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By W. P. Sykes

Seven years ago, Dr. S. L. Hoytl presented a masterful discussion of the hard metal carbides and cemented tungsten carbide. His lecture summarized most of the data then available in the field; many of the details relating to the production, properties and structure of cemented tungsten carbide had never been previously published, for, in fact, this information was only then being acquired. During the intervening years, the cemented carbides have assumed a place of real importance in the commercial field, with an ever widening variety of applications due to constant improvement in the control of production technique and the unremitting search for new compositions that might better the performance of the alloys in one or another type of service. The most recent summary of production methods, properties and guides for the successful application of the cemented carbides appears in the 1936 edition of the Metals Handbook. Of necessity, much detailed information relating to structures and physical properties is not included in such a summary, and it is with such details that the present discussion is concerned. Steps in Preparation While the past 25 years have contributed a valuable store of working knowledge in the field of powder metallurgy, many of the process controls are derived entirely from experience and are not as yet finally explained by a specific physical or chemical phenomenon. For most of the cemented carbides such difficulties are aggravated by our lack of knowledge not only of the complex alloy systems involved, but also by the possible changes in structure and even in composition which may accompany variations in temperature, heating time, and furnace atmospheres. The principal steps in the preparation of these cemented carbide alloys are fairly well known, but to supply a foundation for discussion these steps are briefly outlined as follows : 1. Formation of the metal carbide in the form of powder by heating a mixture of carbon and the metal powder or oxide for several

Jan 1, 1938

By T. A. Wilson, S. L. Hoyt

THE plastic deformation of slender single crystals of zinc has been described in some detail in the paper by Mark, Polanyi and Schmid,1 which has become a classic, and also by one of the present authors in a somewhat shorter account.' The study of single-crystal zinc is termed classical because zinc single crystals offer, perhaps, the best material yet available for the study of atomic behavior during deformation and the effect known as "strengthening" in metals. A considerable amount of additional work has also been done on single-crystal zinc, but as it is not closely related to the present paper it will not be considered. Throughout all the former work, the mechanism of plastic deformation first described by Mark, Polanyi and Schmid has been assumed to hold. This may be said to offer the strongest confirmation of its correctness. Even so, the picture of the process has never been as completely portrayed as is desirable. The first object of the present paper is to describe work that has been done in this field, and which is even yet being carried on, in the hope that a more complete picture may be obtained. Mathewson and Phillips' have recently described a new mechanism of the deformation of zinc based on their study of large rectangular crystals. One of their conclusions was that deformation produced twinning with a rotation of some of the basal planes into positions 94° removed from their original position; a position almost the same as that of the prismatic planes before twinning. A second conclusion was that fracture occurred along these basal planes in their new position, and, therefore that fractures previously regarded as prismatic were in reality basal. Such findings are of great significance and they raise a question as to the generality of such behavior. Professor Mathewson's opinion is that even the slender cylindrical single crystals behave in the same manner as his large rectangular crystals when strained by simple tension.

Jan 1, 1928

By Henry Lewelling

An experimental investigation of the relative effectiveness of standard bullets and "shaped charges" in perforating dense, hard formations is reported. A method is described which simulates the conditions under which a shot is normally fired. Results are evaluated on the basis of depth of penetration, extent 01 Fracturing. extent and nature of formation damage, and other physical characteristics. INTRODUCTION A study was made of the relative merits of bullets and "shaped charges'' as applied to well completions in hard, dense formations such as those encountered in the Permian Basin. The planning of the laboratory program stipulated that core samples should be prepared and mounted in such a way that perforation shots of either kind"" could be fired into them, keeping the factors pertinent to good shooting practice similar to what they would be in a well. The shooting was done in a buried tank. with the sample and shooting equipment covered with water. The depth of water was calculated to he sufficient to simulate the inertial effects of well fluids for the duration of an explosion (a few micro-seconds). Flow measurements were attempted on the specimens after perforation. Due to the lack of uniformity of the limestone, shale breaks. etc., these measurements proved to be of little value to the study. The mounting materials were removed. so that the character of the penetration. fracturing, etc., could be observed. METHOD Laboratory samples were selected from the hard. dolomitic sand cores from Block 31 Field. Core pieces having a 3 3/4 in. diameter and a useful length of 10 to 12 in. were used. Selection was aimed at those pieces having a minimum of shale streaks and other irregularities. The ends were cut off square Manuscript received in the Petroleum Branch office June 28, 1951. Paper presented at the Petroleum Branch Fall Meeting in Oklahoma City, Okla., Oct. 3-5, 1951. with the diamond saw. Prior to lbeing mounted. the cores were soaked in water to prevent them from absorbing water out of the wet concrete, thus weakening it. A set of steel capsules was fabricated for holding the core Samples. Seven-in. casing was cut in two-ft lengths. of which one end was closed by "orange-peeling" and welding, and the other was threaded to accept a standard bull plug. The bull plugs were fitted with copper tube connections .so that pressure could be applied when the capsules were made up. The cores were mounted in the capsules by means of wire centralizers whose function was to hold the Core in proper position while concrete was poured and set. A special aggregate was prepared wing a graded sand and gravel mixture

Jan 1, 1952

By K. F. Veith, R. L. Marovelli, T. S. Chen

An analytical study is made of thermal stress distribution in a thin circular disc subjected to a peripheral thermal shock at various rates of heat transfer. The problem is of importance in predicting the thermal shock response of a rock body of finite size. The theoretical analysis is based on radial heat flow by conduction in the disc and heat exchange by convection between the disc and the surroundings. The case of constant properties and plane stress is treated. Solutions of the stress distribution are presented for both cooling and heating shocks and an average stress theory is formulated. Preliminary experimental verification was obtained from the results of shock tests on thin rock discs insulated on both flat end faces so that heat exchange took place through the exposed peripheral surface. Physical properties vital to the analysis are Young's modulus, tensile strength, coefficient of linear thermal expansion, thermal diffusivity and thermal conductivity. Plots of these properties are presented. Historically, thermal energy has been used for primary rock removal throughout the ages. Although it is not widely known, the fire-setting method of thermal rock fragmentation was still in use 100 years ago in systematic underground mining operations in Scandinavia.' There, the availability of cheap labor and abundant wood fuel made the method competitive with the early blasting powders. By 1880, as high explosives replaced powder, use of the method declined and it was finally abandoned about 1885. Only 40 years ago, some experimental fire-setting methods were used for rock removal underground at Pribram and Zinnwald in Central Europe.2 Compressed air-oil burners replaced the earlier wood fuels. About 15 years ago, gaseous oxygen-oil burners were introduced in the United States and gained acceptance for difficult blasthole drilling and some quarry opera- tions. At present, there is renewed interest in the compressed air-oil burner designs. The literature included information on thermal secondary processes for rock weakening or particle liberation3,4,5,6,7,8 on thermal spallation of rock 9,10,11,12,13 and on the thermal fracture of materials other than rock. The 1955 Symposium on Thermal Fracture14 and the later work of Hassel-man, cover recent developments in thermal shock investigations on brittle ceramics. Although the number of published analytical and experimental investigations conducted on ceramic and refractory materials is large, the literature reveals that there is a lack of information on both the theoretical and actual response of rock to thermal shock. Many of the thermal shock studies on ceramic and refractory bodies are based on the case of heat transfer at the solid's surface by convection in either liquid or air. A similar heat transfer situation was adopted for a theoretical analysis of the thermal stresses in a thin circular disc subjected to a peripheral thermal shock. Experimental thermal shock tests were then conducted on rock specimens to check the analytical results. Specially insulated quartzite, basalt and taconite discs were shocked in either liquid or still air bath at various rates of heat transfer. The work was done in order to resolve the question as to whether theoretically determined tensile stresses are actually realized in a finite rock body undergoing thermal shock. Specifically, if theory predicts that the tensile strength of a rock should be exceeded in a particular type of controlled thermal shock, will fracture occur? This information is needed by Bureau researchers working on thermal and electrical rock fragmentation methods. The object of this paper is to present the main features of the theory and procedure being used in the authors' approach to quantitative prediction of rock response to a thermal shock. THEORETICAL ANALYSIS In the analysis to follow, simple geometry of a thin circular disc is considered. The disc is assumed to be isotropic, homogeneous and perfectly elastic, and to have constant thermal and mechanical properties. The effect of radiation is neglected so that heat is transferred by conduction inside the disc and by convection with its surrounding. In addition, the end

Jan 1, 1967

By C. S. Finney, John Mitchell

The decline of the beehive coking industry was inevitable, but it had filled the needs and economy of its day. A beehive plant required neither large capital investment to construct nor an elaborate and expensive organization to run. The ovens were built near mines from which large quantities of easily-won coking coal of excellent quality could be taken, and handling and preparation costs were thus at a minimum. The beehive process undoubtedly produced fine metallurgical coke, and low yields were considered to be the price that had to be paid for a superior product. Few could have foreseen that the time would come when lack of satisfactory coking coal would force most of the beehive plants in the Connellsville district, for example, to stay idle; and if there were those like Belden who cried out against the enormous waste which was leading to exhaustion of the country's best coking coals, there were many more to whom conservation was almost the negation of what has since become popularly known as the spirit of free enterprise. As for the recovery of such by-products as tar, light oil, and ammonia compounds, throughout much of the beehive era there was little economic incentive to move away from a tried and trusted carbonization method simply to produce materials for which no great market existed anyway. With the twentieth century came changes that were to bring an end to the predominance of beehive coking. Large new steel-producing corporations were formed whose operations were integrated to include not only the making and marketing of iron or steel but also the mining of coal and ore from their own properties, the quarrying of their own limestone and dolomite, and the production of coke at or near their blast furnaces. As the steel industry expanded so did the geographic center of production move westward. By 1893 it had moved from east-central to western Pennsylvania, and by 1923 was located to the north and center of Ohio. This western movement led, of course, to the utilization of the poorer quality coking coals of Illinois, Indiana and Ohio. These coals could not be carbonized to produce an acceptable metallurgical coke in the beehive oven, but could be so treated in the by-product oven. By World War I the technological and economic limitations of the beehive oven as a coke producer were being widely recognized. After the war the number of beehive ovens in existence dropped steadily to a low of 10,816 in 1938, in which year the industry produced only some 800,000 tons of coke out of a total US production of 32.5 million tons. The demands of the second World War led to the rehabilitation of many ovens which had not been used for years, and in 1941, for the first time since 1929, beehive ovens produced more than 10 pet of the country's total coke output. Production fell off again after 1945, but the war in Korea made it necessary once more to utilize all available carbonizing capacity so that by 1951 there were 20,458 ovens with an annual coke capacity of 13.9 million tons in existence. Since that time the iron and steel industry has expanded and modernized its by-product coking facilities, and by the end of 1958 only 64 pet of the 8682 beehive ovens still left were capable of being operated. Because beehive ovens are cheap and easy to build and can be closed down and started up with no great damage to brickwork or refractory, it is likely that they will always have a place, albeit a minor one, in the coking industry. The future role of the beehive oven would seem to be precisely that predicted forty years ago by R. S. McBride of the US Geological Survey. Writing with considerable prescience, McBride declared: "A by-product coke-oven plant requires an elaborate organization and a large investment per unit of coke produced per day. Operators of such plants cannot afford to close them down and start them up with every minor change in market conditions. It is not altogether a question whether beehive coke or by-product coke can be produced at a lower price at any particular time. Often by-product coke will be produced and sold at less than cost simply in order to maintain an organization and give some measure of financial return upon the large investment, which would otherwise

Jan 1, 1961

By E. S. Bumps, M. Baeyert, W. F. Craig

SOME time ago during a study of impact properties of tempered martensite,1 it was postulated that the consistently good ductility of tempered martensite might be caused by its relatively small and peculiarly shaped ferrite grains. The fer-rite grains of tempered martensite have approximately the same size and shape as the martensite "needles." Thus they form an interlocking mass of needle-shaped grains quite different from equiaxed or lamellar ferrite grain structures. When the common mechanical test methods are applied to steel, variations are often observed in the ductility of specimens that have closely similar hardness and tensile strength values. The ductility so measured appears to be structure dependent. When steel from the same heat has been heat treated to produce different structures with the same hardness, the elongation and reduction of area values from the tensile test and the transition temperature determined by the notched-bar impact test vary according to whether pearlite, tempered martensite, or other structural constituents were produced by the heat treatment. It has been widely recognized that tempered martensite gives a consistently good performance, when tempered to the same hardness as many other structures with which it has been compared. In recent years the isothermal transformation of austenite to specific structural products and the quantitative evaluation of the character of these products with respect to their nature and response to deformation has received considerable attention. The objective of the present study was to pursue somewhat further the dependence of ductility upon structure; specifically, it was desired to ascertain whether ferrite grain structure, including both shape and size of the grains, can account for the consistently good performance of tempered martensite in the notched-bar impact test. It was thought that a simple experiment would indicate whether the ferrite grain structure plays any part in the good ductility exhibited by tempered martensite in contrast to other steel structures with different types of ferrite grains. By determining the impact transition temperature, it was proposed to compare spheroidites having similar carbide particle size and spacing but obtained in such a manner that their ferrite grain structures would be very different. Spheroidite obtained by tempering martensite, with its small, needle-shaped grains, was to be compared with spheroidite from pearlite. If the latter is produced by sub-critical annealing, the ferrite grains correspond to the pearlite colonies. Thus, if the pearlite was not too coarse, the ferrite grains of spheroidite from pearlite are equiaxed in contrast to the needle-shaped grains of spheroidite from martensite. It was thought that the ferrite grain structure of spheroidite from martensite might depend to some extent upon the grain size of the prior austenite. The austenite grain boundaries limit the maximum attainable size of the martensite needles and thus of the ferrite grains in the derived spheroidite. In order to evaluate any possible influence of prior austehite grain size, spheroidites were to be prepared from martensites that had been formed from fine-grain austenite and also from coarsened austenite. As the carbide particle size and distribution were to be essentially alike in the various spheroidites, the difference would be in the ferrite grain size and shape. Thus any marked difference in transition temperature could be attributable to the character of the ferrite grain structure. There are certain considerations in assuming that these spheroidites would be equivalent in all respects except ferrite grain structure, and an attempt was made to take them into account. One of the considerations was the choice of the carbon content of the steel. An approximately eutectoid steel was selected for two reasons. First, the pearlitic structure would contain no proeutectoid ferrite which might complicate the picture by producing a non-uniform ferrite grain structure in the resulting spheroidite. Then, too, the high-carbon content would inhibit ferrite grain growth during the sub-critical treatment. Another factor to be taken into account was the choice of an alloying element to assure a martensitic structure throughout on quenching the impact specimens. Nickel was chosen, because it is a common alloying element and resides in the ferrite both upon its formation from austenite and throughout tempering. The formation of alloy carbides, or even a large solubility of the alloying element in cementite, would have complicated the interpretation by changing the composition of the ferrite .during spheroid-ization. The possibility of temper brittleness was minimized insofar as possible by using a tempering temperature as high as consistent with the 1 pct of nickel in the steel, namely, 1150°F. While it certainly is not claimed that no difference other than ferrite grain structure could exist between the spheroidites, nevertheless, reasonable precaution has been exercised within the limits of steel metallurgy. It is believed that any large difference in transition temperatures would reflect the difference in ferrite grain structure and that relatively good ductility in the spheroidites from mar-

Jan 1, 1951

By Alfred Boyles

The experiments described below are a continuation of work on the graphitization of cast iron conducted as part of the program of fundamental research at Battelle Memorial Institute. In previous work it was found that melting in hydrogen increased the amount of eutectic carbide appearing in certain alloys and in others produced marked changes in the size of the graphite flakes. These effects seemed to be closely related to the amount of sulphur and manganese present in the material studied. Iron-carbon-silicon alloys did not respond to hydrogen in the same manner as cast iron and there was no evidence to show that hydrogen was able to stabilize the carbide in such alloys unless additions of sulphur were made. The two alloys examined contained about 2 per cent of silicon. The present paper is concerned with alloys of lower silicon content and describes the structural changes produced by melting in various atmospheres at pressurcs ranging from a partial vacuum up to 300 lb. per sq. inch. Experimental Method The experimental technique was similar to that previously employed, so that direct comparison might be made with earlier work. Alloys were

Jan 1, 1939

By Alfred Boyles

The experiments described below are a continuation of work on the graphitization of cast iron conducted as part of the program of fundamental research at Battelle Memorial Institute. In previous work it was found that melting in hydrogen increased the amount of eutectic carbide appearing in certain alloys and in others produced marked changes in the size of the graphite flakes. These effects seemed to be closely related to the amount of sulphur and manganese present in the material studied. Iron-carbon-silicon alloys did not respond to hydrogen in the same manner as cast iron and there was no evidence to show that hydrogen was able to stabilize the carbide in such alloys unless additions of sulphur were made. The two alloys examined contained about 2 per cent of silicon. The present paper is concerned with alloys of lower silicon content and describes the structural changes produced by melting in various atmospheres at pressurcs ranging from a partial vacuum up to 300 lb. per sq. inch. Experimental Method The experimental technique was similar to that previously employed, so that direct comparison might be made with earlier work. Alloys were

Jan 1, 1939

By W. F. Holbrook, C. E. Wood, E. P. Barrett

The high-frequency laboratory induction furnace with a rotating liquid crucible enables research workers to conduct certain investigations heretofore very difficult or impossible to realize because vessels are not obtainable that are capable of resisting the physical conditions or the chemical actions to which they are subjected. Applications for patents covering commercial uses of centrifugal liquid crucibles were filed in the United States in 1919,' in France in 1925, in the United States and Germany in 1926,2 and in France in 1927.3 In 1928, Schuette and Maier,4 of the Bureau of Mines, reported the construction of a whirling table beneath a high-frequency induction furnace. Shape and Size of Centrifugal Liquid Crucibles When a vessel containing a liquid is rotated, the inner surface of the liquid takes the shape of a paraboloid under the simultaneous action of centrifugal force and gravity. The internal dimensions of the paraboloid rotating liquid crucible are governed by the diameter of the container and its speed of rotation. Melted Wood's metal was poured into cylinders 2 1/2 in. in diameter, which were rotated at 180, 300, and 468 r.p.m. When the metal was solid, a slurry of plaster of Paris was added, and rotation continued until the plaster had set. Fig. 1, a photograph of sections of the cylinders, shows the effect of speed of rotation of the containers upon the shape of the inner surface of the rotating liquid crucibles. Types of Furnaces Three types of high-frequency induction laboratory furnaces using liquid-metal crucibles were designed and constructed by the Blast

Jan 1, 1939

By W. F. Holbrook, C. E. Wood, E. P. Barrett

The high-frequency laboratory induction furnace with a rotating liquid crucible enables research workers to conduct certain investigations heretofore very difficult or impossible to realize because vessels are not obtainable that are capable of resisting the physical conditions or the chemical actions to which they are subjected. Applications for patents covering commercial uses of centrifugal liquid crucibles were filed in the United States in 1919,' in France in 1925, in the United States and Germany in 1926,2 and in France in 1927.3 In 1928, Schuette and Maier,4 of the Bureau of Mines, reported the construction of a whirling table beneath a high-frequency induction furnace. Shape and Size of Centrifugal Liquid Crucibles When a vessel containing a liquid is rotated, the inner surface of the liquid takes the shape of a paraboloid under the simultaneous action of centrifugal force and gravity. The internal dimensions of the paraboloid rotating liquid crucible are governed by the diameter of the container and its speed of rotation. Melted Wood's metal was poured into cylinders 2 1/2 in. in diameter, which were rotated at 180, 300, and 468 r.p.m. When the metal was solid, a slurry of plaster of Paris was added, and rotation continued until the plaster had set. Fig. 1, a photograph of sections of the cylinders, shows the effect of speed of rotation of the containers upon the shape of the inner surface of the rotating liquid crucibles. Types of Furnaces Three types of high-frequency induction laboratory furnaces using liquid-metal crucibles were designed and constructed by the Blast

Jan 1, 1939

By John Eash

DURING recent years nickel has had an increasingly important role as an alloying element in the copper-tin bronzes. Nickel additions not only produce better casting alloys but also make alloys whose properties can be varied by precipitation hardening; thus leading to increased commercial application of copper-nickel-tin alloys. Recent investigations have indicated a decrease in the solubility of tin in the alpha phase as the annealing temperature is lowered and as the nickel content is increased within certain limits. A further change caused by the nickel additions is produced in the excess phase of the copper-tin bronzes. The alpha plus delta eutectoid is replaced by a clear precipitated constituent in the alloys containing up to 15 per cent tin and not less than 1 per cent nickel. This paper has a dual purpose. The first is to present a new determination of the alpha-phase boundary in alloys containing from 0 to 20 per cent nickel, together with the liquidus and solidus temperatures above that field. The second purpose is to give the equilibrium conditions existing in alloys exceeding the alpha phase containing up to 31 per cent tin and 5 per cent nickel, so that the disappearance of the alpha plus delta eutectoid constituent may be explained. After considering the earlier investigations of the related alloy systems and the experimental procedure used in this investigation, the alloys will be discussed in groups as separate quasibinary systems containing constant amounts of nickel. The systems considered contain 0, 1, 2, 3, 5, 10 and 20 per cent nickel. The straight copper-tin system was reinvestigated in order to establish a foundation on which to build the remaining material. The 1 per cent nickel alloys studied give the relations existing in the region of the eutectoid transformation between the copper-tin system and the 2 per cent nickel copper-tin system which has been investigated in detail. The thorough examination of the latter system was made since 2 per cent of nickel is representative of the commercial additions to the cast bronzes and also because it is sufficient to produce

Jan 1, 1932

MODERN mining is based on drilling--everything else stems from that. U. S. and Canadian mining companies and suppliers of mining equipment are constantly seeking new techniques and tools for increased drilling efficiency. Ultimate goal is increased bit-against-rock time. Just how important their efforts are can be seen through a legitimate extension of available statistics. In Canada some 70 million ft of drilling per year is required. While the number of feet actually drilled in the U. S. is unknown, it is possible to compare U. S. and Canadian mineral production, excluding oil and coal. In the U. S. mineral value was $4200 million and across the border $836 million. Taking into account the number of drilled feet required to produce Canada's total, the U. S. total would be 365 million ft in 1953. A saving of 14 per ft would reduce over- all metal and nonmetal mining costs some $3.65 million per year. This does not take into account other indirect savings. Methods have changed and there have been structural and metallurgical advances in blasthole practice in the last ten years. The Editors of MINING ENGINEERING in the articles on the following pages present the most significant innovations coupled with results in the field. Environment plays an important role in selection of materials and equipment -but while unanimity does not exist throughout the industry in reference to drilling problems, a definite trend is evident. For the story of that trend read the articles on the following pages.

Jan 9, 1954

By J. S. Diller

In 1827, chromite was discovered near Baltimore by Isaac Tyson, Jr., who initiated the mining of chrome ore an:! later (1845) .the manufacture of chromium compounds in this country. From 1828 to about 1860 the United States, supplanting Russia, supplied chromite for most of the world. Chrome deposits were found also in California, and the Tyson Company shipped ore to Philadelphia by way of Cape Horn. In 1848, J. Lawrence Smith, an American in the employ of the Porte, discovered large bodies of chromite in Asia Minor. They were developed in 1865 and became the chief source of the world's supply for a number of years. The discovery of the large high-grade bodies in New Caledonia, and later in Rhodesia, with other foreign sources, gives at present an abundant supply for all demands. For a number of years before the great war, the United States produced only a few hundred tons of chromite annually, for local use, but during the war the demand for domestic ore resulted in a production of more than 82,000 long tons of crude ore in 1918, and it was demonstrated that the United States has reserve deposits equal to a war demand of several years' duration. Now that the war is over, the country is conserving its domestic supplies by employing higher-grade but cheaper ore from foreign countries. ChromiUm-bearing Minerals Oxides: Chromite-—chromic iron ore................ FeO.Cr2O3 Picotite—chromic iron ore................. (MgFe)O.(Al,Cr) Chromates: Crocoite—lead chromate................... PbCrO4 Phoenicochroite—basic lead ohromite........ 3PbO.2CrO3 Vauquelinite—phospho-chromate of lead..... 2(PbCu)CrOd.(PbCu)3P2O8 Sulfates: Redingtonite—hydrous chromium sulfate.... Knoxvillitel—hydrous basic sulfate of chromium.............................. Daubreelite-—iron-chromium sulfide (known in meteorites only)...................... FeS.Cr2S3

Jan 1, 1920

By Stanley J. LeFond, Langtry E. Lynd

Elemental titanium has become famous as a space age metal, because of its high strength/ weight ratio and resistance to corrosion. However, the major use is in the form of titanium dioxide pigment, which because of its whiteness, high refractive index, and resulting light-scattering ability, is unequaled for whitening paints, paper, rubber, plastics, and other materials. A relatively minor use is in welding rod coatings, in the form of the mineral rutile. United States consumption of titanium dioxide in concentrates for these applications in 1982 was as follows: pigments, 630,000 st; titanium metal, 31,000 st; and welding rod coatings, 5,000 st. The only commercially important titanium ore minerals at the present time are ilmenite and its alteration products, and rutile. Titanium was discovered by Gregor in 1790, as a white oxide which he recovered from menaccanite, a variety of ilmenite occurring as a black sand near Falmouth, Cornwall. Barksdale (1966) stated that the fundamental chemical reactions on which the present day titanium industry is based were known before 1800, although it was not until 1918 that these pigments were available commercially on the American market. Pings (1972) outlined the early history of the titanium industry in the United States, referring to the work of Guise (1964) and others: Mining of titanium minerals in the United States began sometime between 1880 and 1900, in Chester County, Pennsylvania. Small quantities of rutile were also produced during that time in North Carolina and Georgia. In 1901 rutile was mined from a deposit near Roseland, VA, and was used in making titanium chemicals and for coloring ceramics. Ilmenite in the deposit was produced as a separate item in 1913, and rutile and ilmenite were obtained from this deposit through 1921. The mining of titanium bearing beach sands began in 1916 near Mineral City and Pablo Beach, FL, for the purpose of making titanium tetrachloride to be used in tracer bullets, flares, and smokescreens. The titanium pigment industry was founded in 1918. By 1928 a large part of the domestic production of rutile, ilmenite, and zircon came from Florida. However production ceased in 1929 in Florida with the mining of newly discovered deposits in Virginia which were mined until 1968. The discovery of new deposits in Florida, and the development of better mining and concentrating methods for low-grade sands, led to a return of activities in this area. The large deposits near Tahawus, NY. were brought into production in 1942 by National Lead Co. (now NL Industries, Inc.), and by 1949 this company was the leading producer of ilmenite in the world. In 1948 the extensive deposits of ilmenite and ilmenite-bearing iron ores were discovered in eastern Quebec. The large Trail Ridge sand deposit in Florida was discovered by E. I. du Pont de Nemours & Co., Inc. geologists in cooperation with the US

Jan 1, 1983

By M. Cohen, D. Caplan

The scaling characteristics of three Fe-Cr alloys have been investigated by determining their weight gain vs. time curves at 1600° to 2000° F. The scales formed thereby have been examined using the techniques of X-ray diffraction and spectrographic and metal-lographic analyses in an attempt to explain the discontinuities in the curves and to elucidate the mechanism of scaling. DESPITE the considerable number of investigations that have been carried out on heat resistant alloys, the characteristics of the scales formed at high temperatures are not fully known. The research reported here was undertaken in an attempt to ascertain the mechanism of scaling of the stainless steels. Scaling experiments were carried out first, the weight increase of the specimens being followed continuously with time. It was observed that, as well as showing the expected decrease in oxidation rate with time, the oxidation curves showed breaks corresponding to intermediate periods of accelerated oxidation, after which protectiveness again increased. This phenomenon was observed with austenitic stainless steels (types 302, 309, and 330) and with Fe-Cr alloys (types 410, 430, and 446), but only the latter are treated in this report. An examination of the scales was made using the techniques of X-ray diffraction and spectrographic and metallographic analyses in an attempt to obtain a correlation between the nature of the scales and the oxidation curves. A search through the literature revealed only a very few previous reports of such periods of accelerated oxidation. Dunn' found breaks in the oxidation-time curves of some Cu-Si alloys but saw no rational explanation of the phenomenon. Heindlhofer and Larsen2 attributed a discontinuity in the weight gain-time curve of iron at 1290°F to the formation of blisters, the subsequent cracking of which exposed an unprotected surface and permitted rapid oxidation until a new protective scale had been reestablished. They advanced no explanation, however, for what they termed the peculiar behavior of a 27 pct Fe-Cr alloy at 2000°F which gained weight very rapidly in between two periods of very slow weight gain. Portevin, Pretet, and Jolivet3 in describing breaks in the weight gain-time curves of Fe-A1 alloys suggested that they might be associated with the occurrence of localized and deeply oxidized areas on the specimens. Bandel4 in a general discussion of oxidation curves of heat resistant alloys considered that the discontinuities were due to a local disruption of the protective layer by the growth of iron-rich oxides. Day and Smith" in their report on the scaling of a large number of iron alloys noted but did not explain occasional relatively rapid changes in oxidation rate at higher temperatures. Chevenard and Wache6 found breaks, often two per specimen, in the oxidation curves of an 18-8 type alloy. They suggested that the cause might be a depletion in chromium of the surface layer of metal due to its selective oxidation, the resultant high concentration of iron and nickel in the scale leading to a poorly protective scale. McCullough, Fontana, and Beck' explained the breaks in the oxidation curves of types 304, 430, and 410 alloys as due to mechanical ruptures. Experimental Work Table I lists the chemical compositions of the materials used. Cylindrical specimens 1/4 in. in diam and 11/2 in. long were machined from cold rolled % in. rod. After a fine finish cut with a sharp tool, the specimens were abraded while still mounted on the lathe with Nos. 2, 1, 0, and 00 metallographic grade emery papers. A 3/64 in. hole was drilled at a distance of 1/8 in. from one end to permit suspension in the furnace. Specimen Nos. 1, 2, and 3 were tested with this surface preparation. All others, after being similarly prepared, were electropolished in a perchloric-acetic electrolyte, electrical contact being made by pressing a tapered platinum hook into the drilled hole. The specimens were then washed in hot water, rinsed with distilled water, rinsed with methanol, dried at 120°F, and weighed. Thereafter,

Jan 1, 1953

By Alexander Field

The hot-rolling properties of a series of high-sulfur steels are described. From a consideration of the sulfur, manganese, and zirconium contents of these steels, it is shown that zirconium reacts with the sulfur content of molten steel in accordance with the equation Zr + 2S = ZrS2. Zirconium disulfide appears in the finished state as gray-colored inclusions, similar to manganese sulfide in plastic behavior and general appearance. Zirconium completes its act of deoxidation before proceeding to combine with sulfur and indirectly increases the effective sulfur-combining power of any manganese which may be present. IN A previous paper,1 the experimental methods used and some of the results obtained in an extensive investigation of steels containing zirconium were described. The present paper considers in greater detail one of the most interesting of these effects, namely, the elimination of "red shortness" and the occurrence in steel of a compound of zirconium and sulfur. A consideration of the actual percentages of zirconium, manganese, and sulfur in numerous steels in the light of behavior during rolling has led to new conclusions of the most practical import regarding the reciprocal relationships of these elements. The microscopic examination of high-sulfur steels containing zirconium has also been productive of interesting results. Before discussing the experimental data in question, it may be stated, briefly, that the reaction between zirconium and sulfur in molten steel may he represented by the simple equation, Zr + 2S = ZrS2, and that the zirconium sulfide thus formed occurs in the finished steel in the form of gray-colored inclusions, closely resembling manganese sulfide and, like the latter, exhibiting plasticity at rolling temperatures. Molten steel containing zirconium retains such a negligibly small amount of oxygen in solution that the foregoing reaction goes to completion.

Jan 2, 1924

By S. E. Maddigan, B. R. Zimmerman

Most metallurgists are well acquainted with the contributions already made to the study of metals by the use of X-rays. On the one hand, the radiographic method is constantly becoming of increasing importance as a nondestructive testing procedure, while on the other hand the techniques of X-ray diffraction have made important contributions to the fundamental knowledge in studies of phase diagrams, stress conditions, and so forth. A new, and as yet insufficiently appreciated, tool exists in the application of microradiography to alloy structures. This new procedure in many respects bears the same relation to microscopic investigations as does macroradiography to the gross inspection of metal surfaces. However, where macroradiography is used ordinarily to determine the soundness of the metal structure, this new method can be used not only to investigate micro-un-soundness but also to examine the distribution of the constituent elements within the body of the alloy. When combined with the normal procedures of microscopy, this offers a technique of great potential power. It is intended in this paper to present a few examples of copper-base alloys demonstrating the additional knowledge obtained from the microradiographic method. The detection of micro-unsoundness is demonstrated in Fig. I for a sample of cartridge brass as cast. The sample ap- peared quite sound when viewed under the microscope, but in reality was thickly populated with minute voids. This application of the method conforms in every way to conventional large-scale radiography and has been used to facilitate production of metal for vacuum devices.' The true potentialities of the technique are revealed by comparison of Figs, 2a and 2b, which are respectively a photomicrograph and a microradiograph of a cast alloy of 80 per cent Cu, 10 per cent Sn, 10 per cent Pb. The remarkable difference in appearance provides some concept of the additional information this method may yield when used as an auxiliary to microscopic studies. Fig. 2a shows two phases of the copper-tin system plus segregated_ lumps of lead. Fig. 2b, on the other hand, shows with exceptional clarity the actual dendritic growth of the metal crystals during solidification. The practice of microradiography depends upon the laws of absorption of X-rays. This subject has been reviewed thoroughly in recent papers,l,2,3 but for clarity a brief resume will be given here. As is well known, when a beam of X-rays is transmitted through a, layer of homogeneous material, the intensity is reduced according to the relation: where Il is the transmitted intensity, I0 is the incident intensity, µ1 is the linear absorption coefficient of the material, t1 is the thickness of the material.

Jan 1, 1944

By S. E. Maddigan, B. R. Zimmerman

Most metallurgists are well acquainted with the contributions already made to the study of metals by the use of X-rays. On the one hand, the radiographic method is constantly becoming of increasing importance as a nondestructive testing procedure, while on the other hand the techniques of X-ray diffraction have made important contributions to the fundamental knowledge in studies of phase diagrams, stress conditions, and so forth. A new, and as yet insufficiently appreciated, tool exists in the application of microradiography to alloy structures. This new procedure in many respects bears the same relation to microscopic investigations as does macroradiography to the gross inspection of metal surfaces. However, where macroradiography is used ordinarily to determine the soundness of the metal structure, this new method can be used not only to investigate micro-un-soundness but also to examine the distribution of the constituent elements within the body of the alloy. When combined with the normal procedures of microscopy, this offers a technique of great potential power. It is intended in this paper to present a few examples of copper-base alloys demonstrating the additional knowledge obtained from the microradiographic method. The detection of micro-unsoundness is demonstrated in Fig. I for a sample of cartridge brass as cast. The sample ap- peared quite sound when viewed under the microscope, but in reality was thickly populated with minute voids. This application of the method conforms in every way to conventional large-scale radiography and has been used to facilitate production of metal for vacuum devices.' The true potentialities of the technique are revealed by comparison of Figs, 2a and 2b, which are respectively a photomicrograph and a microradiograph of a cast alloy of 80 per cent Cu, 10 per cent Sn, 10 per cent Pb. The remarkable difference in appearance provides some concept of the additional information this method may yield when used as an auxiliary to microscopic studies. Fig. 2a shows two phases of the copper-tin system plus segregated_ lumps of lead. Fig. 2b, on the other hand, shows with exceptional clarity the actual dendritic growth of the metal crystals during solidification. The practice of microradiography depends upon the laws of absorption of X-rays. This subject has been reviewed thoroughly in recent papers,l,2,3 but for clarity a brief resume will be given here. As is well known, when a beam of X-rays is transmitted through a, layer of homogeneous material, the intensity is reduced according to the relation: where Il is the transmitted intensity, I0 is the incident intensity, µ1 is the linear absorption coefficient of the material, t1 is the thickness of the material.

Jan 1, 1944

By H. S. Rawdon

One of the most vital problems in the manufacture of steel at present is the occurrence of the defects that have been popularly termed "snow flakes," "flakes," or "scabs." Particularly is this the problem of many manufacturers who, during the past 2 yr., have undertaken large-scale production for the first time. A study of the microstructure of such defective material throws considerable light upon the nature of these defects and is essential before measurcs may be taken for the elimination of the defects. Flakes do not appear to be found in the plain carbon steels; they have been found. however, in abundance in some of the simple alloy steels that are being used in such vast quantities; vie., nickel steel of the approximate composition, 0.40 carbon and 3.5 per cent. nickel, and in the chrome-nickel type. The present article summarizes the characteristic features of defective steel of the flaky type as they have been found by laboratory study of numerous specimens, and it aims to show the conditions within the metal that are favorable to the occurrence of this type of defect without entering into the details of mill practice (size of ingot, design of molds, rate of cooling, distribution of cooling stresses, etc.), all of which conditions appear to play a role in the production of these defects. MacrostrUctURe To one familar with flaky steel, the appearance of "snow-flakes" is unmistakable and is not to be confused with other types of defects. Figs. 1 to 6 show the appearance of fractures of steel showing this type of defect; the white silvery area, which always has the appearance of being of a very coarsely crystalline structure, in the specimen stands out in bold contrast to the darker background and readily justifies the use of the term "snow-flakes." Fig. 1 shows the appearance of the faces of the two halves of a nickel-steel forging that has been split to show the interior flakes. Fig. 2 is a nickel-steel bar (carbon 0.40 per cent.,

Jan 1, 1920

By T. H. Troller

FOR a long time propeller-type fans have been considered a very adequate means to move great quantities of air against small static pres-sures. They have been in use for this purpose in mines, as well as in other installations. For static pressures of over 2 or 3 in. of water, the centrifugal blower almost ruled the field until very recently. Some attempts were made to use a number of propellers in line. Such arrange-ments made it possible to obtain pressures higher than 2 in. of water, but they complicated the construction and increased its expense, and the efficiencies were not improved. The more recent development of propeller-type fans has been decidedly influenced by the intensive aerodynamic research in connection with aeronautical development, which has taught us, in particular, how to use airfoils properly. The characteristic that makes an airfoil so valuable is the fact that when it moves through the air a high force component, the "lift," acts on it vertical to the motion, while the "drag" in the direction of the flow is small. The ratio of lift to drag is approximately 20 to 1 at the angles at which the profile is used in practice. An element of the turning blade, the movement of which, relative to the air, is mainly in the direction of the plane of rotation, thus experiences only a small "drag" FIG. 1.-DIAGRAM OF FORCES ON WING SECTION. opposing its rotation, and for this reason a relatively small torque is required at the driving shaft. At the same time there is a strong force component at 90° to the plane of rotation. This force is parallel to the propeller axis in the direction opposite to that of the flow of air, with a correspondingly high pressure increase.

Jan 1, 1936