower. I attempted to prove this in the following manner: Across the mouth of a No. 5) Baker blower I firmly fastened a board with two round holes, 6 inches in diameter, cut in it. The board was fastened so tightly that no air could escape except through the holes. I then drove the blower at several differerent speeds, observing the pressure at which the air excaped through the two openings for each different speed of the blower, and also indicating the engine, whose only work at that time was to drive the blower. From this I calculated the quantity of power required to deliver, with a Baker blower, sufficient air to keep the pressure at a given point, while it escaped freely through the two six-inch apertures into the open air; or, in other words, to deliver air at a given pressure through these two openings. From the total power so consumed it was, of course, necessary to deduct the power which was required to drive the engine itself. This was ascertained by removing from the engine the belt which drove the blower, and then noting the quantity of power consumed in simply turning the engine over without any

Jan 1, 1882

By V. B. Kurfman

Grain refinement of Mg-Al melts by carbonaceous additions has been attributed to nucleation by aluminum carbide. The effects of process and alloy variables are interpreted and predicted in terms of the dispersion and chemistry of this phase. The grain coarsening action of Be, Zr, Ti, R.E., chlorination, temperature extremes, and prolonged holding times is described. Measures necessary to insure an adequate dispersion of the catalyst are discussed. CARBON inoculation treatments have become fairly well known and used for grain refinement of magnesium alloys containing Al. Although there is general agreement that a nucleation process occurs, the process is not understood and the inoculants are used in a rather empirical fashion. The treatment is applied to the class of alloys containing 3 to 10 pct Al, i.e., AZ31A to AM100A. Typical methods involve melting, alloying, and adjusting the temperature to 1400° to 1450°F. Then 0.01 to 0.5 pct C as CaC2, C6C16, or lampblack is added by any convenient means, and the melt poured within 10 to 30 min. Investigators generally have been impressed by an assumed similarity of this refinement process to superheat grain refinement, which depends on heating approximately the same alloys to a temperature in the range of 1550" to 1650°F, then pouring promptly after the melt is cooled to the pouring temperature. Various predictions have been made that carbon refinement would replace superheating in commercial practice due to reduced process costs, but this replacement has not fully taken place because of production difficulties and conflicting observations. Davis, Eastwood, and DeHaven1 agree with Nelson2 and wood3 in suggesting that an excess of inoculant may be harmful. Wood however says that overtreat-ment is not a problem in production use of hexa-chlorobenzene inoculation, and Hultgren and Mitchell4 claim no evidence of harm from excess additions. Various grain coarsening reactions are known to occur, including the possibility of overtreatment mentioned above. Trace amounts of Be,2 Zr, and Ti may prevent refinement by either a carbon treatment or a superheat. Occasionally treatment with cl25 may cause coarsening, although the Battelle refinement process' uses a CC14-C12 blend. Grain coarsening also tends to occur on holding at temperatures below 1350°to 1400°F, especially after a superheat treatment, and for this reason Nelson2 stresses the desirability of a refinement method useful at lower temperatures for open pot melting practice. Since a carbon treatment can be made to work at temperatures below 1400°F, it seems desirable to investigate the mechanism of the refinement and the mechanisms of the coarsening reactions in order to establish control conditions for use in commercial production. The identity of the nucleating phase must first be established and then the factors affecting its chemistry and physical dispersion must be determined. THE IDENTITY OF THE NUCLEATING PHASE Davis, Eastwood, and DeHaven suggested that the nucleating phase in this system is Al4c3,1 but Mahoney, Tarr, and LeGrand8 disagree, largely because they found no evidence of the compound in alloys after carbon treatment and because there is no indication that aluminum carbide should be unstable over the temperature range used in the superheat treatment. This latter objection is based on the assumption that both the carbon treatment and the superheat treatment introduce the same nuclei. Electron diffraction studies have been made to identify the nucleating phase. Samples of grain refined A292 have been selectively etched SO that clean surfaces are obtained and so that secondary phases are in relief. Electron diffraction patterns from these surfaces have established that the carbon treatment of A292 introduces into the metal a large number of small, plate-like particles with a structure very similar to Al4C3. In most cases, the plate-like nature of the particles prevented positive identification but in the cases where the identification could be made the particles proved to be AIN A14C3. However, enough variation in lattice constants was observed so that all compositions from pure A14C3 to the 50:50 solid solution A1N.Al4C3 were probably present.14 In A14C3 and especially AlN.Al4C3 the A1 atoms occur in layers within which they have the same hexagonal symmetry and spacing as the Mg atoms in a single basal plane of a magnesium crystal. The solid solution spacing lies between the 3.16 of AIN and the 3.3? for Al4C3, in satisfactory agree-

Jan 1, 1962

By Raymond Dugdale, Fathi Habashi

There has been a recent interest in studying the action of anhydrous sulfur trioxide on ores to convert the metal values into a water-soluble form as a substitute for leaching by sulfuric acid. For example, Svenke1 converted the small amounts of uranium in slate ash into a water-soluble form by treating the material with SO, at about 600°C. Chao and Sun found that a variety of aluminum-bearing minerals could be sulfatized by SO, in the temperature range 400° to 600°C usually in the presence of a catalyst such as sodium sulfate. Kruse3 patented a process for beryllium recovery from the low grade ore in Utah by first reacting it with SO, at 560° to 750°C then leaching the product with water. In the present report, the action of SO, was examined in the temperature region 100°-300°C which was not investigated by those workers. Experimental Tests were conducted on a beryllium ore sample from Utah, the analysis of which is given in Table 1. It corresponds closely to a saponite ore type as given by Crocker et al. It was in powder form 45% passing a 400

Jan 1, 1973

Jan 1, 1923

By Klaus Schwerdtfeger

The equilibria in the Cr-N system have been investigated in the temperature range 1100° to 1310°C by reacting chromium powder with Nz-Hz gas mixtures. The solubility of nitrogen in chromium in equilibrium with chromium subsitvide ("Cr,N") is given by Chromium subnitride is nonstoichiotnetric; its nitrogen content is always less than that corresponding to the formula CrzN. The lattice paranzeters of quenched samples have been measured; c, and a. parameters are found to increase with increasing nitrogen content. The growth rate of the subnitride layer on chromium plates was measured by a thermogravimetric technique, using a silica spring balance. The self-diffu-sivity obtained from the theoretical analysis of the parabolic rate constant is found to decrease with increasing nitrogen content, i.e., with decreasing vacancy concentration in the nitrogen sublattice. The intrinsic nitrogen diffuivity is derived from another series of rate measurements using "CrzN" plates; the intrinsic diffusivity, DN = 3.2 X 10-a cmZ sec-' at 1200 C, is found to be essentially independent of- the subnitride composition. The concentration gradient was measured in a chromium subnitride layer by the X-ray method and found to be consistent with the derived diffusivity value. TWO chromium nitrides are known to exist:' the nonstoichiometric subnitride "CrzN" and the nitride CrN. In the present work the kinetics of the formation of chromium subnitride from chromium and nitrogen have been investigated at 1100" and 1200°C. In additional experiments the relevant equilibria have been measured. The data are used to evaluate the diffusivity of nitrogen in chromium subnitride. Since chromium nitrides are often found in chromium-containing steels, the results are expected to be helpful in the interpretation of the chemical reactions between chromium steels and nitrogen. Equilibria in the Cr-N system have been determined by several investigators.2"3 The rate of nitriding of chromium was measured by Arkharov et a1 .' in ammonia in the temperature range 800" to 1200°C. The parabolic rate law was observed. Due to the undefined nitrogen activity of the ammonia atmosphere, it is dif- ficult to interpret these rate data theoretically. An additional difficulty arises from the fact that the two-layer scale consisting of CrN and "Cr2N" was formed at the temperatures below 1030°C. The rate of nitriding of technical chromium (95 pct) was measured by Zaks in nitrogen at -1 atm in the temperature range 800" to 1300°C. EXPERIMENTAL METHODS The chromium samples were reacted with Nz-HZ gas mixtures in a vertical tube furnace, wound with Pt-10 pct Rh resistance wire. The gas-tight reaction tube was of high-purity recrystallized alumina. In nitrogen solubility measurements the nitrogen content of chromium was determined by the Kjeldahl method, on samples quenched in the cold part of the furnace. The nonstoichiometry of the subnitride and the nitriding rates were measured thermogravimetrically using a sensitive (+0.1 mg) silica spring balance. For the equilibrium measurements samples of 1 g of chromium powder contained in high-purity alumina crucibles were used. In order to remove most of the oxygen and nitrogen impurities from the chromium, the samples were initially annealed in purified hydrogen until a constant weight was obtained. The chromium plates (approximate dimensions 2 by 1 by 0.08 cm) used for the rate measurements were machined from ingots obtained by arc-melting of iodine-processed chromium. According to manufacturers' specifications the purity of the chromium powder was 99.9 pct Cr and that of the iodine-processed chromium 99.99 pct Cr. Our own spectroscopic analysis of the chromium powder yielded 0.02 pct Fe, 0.05 pct Mn, 0.05 pct Si, and 0.02 pct Ti as major impurities with all the other detectable elements below 0.005 pct. The nitrogen partial pressure of the gas phase was controlled by mixing prepurified hydrogen and nitrogen with constant pressure head capillary flowmeters. Oxygen and water vapor were removed from the mixed gas by passing it through columns of platinized asbestos (450°C) and anhydrone. The gas flowed upward in the furnace with flow rates of 300 to 500 cu cm per min (25"~). Gas tightness of the furnace system was ensured by pressure checks at regular intervals. The furnace temperature was controlled electronically in the usual manner. The reported temperatures were measured with a Pt/Pt-10 pct Rh thermocouple and are estimated to be accurate within ±$C The X-ray measurements were made with a Debye-Scherrer camera and a diffractometer using chromium radiation {\Ka = 2.29092A). EQUILIBRIUM MEASUREMENTS The experimental results of the equilibrium measurements are contained in Tables I to In. Fig. 1 shows the solubility of nitrogen in solid chromium in the temperature range 1100" to 1310°C. In Figs.

Jan 1, 1968