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By M. E. Nicholson

IN order to understand how alloying elements influence hardenability through their effect on the rate of pearlite nucleation, it is advantageous to use a model to describe the mechanism of pearlite nucleation. The model which currently is most widely accepted has been described, among others, by Mehl et a1.1-3 and by Hultgren.4 Pearlite nucleation involves both the nucleation of ferrite and cementite.4,5 Cementite nucleates first, followed rapidly by the formation of ferrite at the cementite-austenite interface. The conclusion that cementite is the first phase to form during the process of pearlite nucleation is based, in part, on the observation that proeutectoid cementite is continuous with pearlitic cementite and that the orientation relationship between proeutectoid ferrite and austenite is not the same as that between pearlitic: ferrite and austenite.6,7 Recently, Smith" has suggested that the dissimilarity in orientation relations, instead of indicating the pearlite nucleation sequence, may be evidence that pearlite is nucleated in a grain adjacent to the one in which it is growing. Also, Modin9 as shown that ferrite in pearlite may be continuous with proeutectoid ferrite, and he has also shown that proeutectoid cementite is not always continuous with pearlitic cementite. Thus, it appears that the conclusion that cementite always initiates the pearlite nucleation process is open to serious question. The author believes that important evidence on the question of how pearlite is nucleated exists in the rates of pearlite nucleation of different steels. The following is a review and analysis of this evidence. If the nucleation of pearlite is considered as requiring the nucleation of both cementite and ferrite, then the time to nucleate pearlite consists of the time to nucleate the first phase to form, plus the time to nucleate the second phase at the advancing interface of the first. In the absence of a visible proeutectoid constituent, the second phase must be nucleated very soon after the first. If cementite is the first phase to form, the time to nucleate pearlite will be approximately equal to the time to nucleate cementite. Since the nucleation rate of a phase precipitating from solid solution increases with the degree of supersaturation, it would be expected that the rate of pearlite nucleation should increase with increasing carbon content. Digges10 has shown that the reverse is true. He determined the quenching velocity necessary to suppress pearlite formation in plain carbon steels as a function of carbon content. His results showed that pearlite formation could be suppressed with lower quenching velocities as the carbon content of the steel increased, at least up to 1.25 pct C, the highest carbon content he studied. Thus, it would appear that in plain carbon steels, in which pearlite is formed at the nose of the C-curve, the hypothesis that cementite nucleates first does not predict the observed change in nucleation rate. The validity of the current model of pearlite nucleation may be tested also by determining whether or not it predicts the relative influence of alloying elements on the nucleation of ferrite and pearlite. This can be done best by a consideration of the changes in a TTT diagram produced by a change in alloy content. Hultgren4 suggests that the general shape of a TTT diagram, as well as what constituents will form from austenite, can be predicted from the relative nucleation rates of ferrite and cementite. This is illustrated in the schematic diagram for a hypoeutectoid low alloy or plain carbon steel shown in Fig. 1. The C-curves for ferrite nucleation and for cementite nucleation are represented by AA' and CC', respectively, and the start of ferrite formation and pearlite formation are represented by AX and BC respectively. Adopting the current theory, Hultgren suggests that between X and C pearlite forms directly from austenite, since cementite nucleates more rapidly than ferrite in this temperature range. Conversely, at temperatures above Tx, ferrite is the first to nucleate and proeutectoid ferrite is formed. As proeutectoid ferrite grows, austenite becomes enriched in carbon, so that the cementite nucleation rate is increased. As a result, pearlite nucleation above temperature Tx is accelerated, beginning along BX and not along C'X. Temperature T, represents the temperature at which the nucleation rate of ferrite equals that of cementite. By extending this type of reasoning, using the principle that the nucleation rates of ferrite and cementite increase with increasing supersaturation of austenite with respect to these phases, it should be possible to predict the influence of carbon content on the shape of the isothermal transformation diagram. For a slightly higher carbon content than that of Fig. 1, the curve A A' representing the beginning of ferrite formation should be moved to the right, whereas the curve CC' representing the beginning of cementite formation should be moved to the left. For hypoeutectoid plain carbon and low alloy steels, this prediction does not agree with existing data. Instead, as the carbon content is increased, the pearlite curve moves to the right along with the ferrite curve and always appears to join it tangen-tially. This behavior is demonstrated by the TTT-curves of a series of manganese steels" shown in Fig. 2. In this figure, TTT-curves for four alloys containing 0.20, 0.40, 0.60, and 1.20 pct C are superimposed. The curves are identified in the figure legend. The letters F, P, and C are used to indicate the start of ferrite, pearlite, and cementite formation, respectively. In these steels, it appears that the nucleation of ferrite and of pearlite are related processes. As a result of the foregoing evidence, it is proposed that the formation of pearlite be considered as follows: Either ferrite or cementite may nucleate from austenite, then grow until the remaining phase is nucleated at the interface between the growing phase and austenite. (The growth of the first phase to form is assumed to be accompanied by a composition change in the adjoining austenite.) According to this model there are two modes of nucleating pearlite: 1—where cementite initiates the succession

Jan 1, 1955

By B. K. Shibler, I. S. Solet, H. W. St. Clair

"This study was undertaken to provide a more adequate knowledge of the chemistry of the sulfide volatilization process for recovery of tin from low-grade Bolivian ores. The investigation was partly supported by the Department of State under its program for scientific cooperation with South American republics.The results of this investigation demonstrate the conditions under which cassiterite (Sn02) may be converted to stannous sulfide by reaction with pyrite or sulfur vapor. Quantitative data are given on the rate of sulfidization and on the vapor pressure of stannous sulfide.INTRODUCTIONAlthough the United States is the world's largest consumer of tin, virtually no tin ores occur within our national borders. Most of the world's tin supply comes from alluvial deposits in the Far East and in Africa, The major sources of tin ores are Malaya, Indochina, Bolivia, Belgian Congo, Nigeria, Thailand, Burma, China, and the United Kingdom. Bolivia is the only important source of tin in the western hemisphere. It was the chief source of tin f or the United States during World War II. The Government-owned tin smelter at Texas City, Tex., was built primarily for smelting Bolivian ores and depends largely on Bolivian ores for its operation. Bolivia is the only major tin-producing country in which the tin ores occur as vein or lode deposits requiring underground mining. Most of the tin from the Far East and Africa is mined by dredges from alluvial or placer depos its. It is recovered as a high-grade concentrate of cassiterite relatively free from impurities. The tin minerals in the lode deposits are more intimately associated with other minerals and more difficult to separate into a clean concentrate. Furthermore, a large part of the tin in the original ore is lost during concentration. The ores as mined contain only a few percent of tin, so they must be milled to separate the gangue minerals and produce a concentrate containing 30 to 40 percent tin before they are shipped to the smelter. The losses of tin that occur during milling vary from 18 to 65 percent. The average recovery of tin from Bolivian ores is probably 50 to 60 percent."

Dec 1, 1954

By BUREAU OF MINES

This report is submitted in accordance with the provisions of the Synthetic Liquid Fuels Act of April 5, 1944 (30 U.S C. 321-325, as amended), which require that: "The Secretary of the Interior shall render to Congress on or before the first day of January of each year a report on all operations under this Act." Owing to the broad scope of the content and the diversity of interests represented, the Annual Report for 1953 has been divided into two separate publications. Each has been published by the Bureau of Mines as a Report of Investigations, and the respective titles follow: R. I. 5043, Part I - 011 From Coal. R. I. 5044, Part II 011 From 011 Shale. - Identical in each report, the introduction summarizes research progress made in 1953 under the entire Synthetic Liquid Fuels program. A free copy of each of these publications may be obtained by a written request to the Bureau of Mines, Publications Distribution Section, 4800 Forbes Street, Pittsburgh 13, Pa. The R. I. number and title of the publication desired should be indicated.

Apr 1, 1954

By BUREAU OF MINES

This report is submitted in accordance with the provisions of the Synthetic Liquid Fuels Act of April 5, 1944 (30 U.S.C. 321-325, as amended), which require that: "The Secretary of the Interior shall render to Congress on or before the first day of January of each year a report on all operations under this Act." Owing to the broad scope of the content and the diversity of interests represented, the Annual Report for 1953 has been divided into two separate publications. Each has been published by the Bureau of Mines as a Report of Investigations, and the respective titles follow: R. I. 5043, Part I - Oil From Coal. R. I. 5044, Part II - Oil From Oil Shale. Identical in each report, the introduction summarizes research progress made in 1953 under the entire Synthetic Liquid Fuels program. A free copy of each of these publications may be obtained by a written request to the Bureau of Mines, Publications Distribution Section, 4800 Forbes Street, Pittsburgh 13, Pa. The R. I. number and title of the publication desired should be indicated.

Apr 1, 1954

By K. D. Jacob, W. L. Hill

THE bulk of natural phosphates is comprised of calcium phosphates, which are usually apatites;1 calcium aluminum phosphates such as pseudowavellite;2 and aluminum phosphates, which occur in extensive deposits, notably on Grand Connetable Island.3 Nearly all deposits of current commercial value are apatite, often with admixed material of other classes. In the trade coarsely crystalline material, mainly fluorapatite of igneous origin, moves as apatite, whereas the fine-grained material of sedimentary origin is marketed as phosphate rock. The latter classification includes the phosphate shales in western North America. Although several genetic varieties of phosphate rock are recognized,4 most known reserves are of marine origin. Calcium phosphate is concentrated from Florida land pebble and Florida hard rock deposits and from Tennessee brown rock deposits. Phosphate Rock as a Fluorine Carrier: More than two decades ago Reynolds and Jacob surveyed the fluorine content of commercial phosphate rock from various parts of the world.3,5 Later these samples were reanalyzed by a new and more reliable method of determining flourine.6,7 The revised results with interim additions of new samples, published a few years ago in a brief summary,' are shown in Figs. 1-3. Through the points representing the respective varieties of rock medial straight lines are drawn. In some instances the lines are well defined by the points; in others, where scattering renders the position of the best line uncertain, the greater weight is given points near the end of the covered range. Wherever distinct varieties are not recognized among regional deposits the custom is to identify the sample with the geographical location of the deposit.

Jan 10, 1954

By Donald L. Everhart

SOONER or later intelligent exploration for uranium leads to these questions: Where did the metallic ions that formed the orebodies come from? What processes and geologic factors were involved in ore replacement? These matters, of course, make a big difference in how best to look for orebodies. Before these questions are discussed it might be well to point out other factors bearing on the subject. The whole business of uranium exploration is only a little over ten years old, participation by the public is only about six years old, and real interest and activity by more than a few large mining companies has arisen only in the past two or three years. Throughout this short period, uranium exploration has been affected by the unique influences of necessary security measures and by division of the over- all job into individual projects by a large number of specialists in diverse fields. This has meant that a normal interchange of information on the nature of uranium deposits has really only just begun. Com- pared to the vast amount of published studies on iron, copper, lead, zinc, and gold deposits over the past 50 to 75 years, current knowledge of uranium deposits is in its infancy and much of the pertinent information is still scattered about in a number of unpublished sources. The volume of reports on all phases of uranium exploration is now beginning to mount at a remarkable rate, and geologists with widely varying specialized backgrounds in uranium geology are engaging in spirited debates over the origin of uranium and the relative importance of geologic controls of various deposits.

Jan 9, 1954

By W. H. Durrell

DISCOVERY of large iron ore deposits in New Quebec and Labrador is, undoubtedly, one of the outstanding mining events of the twentieth century. To give an idea of size, the present concession is almost equivalent to a strip a mile wide around the earth at the equator. Importance of this iron ore area can best be appreciated by comparison to the famous Mesabi Range. On Mesabi, the area of favorable rock is 110 miles long and from 1 to 5 miles wide, with a, productive zone about 70 miles long. On the con- cessions the area of favorable rock in the Labrador Trough is 225 miles long and from 10 to 60 miles wide. In Quebec-Labrador, exploration already discloses that the productive zone is 90 miles long, with good chances of being extended at both ends. The Mesabi is covered generally by thick over- burden, and the iron ore deposits were found by T- test-pitting and systematic test-drilling. In Labrador and Quebec, most ore has been developed from a few surface deposits, and when it is considered that at least 95 pct of the area is covered by over- burden, and that there remains thousands of square miles of favorable territory still to be explored, it can be seen that the possibilities for developing additional ore are tremendous.

Jan 4, 1954

By E. J. Eisenach, Edward Matsen

AT the present time the Climax Molybdenum Co. is the largest molybdenum producer in the world and the operator of the largest underground mine in North America. It has grown steadily and rapidly since its beginning in 1917. Only 250,000 lb of MoS2 were produced during the first year from 1917 to 1918 when the company was formed. Operations were suspended shortly thereafter because of the lack of a market and knowledge of the uses of molybdenum. During World War I it was used as a substitute for some rare metals and for minor chemical purposes. After 5 years of intensive research and sales promotion, Climax metallurgists succeeded in finding proper applications for the newly discovered metal and the mine was reopened in 1924. Demand for molybdenum increased gradually and in 1930, 3.5 million lb of MoS2 were produced. In the meantime, research work for additional uses of molybdenum continued until it had established itself as one of the most important alloying elements in producing high quality steels. After the start of World War 11, from January 1942 to October 1953, 43 million tons of molybdenum ore were mined and 484 million lb of MoS2 were produced. Climax mine is located in Colorado, 100 miles southwest of Denver and 12 miles northeast of Leadville on the Continental Divide of the Rocky Mountains. The principal mine workings range from 11,170 to 12,000 ft in elevation. Topographically, it lies in the base of a large cirque that is surrounded by Mt. Bartlett to the north, Clinton Peak and McNamee Peak to the east and Ceresco Ridge to the south. This cirque opens to the west and to the Ten Mile Valley.

Jan 3, 1954

By Robert E. Thurmond, E. D. Spaulding, Walter E. Heinrichs

DISCOVERY of a commercial ore deposit has resulted from a program emphasizing geophysical techniques and concentrating upon exploration of alluvial-covered areas. United Geophysical Co. selected these areas as offering the best possibility of success, for here the surface evidence of ore deposits has been hidden from the eyes of prospector and geologist alike. Pima mining district, Pima County, Arizona, was selected for initial exploration. The project was successful in that a commercial ore deposit was discovered and proved through drilling and extensive underground development.

Jan 2, 1954

By Herbert Cremer

The United States,-the largest nickel consumer in the world, produces virtually no nickel from domestic ores. Dependence upon outside nickel - sources and increasing strategic, importance of nickel focused the attention of the United States on deposits within its boundries. The most likely domestic sources of nickel are low-grade oxide and silicate deposits, such as the Cle Clum deposit, Kittitas County, Wash., and the Riddle deposit, Douglas County, Oreg. The Federal Bureau of Mines, Northwest Electrodevelopment Laboratory, Albany, Oreg. has been investigating electric smelting of low-grade oxide and silicate nickel ores. These smelting studies have been on selective reduction to produce low-carbon ferronickel. Selective reduction is based upon the relative reducibility of: nickel, iron, and chromium, in the order named, when the charge contains insufficient carbon or other reductants to reduce the entire quantity of these metals present in the ore.

Jan 1, 1954

By W. H. Mathews

"The Hardie group of cinnabar claims is in the interior of British Columbia; 25 miles northwest of the city of Kamloops. It is one of a number of mercury; properties scattered along a north trending belt 20 miles long and up to 5; miles wide. In all but one of these properties cinnabar is associated with; dolomite veinlets in zones of carbonate alteration in bedded rocks of Triassic; and Cretaceous (?) age; or in intrusives cutting these bedded rocks. No dolomite alteration or cinnabar mineralization is known in the undoubted Tertiary rocks adjacent to the mercury belt.The mercury showings of the Hardie group lie for the most part in a granitic stock cutting Cretaceous (?) volcanics. The rock in this intrusive shows marked variations in texture and has been described in earlier reports as granite and granodiorice, granite porphyry, and trachyte or dacite porphyry. At Hardie mountain the cinnabar mineralization, unlike that of the other properties, is associated with a fine-grained, almost chalcedoni c, quartz; carbonates, though present, are of minor importance. Some of the most interesting showings are found in an adit in the southeastern part of the property where cinnabar mineralization shows a very distinct structural but not a genetic relationship to a brown porphyry dyke 2 to 8 feet wide cutting a phase of the stock that may best be described as aplitic"

Jan 1, 1954

By R. M. Creamer

Attempts have been made to electroplate titanium and zirconium from aqueous, nonaqueous, and fused-salt electrolytes. Metals were produced only in fused-salt electrolytes, the major product being sponge metal. All other electrolytes gave only partial reduction of the metal ions. Fused alkali borate electrolytes containing titanium salts gave titanium boride powders and coatings of poor adherence. Some of the problems encountered in the deposition of these metals and some of the aspects of titanium and zirconium chemistry involved are discussed. INTRODUCTION Titanium and zirconium are both relatively light, noncorrosive metals with both military and civilian uses. This has led to intensive investigations into the metallurgy of these metals. Both metals are high in the Electrochemical Displacement Series and are difficult to prepare in a pure state. At present they are prepared by reducing their chlorides, using magnesium. Electrolytic reductions have resulted in the preparation of fine powders or sponge of variable quality. It is believed that a good process of electroplating these metals on a baser metal would result in a very desirable product. The objective of the research summarized in this report was to investigate methods of electrodepositing these metals, with the idea of producing uniform, coherent plates. Most of the work was concentrated on titanium, the more abundant of the two metals. A system developed for titanium should be applicable to zirconium owing to their chemical similarity. Information gained from these experiments may also be applicable to the electro-winning of the metal.

Jan 1, 1954

By D. D. Blue

To insure domestic production of aluminium for, essential civilian and defense uses, the Government, under authority of the Defense Production Act of 1950, programed and promoted an aluminum-expansion program that will more than double the primary production capacity that existed in 1949. In view of this vastly increased production, the raw materials, with respect to both quantity and sources, are reviewed. The raw-material consumption pattern, the requirements during an expansion period when excess quantities of materials for starting up new facilities are consumed, and the probable requirements for production of 1.7 million tons per year of primary aluminum are discussed. The raw materials that presented the most difficult supply problems were bauxite, electrical power, and fluoride salts, and the supply pattern for these materials probably will undergo changes. A major part of the electrical energy for the increased capacity was to come from thermal generation, Jamaica-was to become a major source of bauxite, and synthetic fluoride salts were replacing natural cryolite in increasing quantities. Other raw-material requirements discussed are: Soda ash; lime, and limestone; starch; filter cloth; fuel; alumina; the carbonaceous materials, green and calcined petroleum coke, high-and low-temperature pitch and coke or anthracite; cryolite; aluminum fluoride; the materials going into production of synthetic fluorides, acid-grade fluorspar, and sulfuric acid; and labor. INTRODUCTION The raw materials for the aluminum industry that have received the most publicity are bauxite, the ore that supplies elemental aluminum, and electrical energy, the means by which aluminum oxide is reduced to metal. A number of other important materials are, however, required in large quantities in the production of primary aluminum metal.

Jan 1, 1954

By J. W. Spretnak, R. Speiser

IT has been suggested that boron in steel may form a film entirely around the austenite grain and that this film is responsible for the boron hardenability effect. In this connection, it is of interest to examine some of the ramifications of the concentration range of boron usually employed in hardenable steels, namely 0.0005 to 0.003 pct in a grain size range of ASTM grain size No. 1 through No. 10. The ratio of the iron to boron atoms and the number of unit cells of y iron per boron atom are listed in Table I. Even at the highest concentration considered, there are 1600 unit cells of y iron per boron atom, assuming a uniform distribution of boron. To investigate the possibility of the boron film formation, the number of boron atoms required to cover the grain surface completely must be calculated. With some transition elements, boron crystallizes in sheets composed of equilateral hexagons very much like graphite.' The selected value for the length of a side is 1.80Å. A simple calculation shows that two boron atoms cover an area of 8.4x l0 -16 sq cm. Table II lists the number of atoms of boron required for the formation of the monatomic film and Table III lists the number of boron atoms per grain. The hypothetical cases of 100 pct and 10 pct adsorption are calculated (all boron atoms in a grain and 10 pct of all boron atoms in a grain are located at the grain surface respectively). In Table 111, all combinations of grain size and composition below and to the left of the solid line (100 pct adsorption) and the dashed line (10 pct adsorption) are excluded as to the possibility of covering the grain surface with a continuous boron film. Thus, even for 100 pct adsorption, the smaller grains can form the film only at the higher concentrations. For the best case, grain size No. 1 and 0.0030 pct B, the required degree of adsorption is 3.9 pct. The above calculations deal only with the number of boron atoms required to form a monatomic film and do not take into account the mechanism of concentration of boron at the grain surface and the possible limitations to the extent of this concentration at a constant temperature, as for example in the austenitizing process. The question next arises as to how this surface concentration can occur during an isothermal treatment. Such surface enrichment of boron must occur through the phenomenon of surface adsorption, i.e., the concentration of solute atoms in solid solution in the vicinity of the surface without precipitation. A solute atom will tend to concentrate at the grain boundary if it reduces the interfacial tension. The possibility of adsorption effects involving both boron and carbon in iron has been discussed.' In general, the tendency for a sol-

Jan 1, 1954

By B. R. Klahold

Each year hundreds of mineral specimens and numerous inquiries regarding tests and analyses of minerals and related inorganic substances are received by the Bureau of Mines. In response to this demand, in years past Information Circulars were published containing a list of laboratories. This paper is a revised version of Information Circular 7523, The listing has been changed from a regional basis to one of States arranged alphabetically and grouped by cities, again alphabetically, with Alaska and Canada listed at the end. All the services given at these laboratories are listed on one page for convenience and brevity. This list is compiled as a public service, and none of the laboratories listed herein are recommended over any other nor can the Bureau of Mines vouch for their results.

Jan 1, 1954

By Irving Hartmann

The record of safety in the use of permissible explosives in United States coal mines has been excellent, due in great measure to the persistence with which research has been carried on in the Bureau of Mines, to the development of permissible explosives, and to the cooperation of mine operators and workers in using permissibles in a recommended manner and in the effective though gradual replacement of black powder and other nonpermissibles. The demand for increased rate of coal production, changes in mining conditions and minim methods, and introduction of new mining machinery have resulted in modified or new blasting practices. To keep abreast of these developments the Bureau of Mines conducts investigations under actual mining conditions at the Experimental coal mine near Pittsburgh, Pa. Several years ago an extensive study was complete to determine conditions under which the allowable charge limit for permissible explosives per shot hole might be raised from 1.5 to 3 pounds without undue risk of gas or coal-dust ignitions. As a result of the study, this increase in the charge limit was authorized under certain specified conditions in 1948,5/ greatly facilitating production schedules.

Jan 1, 1954

By M. H. MacLeod

"IntroductionTHE ORE PASS raise system at the H.B. mine as contracted by the Patrick Harrison Company consisted of two raises 6 ft. by 10 ft. in section •at 60 degrees to the horizontal. No. 88-88 raise, the longer of the two, was a straight raise 690 feet long, with access only from the bottom. In addition, this raise had two branch knuckle-backs only one of which was driven by. the Patrick Harrison Company. The other, known as 88-89 raise, was 540 feet long with knuckle-backs at 280 feet and 410 feet. Its access, also, was from the bottom (see Figure 1)."

Jan 1, 1954

By W. A. Cole

This report covers the preliminary phase of an investigation of some clays and shales and other materials in North and South Dakota to determine the feasibility of lightweight -aggregate manufacture in the two States. The background of the light - weight -aggregate industry, on a national basis, and results of preliminary laboratory testing of samples of North and South Dakota clays and shales from various localities are presented herein. The countrywide search for lightweight aggregates was necessitated toward the end of the 19th century by the change in building design from thick, heavy, load- bearing walls to a framework of structural steel .beams and columns with thin walls, followed shortly by the use of reinforced concrete and structural concrete as materials for the load-supporting frame. Ordinary concrete, with sand and gravel aggregate, weighs about 150 pounds to the cubic foot. A lighter concrete was needed to relieve the dead load and make it possible to construct higher buildings or add stories to existing buildings.

Jan 1, 1954

By R. K. McGeary, B. Lustman

Orientation relationships and rates of annealing of 97 pct cold rolled zirconium have been studied by X-ray techniques, metallography, and by hardness measurements. The process of annealing occurring by the formation of domains, and their subsequent growth without recrystallization, is demonstrated. NUMEROUS investigators1-' have revealed sub-grain formation after annealing cold worked metal single crystals and have generally described the results in terms of a dislocation mechanism of polygonization.5,6 in heavily cold rolled polycrystal-line aluminum the first stages of heating cause an apparently spontaneous subdivision of regions of the deformed matrix into a great number of slightly disoriented domains followed or accompanied by rapid growth of certain domains to form a recrystallization texture.7,8 In the present investigation the isothermal rate of annealing of cold worked polycrystalline zirconium has been studied by X-ray techniques, metallography, and by hardness measurement. It will be shown that, rather than by the usual nucleation and growth mechanism,"12 the process of annealing can best be explained by the formation of domains early in the annealing treatment and the subsequent growth of these domains without recrystallization. Experimental Procedure All the experimental work was performed on an arc-melted ingot of high purity zirconium crystal bar made by Westinghouse in a production scale deBoer unit. The weight percentage of impurities in the zirconium were as follows: C, 0.04; Fe, 0.05; Hf, 0.014; W, 0.01; Ti, Ni, and Al, 0.003; Si and N, 0.002; Cr and Cu, 0.001. Metallographically the zirconium showed only a single phase. The 4 in. diarn ingot was forged at 760°C to a 1 1/2x3 in. plate and was then rolled at 760°C to 0.150 in. thickness and annealed at this temperature for 20 min to produce an equiaxed grain structure of about 0.1 mm average grain diameter. The hot rolled plate was roller-leveled, surface ground to 0.135 in., cold rolled 83 pct reduction in thickness on a two-high mill, and then to a total reduction of 97 pct on a Sendzimir mill. The 0.004 in. strip material so produced received no subsequent mechanical treatment. Specimens % in. square were sheared from the rolled strip and isothermally annealed at 104 mm Hg in an all glass vacuum system equipped with a Vycor furnace tube. The temperature data presented are the average temperatures during the runs and did not vary more than about k3"C. X-ray Diffraction Methods: When zirconium is drastically cold rolled, a high degree of preferred orientation results in which prism poles, {1010}, are perpendicular to the rolling direction. After fully annealing this material an entirely new texture develops which corresponds to a 20" or 40" rotation of the deformation texture about hexagonal axes of

Jan 1, 1954

By H. L. Gilbert, H. A. Johansen, R. G. Nelson

High purity electrolytic chromium plate has been hydrogen-reduced and arc-melted under inert atmosphere to give sound ingots. These ingots may be hot forged to break the as-cast structure and then worked at 500°C to finished form. An intermediate and final high temperature anneal gives best ductility and grain refinement. HE increasing interest in refractory metals for I use in high temperature gas turbines, jets, and rockets has led to great efforts in exploiting the fifth and sixth groups of transition elements. Much of the interest has centered upon production of metals that can be worked and fabricated by normal means to produce various engine parts or components having the high temperature characteristics of oxidation resistance and high creep strength required for such uses. If these pure elements do not exhibit all of the desired characteristics, it may be possible to obtain a high purity alloy that will. Since, in all cases, development of these transition elements has depended to a large extent upon removal of oxygen and nitrogen as a means for producing ductile metal, the hypothesis has been accepted that oxygen is the normal embrittling material in a high grade electrolytic chromium metal. Various methods have been employed in an effort to remove this oxygen by direct or indirect attack.' Many workers have endeavored to produce pure chromium through reduction of the oxide by carbon or active metals, while others have recommended fusion electrolysis of chromium salts or reduction of these salts by active metals, such as sodium or calcium. Hydrogen reduction of the oxide or chloride and thermal dissociation of the iodide have been reported to give high purity metal. Experimental Work The U. S. Bureau of Mines, Northwest Electro-development Laboratory, has systematically re-examined the more promising methods and developed two which produce metal having ductility at temperatures lower than heretofore described. It has been found' that oxide-free chromium chlorides in a NaCl-KCl carrier salt may be mag- nesium-reduced and the byproduct salts distilled off in vacuo to give a high purity chromium sponge. Fusion analysis conducted under the supervision of W. W. Horton of Knolls Atomic Power Laboratory showed the oxygen and nitrogen both to be below 10 parts per million on a selected sample. A small amount of carbon is carried over in the final metal from the chlorination and reduction steps which are carried out in graphite crucibles. This trace of carbon is not detrimental to hot ductility. A more practical method for producing ductile metal is through hydrogen reduction of high purity electrolytic chromium. Normal electrolytic chromium will, if "developed" for a few minutes at 1100°C in high vacuum, be found by the method of Adcock:; to contain about 1 pct chromium sesquioxide (Cr2O3). This small amount of oxygen may be effectively reduced by hydrogen.2, 4 The method employed was to crush electrolytic chromium plate in a gyratory crusher to pass 60-mesh; finer crushing appears to offer no advantage. A nitric acid leach removed the iron picked up during crushing. The leached powder was rinsed until neutral with distilled water and vacuum-dried.

Jan 1, 1954