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By N. A. Gjostein

The real and apparent dependence of the surface self-diffusion coefficient, Ds, of gold on crystallo-graphic orientation has been investigated by isolated scratch smoothing and grain boundary grooving experiments. No systematic variation of Ds with orientation was found along the [100] zone. In view of the experimental scatter in these results, however, only aniso-tropy ratios, p, greater than -1.3 would be detectable. Anomalously low values of Ds were found on the [0ll] and [110] zones when the diffusion direction lies along (the scratch or grain boundary groove is perpendicular to) these zones. By comparing these results with a previous y plot study of gold, it is hypothesized that this is not an intrinsic diffusivity effect, but rather it results from a decreased driving force for mass transfer at orientations where the y-plot curvature is negative and appreciable in magnitude relative to y. The characteristics of this type of anisotropy do not appear sEVERAL investigations1-7 have dealt with the anisotropy of the surface self-diffusion coefficient, Ds, of metals as measured by the decay of single or multiple to be in agreement with the hypothesis of fast diffusion along ledges in the surface structure. In certain cases the Fourier method of determining Ds, described in Paper I of this series9 was compared with the second moment analysis in order to determine whether or not the method of analysis affects the anisotropy ratio. While the type of analysis does influence the magnitude of the anisotropy ratio, this effect is not associated with the shape of the profile, but rather is connected with the iterative volume diffusion correction used in conjunction with the second moment analysis. It is further demonstrated that the volume diffusion correction can be too large by either method when the y-plot curvature effect is large. Certain orientations exhibit an unusual temperature dependence of Ds ; this is discussed in terms of the y-plot curvature effect and/or the influence of impurities on Ds . scratches in the surface. Depending on the system investigated, both large1"3'6'7 and small4'5 anisotropies in Ds have been found. Although adsorbed impurities undoubtedly play an important role in determining the magnitude of the anisotropy,8 there are other factors that can give rise to an apparent anisotropy in Ds, thus obscuring the true nature of an intrinsic anisotropy in

Jan 1, 1968

By E. E. Brownson

THIS paper will be confined to the treatment of methods as applied in the laboratory of the Boston and Montana Reduction Department of the Anaconda Copper Mining Co. at Great Falls, Mont. As the electrolytic plant of this company operates at a current density of approximately 35 to 40 amperes per square foot when running up to capacity, the arsenic and antimony content of the anodes delivered to the, plant is of considerable importance as bearing on the purity of the refined cathodes turned out. Owing to the rather high relative percentage of antimony, it has always been the custom to determine antimony as well as arsenic in all forms of copper. Thus, anodes have been analyzed in which the antimony was about equal to the arsenic although the average shows about 2 parts of arsenic to 1 of antimony. In the refined copper the relative proportions of the two impurities vary considerably, but probably in the average are about equal. In this latter case, the percentage of the two is so small that ordinarily no attempt is made to separate them, the report of analysis showing percentage of As and Sb combined. Although rapid and exceedingly accurate determinations of arsenic may be made by means of various distillation schemes, the determination of antimony, either by itself or together with arsenic, has always been more or less cumbersome and has required a considerable amount of time. By the methods, details of which follow, the determination of arsenic and antimony, either separated as in the case of anodes or together in case of refined copper, is accomplished in 24 hr. from the time the sample is received by the chemist.

Jan 8, 1913

By Roy D. McLellan

Electrolytic production of cadmium at the Great Falls plant started in the first part of the year 1925. Prior to that time, an experimental unit had been in operation for a few months during the year 1922. At present the plant is the largest producer of cadmium, not only in the United States but in the world. Electrolytic cadmium is characterized by its very low content of impurities. The main impurities, which are lead, copper, zinc and iron, do not aggregate more than 0.05 per cent., leaving a cadmium content better than 99.95 per cent. The consumption of cadmium has increased rapidly since the war, with the growing use in the plating industry. Cadmium plating has come into prominence because of its connection with the automobile and radio industries. As a protective coating, a deposit of cadmium is superior to zinc. Cadmium is also used extensively in alloys. Important among these is the alloy with copper used in telephone and trolley wire. In proportion of 0.5 to 1.2 per cent., cadmium adds materially to the strength and wearing qualities. Practically all commercial zinc concentrates contain a small amount of cadmium. In the electrolytic zinc process, the cadmium that is dissolved in the regular leaching operation is removed from solution with metallic zinc, generally added in the form of zinc dust. This precipitate also contains the copper taken into solution and the excess of zinc dust, which is required in order to insure a complete removal of all impurities. The precipitate is treated by a separate process to recover the copper, cadmium and excess zinc. In order to make the metals more soluble and to render insoluble such impurities as iron, arsenic and antimony, the precipitate is roasted. The roasting is carried out in gas-fired McDougall furnaces, with a roasting temperature of about 700' C. The roasted residue is leached with dilute sulfuric acid, spent electrolyte from the zinc electrolyzing, containing 10 to 12 per cent. free H2S04. The leaching is done in cylindrical tanks of 30 tons capacity, agitated

Jan 1, 1930

By E. O. Wagner, V. F. Parry, J. B. Goodman

The low-rank coals containing 10 to 50 pct natural bed moisture represent over half of the tonnage reserve of the available solid fuels of the United States, but only about 2 pct of United States coal production is derived from these fuels. Increased utilization of these large reserves will result if the bed moisture can be removed at the mine in high-speed low-cost processes. This paper presents a theoretical and experimental study of the factors affecting high-speed drying of coal dusts. The time required to heat particles of coal is proportional to the square of their diameter, and it is calculated that the probable time in minutes is equal to 6D2. In other words, a 1/16 in. coal particle should be heated to drying temperature in 1.5 to 2.0 sec. Likewise, 1/8 in. particles should be heated in about 6 sec. The net heat required to dry subbituminous coal and lignite varies from 240 to 375 Btu per pound, depending upon the moisture removed, and this heat can be obtained from 42 to 61 cu ft of hot gases at 600°F. The necessary heat also can be obtained from 7.5 to 11 cu ft of gas at 2000°F. A description of the design and operation of a pilot plant for flash drying coal dusts is presented. This plant dries 1/16 in. by 0 coal dust in suspension in 1.5 to 2 sec with 600°F gas at a rate of 1300 lb per hour per square foot of column area and operates continuously at an efficiency of about 85 pct. The design and operation of another pilot plant for drying 1/8 in. by 0 coal dusts Is also described. This unit dries coal in the fluidized state using the sensible heat of gases introduced at 2000°F and processes coal at a rate of about 1500 Ib per hour per square foot of grate area at 85 to 90 pct efficiency. Over 90 pct of the bed moisture of low-rank coal dusts can be removed by the methods described. The heating value of lignite can be increased 45 pet and that if subbituminous coal 25 pct in a few seconds. The physical and chemical properties of coal dusts before and after drying are presented in the report, and it is shown that the bulk density of the dried coal is equal to that of the raw coal. This phenomenon makes it possible to ship 25 to 45 pct more heat in a railroad car with consequent savings in freight costs. Introduction For several years the Subbituminous Coal and Lignite Section of the Coal Branch of the Bureau of Mines at Golden, Colo., has been concerned with upgrading low-rank coals by removal of natural bed moisture. These fuels contain 10 to 50 pct total moisture, which reduces their industrial value considerably. In 1938, investigations were initiated in cooperation with the University of North Dakota to study drying of lignite by the Fleissner process with heat derived from high-pressure saturated steam. Two pilot plants were built, and two reports were published giving the results of this work.l,2 It was demonstrated that lump lignite and subbituminous coal

Jan 1, 1950

By B. M. Larsen, T. E. Brower, J. W. Bain

A mass of circumstantial evidence is presented to indicate that the main source of alloy losses in open-hearth tapping is oxidation by air, with the steel apparently reacting with an amount of oxygen equivalent to about 30 times its own volume of air. The effect is erratic from heat to heat, depending largely on turbulence and distance of free fall of the stream of liquid metal. THIS paper reports another phase in a general study of oxidation in the open-hearth, various aspects of which have already been discussed in previous papers.1,2,3 It is based on experiments conducted on commercial, basic open-hearth furnaces at various times when opportunity offered, beginning about 1938, in an attempt to determine the mechanism and measure the amount of air oxidation during the flow of the tapping stream through the air into a ladle. This effect is closely connected, not only with alloy losses and control of chemical analysis, but possibly with various questions regarding inclusion content and steel quality and with a true picture of the deoxidation of steel in general. Thus it is believed that discussion of a large part of the results to date may be of assistance to others who are studying problems related to deoxidation or to steel cleanliness and quality. The literature reveals that strangely little attention has been devoted specifically to the effect of pouring steel through open air. Bardenheuer and Henke4 in 1939, in a paper devoted largely to overall losses of manganese in the basic open-hearth, reported that for a number of heats tapped into a tilted ladle held just beneath the runner so that the maximum distance of drop of the stream through the air was held to less than about 30 in., there was in most cases almost no loss of manganese from furnace to ladle. Hultgren,5 in 1945, showed that in high-carbon basic electric steel deoxidized in the furnace and containing no large inclusions as it left the furnace, large silicate inclusions, often rich in manganese oxide, were present in samples dipped from the pool in the ladle; also that the rise in content of large inclusions (above 0.01 mm dim) was greater when the metal stream was made to spray or flow in a turbulent manner. Our interest in this phase of oxidation in the open-hearth was first aroused by a study of alloy efficiencies on ladle additions. The frequency curves of manganese efficiency (net recovery of metal added in ladle) given in fig. 1 are of interest in this connection. Lowest, and also most variable (47 to 95 pct), recovery was in low-carbon heats having no coal additions to the ladle, progressing upward to a maximum average and least variable (82 to 97 pct) recovery in high-carbon heats killed with aluminum and silicon. Both coal additions and higher carbon contents in the tap stream, as well as additions of silicon and aluminum, help to lower the amount of manganese loss. But the most interesting point is the amount of manganese oxidized in many heats tapped at 0.50 to 1.06 pct carbon. It has been shown in a previous paper3 that the amount of oxygen in the tap stream in such heats is very small, usually below 0.01 pct, too small to oxidize any appreciable amount of manganese. Also, the fact that manganese should be oxidized at all in a metal solution containing such more stable oxide-forming elements as aluminum and silicon is an indication of some rather intense oxidizing effect such as could be caused by reaction with the air during ladle filling. Oxygen Balances from Tap Stream to Teeming Stream: Data in the form of alloy efficiencies, such as those shown in fig. 1, are not a proper measure of such a general oxidation effect. Having available

Jan 1, 1951

By A. Lee Barrett

The Maintenance Committee of the Coal Division of the American Institute of Mining and Metallurgical Engineers is presenting with this report the first of a series of cost comparisons which it plans to present the Institute. The plan is to assemble maintenance cost on all equipment connected with mechanical operations at the face of coal mines, to arrange these costs by districts, to make comparisons between districts, and within districts. This particular report covers data with respect to mobile loading machines, including both "on-track" and "off-track" equipment. It is anticipated—in fact, considerable data have already been accumulated—that next year complete maintenance costs by districts can he presented for complete loading units, including the various classes and combinations of on-track and off-track equipment. Data have also been collected with respect to some phases of maintenance methods and certain recommendations of the committee are included dealing with maintenance problems. In the assembly of these data more than 120 questionnaires were sent to operating companies throughout the United States. At the time the report was written 33 questionnaires had been returned with completed information and an additional group of companies had written that the information requested was not at present available but that they hoped to have such information available in the not far distant future. The replies as

Jan 1, 1947

By A. Lee Barrett

The Maintenance Committee of the Coal Division of the American Institute of Mining and Metallurgical Engineers is presenting with this report the first of a series of cost comparisons which it plans to present the Institute. The plan is to assemble maintenance cost on all equipment connected with mechanical operations at the face of coal mines, to arrange these costs by districts, to make comparisons between districts, and within districts. This particular report covers data with respect to mobile loading machines, including both "on-track" and "off-track" equipment. It is anticipated—in fact, considerable data have already been accumulated—that next year complete maintenance costs by districts can he presented for complete loading units, including the various classes and combinations of on-track and off-track equipment. Data have also been collected with respect to some phases of maintenance methods and certain recommendations of the committee are included dealing with maintenance problems. In the assembly of these data more than 120 questionnaires were sent to operating companies throughout the United States. At the time the report was written 33 questionnaires had been returned with completed information and an additional group of companies had written that the information requested was not at present available but that they hoped to have such information available in the not far distant future. The replies as

Jan 1, 1947

By AIME AIME

PRACTICALLY all the Section delegates as well as a sprinkling of Institute officers and mere members were on hand for the annual business meeting of the Institute on Monday afternoon of the Annual Meeting. President McAuliffe presided, with C. H. Mathewson as associate chairman. Americo Albala was first called on to discuss the work of the Pan American Institute of Mining Engineering and Geology. C. Will Wright said that the need for such an organization was evident, and a resolution was passed asking the incoming President to appoint a committee to investigate cooperation with that body, of which Mr. Albala is executive secretary.

Jan 1, 1943

By J. A. Cahill, A. D. Kirshenbaum

Using an alumina or zirconia crucible with an alumina sinker or a molybdenum sinker coated with zirconium dioxide, the density of liquid iron was determined by the immersed-sinker method over the temperature range of 1800" to 2500°K. The density, with respect to temperature, is ex-Dressed by the equation Dg/cm = 8.523 - 8.358 X 10 T'K The molar Volumes and thermal coefficients of expansion were calculated. Iron, upon me1ting, was found to expand 3.5 pct. A basic knowledge of the physical properties of materials at high temperatures is becoming increasingly important. A check of the literature shows, that in spite of the importance of iron, very few measurements have been made of its physical properties in the liquid state. Density measurements have been made by Benedicks and his collaborators1g using the method of balanced columns, by Desch and smith4 using the immersed sinker method with an alumina sinker, by Lucas using the maximum bubble method5 and by Stott and endall' who used an alumina pyknometer. In the method of balanced columns, the difference in level of molten iron in two arms of a U-tube, together with the corresponding difference of pressure had to be measured. The formation of gas bubbles in one or both arms was a great source of error. These values are very erratic. They vary from 6.83 to 7.45 g per cm3 at the melting point (1805"~) and from 6.45 to 7.15 g per cm3 at 1890°K. Stott and Rendall determined the density at 1837"K, with a reproducibility of *0.2 pct. They used an alumina pyknometer fired to 1973°K. The vessel was filled in a vacuum furnace by immersion in the liquid metal. When thermal equilibrium was attained, the pyknometer was withdrawn, cooled, the ingot removed and then weighed. The chief disadvantage of the method was the difficulty of inserting the pyknometer without cracking it. The authors have been able to determine the density of liquid iron from its melting point up to 2500°K, by using the immersed-sinker method, with A1203 or ZrOz crucibles and A1203 or molybdenum sinkers coated with Zr02, Fig. 1. EXPERIMENTAL Apparatus. In these studies the source of heat was the carbon tube resistance furnace with an argon atmosphere described previously.7 Experimental runs were made using either Ala3 or ZrOz crucibles. The sinkers used were 1) pure A1a3 and 2) molybdenum coated with ZrOz. The crucible, 2 1/8 in. in diam and 3 in. high, was centered in the furnace on an Ala3 of Zr02 pedestal. The sinker, 1/2 in. in diam and 1 1/2 in. long, together with a counter weight, was suspended from an analytical balance into the melt by a molybdenum wire. Procedure. The procedure, as described previously,' consisted in measuring the weight loss of the sinker in the liquid iron while determining simultaneously the liquid iron temperature by means

Jan 1, 1962

By S. C. Hollister

An evaluation of the function of the engineer, so that means whereby education can best serve his needs can be adopted. THERE has been a steady increase in specialized branches of engineering during recent years. Some of these are simply specializations in the function of engineering, such as welding engineering, tool and die engineering, petroleum engineering, and refining engineering. Others are associated more closely with the basic sciences, as for example, geological engineering or engineering physics. Still others tend toward the border line of business, such as administrative engineering or general engineering.

Jan 1, 1950

By Jules E. Jenkins

IN the past quarter century the seismograph has played an increasingly important role in evaluating vibratory effects transmitted to adjacent communities by industrial blasting operations. In this period research has advanced through two major phases—from falling pin seismometers to three-component recording seismographs. The initial phase of this research is now regarded as the era of recording, during which the seismograph merely recorded occasional events. It has emerged from this stage into the era of control and analysis and in this later period has been recognized as a full-fledged industrial tool. Although the falling pin machines of earlier years indicated probable amplitudes of industrial blasting vibrations, they gave no reliable measure of such displacements, nor did they provide essential information concerning direction or frequency of motion. The first contribution of the three-component recording seismograph was the weight-for-distance formula developed by the U. S. Bureau of Mines. This empirical formula enabled users of commercial explosives to determine beforehand the probable vibratory effects of a blast when the weight of the explosives charge and the distance from the shot point were known. This formula has withstood the test of time and is still applicable for blasts detonated by instantaneous methods. The second major contribution of the three-component recording seismograph followed the introduction in 1945 of short period or millisecond delay detonation. This might be described as a two-stage contribution, the first of which revealed a 50 pct reduction in the vibration magnitude when millisecond detonation was used rather than instantaneous discharge. This second part of this double contribution led to the discovery of the vibration dip phenomena, see Fig. 1. In Fig. 1 the horizontal coordinates indicate the displacements amplitude in inches, and the vertical coordinates, the explosive weight in pounds. The top curve is that of the U. S. Bureau of Mines for instantaneous detonation. Its curvature conforms to the two-thirds power of the explosive weight as provided in the weight-for-distance formula; hence the vibratory effects increase in proportion to an increase in the explosive charge. If the other curves shown below are temporarily disregarded, it may be considered that the entire area below this top curve represents both useful and waste energy. As mentioned previously, when millisecond delay detonation was first investigated it was found that in general the U. S. Bureau of Mines curve could be decreased by about 50 pct, or to the position of the middle curve. At the outset it was assumed that this curve would likewise increase in some proportion to the explosive charge, as did the top curve, that is, the curve would indicate a continuous upswing. As seismographic data accumulated this assumption was found to be erroneous in part. It was discovered that

Jan 1, 1957

By A. T. Aldred

HIS note reports the existence of several new scandium intermetallic compounds of the A2B and AB stoichiometries where the A element is scandium and the B element is from group VIII or IB of the periodic table. Alloys were arc melted from high-purity materials using 2-g charges. Typical lot analyses for the materials used are given in Table I. Chemical analyses were not made on the alloys as there was little or no weight loss on melting. After annealing the specimens for 14 days at 600°C and water quenching, metallographic and X-ray techniques were used to determine the occurrence of the various phases. Table II lists the relevant data for the A2B phases. The Ti2Ni structure,2 has ninety-six atoms in a face-centered cubic cell, whilst the Al2Cu structure is body-centered tetragonal.3 The occurrence and stability of the various A2B type phases in transition metal alloy systems has recently been considered by Nevitt.4 The Ti2 Ni-type phases occur over a relatively narrow range of radius ratios from 1.14-1.26 with A partners mainly from the titanium group and B partners predominantly from the cobalt group. This suggests that both a favorable relative size of the atoms and a favorable electron concentration are necessary conditions for the existence of this structure type. A12Cu-type phases involving Ti group elements as A partners are formed with B partners from the cobalt and nickel groups, predominantly the latter, and have a higher radius ratio (1.27-1.29) than the Ti2Ni-type phases. The occurrence of both Sc2Pd and Sc2Co can be rationalized in terms of these considerations but SczNi is anomalous because of its high radius ratio. The radius ratios are calculated from the Goldschmidt CN12 radii and it might be postulated that the scandium atom is reduced in size in the compound. Unfortunately the apparent atomic size of scandium in the compound cannot be calculated from a knowledge of the structure and lattice dimensions. The crystal structure of the Sc2Au compound could not be identified from the powder diffraction pattern, but it is interesting to note that it is isostructural with a series of A2Au phases where A is a rare earth element.5 Pertinent information concerning the AB phases found in this investigation is given in Table 111. All the phases have the ordered bcc CsCl structure. The occurrence and stability of CsC1-type phases have recently been discussed by Dwight,7 who concludes that the relative sizes of the atoms do not appear to be a controlling factor (the radius ratios of all the known phases vary between 0.985 and 1.439) but that the occurrence of the phase is predominantly dependent on the relative positions of the A and B partners in the periodic table. As a measure of the stability of a given CsCl phase it has been customary to define a lattice contraction on alloying, DAB — dAB, where DAB is the AB interatomic spacing as calculated from the Goldschmidt CN8 radii and dAB is the AB interatomic distance in the compound (= v3/2 ao). Values of the parameter DscB -dScB for the compounds found in this investigation are given in column 5 of Table III and are plotted in Fig. 1. If the lattice contraction does in fact reflect the stability of a phase then Fig. 1 shows two very interesting trends when the position of the B partner in the periodic table is considered. Firstly, within any given group the stability increases in order on going from the first to third long period. Secondly, within any given period the stability increases in order as the B partner is taken from the copper, nickel, and cobalt groups. In the case of the second long period, the lattice contraction reaches a maximum at ScRh and then decreases to ScRu. The same trend could

Jan 1, 1962

By Thomas T., Read

DESIRABLE as it is to summarize what has been set forth in preceding chapters, the task can only be approached with great hesitation. What follows represents the personal views of the author at the moment of writing, reserving the privilege to change them on more mature reflection or in the light of further evidence. With that reservation they may be stated somewhat as follows. Education for the mineral industries falls into two categories; general education and technical vocational, using the word vocational not in its usual sense but to signify preparation for specific activities, in which sense a law school is a vocational school. Even at the beginning, as indicated in the first chapter, mineral industry education was partly general and, partly technical and that relationship still persists, because technical education requires a firm basis of general education. Our general American system is to provide free public' general education through the twelfth grade, or completion of high-school work, though there are already many technical vocational high schools, and even in a community where nearly all the young people are preparing for entrance to college there will be some who wish to qualify for employment at the end of the high-school course, or even on completing junior high. Our educational system, therefore, has not only to provide education for those who intend to proceed beyond the twelfth grade but also for those who, for a variety of reasons, may wish or be forced to cease full-time education at any level between the first and twelfth grades. This study has been chiefly concerned with the problem of what kind and how much technical education to provide for those who have completed the twelfth grade and who wish to make their living in the mineral industries. The obvious fact that the mineral industries employ all sorts of trained persons,

Jan 1, 1941

By H. S. Cannon, F. N. Rhines

IT. H. Hausner( Sylvunia Electric Products Inc., Bay-side, N. Y.)—The results reported by the authors are interesting because they contribute some information on the principles of sintering and also because of a certain practical value for the manufacture of powder . metallurgical parts in production. Pressed powder compacts are frequently sintered in a boat in several layers so that the lower layers are actually sintered under the weight of the upper layers and, therefore, are frequently deformed. The authors gave information on this deformation process by determining the effect of the load on the density. The experimental setup of the authors, however, has a disadvantage—that the sintering occurred in a cylindrical container so that the deformation was stopped in the direction of the diameter. The authors should have rather called this a study of hot-pressing than of sintering. I want to call the attention of the authors and others interested in sintering under load to the experimental work described by Dawihl and Rix.' These authors sintered cylindrical compacts under a lengthwise ten-sional load of 0 to 25 g and found that the shrinkage in length and diameter changes considerably with the load, but that the volume shrinkage is affected very little by the load. H. S. Cannon (authors' reply)—We wish to thank Dr. Hausner for calling attention to the experimental work of Dawihl and Rix. The fact that they found volume shrinkage little affected by varying tensional loads during sintering seems to support the contention that the forces due to loading are equivalent to and additive to the forces which cause densification. This contention is the basis of our comparison of sintering and creep.

Jan 1, 1952

By R. F. Mitchell, G. F. Dillon, A. F. Armington

In this paper the present methods of boron preparation are discussed with emphasis on the iodide intermediate. Several methods of boron triiodide preparation were investigated, the most satisfactory method being the preparation from the elements. A yield of 60 pct based on iodine is found for this method. Zone-refining, sublinzation, distillation, and fractional-recrystallization results are given for the boron triiodide, with distillation producing the best results. Several methods of decomposition are also discussed. The purity of the resulting iodide boron approximates the puritjl of the best available bromide boron, ELEMENTAL boron has been suggested as a possible high-temperature semiconductor by several workers,' but has never been exploited as a device material. The principal difficulty with boron is the unavailability of pure crystalline material from which accurate information on electrical properties could be obtained. Most boron crystals presently produced are very imperfect in structure and of questionable purity, particularly in relation to carbon content. Several methods of boron purification have been reported in the past few years, all of which produce material with a purity better than 99.0 pct. Most of these methods have been the subject of a recent review by Starks' and will not be elaborated upon in this report. However, of all the purification methods reported, only those using halide intermediates produce a purity approaching that usually required for electronic applications. The bromide intermediate has been most used for the preparation of high-purity boron.'y3 This material is easily prepared from the elements and can be effectively purified by distillation and decomposed by hydrogen reduction. The resulting product contains a trace of silicon, and an uncertain amount of carbon, believed to be approximately 100 ppm. It has been recently reported by Russian workers that high-purity boron can be produced using an iodide intermediate.' In the work cited, boron is reported free of spectro-scopically determined impurities, but the reported detection limits are quite high (- 100 ppm). In addition, no data is given on the carbon content of the product. In the present paper, boron triiodide was chosen as the intermediate for several reasons. First, carbon tetraiodide, which could be a major impurity, is reported to be unstable above 200" and hence could be easily separated from the boron triiodide by its decomposition, since temperatures greater than this are attained during the purification process. The low melting point (45°C) and boiling point (20B°C) and the relatively high vapor pressure of boron triiodide should allow the application of any physical purification technique to the material. The possibility of a lower decomposition temperature than that used for the bromide process is another advantage which might cut down extraneous contamination. The iodide, however, does have certain disadvantages when compared with the bromide, the production cost being the most significant. This is the result of a higher halide-to-boron weight ratio, which means more intermediate must be employed. The cost of the starting material is also greater for the iodide. This cost could be considerably reduced however, by recycling the iodine byproduct. Epitaxial growth of boron, which is probably the best method of producing junctions, should be possible with either the bromide or the iodide as the intermediate. However, this has been attempted only on a limited scale up to the present time because of the unavailability of good crystals. The authors have been relatively successful in laying down a heterotaxy of boron on silicon, however. This will be reported at a later date. Several crystalline modifications have been reported for boron, four of which are now believed to be real.' These are the a! and 0 rhombohedral and the a, and 0 tetragonal. In general, the a! rhombohedral is the low-temperature form and the B rhombohedral is the high-temperature form. The tetragonal structures are detected between 1000"

Jan 1, 1964

By R. R. Vandervoort

The creep behavior of Nb(Cb), Ta, Mo, and W was determined under conditions of constant atomic dif-fzisivity, constant stress to elastic modulus ratio, and nearly equivalent grain size, and the steady-state creep rates obtained from these tests were correlated with calculated stacking fault energies for the metals. These results, in conjunction with similar data for several fccMetals,13 suggest that stacking fault energy may influence the creep strength ofbcc metals. The interrelationship between steady-state creep rate, subgrain size, and stacking fault energy was examined. It was found that the subgrain size for a given creep stress, increased as stacking fault energy increased, but that this relationship did not cormpletely account for the effect of stacking fault energy on creep rate. The crystallography and energetics of stacking fault formation in bcc metals has been discussed by a num-ber of authors,1-5 and impurity stabilized stacking faults on (112) planes have been observed in Nb,6,7 w,8,9 Fe,] and V" by transmission electron microscopy. However, a crucial question is whether or not stack-ing faults influence the mechanical strength of bcc metals. Potentially, stacking faults could increase strength by reducing the mobility of the partial dis-locations bounding the fault, by acting as barriers to slip dislocations, and by retarding the climb of dislo-cations during high-temperature deformation. The objective of this study was to seek a correlation be-tween creep strength and stacking fault energy for several bcc metals; namely, Nb, Ta, Mo, and W. The creep behavior of most polycrystalline metals and alloys at high temperatures and moderate stresses can be described by the following relation:11,12 im=Af(s) where i, = minimum creep rate, A = constant, j(s) = a function involving metallurgical structure, a = applied stress, E = average elastic modulus at the test tempera-ture, w = constant (equal to 5 for most pure metals), D = diffusion coefficient. One factor in the structure function F(s) which sig- R. R. VANDERVOORT, Member AlME is Research Metallurgist, Process and Materials Development Division, Chemistry Department, Lawrence Radiation Laboratory, University of California, Livermore, Calif. Manuscript submitted February 28, 1969. IMD nificantly affects the creep resistance of fcc metals is stacking fault energy, and creep rate has been shown to vary directly with stacking fault energy to the 3.5 power." In the latter investigation, four fcc metals of widely different stacking fault energies (Ag, Cu, Ni, and Al) were creep tested at a constant stress to modulus ratio of 1.21 x 10-4, at a constant diffusivity of 2.7 x 10-12 sq cm per sec, and at nearly equivalent grain sizes of about 0.7 mm. The creep data were then correlated with stacking fault energies. In the present study, a similar procedure was followed. All materials used in this work were consolidated by powder metallurgy techniques. Impurity contents in the as-received materials are listed in Table I. Chemical analyses showed that no measurable contamination of the test specimens occurred during pretest annealing treatments or creep testing. Specimens with a gage section 0.75 by 0.125 by 0.050 in. were creep tested in tension in a vacuum of less than 10-9 torr. Deformation at temperature was measured by tracking fiducial marks on the gage section of the specimen with an optical comparator. Optical deformation measurements also permitted observation of the macroscopic characteristics of the deformation Table I. Typical Specimen Impurity Content, ppm Nb Ta Mo W C 45 10 155 6 O 185 30 4 10 N 30 6 3 2 H 5 I 1 <1 als 3 10 2 15 Ca <5 I3 5 Cr 5 <3 10 <5 Cu 10 50 2 15 Fc 10 10 150 35 Ni 2 150 20 <5 Si <I0 1 3 <10 Ta 100 Ti 10 8 1 Zi 15 50 1 3 Table II. Test Conditions for Constant Stress-Modulus Ratio of 6 X 10.&apos; and Constant Diffusivity of 2.7 X 10-12 sq cm per see, and Grain Size Values for the Given Pretest Annealing Treatments Literature references Pretest Annealing for E and D Treatment Stress, Temperature, ___"&apos;Values__ Grain Tempera-Metal psi "C E D Size, mm ture, .C Time hr Nb 745 1525 14 15 to 17 0.83 1650 I Ta 1220 1770 18 19.20 O.91 1800 I Mo 1975 1630 18 21 0.77 2200 I W 2140 2265 18 22 040 2400 5

Jan 1, 1970

By A. W. WALKER

All branches of production engineering showed steady and definite progress during 1941. Most of it has been of the slower and more conservative type rather than the sensational. To a large degree the changes have been influenced by the expanding war economy, and this tendency will probably be even more marked during the coming year. The stress of the times is placing more emphasis on the principles of engineering and conservation, with the object of obtaining the greatest possible recovery with a minimum waste or expenditure of equipment. Also available material supplies are often being turned to new uses.

Jan 1, 1942

By N. Mao

This paper presents the results of a research effort to develop a technique for estimating in situ stresses by measuring stress-induced velocity anisotropy around a borehole. Relevant parameters required to make the estimate were identified and measured in the laboratory on a 35.6 cm (14.0 in) cube of Nugget sandstone with a 10.2 cm (4.0 in) diameter hole, under biaxial loading. Two pairs each of radially and tangentially polarized transducers were placed inside the hole with displacement directions either parallel or perpendicular to the principal stress directions. With this configuration, relative travel times were measured by both a pulsed phaselocked loop technique and a cross correlation of digitized waveforms. The biaxial velocity data were used to back-calculate the applied stress. The standard deviation of the differences between the calculated and applied stresses is 0.62 MPa (90 psi) for a stress level up to 8.63 MPa (1250 psi).

Jan 1, 1984

By W. E. Bergman, P. G. Carpenter, H. B. Fisher

The conditions under which barium carbonate can be used to remove sulfates from drilling muds are limited The amount of sulfate remaining in solution in the system after treatment with barium carbonate is shown to be a function of the concentration of the carbonate and barium ions and the concentration of other electrolytes. Barium hydroxide may advantageously replace barium carbonate when the contamination is not entirely due to anhydrite (calcium in the system is then stoichiometrically less than sulfate) or when the carbonate concentration is high. The effect of substances such as quebracho, phosphates, and chromates, which form complexes or precipitates with barium, is discussed. INTRODUCTION As the complexity of the operations in drilling for oil has increased, more attention has of necessity been directed to the problems pertaining to the maintenance of good drilling mud properties. As a result, chemical treatment of muds has become an important factor in recent years. Some of these treatments have been designed to eliminate the deleterious effects of contaminants in aqueous mud systems by precipitation or other means. The most common of substances encountered during drilling include sodium chloride, cement, and calcium sulfate while various other contaminants: usually in small amounts, may be introduced from the water, clays, and other materials used in preparation of the mud. In certain cases, for example where continued salt-water flow is encountered or massive anhydrite is drilled, special muds may be used so that the physical properties of the mud will remain satisfactory for drilling. In other cases, it is desirable to remove the contaminants so that soluble electrolytes in the system are maintained at low values. For sulfate contamination, the conlmon practice in the field is to add barium carbonate to precipitate the sulfate as barium sulfate Ordinarily such a procedure gives satisfactory results. There have been important instances, however, where addition of barium carbonate was not effective in removal of soluble sulfates from drilling muds. and it is to these cases that the present paper is directed. While it is generally known that barium carbonate is not always effective in removing soluble sulfates from drilling muds, certain inconsistencies appear in the literature as to the limitations of its use, and little explanation for the limitations are given. Varnell and Kimbrel state that "the treatment (with barium carbonate for removal of sulfate) is simple and consists in maintaining a pH of 9 with caustic soda and quebracho." They caution that concentrations of quebracho greater than 1 lb./bbl. may inhibit the reaction. In another publication&apos;, a pH of 10.5 is considered "the maximum desirable," and the indication is that as much as 2.5 lb. quebracho per barrel may be present in the particular mud under discussion. Lancaster and Mitchell5 state that appreciable amounts of phosphates in the mud will inhibit the reaction with barium carbonate and that the phosphate treatment should be discontinued at least 24 hours before addition of the carbonate. Experimental work was initiated to ascertain the factors involved in using barium carbonate for the removal of sulfate contamination in drilling muds. While the experimental data herein reported are limited, they focus attention on the pertinent factors which must be considered for successful treatment. These factors are discussed from a practical and a theoretical view, the latter being supported by equilibrium data found in the literature. Further, it will be appreciated that the factors involved in this specific study will be closely analogous to those in certain of the other chemical treatments which involve a precipitation of the soluble contaminant. A thorough comprehension of these factors should result in a more fruitful application of this type of chemical reaction to the treatment of drilling muds. EXPERIMENTAL A. Reagents Two muds were used during this investigation. For one series of tests, bentonite suspensions were prepared by dilution of a stock suspension containing 8 per cent by weight of bentonite (Aquagel). For another series, a 6.4 per cent ben-tonitic mud weighted to 9.7 lb./gal. with barium sulfate (Mag-cobar) was used. Distilled water was used in all preparations. The quebracho (72% tannin extract) was obtained from the Thompson-Hayward Co. of Tulsa and contained 11.4 per cent moisture (105 C.). All other materials were reagent grade, and concentrations were corrected for water of crystallization, if any. All concentrations are expressed in pounds per barrel (42 gallons). B. Technique The systems — either mud or water — were contaminated with either sodium or calcium sulfate after treatment with the desired amounts of sodium hydroxide and quebracbo. For treatments with barium carbonate an approximately 3-fold excess (5 lb./bbl.) was used over that computed to be required to precipitate all the sulfate as barium sulfate. Barium hydroxide was used in concentrations of 2 lb./bbl. — about

Jan 1, 1949

By P. G. Carpenter, H. B. Fisher, W. E. Bergman

The conditions under which barium carbonate can be used to remove sulfates from drilling muds are limited The amount of sulfate remaining in solution in the system after treatment with barium carbonate is shown to be a function of the concentration of the carbonate and barium ions and the concentration of other electrolytes. Barium hydroxide may advantageously replace barium carbonate when the contamination is not entirely due to anhydrite (calcium in the system is then stoichiometrically less than sulfate) or when the carbonate concentration is high. The effect of substances such as quebracho, phosphates, and chromates, which form complexes or precipitates with barium, is discussed. INTRODUCTION As the complexity of the operations in drilling for oil has increased, more attention has of necessity been directed to the problems pertaining to the maintenance of good drilling mud properties. As a result, chemical treatment of muds has become an important factor in recent years. Some of these treatments have been designed to eliminate the deleterious effects of contaminants in aqueous mud systems by precipitation or other means. The most common of substances encountered during drilling include sodium chloride, cement, and calcium sulfate while various other contaminants: usually in small amounts, may be introduced from the water, clays, and other materials used in preparation of the mud. In certain cases, for example where continued salt-water flow is encountered or massive anhydrite is drilled, special muds may be used so that the physical properties of the mud will remain satisfactory for drilling. In other cases, it is desirable to remove the contaminants so that soluble electrolytes in the system are maintained at low values. For sulfate contamination, the conlmon practice in the field is to add barium carbonate to precipitate the sulfate as barium sulfate Ordinarily such a procedure gives satisfactory results. There have been important instances, however, where addition of barium carbonate was not effective in removal of soluble sulfates from drilling muds. and it is to these cases that the present paper is directed. While it is generally known that barium carbonate is not always effective in removing soluble sulfates from drilling muds, certain inconsistencies appear in the literature as to the limitations of its use, and little explanation for the limitations are given. Varnell and Kimbrel state that "the treatment (with barium carbonate for removal of sulfate) is simple and consists in maintaining a pH of 9 with caustic soda and quebracho." They caution that concentrations of quebracho greater than 1 lb./bbl. may inhibit the reaction. In another publication&apos;, a pH of 10.5 is considered "the maximum desirable," and the indication is that as much as 2.5 lb. quebracho per barrel may be present in the particular mud under discussion. Lancaster and Mitchell5 state that appreciable amounts of phosphates in the mud will inhibit the reaction with barium carbonate and that the phosphate treatment should be discontinued at least 24 hours before addition of the carbonate. Experimental work was initiated to ascertain the factors involved in using barium carbonate for the removal of sulfate contamination in drilling muds. While the experimental data herein reported are limited, they focus attention on the pertinent factors which must be considered for successful treatment. These factors are discussed from a practical and a theoretical view, the latter being supported by equilibrium data found in the literature. Further, it will be appreciated that the factors involved in this specific study will be closely analogous to those in certain of the other chemical treatments which involve a precipitation of the soluble contaminant. A thorough comprehension of these factors should result in a more fruitful application of this type of chemical reaction to the treatment of drilling muds. EXPERIMENTAL A. Reagents Two muds were used during this investigation. For one series of tests, bentonite suspensions were prepared by dilution of a stock suspension containing 8 per cent by weight of bentonite (Aquagel). For another series, a 6.4 per cent ben-tonitic mud weighted to 9.7 lb./gal. with barium sulfate (Mag-cobar) was used. Distilled water was used in all preparations. The quebracho (72% tannin extract) was obtained from the Thompson-Hayward Co. of Tulsa and contained 11.4 per cent moisture (105 C.). All other materials were reagent grade, and concentrations were corrected for water of crystallization, if any. All concentrations are expressed in pounds per barrel (42 gallons). B. Technique The systems — either mud or water — were contaminated with either sodium or calcium sulfate after treatment with the desired amounts of sodium hydroxide and quebracbo. For treatments with barium carbonate an approximately 3-fold excess (5 lb./bbl.) was used over that computed to be required to precipitate all the sulfate as barium sulfate. Barium hydroxide was used in concentrations of 2 lb./bbl. — about

Jan 1, 1949