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By Harry M. Mikami

Chromite is the only ore mineral of metallic chromium and chromium compounds and chemicals. Because of this fact, chromite and chrome ore are used synonymously in trade literature. In commercial market quotations, chrome ore is the term commonly used. Chromite per se, because of properties imparted by its chromium content, is used in refractories and in special purpose molding sands for metal casting. There are many other minerals containing some, generally minor, amounts of chromium, but none are commercial sources of the element (Thayer, 1956). Chromium and chromite have many diverse uses that, directly and indirectly, critically affect vast segments of our modern industrial system. Most important are probably the metallurgical applications wherein chromium is a component of heat-, abrasion-, corrosion-and oxidation-resistant and high-strength alloys of many types. Stainless steels are the largest volume category of chrome-bearing alloys. Chromium chemicals are used in leather tanning, in pigments, dyes and mordants, printing, chemical process industries, photography, pharmaceuticals, metal plating, pure chromium metal production, and for many other purposes. Chromite is a necessary constituent in basic refractories indispensable for the production of steel, copper, cement, and glass. Under present conditions, the US and North America, with the possible exception of Cuba, have no commercial ore reserves. There are chromite deposits, as will be described, but they would be used only under highly abnormal conditions if all outside sources were cut off for an extended period. All chromite used in the US is imported from the eastern hemisphere in which are contained the principal world reserves. The main suppliers in 1980 were the Republic of South Africa (43%), the USSR (21% ), the Philippines (12%), Albania (11 %), Turkey (8%), and others (5%). The strategic nature of chromite is obvious. End Uses-Grades and Specifications As noted before, the three principal uses for chromite are metallurgical, refractories, and chemical with a fourth minor use as foundry molding sand. For metallurgical applications chrome ore is first reduced in electric carbon arc furnaces to various types of ferrochromium alloys. There are high, medium, and low carbon ferrochromiums with carbon ranging from 0.01 up to 10%. Chromium itself ranges from 50 to 73 %. Ferrosilicon chromium and ferrochromium-silicon grades have chromium from 33 to 67% and silicon from 3 to about 48%. Since iron is reduced with chromium, the Cr:Fe ratio of the ore will determine the ultimate grade of the ferrochromium whereas carbon and silicon can be controlled during processing. MgO, A12O3, CaO, and excess SiO2, are removed in slag. A small amount of pure chromium metal is prepared by alumino-thermic and electrolytic processes from essentially iron-free chrome components that have been made via the chemical route. The higher grades of ferrochromium with chromium in the 66 to 73% range can only be made from ores with not only high chromium content, but low iron, i.e., high Cr:Fe ratio. These ores, conventionally termed metallurgical grade, have Cr2O3 contents of 45 to 56% with Cr: Fe ratios of 2.5 to 4.3. A standard composition is generally 48% Cr2O3 and 3:1 Cr:Fe ratio. Very high grade ores are often blended with lower grades even with the high iron chemical grade. For some ferrochromiums, additions of high alumina refractory grade are used as slag conditioners to facilitate smelting while still contributing chromium values. A lower grade ferrochromium, the high carbon charge chrome, has become the predominant grade in use today for making chromium-bearing steel alloys. This

Jan 1, 1983

By Colin J. Dixon

The full realization of the potential of computers in geological in- formation system demands new approaches to the machine representation of information. At the same time, the feasibility of such a system, particularly in commercial field, demands greater freedom in input preparation and a degree of standardization in the arrangement of subject matter system. The paper describes some of the basic notions of project "GEOSEMANTICA 70". The aim of the project is to devise means of storing real geological informations in a machine rather than the representation of the information in human language form. This is seen as the only long-term solution to the problems of the complex vocabulary of geology and the complex syntax of geological description. Effectively, a machine language is being defined, consisting of a set of symbols and a date structure for representation of geological and related information. Beyond this, is the definition of a set of rules allowing the use of constrained text as an input/output medium. The investigation is oriented primarily to the representation and handling of information about mineral deposits and the associated geographic, economic and engineering information.

Jan 1, 1969

By W. N. Roberts

Hadfielcl steel has been studied by transmission electron microscopy to determine the microsl.rtic-ture of the cold-worked material, which has been a subject of controversy for many years. The presence of fcc deformation twins in specimens deformed in tension, by hamnzering, and by explosive -shock loading at room temperature lzas been established by electron diffraction. No evidence of a mar tensite was detected in any of the speciwens. Small amounts of E martensite were idenLified in the hamnleved specimens. DESPITE numerous researches on Hadfield steel since its discovery in 1882, there is still disagreement on the nature of transformations in the cold-worked material. Collette el al.,' using X-ray and electron diffraction, have found evidence for stacking faults, E martensite, and a martensite in Hadfield steel deformed in tension at room temperature. Nishiyama and Simizu,' using electron microscopy, have found stacking faults and E martensite in hammered Hadfield steel. White and Honeycombe have concluded from X-ray diffraction that Hadfield steel remains fully austenitic even after severe cold work at -196 Previous work by the author, indicating the presence of a, martensite in deformed Hadfield steel, was in error due to a faulty interpretation of the electron-diffraction patterns. Various workers,5'7 over the years, have speculated on the presence of deformation twins in Hadfield steel, largely from such circumstantial evidence as the persistence of slip bands with repeated polishing and etching, the presence of serrations in the stress-strain curve, and the absence of evidence of a martensite by X-ray measurements. The advent of electron-transmission microscopy and se- lected-area diffraction has made possible the positive identification of fine deformation twinning. PROCEDURE For tensile tests, standard ASTM specimens of 2-in. gage length, ground from 0.12-in. Hadfield steel sheet, were solution-treated at 1050°C for 30 min in a salt bath, to avoid decarburization, and water-quenched. The grain size was about 0.01 sq mm. Chemical analysis of the steel after heat

Jan 1, 1964

By Ellis Clark

THE greater portion of the brown ore in the vicinity of Easton, along the north slope of the Lehigh Mountain or Durham range of hills, is obtained from mines instead of from open cuts or quarries, as is the case in the ore-beds in the western part of Northampton County, in Lehigh County, and in Berks County. The reasons for this method of procedure are various, and the principal causes of the shaft and regular mine system of working being adopted instead of the open air cuts, are : First, the large amount of stripping that would be necessary, as the richer and more valuable portions of the ore do not appear to be found as near the surface as those in other portions of the Kittatinny valley; second, the occurrence of the ore in regular beds, interstratified with the clay, and, to a less extent, in pockets or erratic deposits, as is the case in the mines of Lehigh County; and third, on account of many of the mines being situated at the immediate base of the Lehigh Mountain, where the surface water would be in such large quantities as to be with difficulty handled, and where the subsequent caving in of the sides of the open cut would be almost certain to expose the gneiss rock, which is water-bearing, the large quantities of water coming from which would probably drown out the ore-bed. Shafts, and a regular system of gangways and mining are therefore required by the configuration of the surface, the depth of the deposits and their geological structure. The ordinary size of the shafts is about four feet square, but where an extensive plant of pumping machinery is required the size may be increased to eight feet by six, with two compartments for the hoisting and pump-shaft respectively. A man-way, consisting of ladders with rests at intervals of twenty or thirty feet, is comprised in the pump-shaft, the wire rope being used for purposes of ascent and descent only in exceptional cases, on account of accidents which

Jan 1, 1879

By F. A. Crossley

The key to disagreements between Blackburn's findings and mine is the word equilibrium". My work attempted to define the equilibrium diagram of the titanium-rich end of the Ti-A1 system. It can readily be shown that Blackburn's conclusions are based primarily on the examination of structures substantially removed from equilibrium. The diagram presented in Fig. 16 is properly labeled a "phase diagram". However, it appears that Blackburn either does not understand or does not accept the difference between "phase diagram" and "equilibrium diagram" as defined in the Metals Handbook.17 The conflict lies not in Blackburn's data but in his interpretation of it, and his use of "transformation", "phase diagram", and "equilibrium diagram" as synonymous terms. I share his view that the light microscope is much inferior to the transmission electron microscope for the study of transformations; but this fact does not render the light microscope useless or untrustworthy. The difficulties experienced with the Ti-A1 system have not been due to the limitations of the light microscope, but rather to the extreme sluggishness in achieving equilibrium at temperatures below 1000° C. Were it not for the light microscope employed with polarized light, the twin phase syndrome' might still be unrecognized and, as a consequence, still adding to the confusion of Ti-A1 investigations. (Ref. 1 should read ... Contract No. N161-25952 ... vol. 236.) Other, more sophisticated techniques, including electron transmission, simply confirm the erroneous tentative conclusions drawn from observations of structures due to the twin-phase syndrome. By the standards of most of the investigations of the Ti-A1 systems, seven of the fifteen compositions investigated by Blackburn were seriously contaminated with oxygen. The writer has found that 0.1 wt pct 0 shifts the a + Ti3A1 boundary to 1 at. pct lower A1 content at 700°C. At constant aluminum content, this corresponds to a temperature shift of the boundary of +25°c.18 Blackburn advises that the first group of alloys contained 0.1 to 0.15 wt pct 0, bur he does say whether the analyses were performed on as-received material or on specimens in their final state of heat treatment. This is especially important considering the 20-mil-thick starting materials. If specimens had been annealed in the two-phase a + 6 region it would have provided an indication of the final degree of oxygen contamination since up to about 12 at. pct A1 the boundaries of this region are well-defined for low-oxygen alloys. Blackburn questions the capability of light microscopy in determining phase boundaries in the Ti-A1 system. I submit that the a/a + Ti3A1 boundary in Fig. 1 of Ref. 1 over the composition range from 10 to 18 at. pct A1 was determined by dilatometry and supported by electron diffraction. Specimens of alloys containing 8, 10, 12, and 14 at. pct A1 were aged at 550°C for 1000 hr (under stress of 5000 psi to accelerate the tendency to equilibrium) and then fractured in tension at room temperature. Collodion was applied to the as-fractured (unetched) surface and, when stripped, carried away particles identified by electron diffraction as Ti3A1. Perhaps Blackburn will explain why these electron diffraction data were ignored. At this time, a technique for revealing or indicating

Jan 1, 1969

By Gregory M. Dexter

Recent litigation in Pennsylvania between three coal-mining companies and a private water company resulted in the payment by the coal companies of the equivalent of about $500,000 to buy a new water supply to replace that which had been damaged by acid drainage from strip mining. An investigation of the relevant facts indicates that the water could have been treated by spending about $40,000 on equipment and $15,000 yearly for chemicals, labor, and power until the contarnination could be reduced about 80 pct. The water company's supply, furthermore, had deteriorated largely by reason of dry weather before stripping was begun by the coal companies. Payment to the water company should not have exceeded $300,000 and could have been as low as $100,000. Strip mining of coal is common in Pennsylvania. The most important objection to it in Pennsylvania is generally acid pollution of runoff water. An outline of the methods, therefore, that could be used to reduce such pollution, to compare acid-contaminated waters. and to treat such waters to make them satisfactory for public and industrial use is worth-while. The watershed of the West Penn Water Co. covers about 4.5 square miles, 20 miles west of Pittsburgh, and has two 90,000,000 gal reservoirs supplying about 1,300,000 gal daily for public and industrial use of which 450,000 gal daily are for two railroads. The pollution arises from weathered derivatives of typical'" Coal Measures"' rocks, the principal source being pyrite (and marcasite) in Pittsburgh and Rooster coals. Springs and seeps on hillsides issue from sandstone and limestone formations intersecting shale or clay land surfaces, or from perched water tables. The two reservoirs create an artificial permanent water table. Soap-hardness tests on three seepage samples taken in a dry summer ranged from 150 to 500 ppm. Water sampled came from aquifers above Pittsburgh and Rooster coals, obviating the possibility of contact with pyrite-containing coal. Since acid contamination of mine waters is the result of chemical reactions of oxygen and water with pyrite, it will be reduced by the exclusion of either air or water. The Sunnyhill Coal Co. has applied this principle in its "contouring" method of strip mining by burying contaminated coal-waste material under a compact, smoothed-up surface of top-soil, gravel, clay, and sand at a cost

Jan 1, 1950

By J. E. Hanlon, S. R. Butler, R. J. Wasilewski

It is known that stoichiometric NiTi transforms to a structure of lower symmetry near room temperature. The present investigation deals primarily with the changes in the electrical and magnetic properties which occur at the transformation. The effects of composition and various heat treatments on electrical properties are also discussed. In recent investigations by Purdy and Parr,' Wang et a1.,2 Dautovich and Purdy,~ Dautovich et a1.,4 and the authors, ~,' NiTi has been observed to undergo a martensitic phase transformation from the ordered CsCl (B2) structure to one of lower symmetry. The crystal structure of the low-temperature modification is still not completely worked out. This transformation occurs near room temperature for the stoichiometric composition. The thermodynamic, elastic, crystallographic, and microstructural characteristics of this transformation for some compositions have been previously reported.'-= In the present investigation, the changes in the electrical transport properties and magnetic susceptibility of NiTi when it undergoes the martensitic phase transformation have been measured. The approximate composition range covered is 48 to 52 pct Ti.* *All compositions are given in atomic percent._____________________ EXPERIMENTAL PROCEDURES AND RESULTS 1) Sample Preparation. The NiTi alloys were prepared from iodide titanium (>99.92 pct Ti) and vacuum-premelted carbonyl nickel (>99.95 pct Ni) by repeated arc melting under gettered argon and casting in a water-cooled copper mold. After the cast buttons were hot-forged at 800" to 950°C, the oxidized surface was removed by grinding and etching. Samples were cut from the worked polycrystalline buttons. After fabrication, the samples were annealed 1 hr at 900°C and water-quenched. The composition of the alloys was assumed to be the same as in the initial feed. This assumption was supported by material balance checks on 100-g arc-melted buttons which demonstrated quantitative recovery to within k0.02 pct. The oxygen content of the alloys was '150 ppma (weight) and the carbon content was 30 to 50 ppm. 2) Electrical Resistivity and Hall Effect. The electrical resistivity was measured over the composition range 48 to 52 pct Ti for temperatures varying from 4.2"K to 900°C. The high-temperature and many of the low-temperature experiments were carried out using conventional 4-probe dc techniques.7 The Hall coefficient and ac resistivity were measured at 20 cps using the apparatus shown schematically in Fig. 1. The equipment is basically an ac potentiometer: The resistive or Hall voltage of the sample is balanced by a comparison voltage provided by a dividing network across a standard series resistance. The off-balance signal is amplified by a Tektronix 122 amplifier and detected by a Princeton Applied Research (PAR) phase-sensitive detector. The precision of the resistivity and Hall coefficient measurements is i0.1 and i3 pct, respectively. The uncertainty in the data is increased by i2 pct from the precision limits because of uncertainty in dimensions and possible end effects. The temperature dependence of the electrical resistivity and Hall effect for a stoichiometric (50.0 pct Ti) NiTi sample are illustrated in Fig. 2. Above 75"C, this sample has essentially the B2 structure, while below about 0°C it is completely in the low-tempera-

Jan 1, 1968

By Lester Tarnopol, Ralph Hultgren

A considerable interest in the subject of superlattices has been manifested by many papers and reviews that have recently appeared, both in physical and metallurgical publications. This interest is due largely to the apparent simplicity of the ordering process, which permits the explanation of many phenomena on the basis of elementary theory. Moreover, ordering may cause important changes in the physical properties of alloys. In this paper, we shall discuss the causes of superlattices in terms of simple properties of the elements that give rise to them, together with a series of experiments performed to test our conclusions. Evidence is presented that in some cases the process of ordering is more complex than might be supposed. While the different species of atoms are usually found in random positions in alloy lattices, in some cases unlike atoms tend to be nearest neighbors. Bethe's1 "order of neighbors" is a statistical measure of thib tendency. At suitable compositions it is possible for atoms in large regions to be regularly arranged, which causes superlattice lines to appear. in X-ray diffraction patterns. Bragg and Williams2 haw dealt with this "long-distance order" in their fundamental work 011 superlattices. Excellent discussions of superlattices are to be found in current reviews TheRmodynamic Considerations Thcrmal vibration tends to destroy order. The magnitude of the effect can be determined from the entropy of mixing, which is calculate from first principles. Since the ordered state has the lower entropy, it must also have a lower internal energy to be stable at any temperature. The difference in internal energy determines the critical temperature at which long-distance order disappears. According to the, theory of Bragg and Williams,~

Jan 1, 1939

By Lester Tarnopol, Ralph Hultgren

A considerable interest in the subject of superlattices has been manifested by many papers and reviews that have recently appeared, both in physical and metallurgical publications. This interest is due largely to the apparent simplicity of the ordering process, which permits the explanation of many phenomena on the basis of elementary theory. Moreover, ordering may cause important changes in the physical properties of alloys. In this paper, we shall discuss the causes of superlattices in terms of simple properties of the elements that give rise to them, together with a series of experiments performed to test our conclusions. Evidence is presented that in some cases the process of ordering is more complex than might be supposed. While the different species of atoms are usually found in random positions in alloy lattices, in some cases unlike atoms tend to be nearest neighbors. Bethe's1 "order of neighbors" is a statistical measure of thib tendency. At suitable compositions it is possible for atoms in large regions to be regularly arranged, which causes superlattice lines to appear. in X-ray diffraction patterns. Bragg and Williams2 haw dealt with this "long-distance order" in their fundamental work 011 superlattices. Excellent discussions of superlattices are to be found in current reviews TheRmodynamic Considerations Thcrmal vibration tends to destroy order. The magnitude of the effect can be determined from the entropy of mixing, which is calculate from first principles. Since the ordered state has the lower entropy, it must also have a lower internal energy to be stable at any temperature. The difference in internal energy determines the critical temperature at which long-distance order disappears. According to the, theory of Bragg and Williams,~

Jan 1, 1939

By Ellis Clark

The greater portion of the brown ore in the vicinity of Easton, along the north slope of the Lehigh Mountain or Durham range of hills, is obtained from mines instead of from open cuts or quarries, as is the case in the ore-beds in the western part of Northampton County, in Lehigh County, and in Berks County. The reasons for this method of procedure are various, and the principal causes of the shaft and regular mine system of working being adopted instead of the open air cuts, are: First, the large amount of stripping that would be necessary, as the richer and more valuable portions of the ore do not appear to be found as near the surface as those in other portions of the Kittatinny valley; second, the occurrence of the ore in regular beds, interstratified with the clay, and, to a less extent, in pockets or erratic deposits, as is the case in the mines of Lehigh County; and third, on account of many of the mines being situated at the immediate base of the Lehigh Mountain, where the surface water would be in such large quantities as to be with difficulty handled, and where the subsequent caving in of the sides of the open cut would be almost certain to expose the gneiss rock, which is water-bearing, the large quantities of water coming from which would probably drown out the ore-bed. Shafts, and a regular system of gangways and mining are therefore required by the configuration of the surface, the depth of the deposits and their geological structure. The ordinary size of the shafts is about four feet square, but where an extensive plant of pumping machinery is required the size may be increased to eight feet by six, with two compartments for the hoisting and pump-shaft respectively. A man-way, consisting of ladders with rests at intervals of twenty or thirty feet, is comprised in the pump-shaft, the wire rope being used for purposes of ascent and descent only in exceptional cases, on account of accidents which

Jan 1, 1879

By Michel Dupuy, Daniel Calais

The study of self-diffusion of plutonium in E phase has been carried out by the welded couples method. The tracer used was puZ4O which is detected by its X-ray emission (conversion lines of uranium which are computed between 13 and 21 kev). Intensities were measured with a scintillation counter. Each layer was removed in a direction parallel to the original interface with a grinding machine and a thickness measured with a pneumatic comparator. The concentration-penetration curves obtained were corrected for the effect of heating time from room temperature to annealing temperature and for the expansion due to phase transformations of plutonium. They were analyzed by the generalized Gruzin method. Self-diffusion of plutonium in E Phase is very fast cm per sec between 500" and 620°C) and the diffusion zones are 2 to 3 mm wide for annealing times ranging from 30 min up to 10 hr. The Arrhenius law gives the temperature dependence in the form: From the point of view of self-dqfusion, PUE phase falls into the anomalous bcc metals category (Tip , Hfp, Zrp, Uy) with a low-frequency factor and an activation energy lower than those provided by standard correlations. No theory proposed hitherto to explain these anomalies (influence of dislocations, of extrinsic vacancies bonded to inlpurities, of bi-vacancies) can clearly explain the self-diffusion coeffzcients of plutonium. DIFFUSION in bcc metals is a present-day problem. A recent symposium (Gatlinburg, 1964), followed by a book,' has been devoted to it. A great many experiments seem to show that diffusion in certain bcc metals obeys unexpected laws. The activation energies measured are sometimes strangely low (B hafnium, y uranium). For certain metals (0 zirconium, p titanium) the curves of log D (D = diffusion coefficient) as a function of 1/T (T = absolute temperature) are not linear. The frequency factors Do, which are of the order of 1 sq cm sec-' in fcc metals, vary from 1 to 10~6 sq cm sec-'. Various theories have been put forward to explain these anomalies; none is yet satisfactory. We wished to introduce a new experimental result by studying the self-diffusion in c plutonium. This allotropic phase, stable from 475°C up to the melting point (640°C), is in fact bcc. Unfortunately, nothing is known of the characteristics of the point defects in this phase, which limits the scope of the hypothesis which can be made about the mechanism(s) of self-diffusion in plutonium. 1) EXPERIMENTAL METHODS 1) Principle. We used the welded couple method. The two pellets of the couple initially have different 240 isotope contents (X emitter). After diffusion, the concentration/penetration curves are drawn up by the generalized Gruzin method. 2) Gamma Spectrography. The metal used in our study is plutonium, either low in puZ4O (isotopic content 1 pct) or high in puZ4O (8 pct). The latter also contains plutonium 241 (-1 pct) and 300 ppm of ameri-cium produced by the reaction Pu2U-AmM1 + 8-. The emission spectra of these two plutoniums placed in leak-tight vinyl bags have been studied by y spectrograph~. The detector is a thin crystal of thallium-doped sodium iodide. The activity of the plutonium rich in 240 is about twice that of the plutonium low in 240 in the energy band of 17 kev (L conversion lines of uranium); this band was used in these measurements. 3) Preparation and Examination of the Diffusion Couples. Diffusion couples were made from plutonium with a high and low PU"' content. Pellets (6 6 mm. thickness 3 mm) mounted on a polishing disc with ground parallel faces were polished mechanically on both sides. In this way, pellets with two parallel faces were easily obtained. The polished pellets were joined by a 6 phase anneal (420°C, 1 hr) in a small screw press (pressure of 20 kg per sq mm cold); a centering ring enabled the two pellets to be pressed coaxially. The couples then were subjected to the diffusion treatment by annealing in the E phase in sealed silica ampules in argon at atmospheric pressure. The annealing temperatures and times are given in Table I. The couples were encased in a mild steel ring, the joint interface being thus parallel to the ground face of the ring. The diffusion couple/ring assembly underwent successive abrasions by means of a magnetic plate grinder. The thickness of the abraded layer was measured with a Solex pneumatic comparator when it was less than 0.1 mm (accuracy 0.2 p) or with a mechanical micrometer (accuracy 3 p) for passes of the order of 0.2 mm. All these operations were done in glove boxes, as plutonium is particularly toxic. After each abrasion we determined the emission spectrum of the ground face. The emissive surface is defined by means of a diaphragm 3 mm in diam. We noted more particularly the X activity in the 17-kev

Jan 1, 1969

By G. H. LeFevre

THE Metal Sales Department, with offices in New York, is responsible for the sale of the Company's products, with the exception of gold and coal. At present the department handles the sales of lead, zinc, silver, antimonial lead, , cadmium, bismuth, arsenic trioxide, and tellurium; gold is shipped direct to the United States Mint and coal is marketed by United States Fuel Company's own sales organization. The department keeps in close touch with the metal markets and collects information on marketing conditions, which it makes available to other departments of the Company. The electrolytic lead produced at the U. S. S. Lead Refinery, Inc., is a high-uality product marketed as corroding grade under the "U. S. S.-ELECTRO" brand. It is largely sold to manufacturers of paints, pigments, lead oxides, and storage batteries.

Jan 1, 1948

By G. H. Gronhovd, W. H. Oppelt

Complete gasification to produce synthesis gas for manufacture of synthetic chemicals and fuels offers possibilities for utilization of the vast lignite fuel deposits in the U.S. The design of a slugging, fixed-bed, pressure gasification pilot Plant is described. Results are presented for initial operation of the plant at moderate pressure and using low-temperature char as fuel. Gasification of solid fuels is becoming increasingly important in the future overall energy picture, both in this country and abroad. Snythesis gas from gasification of coal consists chiefly of carbon monoxide and hydrogen, and after suitable purification and modification this gas can be used in the production of synthetic ammonia, methanol, higher alcohols, and synthetic liquid fuels, or as a reducing gas in the metallurgical field.' Most synthesis gas used in this country is made from natural gas, petroleum oils, and refining tail-gases, but the direct gasification of coal will become more attractive as costs of petroleum oils and natural gas increase.' A gasification process designed for use with brown coal and lignite was developed by the German Lurgi Co. prior to World War 11. In this process a fixed bed of lump-sized fuel is gasified with steam and oxygen at pressures ranging from 370 to 440 psi. Effective heat exchange between the ascending high-temperature gases and the descending solid fuel results in low gas outlet temperatures, high thermal efficiency, and favorable oxygen consumption. Lurgi gasifiers are used commercially for the production of synthesis gas or as a substitute for coal gas in many countries, including Germany, Czechslovakia, Great Britain, South Africa, Australia and Pakistan.3-6 The chief disadvantage of the conventional Lurgi gasifier which operates under nonclinkering conditions is that large quantities of excess steam must be supplied with the oxygen-steam mixture to reduce the temperature in the fuel bed below fusion temperature of the ash. Most of the steam leaves the gasifier undecomposed with the product gas and, after cooling, produces large amounts of dilute liquor. Evaluation of fixed-bed gasification experiments using dry-ash removal indicated that by increasing the oxygen concentration in the oxygen-steam blast the temperature in the combustion zone could be raised high enough to operate under slagging conditions. 7-8 Operation of a fixed-bed pressure gasifier under slagging conditions would reduce the steam requirements and the volume of waste liquor and would increase the steam decomposition, the overall thermal efficiency of the process, and the rate of gas production per unit cross sectional area of the gasifier. Because the Lurgi gasification process, modified for slagging operation, offered possibilities for efficient gasification of American lignite, the Bureau of Mines decided to investigate the process on a pilot-plant scale at the Grand Forks, N. D., Lignite Research Laboratory. DESIGN Description of Pilot Plant: A flowsheet of the Grand Forks slagging gasification pilot plant is presented in Fig. 1. The gasifier unit consits of the coal lock, the gas generator, and the slag lock. The fuel, which is periodically charged to the coal lock, moves by gravity flow into the generator and is continuously gasified by an oxygen-steam mixture introduced at the bottom of the gasifier. Molten slag is formed at the hearth and flows through a central taphole into a water quench bath. The slag-water slurry is periodically discharged from the slag lock. Process steam is generated and superheated in separately-fired, oil-burning units. Oxygen is supplied to the gasifier from a gas storage bank located some distance from the pilot plant. The capacity of the oxygen storage bank is about 130,000 standard cu ft at 2200 psig. Liquid oxygen is delivered by truck and is converted to gas during the filling operation. The superheated steam and oxygen are metered separately, then mixed and fed to the gasifier tuyeres. The gas generator is surrounded by a water jacket. The steam formed is separated in the steam drum and then discharged to the gas offtake, thus equaliz-

Jan 1, 1961

By H. M. Howe

PART I. INTRODUCTORY. § 24. INTRODUCTION.-This paper discusses the chief existing data as to the temperature, in iron-carbon alloys, of Ae.3, the upper limit of the transformation range when in equilibrium, as distinguished from Ac3, the temperature at which the end of the transformation is noted in heating up, and from Ar3, that at which its beginning is noted in cooling down. The former is in fact carried above Ae3 and the latter below Ae3 by lag. I touch incidentally on the influence of manganese on Ae3 (§ 29, p. 1102). The sections, tables, and illustrations, are numbered consecutively with those in the accompanying papers by Howe and Levy on Determination of, the Position of Ae3 in Carbon-Iron Alloys, and by Burgess, Crowe, and Rawdon on Thermal and Microscopical Examination of Professor Howe's Standard Commercial Steels, to which the present paper forms a sequel. § 25. The contradictoriness of our present evidence is shown by grouping it together in Fig. 14. For instance, both Goerens and Meyer (Series 2) and Meuthen (Series 12) used practically stationary temperature, and thus reduced the influence of lag very greatly; yet Ae3 for 0.32 carbon steel according to the former investigators is 894°, but according to Meuthen it is at or below 770°, a discrepancy of 124° or more. In view of our ability to measure these high temperatures within a few degrees, the existence of such a discrepancy is as unwelcome as it seems needless. I attack the thankless task of bringing some order out of this chaos.

Jan 6, 1913

By R. Taggart, J. W. Barton, G. R. Purdy, J. G. Parr

The constitution and mechanical properties of heat-treated alloys containing up to 10 pct* Ni in Ti have been investigated. The effects of quenching and of various isothermal treatments ale described, and C-curves are presented. The production of the precipitated and the martensitic hexagonal phases on quenching is discussed. MARGOLIN, Ence, and Nielsenl have determined the titanium-nickel phase diagram. A study of the transformations in gas-quenched and tempered powder specimens was made by Polonis and Parr.' Some isothermal transformation work was carried out by Margolin and ~unshah, who determined transformation curves for 4 and 6 wt pct alloys, while Robinson et al.investigated the formation of the w phase in a quenched and tempered alloy, Margolin and Bunshah showed that while a martensitic transformation could be obtained on quench- ing thin sections of a 4 wt pct alloy, a 6 wt pct alloy precipitated a nonmartensitic phase. The present investigation was undertaken to obtain more information on the transformations in quenched, quenched and tempered, and isothermally transformed lump specimens of alloys containing up to 10 pct Ni. Isothermal transformation curves have been determined for 7 and 10 pct alloys and cooling curves have been obtained for quenched alloys containing up to 7 pct Ni. The mechanical properties of 2, 5, and 10 pct alloys were studied, with the object of relating properties to microstructures. EXPERIMENTAL METHODS Alloys containing up to 10 pct Ni were prepared from sponge titanium and spectrographic standard nickel by levitation-melting and chill-casting in a split copper mold. The 5 and 10 pet alloys were prepared from sponge Ti having an as-melted hardness of 115 Vpn. The other alloys were made from a sec-

Jan 1, 1961

By Edward Hyde

THE HIGH-TEMPERATURE SCALE IN OPTICAL PYROMETRY AT the basis of optical pyrometry lie the theoretical and experimental data of the so-called blackbody. The black body is essentially a theoretical conception, with certain simple properties attributed to it -fundamentally, the property that its radiation at any temperature is a unique function of the temperature and does not involve any other variables. As a theoretical conception, an equation has been developed by Boltzmann connecting the total radiant power with the temperature, and another equation by Planck connecting the distribution of radiant power throughout the spectrum with the temperature. The integral of the latter with respect to wave-length conduces to the former and permits the evaluation of the constant c1 of the Planck equation, ass given in the form. J-= cl?-5 c2 (1) e ? T ? 1 assuming that the constant Q of the Stefan-Boltzmann law E=a(T4-T40) is known. The other constant c2 is arrived at by other methods, which will be discussed later. This equation for the black body lies at the foundation of optical pyrometry. To make the discussion complete, it should be stated that the theoretical black body is quite closely realized by a hollow enclosure with walls at a uniform temperature and radiating through a small orifice. The electrically heated black body, first introduced by Lummer and Kurlbaum, is an essential part of the equipment of a pyrometric research or testing laboratory. Numerous investigations have shown that its radiation conforms to that of the theoretical black body within experimental errors. Hence by operating the electrically heated black body at the melting point of some pure metal for which the temperature of melting has been determined on the vas scale. a standard is obtained for comparison with

Jan 9, 1919

By J. R. Cahoon, W. V. Youdelis

FOR the diffusion of copper in silver-rich alloys, there have been only two previous investigations, that of Seith and Peretti in 1936, and that of Sawatzky and Jaumot2 in 1957. Seith and Peretti obtained a value of 24.8 keal per g-atom for the activation energy of diffusion whereas Sawatzky and Jaumot obtained a value of 46.1 keal per g-atom. Admittedly, Seith and Peretti used relatively high concentrations of 2 at. pet Cu and polycrystalline diffusion couples, while Sawatzky and Jaumot investigated tracer diffusion in single crystals of silver. The difference in the results, however, seems too large to attribute solely to solute concentration, as a change of over 20 keal per g-atom in the activation energy suggests a change in the mechanism of diffusion. Therefore, in the present investigation the diffusion coefficient for copper in polycrystalline Ag-2 at, pet Cu alloy is re-established using conventional sandwich-type diffusion couples and electron-probe microanalyses, and the results are compared with those of the previous studies. The diffusion couples were prepared from high-purity silver (99.999 pet) and high-purity copper (99.999 pet). The silver disks, 1/4 in. long and 4 in. in diam, were machined from an ingot which had been solidified in a dynamic vacuum of 10-3 mm of Hg to eliminate oxygen absorption which otherwise would result in copper oxide precipitation in the weld zone. The alloy disks of similar dimensions were machined from an alloy ingot (nominal composition 2 at. pet Cu) which had been unidirectionally solidified to obtain a predictable solute concentration,3 and homogenized for 1 week at 800°C. Sandwich diffusion couples were made by pressure welding an alloy disk between two silver disks in an induction heating coil. The couples were diffusion-annealed at temperatures of 800°, 756°, 699°, and 630°C in tube furnaces in which the temperature was controlled to better than ± l°C. The diffusion couples were examined metallographically for weld defects, and couples showing even minute defects at the weld interfaces were rejected. Concentration penetration curves were established using an A.R.L. Microprobe analyzer. CuKO radiation was counted and converted to concentration using 0.5 and 1.0 wt pet Cu chemically analyzed standards. Initially, four continuous profiles were obtained, and averaged to obtain the final diffusion curve. The initial analysis was performed commercially and the welds were not located with respect to the profile. Therefore, the results were rechecked by the authors using the Mellon Institute A.R.L. probe. In the latter case, concentrations were obtained at 10-µ steps for four different traverses, and then averaged to obtain

Jan 1, 1968

By C. F. Floe, N. J. Grant, A. Joukainen

A CCORDING to Guertler,¹ Smith and Hamilton were the first to study the Cu-Ti alloy system, but because of the presence of large amounts of impurities their data are inconclusive. Hensel and Larsen² in 1930 and Kroll³ in 1931 determined the high copper end of the diagram. In 1939 Laves and Wallbaum,4 in a short summary of compound determinations in titanium binary alloys, mentioned the existence of a face-centered cubic compound, Ti2Cu, with 96 atoms per unit cell, and also a compound, TiCu3, which was said to have a deformed hexagonal close-packed structure in which ordering had been observed. The existence of a compound, TiCu, was also found but the crystal structure was not determined. Craighead, Simmons, and Eastwood determined the effect of copper on the allotropic transformation in titanium. The investigation was limited to alloys containing from 0 to 5 pct Cu, using titanium of fairly high impurity content. Experimental Procedure The methods used for determination of the diagram included metallographic examination and X-ray and thermal analyses. The system was first worked out using the higher purity "Process A" sponge titanium and oxygen-free copper. The high titanium region was next determined more accurately using iodide titanium and vacuum-melted, oxygen-free copper. Preparation of Alloys: The alloys were prepared by arc melting under prepurified helium atmos- pheres in water-cooled copper crucibles. The high purity iodide titanium alloys were prepared by melting three compositions along with a specimen of unalloyed titanium in a single charge. A multiple crucible was used which consisted of a copper plate with four cup-like depressions. The unalloyed titanium was melted first and acted as a getter for any oxygen and nitrogen in the melting chamber. Since these elements harden titanium, the hardness of the standard specimen was an index of the highest probable contamination of the alloy melts. The sponge titanium alloy melts weighed from 100 to 200 g each and the iodide titanium melts from 20 to 25 g. In order to insure greater homogeneity most of the alloys were melted, turned, and remelted twice. The larger buttons made from sponge titanium were sectioned or crushed before remelting. These alloys up to 30 pct Cu were further homogenized by forging at 925°C. They forged readily up to 20 pct Cu but numerous cracks were formed in the alloys containing from 20 to 30 pct. Above 30 pct Cu the sponge titanium alloys were homogenized by heating for 200 hr at 850°C under prepurified helium. Similarly, the iodide-grade titanium alloys containing up to 3 pct Cu were homogenized at 1000°C for 24 hr and all others at 880°C for 200 hr.

Jan 1, 1953

• One effect of the British devaluation of the Pound Sterling, with its resultant lowering of the pay limit, was the addition of considerable tonnages of previously marginal ore in gold mining. Crown Mines, Ltd., reported that 1,245,000 tons of such ore had been added to available reserves. But for devaluation, a steady decline in ore reserves had been a feature of operations during the previous ten years, and would have continued. •Loree Colliery of the Hudson Coal Co. is using a Humphrey spiral cleaning plant to meet requirements of the state in the matter of stream pollution. However, the process is producing a salable product. •Noranda is considering plans for constructing a commercial sized unit designed to produce elemental sulphuric acid and sintered iron oxide from pyrite. Test plant results have indicated the No. 5 ore zone can be treated by the new process economically. •A magnetic fluid clutch, and magnetic amplifiers for motor and generator control, have been developed under Navy contract by Vickers' Electric Division, in St. Louis, Mo. This constitutes the first commercial production of the clutch recently developed by the Bureau of Standards. •Fuel experts estimate coal production will run up to 500 million tons this year based on the expectation that business conditions will continue to be good. They also expect that in the future the use of coal will increase by 50 pct over today's level. These expectations are based on the fact that it provides the bulk of the heat, light, and power for making steel, for manufacturing, and for generating electricity as well as the development of the coal burning gas turbine and processes for making gas, gasoline, and oil from coal. •Entombed miners may benefit from a two-way communication system which utilizes the earth's strata as a network for electric signals. The use of FM radio waves makes this possible. The invention includes a portable transmitter-receiver unit kept near the face, and a more powerful portable equipment of the same sort above ground. In use, two probes on wires from the apparatus are driven into the earth. • The Union of South Africa has launched a uranium production project which government leaders think will help the West maintain world atomic supremacy. Experiments under way in the pilot plants are expected to lead to the establishment of a chain of processing factories along the Witwatersrand in which uranium will be reclaimed from gold tailing. •Recent developments in mechanized mining at the Bureau of Mines oil-shale mine near Rifle, Colo., have lowered mining costs to 29 cents per ton of shale. The cost of producing crude shale oil from 30-gal-per-ton-shale, using the new mining and processing techniques, would be about $1.50 per barrel. This is 500 lower than any previously stated price. • COMINCO is planning to open the old Bluebell lead-zinc mine near Nelson, B. C., on a 500-ton-per-day basis. The old workings will be pumped and a 970-ft incline sunk. A mill will be constructed at the property.

Jan 7, 1950

By Emerson F. Heald

A systematic study was made of new and old data on chemical activities in Fe-Pt alloys at elevated ternperatuves. Experimental results may be expressed in terms of the excess free energy using Least-squares analysis of the data gave the following values for the constants: for the temperature range 1130° to 1350°C, and tentatively to 155O°C, B = -3.326564 and C = 0.221051; for the temperature range 650" to 850°C, B = -2.555690, C = 1.762735, and D =0.097196. In the study of iron-containing silicate systems, it is sometimes desirable to have a direct experimental measure of the activity of iron in the system. The well-known solubility of iron in platinum, often a headache in experimental work on iron compounds under reducing conditions, can be used to advantage in this respect. If the activity of iron in an Fe-Pt alloy in equilibrium with the silicate is known as a function of the composition of the alloy, chemical analysis of the alloy will give a knowledge of the activity of iron in all of the phases in the system. The present study was undertaken in order to elucidate the characteristics of Fe-Pt alloys as iron activity indicators. This work is intended to tie together some previous work, which may be summarized as follows. Larson and Chipman1 determined the activity of iron in Fe-Pt alloys at 1550°C by equilibrating platinum metal with calcium oxide-iron oxide-silica melts of known iron activity. Compositions of the resulting alloys were determined by chemical analysis. A similar study was carried out by Taylor and ~uan,' who worked at 1300°C. They brought the Fe-Pt alloys into equilibrium with iron oxide under conditions of known partial pressure of oxygen, and thus, from the work of Darken and ~urr~,~ conditions of known iron activity. Compositions were determined indirectly, by following the change in weight of the sample. Sundaresen et el* used the electromotive force of cells in which the alloy formed one electrode in order to measure the activity of iron in the alloy at 650" and 850°C. These temperatures were chosen to be above and below the first-order phase transition which takes place upon the ordering of Fe3Pt and the second-order transition which occurs upon the ordering of FePt3. EXPERIMENTAL 1) High Temperatures. The starting materials used were thin platinum foil, about 0.002 mm thick, and Fisher Certified reagent ferric oxide, Fez03, which had been heated for 24 hr at 1000°C. An intimate mixture of 80-mesh Fez03 and platinum platelets was placed in a thin platinum foil envelope. The latter was suspended from thin platinum wires in the hot zone of a vertical-tube, platinum-wound furnace of the type described by Muan and ~sborn.~ A capillary gas mixer similar to that used by Darken and Gurry3 was used to prepare a precisely known mixture of carbon dioxide and hydrogen, which was allowed to flow upward through the furnace tube. The partial pressure of oxygen in contact with the sample was thereby fixed at a value which was calculated from the charts prepared by porter? Temperatures were measured with a Pt-10 pct Rh-in-platinum thermocouple, which was calibrated using the melting points of gold (1062 .@C) and diopside, CaMgSizOB (1391.5"C). Temperature control was maintained to within i3"C with a Geophysical Laboratory proportional controller, using the furnace resistance as the sensing element. Samples were quenched by passing a small current through the platinum suspension wires, allowing the sample to drop into a bath of dibutyl phthalate at the bottom of the furnace tube. Prior to chemical analysis the samples were washed with acetone and dried. 2) Chemical Analysis. It proved possible, in almost all cases, to separate the Pt-Fe platelets physically from particles of iron oxide. The platelets were dissolved in a small volume of aqua regia, evaporated to dryness, and redissolved to 0.1 M HC1. In order to determine iron in the platinum alloy potentiometrically, it is necessary first to remove the platinum. A 10-cm column of Amberlite IR-120 cation exchange resin in the hydrogen form provided separation quickly and quantitatively: The mixture of iron and platinum in 0.1 M HC1 was added to the top of the column, and washed with about 100 ml of 0.1 M HC1. Under these conditions, the iron, principally in the form of cations such as FeC1" and FeCl;, is held quantitatively in the uppermost centimeter of the column. The platinum, in the form of anions such as PtC&- , is washed through without being adsorbed. After a qualitative test with stannous chloride indicated all of the platinum was removed, the iron was

Jan 1, 1968