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OF the many categories into which scientific knowledge has been arbitrarily 'divided, the one that has proved most. applicable in our attempts to gain an insight into the details of steelmaking processes is physical chemistry. To the young metallurgist who has only recently survived a college course in this subject, the application of its principles to reactions in liquid steel should not be difficult. The many excellent textbooks of physical chemistry provide ample material on the principles of this subject for the student of steelmaking processes. It is the purpose of this chapter to provide a concise review of the principles of physical chemistry that have proved useful in studies of steelmaking and at the same time to present some of the data that are essential to the application of physical chemistry to reactions at high temperatures. Certain parts of physical chemistry require rather formidable mathematics for their complete development, but in the main those applications in which we are here interested can be expressed in fairly simple terms. Many of the equations are logarithmic, and we shall use the symbols In X and log X to represent, respectively the natural and the common logarithm of X. The two are related-by In X = 2.303 log X. Logarithms may, be read from a good slide rule with sufficient accuracy for our purposes. In a few spots a knowledge of the calculus will be helpful. MATTER Innumerable forms of matter may, be recognized, and these may be converted by chemical processes into others, as ore, coke, and air are converted into iron, slag, and gas.. Whenever such a change occurs there is a corresponding change in the amount of energy associated with the matter. The process may require an input of energy, as in the electrolytic production of aluminum, or it may result in an output of energy, as in the combustion of fuel. The basic laws of the conservation of matter and of energy tell us that we cannot change the total amount of matter or the total amour t of energy.. When the fuel pile is used up, we realize that it has simply been converted into other forms of matter; .i.e., ash

Jan 1, 1964

By Larsen. Edward P.

The principle of "bed blending" in the agglomeration of materials is about 56 years old, but de- spite all education via technical papers, operating reports and results from functioning installations, the concepts of blending are still somewhat vague. Confusion exists between "mixing", "blending," and the basic role of each. The terms "blending" and mixing" are often used interchangeably, yet they describe two different processes. As properly understood and applied, a blend is a combination of different varieties of material which produces a desired quality, or the mingling of different elements to form a harmonious whole. In other words, blending is a process of combining granular materials by mechanical means, wherein the final product, or a portion thereof, must contain an exact proportional amount of every one of the several different materials which contributed to the mass and wherein all particles are so thoroughly intermingled with each other as to have lost their individual identities and become a part of the whole so that when a portion of the blend is taken at any time it will be substantially identical, chemically and physically, to any other portion taken throughout.

Jan 1, 1962

By Wheeler O. North

The United Eastern Mining Co.'s property is in the Oatman, Gold Roads mining district of Mohave County, Ariz. The mine and mill are 26 mi. (41.8 km.) southwest of Kingman, the nearest railway connection. The ore consists of a mixture of calcite and quartz with some andesite. The values, which are mainly gold, alloyed with approximately 34 per cent., by weight, of silver, are extremely fine so that fine grinding is a most important factor in extraction. The milling process, briefly, consists of single-stage, coarse-crushing, two-stage ball milling in cyanide solution, followed by combined mechanical and air agitation, and by straight counter-current decantation. The Merrill zinc-dust precipitation method is used to recover the values, and is preceded by the Crowe vacuum treatment of the solution. The most notable features of the plant are the absence of filters, and the use of short peb mills loaded with steel balls, for fine grinding. As originally designed, the capacity of the mill was to be 200 tons per day, although the grinding end was to be capable of handling double that amount. By adding extra agitators and thickeners and by some alterations to the grinding end, the daily capacity has been raised to 285 tons. This, it is hoped, may be increased to 300 tons during the warm months of the present year. Tonnage Milled per Day 1917 average....... 234; maximum month.... 272; minimum month..... 146 1918 average....... 253; maximum month,... 276; minimum month..... 217 As this article primarily deals with plant operations, those interested in the mechanical description are referred to the article by Mr. Otto Wartenweiler,1 the designing engineer, which gives the details and costs of design and construction. The following changes have been made since that article was published: Two special simplex Dorr classifiers have been substituted for the two duplex Callow screens and bucket elevator, which classified the Marcy discharge and returned the oversize for regrinding. Three Dorr

Jan 1, 1920

No. 484.-A mining engineer and geologist of long and varied experience in North and South America is open for an engagement. Exploration and development work preferred. Rare minerals a specialty. No. 485.-Member, mining engineer, technical graduate, married, age 28, exempt, with 9 years experience at gold and silver, copper, lead, and coal mines, 4 years with present employers, is open for engagement as mine superintendent or foreman, or in charge of cyanide plant. Boston or New York interview after Oct. 10. Present position, day foreman at producing gold-silver mine in Montana. References. No. 486.-Member, age 34, married, varied experience in iron, copper, nickel, talc, etc., principally as surveyor, mine and surface geologist, and superintendent of explorations, is open for engagement. Preference, connection with some eastern consulting engineer or firm of engineers. No. 487.-Member, mine superintendent, 18 years' experience in the West and in the Lake Superior districts. Thorough business and technical training. Personal interview, preferably Chicago.

Jan 10, 1918

By G. L. Craig

COPPER containing a small amount of arsenic has been used extensively abroad, and a number of reports, particularly those by English workers, have indicated that such copper is better suited for certain uses than high-conductivity copper. Inasmuch as a large percentage of the copper fabricated is used for nonelectrical purposes where high conductivity is not at all essential, it has been suggested that arsenical copper might be at least as suitable as high-conductivity copper for many purposes. An investigation spon-sored by the Calumet & Hecla Consolidated Copper Co. at Battelle Memorial Institute was therefore undertaken with the object of determin-ing the effect of small amounts of arsenic (up to 0.75 per cent) on the properties of copper. In this work the effect of arsenic on the basic properties of tough-pitch and of phosphorized copper have been critically studied and many data collected from laboratory experiments which have been supplemented by mill-scale tests. The results of these tests, with coppers of the type referred to, in the annealed condition and after various degrees of reduction, show that the basic properties of copper are not greatly affected by small amounts of arsenic, an increase in strength being observed with increasing arsenic with no corresponding decrease in ductility. It is well known that the evaluation of material for plastic deforma-tion, on the basis of laboratory tests, may not be directly comparable with its performance in commercial operations. In order, therefore, to substantiate the data obtained at the Institute, the cooperation of the Wolverine Tube Co. was obtained for a series of production tests on the fabrication characteristics of phosphorized arsenical copper in the manu-facture of seamless copper tubing. In these tests the behavior of the arsenical coppers was carefully observed in comparison with that of representative types of phosphorized arsenic-free copper, which were fabricated under the same conditions.

Jan 1, 1933

By Edward Walsh

The difficulty of securing for experimental research the actual conditions to be found in practice very frequently deters many from engaging in such work. Probably no metallurgical operation is more difficult to imitate in the laboratory than the blast-furnace process. So many complex reactions take place within the furnace, under such varied conditions of time and temperature, with innumerable mechanical, physical, and chemical mutations, that while the results reached may approximate those obtained in practice, there is always something wanting. Much work of this kind has, nevertheless, been done, and is now being undertaken. We are indebted to the bold minds who have attempted it for our present real knowledge of the blast-furnace process. Not that those who have performed series of experiments at a few given temperatures can claim the honor. It required more than this—the ability to make a summary of all preceding experiments, to supply those which were wanting, and to confirm those that were doubtful. Sir I. Lowthian Bell, whose able papers before the Chemical Society and the British Iron and Steel Institute (forming the basis of his great work, The Chemical Phenomena of Iron-Smelting) has

Jan 1, 1889

By J. H. McCarthy, J. M. Botbol, R. B. McCammon, G. H. Gott

Four areas have been identified as favorable drill site locations for determining whether a suspected porphyry copper deposit exists in Rowe Canyon, NV. Favorability is bated on the similarity to a deposit model constructed from geochemical data for the porphyry copper deposit near Ely. Favorability is defined as the coincident number of positive anomalies for zinc, silver, aresenic, antimony, and iron. The favorable areas coincide with an observed magnetic high and areas in proximity to major faults.

Jan 1, 1983

By H. Rosenthal, A. L. Jamieson

Stress-corrosion cracking of copper-base alloys is of considerable importance and has been the subject of many investigations which employed various accelerated tests and long-time service tests. The outstand¬ing accelerated tests used are variations of either the mercury cracking test reported by Rogers in 1905( 1)2 or the ammonia test reported in 1910(2). The ease of applica¬tion of the mercury test is probably the reason industry adopted it. Subsequent investigation of this test(3,4) revealed that a minimum threshold stress was necessary before mercury cracking could develop. Since season cracking has been found in some instances in caliber 0.3o ammunition which has passed the mercury test, it is evident that the threshold stress value of the mercury test may be too high for dis¬tinguishing between acceptable and un¬acceptable caliber 0.30 cartridge cases. This condition has naturally led to the study of an ammonia test with its ability to cause cracks with almost any stress level. But the lack of a definite threshold value means that standards are necessary for evaluating the results of the ammonia test.

Jan 1, 1945

By R. I. Jaffee, F. C. Holden, H. R. Ogden

The properties of quenched Ti-Fe alloys have been correlated with their microstruc-tures. For specimens quenched from equilibrium in the a-ß field, the dominant micro-structural variable is the a-ß ratio. A comparison of specimens having equiaxed a-ß structures with those having acicular a-ß structures shows that the equiaxed specimens have better tensile ductility, but lower impact resistance. There is evidence to show that specimens with acicular structures reach equilibrium in the a-ß field more rapidly than specimens with equiaxed structures. Both strength and ductility are lowered by heat treatments below 700°C. IN previous work,1, 2 certain principles of the physical metallurgy of a-ß titanium alloys have been evolved. Most of these principles have been based on data obtained on alloy systems which undergo no eutectoid reaction, or in which the eutec-toid reaction is so sluggish as to be inoperative. The alloy systems previously studied included the Ti-Mn alloys, with and without a-stabilizing additions, and the binary Ti-Mo alloys. The most important of these principles are: I) The compositional factors which affect mechanical properties are solid solution strengthening, the martensite transformation, and instability of

Jan 1, 1957

By M. R. Annis

Drilling mud rheological and gel property changes due to elevated temperatures frequently cause problems in drilling deep wells. A laboratory investigation of the effects of time, temperatures up to 3001; and mud composition on these properties was made with concentric-cylinder, rotational viscometers of the Farm type. The viscometers were sealed from the atmosphere to prevent dehydration of the sample. Gel strengths were found to be more sensitive than viscosities to changes in temperature and mud cornposition. The high-temperature gel strengths of bentonitic clay drilling fluids were not predictable from low-temper.atl4t-e measurements. At high temperatures, [lie clay flocculates. The floccu-lation temperature depends on the concentration and type of solids in the mud and the degree of chemical defloccula-tion. As the bentonite content of a mud increases, floccrrla-tion temperature decreases. Lignosulfonnte treatment raises the flocculation temperature. To minimize adverse high-temperatrrre effects on mud properties, the mud should be maintainted at minimum solids content, properly treated with. a defloccullant which is stable at the maximum ten?perature encountered and maintained at a pH high enough to insure activation of the deflocculant for the duration required. The Methylene Blue Test for cation exchange cnpacity of a clay was found to be a useful guide in deter.niinirig when a mud contains a dangerously high clay conWnt. INTRODUCTION In drilling a well it is desirable, for several reasons, to know the effects of time and temperature on the rheological and gel properties of the drilling fluid in the hole. Problems associated with drilling fluids normally occur down-hole: so it is reasonable to be interested in the properties of drilling fluids at the conditions which exist down-hole. It has long been observed that high pump pressures are often needed to start circulation after a trip and that the "bottom-up" mud that is circulated back to the surface is usually more viscous than it was before "cooking" at the bottom of the hole for several hours. Burk-hardt' showed that a knowledge of rheological proper-ties of muds under down-hole conditions is necessary to predict pressure surges. He showed that the viscosity of a mud greatly influences the magnitude of pressure surges and the likelihood of lost returns. McLean et aL~ showed that the rheological properties of a mud under down-hole conditions are very important to cementing operations. This paper presents data showing the effects of time and temperature on rheological and gel properties of water-base drilling fluids. Measurements of gel strengths and rheological properties were made with two different concentric-cylinder rotational viscometers of the Fann type. One was the conventional six-speed viscometer modified to operate at temperatures up to 350F and at the vapor pressure of the liquid at test temperature. The other viscometer was newly designed to operate at temperatures up to 500F and pressures up to 1,000 psi. Tests with both instruments were made under essentially the same operating conditions. The new viscometer is shown in Fig. I. In this investigation, great emphasis has been placed on the rheological properties of clay suspensions, since clays are largely responsible for a mud's thixotropic and gel-

By H. G. Schneider

The Smackover oil and gas field lies in Ouachita and Union Counties, Ark., in the south-central part of the state, in T.15 and 16S., R.15, 16, and 17W. It is 10 miles north of El Dorado, the principal business and railroad center in the south-central part of the state, and extends from the town of Smackover in all directions. Productive territory having an aggregate area of nearly 55 sq. mi. has been developed. It extends 6 miles from north to south and 12 miles from east to west. The field may be divided into two parts: the east district, which includes the area east of the town of Smackover, and the west district, which includes the area west of the town of Smackover. In relation to the neighboring productive fields of Arkansas, the Smackover field is 9 miles north of the El Dorado oil and gas field, 8 miles slightly west of north of the East El Dorado oil and gas field, and 16 miles east of the Stephens oil field. Smackover was discovered in May, 1922, when the Oil Operators Tnist drilled well No. 1 on the J. T. Murphy farm, in the southeast quarter of sec. 8, T.16S., R.15W. This well is located almost on the top of the Norphlet dome and was drilled to the Nacatoch sand. It had an initial open flow volume of 30,000,000 cu. ft. of dry gas per day, and a rock pressure of 950 lb. per sq. in. In July, 1922, the V. K. F. Co. completed the first oil well in sec. 29, T.l5S., R.l5W., on the north side of the Norphlet dome, and 3 miles north of the first gas well. This well started the active development of the north and northwest sides of the dome.] The field was extended westwards, when oil was discovered in the Nacatoch sand, during October, 1922, in sec. 4, T.l6S., R.l6W., 51/2 miles west of the original gas well. This opened up the so-called "light oil district," which is located on a structural terrace, for which the name

Jan 1, 1924

Discussion of the paper of Godfrey T. Vivian, presented at the Cleveland meeting, October, 1912, and published in Bulletin No. 76, October, 1912, pp. 1103 to 1109. COURTENAY DEKALB, Tucson, Ariz. (communication to the Secretary*) :--Mr. Vivian's paper is interesting as an evidence of renewed attempts to solve the problem of adapting the centrifugal machine to the uses of the metallurgist. It would not seem that the Gee machine has solved the problem, because it is manifestly of use only with quite high-grade material, since low-grade pulp could not stand the cost of treatment by a discontinuous process. The mechanism, however, would seen to accomplish grading more perfectly than the ordinary centrifugal basket. This is an entirely different thing from concentration, which is intended to yield a finished marketable product. The real problem is to design a successful continuous centrifugal machine. Ten years or snore ago a machine, which might be described as having an inverted step-basket, offered much promise, and was constructed and tested at considerable cost, but it presented insuperable difficulties. The construction of a successful continuous centrifugal would be welcomed by the whole industrial world, since its uses would be most extensive. Mr. Vivian suggests the utilization of the centrifugal machine as a substitute for slime filters in the cyanide process, but he, has apparently not tried the experiment. I tested the efficiency of centrifugal machines for this purpose in 1897-8, having to extract the cyanide solution from a highly argillaceous slime of the sticky kind which the Mexican call ?lama." Our filter-presses yielded cakes containing usually :30 per cent. of moisture, and so dense as to preclude washing. The centrifugal machine readily Brought the moisture content down to 9 per cent. and permitted fairly successful washing. Despite these advantages, the cost of power, labor, and repairs, and the loss of time in discharging the cake, exceeded the costs and

Jan 5, 1913

By O. Mellgren, A. M. Gaudin, P. L. De Bruyn

The adsorption density of ethyl xanthate on pyrite was determined as a function of xanthate concentration. Surface preparation of the mineral appears to have asafunctionsome effect on the subsequent adsorption process, A monolayer of xanthate on the surface is exceeded only in presence of oxygen. The effect of OH- , HS- (and x and CN- S=)and on the amount of xanthate adsorbed was investigated. Competition between OH- and X- (xanthate) ions for specific adsorption sites is indicated over a wide pH range. IN the flotation of sulfide ores, xanthates are most commonly used to prepare the surface of the mineral to be floated so that attachment to air takes place. The quantity of agent required to make the mineral hydrophobic is usually very small, of the order of 0.1 to 0.25 lb per ton of mineral. Details of the mechanism of pyrite collection are for the most part unsettled. Adsorption of collector has long been believed to involve an ion exchange mechanism as demonstrated for galena' and for chalcocite.2 In the work on chal-cocite it was also demonstrated that a film of xanthate radicals unleachable in solvents that dissolve alkali xanthates, copper xanthate, or dixanthogen was formed at the surface of the mineral. The unleachable product increased with increasing addition of xanthate up to a maximum corresponding to an oriented monolayer of xanthate radicals. Pyrite is extremely floatable with xanthate if its surface is fresh.9 ut the floatability decreases rapidly as oxide coatings increase in abundance. Pyrite shows zero contact angle when in contact with ethyl xanthate solution at pH higher than about 10.5;4 at neutrality, a contact angle of 60" is obtained at a reagent concentration of 25 mg per liter. Alkali sulfides and cyanides are pyrite depressants. In this study of pyrite collection the writers have sought to relate measured xanthate adsorption to the method used in preparing pyrite, to the presence or absence of oxygen, to concentration of hydroxyl, hydrosulfide, sulfide, and cyanide ions. The principal experimental tool has been radioanalysis," " using xanthatcx marked with sulfur 35. Experimental Materials Pyrite: Unlike most sulfides, pyrite is a poly-sulfide. The structure given by Bragg7 resembles that of sodium chloride, the iron atoms corresponding to the position of sodium and pairs of sulfur atoms corresponding to the position of chlorine. The edge of the unit cell in pyrite is 5.40 A and in halite 5.63 A. The S-S distance in pyrite is 2.10 A; the Fe-S distance, 3.50 A: and the Fe-Fe distance, 3.82 A. Natural pyrite from Park City, Utah, was used in this investigation. Pyrite 1 was obtained by hand picking pure crystals. Pyrite 2 and Pyrite 3 were obtained from finer textured crystalline material containing inclusions of silicates. The same cleaning technique was utilized for the preparation of Pyrite 2 and Pyrite 3, whereas a different cleaning technique was used for Pyrite 1. Pyrite 1 was prepared as follows: The crystals were ground in a porcelain ball mill and the 200/400 mesh fraction was separated by wet screening with distilled water, followed by washing for 1 hr with deoxygenated distilled water acidified with sulfuric acid to pH 1.5. The acid was removed by rinsing with deoxygenated distilled water on a filter until a pH of 6.0 was reached in the effluent. This filtration was carried out under nitrogen. The sample was then dried in a desiccator under nitrogen. The period of time for which this pyrite sample was in contact with water containing oxygen was about 4 hr. The specific surface as determined by the BET gas adsorption method was 582 cm2 per g. Final material assayed 53.12 pct sulfur and 46.5 pct iron (theoretical, for FeS,: S, 53.45 pct; Fe, 46.55 pct). After crushing, Pyrite 2 and Pyrite 3 were washed with 1 M HCl. rinsed, and fed to a laboratory shakinq table to remove the small amount of silicates. The concentrate obtained was ground in a laboratory steel ball mill. The 200/400 mesh fraction was separated by classification in a Richards hindered settling tube. This fraction was then given a final wash with 0.1 M HCl and deoxygenated water was filtered through the sample. The final effluent showed a conductivity equivalent to that of a solution having a salt concentration of 0.3 ppm. Aqueous hydrogen sulfide solution was then added to the sampln (about 100 ml saturated H,S solution to about 1000 g pyrite under a few hundred milliliters of water) which was stored wet under nitrogen. The sample stored in this manner showed no indication of formation of iron oxides, whereas iron oxides appeared

Jan 1, 1957

By H. Kahata, I. Iwasaki, Y. Takahasi

A combined process of segregation roasting-flota-tion or magnetic separation was developed to recover nickel from lateritic iron ores and oxidized nickel ores. An ore was mixed with a halide, such as sodium or calcium chloride, and a solid reductant, and roasted, whereby the nickel content was segregated out as discrete metallic particles. Either by magnetic separation, or by flotation using a sulfhydryl collector together with a heavy metal salt as an activator, the metallic nickel could be concentrated, Effects of such variables as the types and amounts of the halide and solid reductant addition and of the roasting conditions were extensively investigated. The concentration results on several types of ores from Japan, the Philippines, and New Caledonia are presented. Laterite is a residual product of rock decay in tropical and subtropical regions, and consists mainly of hydrated oxides of iron and alumina. Those derived from serpentine sometimes become enriched in nickel, cobalt, and chromium contents. Oxidized nickel ores are of the similar origin, but their nickel as well as silica contents are higher due to gamierite-type silicates. Apparently, nickel enrichment is more pronounced in the transition region between the surface layer of iron laterite and the underlying serpentine. Iron laterites often contain over 50% iron, and their reserve is reported to exceed 22 billion tons, corresponding approximately to 20% of the world iron ore reserve.1 It is readily apparent, therefore, why the iron laterites have attracted much attention of the steel industry as a potential source of iron ores. Numerous attempts to remove nickel and chromium as byproducts, have been reported in literature.' Worldwide discoveries of high-grade iron ore deposits in recent years have inevitably lessened the interests in iron laterites. However, in view of the tremendous potential for their gross value and supplies of nickel, cobalt, chromium, and alumina along with iron, the problem remains as a challenge. Much of the chromium in laterites is present in the form of relatively coarse particles of chromite, and various classification methods have successfully been applied for its removal.2,3 The nickel, however, is intimately associated with limonite, and ordinary concentration techniques are totally ineffective. Much attention has, therefore, been given to hydro-metallurgical or pyrometallurgical means. Yet, all the known processes appear to have limitations either economically or for the use of products as iron raw materials due to a high residual content of nickel. Some attempts have been made to pre-roast laterites or oxidized nickel ores, particularly with sulfidizing agents, and to remove nickel either by magnetic separation,' or by flotation.4 It is apparent that any such concentration process would require grain growth of nickel during roasting for effective separation. Oxidized copper ores are reported to be concentrated by the segregation roasting-flotation process,5 in which the ores are roasted with a chloridizing agent and a carbonaceous reductant in order to promote the growth of metallic copper through repeated cycles of copper chloride volatilization and its reduction on the solid reductant surfaces. Examination of a vapor pressure-temperature diagram of various metal chlorides indicates that a separation of nickel from iron may be effected by a similar process. In fact, the segregation roasting of laterites was reported to increase the extraction of nickel by the ammonia leach process, as compared to the ordinary reduction roasting.6 In the present article some of the preliminary experimental results of the segregation roasting, followed by either flotation or magnetic separation, on laterites and oxidized nickel ores are reported. The effects of various parameters in the roasting as well as in the concentration steps are discussed. MATERIALS AND METHODS An oxidized nickel ore from Thio, New Caledonia, and three laterites from Homonhon, the Philippines, Wakasa and Miyagawa, Japan, were selected for the

Jan 1, 1967

By W. P. Evans, R. W. Buenneke

Warren and Averbach's multiple order, Fourier method was applied to solid specimens of SAE 1045 steel. The material was hardened to three hardness levels and specimens of each hardness were shot peened to three intensities. Particle size, root-mem-square strain, mean strain, md macro residual stress were determined for each. Microstrains caused by either hardening or peening varied markedly over microregions. In general, increasing the hardness or peening intensity increased the rms strain and decreased the particle size. Similar effects were observed by varying hardness and peening intensity independently. At a Rockwell hardness of C 50, peening had little effect on line broadening, but both mean strain and macro residual stress increased. Mean strain was independent of column length. Induced macro residual stress by peening was affected most by initial hardness, but not by specific peening intensity. The purpose of this work is to establish the state of residual strain and particle size by X-ray diffraction in hardened and cold-worked plain carbon steel and attempt to relate these X-ray measured parameters to fatigue performance. X-ray line broadening (and its micro implications), along with X-ray residual stress (and its macro implications), may be basic indicators of the inherent fatigue resistance of the material. X-ray line broadening is caused by variable lattice strains and small particle size. Both are a result of plastic deformation which accompanies hardening or cold working processes. Therefore, X-ray line broadening is a good measure of both. warren1 has recently reviewed the Warren and Averbach2,3 Fourier analysis of line broadening. Strain and particle size effects can be separated because broadening due to particle size is independent of order of the diffraction peaks, while broadening due to strain is not. Microstrain is obtained as a root-mean-square strain averaged over discrete distances within the crystals causing diffraction. These distances are quite small, varying from 10 to 10081, and may be interpreted as the gage length over which the strains are averaged. Because of their variable nature, the X-ray line is broadened. The plot of rms strain vs distance (or column length) within the specimen gives a measure of their variability. Small particles also cause X-ray line broadening as already mentioned. A particle is interpreted as a region within a crystal or grain which diffracts X-rays coherently. This region is one of given orientation and may be bounded by a small angle grain boundary, dislocations, a twin boundary, or a stacking fault. The present work covers measurement of X-ray line broadening and macro residual stress on an SAE 1045 steel, quenched and tempered to various hardnesses. Various amounts of cold working were produced by shot peening the surfaces to various Almen intensities. Particle size, root-mean-square strain, and mean strain were calculated from the Fourier coefficients of the X-ray diffraction profiles in a direction normal to the peened surface. No effort was made to separate the various causes of particle size broadening. Macro residual stresses were reported in directions parallel to the peened surface. I) X-RAY METHOD The Fourier coefficients were determined for the 110 and 220 X-ray profiles. They were corrected for instrumental broadening by the method of Stokes,4 using an annealed reference specimen of similar geometry presumed to be free from broadening due to small particles and distortions. The nth Fourier cosine coefficient, A,, is related to a particle size coefficient, Ap, and a distortional coefficient, ADn, by the equation:

Jan 1, 1963

By A. J. Shaler, J. Prieto Isaza, John Wulff

TANTALUM metal has a number of unique properties which give it widespread application in modern technology and in research. In electronic apparatus involving high temperatures in vacuo some of the refractory metals become brittle. Tantalum retains its ductility at elevated temperatures, and this property, together with its low vapor pressure and its ability to absorb gases, make it important in this field. Its chemical inertness in the presence of acids, halogens, and other corrosive media, makes it useful in chemical apparatus and in neuro and orthopedic surgical applications. As an addition to tungsten carbide in steel-cutting grades of cemented-carbide tools, the carbides of tantalum and of its sister element columbium have found considerable use. The present-day method1 of manufacturing tantalum is to sinter a powder compact of the metal in vacuo. Because tantalum- columbium alloys are difficult to work and since tantalum ores almost always contain columbium, the two metals must be separated chemically, the products of the separation being generally in the form of potassium tantalum fluoride and potassium columbium oxyfluoride. These salts are used in fused-salt electrolytic baths from which coarse metallic powder is deposited as a sponge at the cathode. Finer powder can be made from the coarse product or from tantalum scrap by first submitting it to an embrittling heat treatment in hydrogen and then crushing it. The fine hydrogen- containing powder may subsequently be degassed in vacuo at a high temperature. Prompted by the success of others2,3 in the magnesium reduction of titanium and zirconium halides, one of the authors under- took4 an investigation of the thermo- chemistry of the reaction between solid magnesium and gaseous tantalum penta-chloride, a subject which had not previously been studied. He found that the heat of formation of tantalum pentachloride is approximately 364,250 cal per mol at temperatures lower than the melting point of magnesium. A value of 83 units was found for the standard entropy at these temperatures. With these values, it was shown that magnesium and tantalum pentachloride are capable of reacting exothermically at temperatures less than the melting point of magnesium, and that no great violence is to be expected when these substances are heated together. The exothermic nature of the reaction indicated that the process should be efficient and should not require much externally applied energy. Tantalum pentachloride is not commonlv made commercially, and any process using it therefore involves the subsidiary problem of producing and handling this substance. A series of experiments was carried out in which dried chlorine saturated with carbon tetrachloride was passed over heated tantalum, either in the metallic state or combined

Jan 1, 1947

Prof. Frank H. Probert, dean of the College of Mining of the University of California, visited the mining areas in the devastated regions as a member of the Bureau of Mines committee, which is studying the problems presented in the rehabilitation of mines there. He says that the absolute destruction of the coal mines in the Pas de Calais section makes it-necessary to use either the Westphalia or the Saar valley coal. The Saar mines, however, produce a poor quality of coking coal: therefore, it will not be possible to operate blast furnaces very efficiently unless provision is made for the introduction of better coal. He believes

Jan 6, 1919

By K. A. Svanstrom, W. R. Opie

Problems associated with deposition of titanium infused chloride baths using TiCl4 as a feed material are reviewed. A potentially workable cell design using Alumdum diaphragms is discussed. Problems inherent to diaphragm-type cells are emphasized and experiments described which led to the development of a cell without a diaphragm. INVESTIGATORS assigned the problem of developing a commercial electrolytic process for making titanium metal have found that they are faced with the difficulty of overtaking rapidly improving magnesium and -sodium reduction processes. The ultimate goal must be a simple process that can be conducted with low-cost raw materials in equipment that is inexpensive to build and operate. This paper deals with some work of a preliminary nature conducted by personnel of the Research Laboratories, National Lead Co., Titanium Division. Many others have reported on the general subject of depositing titanium from fused salt electrolytes. A partial bibliography is attached. PRIMARY CONCEPTS Anyone attempting to deposit titanium metal from fused chloride electrolytes using TiC14 as a source material is faced with at least the following problems: 1) Getting the titanium into solution in the bath. 2) Controlling oxidation and reduction reactions associated with multiple valency of titanium, which result in low electrical efficiency. a) Prevention of dichloride oxidizing to trichloride and trichloride to tetrachloride at the anode. b) Prevention of trichloride from being reduced only to dichloride at the cathode. 3) Prevention of metal formation away from the cathode thru disproportionation of titanium dichloride to satisfy the equilibrium. 3 TiCl2 == 2 TiCl3 Ti [I] 4) Protection of reduced chlorides in the bath from reaction with oxygen from the bath container or air. 5) Removing from the bath the deposited metal formed without allowing it to become contaminated with oxygen or nitrogen. 6) Selecting cell materials of construction which will not contaminate the metal product or cause cell inefficiencies. EARLY EXPERIMENTS The initial attempts made to electrodeposit titanium from fused chloride baths using TiCl4 as a source material indicated that TiCl4 was essentially insoluble in molten chlorides of alkali and alkaline earth metals. If, however, the TiCl4 was introduced close to a nickel cathode some metal could be formed and appreciable quantities of reduced chlorides would be present. These reduced chlorides reacted with any oxygen present in the atmosphere above the bath and would also diffuse quickly to the anode (graphite) where they would react with chlorine and be evolved as TiCl4. The net electrolytic efficiency of such a cell is essentially nil. The TiCl4 evolves from the anode at almost the same rate that it is introduced in the vicinity of the cathode although a small amount of titanium metal can be formed on the walls of the cathodic pipe. It becomes apparent from the operation of such a cell that: metal can be deposited on the cathode, although of small particle size and a nonadherent nature, and when reduced chlorides are present in the electrolyte, TiCl4 can be absorbed, probably by the following reactions: TiCl4 + TiC12 - 2 TiCl3 [21 2 TiCl3 + 2 faradays - 2 TiC12 + C12 [31 DIAPHRAGM CELLS These facts encouraged the development of cells containing diaphragms to prevent migration of reduced chlorides from the cathode area to the anode. Small-scale cells for process development are described by Alpert, Schultz, and Sullivan.20 A larger brick-lined cell incorporating internal heating by passing ac through the bath is shown in

Jan 1, 1960

THIS chapter and Chapter 19 deal with the heat quantities involved in open-hearth steelmaking, including the thermal efficiency of the furnace as a generator of high-temperature heat, the heat storage in the steel and slag produced and in the furnace walls, and the heats of the various chemical reactions involved in combustion, in the formation of slag, and the refining of steel. The fundamental laws to be considered are the first two laws of thermodynamics as applied to problems involving sensible and potential (or latent) heat only: 1. Heat input equals heat outflow plus storage. 2. Heat may be transferred only from a hotter body to a colder one. The first of these laws relates to the various heat quantities or the heat balance of the process. No one has as yet made an open-hearth heat balance that came out almost exactly balanced. The cause probably lies in the difficulties of accurate temperature and flow-rate measurements at the high temperatures involved and the inherent complexities in flow distribution and air leakage present in any real open-hearth furnace system. Some idea of the magnitude of the heat quantities involved can be obtained by a brief, crude outline of the heat balance of a 90-ton heat of steel. We will assume a 60 to 70 per cent hot- metal charge in a fairly fast working and only moderately efficient furnace, burning fuel oil, with a fuel consumption of around 4 million Btu per net ton of ingots produced. The time from start of charge to tap is 9 hr. During this period, the oil burned represents 360 million Btu and the sensible heat in the preheated air at the port ends is 117 million Btu, so that the total heat input at the ports is 477 million Btu. Heat stored in the steel and slag at the end of the heat, plus the various amounts absorbed by certain bath reactions, amounts to a total of 195 million Btu, but 120 million of this is supplied by the heat in the hot metal and by various heat-evolving reactions in the bath,

Jan 1, 1951

THIS chapter and Chapter 19 deal with the heat quantities involved in open-hearth steelmaking, including the thermal efficiency of the furnace as a generator of high-temperature heat, the heat storage in the steel and slag produced and in the furnace walls, and the heats of the various chemical reactions involved in combustion, in the formation of slag, and the refining of steel. The fundamental laws to be considered are the first two laws of thermodynamics as applied to problems involving sensible and potential (or latent) heat only: 1. Heat input equals heat outflow plus storage. 2. Heat may be transferred only from a hotter body to a colder one. The first of these laws relates to the various heat quantities or the heat balance of the process. No one has as yet made an open-hearth heat balance that came out almost exactly balanced. The cause probably lies in the difficulties of accurate temperature and flow-rate measurements at the high temperatures involved and the inherent complexities in flow distribution and air leakage present in any real open-hearth furnace system. Some idea of the magnitude of the heat quantities involved can be obtained by a brief, crude outline of the heat balance of a 90-ton heat of steel. We will assume a 60 to 70 per cent hot- metal charge in a fairly fast working and only moderately efficient furnace, burning fuel oil, with a fuel consumption of around 4 million Btu per net ton of ingots produced. The time from start of charge to tap is 9 hr. During this period, the oil burned represents 360 million Btu and the sensible heat in the preheated air at the port ends is 117 million Btu, so that the total heat input at the ports is 477 million Btu. Heat stored in the steel and slag at the end of the heat, plus the various amounts absorbed by certain bath reactions, amounts to a total of 195 million Btu, but 120 million of this is supplied by the heat in the hot metal and by various heat-evolving reactions in the bath,

Jan 1, 1964