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By C. P. PERIN, DONALD BELCHER

T HE production of pure iron by electrolyzing solutions of its salts has been the object of scientific curiosity and research for about 80 years; and in the last two decades a realization of the unusual physical and chemical qualities of electrolytic iron has turned the attention of chemists and metallurgists toward a commercial application of this accumulated knowledge. Thus Burgess and Hambuechen in America, . Cowper-Coles in England, and Fischer in Germany- devised methods, more or less successful, for the electrolytic refining of iron, but none of these processes has yet attained large-scale operation. During the war some interesting ,work was done in France and England on building up worn or defective machine parts by electrodeposition of iron. It remained for the Société "Le Fern in France to carry on the process commercially. For six years Les Fonderies et Forges. de Sainte-Maire et Gravigny and the works of Bouchayer & Viallet at Grenoble have manufactured pure-iron boiler tubes in competition with established practice. The French process originated in the researches of Anthelme Boucher in 1910, and was, not put into operation until several years of experimentation had passed.

Jan 1, 1921

By Michael J. Messel

THE critical shortage of asbestos fiber in the world today brings to the foreground the question of locating and developing new deposits. The object of this paper is to discuss some of the more important factors which should be considered in the examination and valuation of a new asbestos enterprise. Some of the more important uses of asbestos fiber are for textiles, heat insulators, building materials, filters and a series of other uses. The properties of this mineral, such as fibrous structure, color, strength, silkiness and flexibility, coupled with resistance to fire, certain chemical action and decay make its application unique for certain industrial uses which consume over 500,000 tons annually. These same unique properties which make this mineral so valuable also make a deposit one of the most difficult to appraise accurately, because of the many undeterminable and varying factors which must be considered before a deposit can properly be termed commercial. The majority of the asbestos fiber today, having the above mentioned properties, is sold by grades which are based on fiber length. Present day fiber prices vary over a wide range from $800 to $225 for crude fibers and $300 to $20.00 per ton for milled grades. For valuation purposes a careful study should be made of existing fiber prices and markets. EXAMINATION OF DEPOSITS In carrying out prospecting and examination of a deposit, considerable caution is required to get the necessary information in the form that will have the most value for the final determination. There are two main classes of asbestos fibers, chrysotile and the amphiboles, the chrysotile being, by far, the most important both in abundance and uses. This paper will stress mainly chrysotile deposits, however, the amphiboles have many important uses, especially amosite and crocidalite. Their valuation presents special problems as other factors may be involved, especially as they are not graded according to any well defined and adopted standard but usually according to the use for which they are being supplied. Most chrysotile deposits occur in two main types of rock, (I) mainly in basic igneous, such as dunite and peridotite, (2) to a lesser extent in sedimentary rocks, such as dolomite and limestone. All of these require a certain degree of metamorphism to be favorable to asbestos formation. Approximately 90 pct of the asbestos deposits are derived from serpentinization of dunite or peridotite, whereby the magnesiumsilicate olivine was altered to hydrous magnesium-silicate serpentine. Under certain favorable geological conditions, this serpentine takes a fibrous form having a definite crystal structure, probably due to molecular rearrangement, and is known as chrysotile. The fiber veins are usually ir-

Jan 1, 1947

By George Burrell

J. S. HALDANE, M. D., F. R. S., Oxford, England (communication to the Secretary?).-The valuable paper of Messrs. Burrell and Gauger is of special interest to me as, through the courtesy of the management, I had an opportunity of visiting the Portland mine, Cripple Creek, in 1911, in connection with the investigations on acclimatization to high altitudes, carried out on Pike's Peak, near Cripple Creek, by Professors Yandell, Henderson and Schneider, Dr. Douglas and myself.1 The analyses of one or two samples of the vitiated air were entirely confirmatory of those of the authors. A fatal accident owing to two men being lowered down a shaft filled with the gas had occurred in a neighboring mine just before our visit.

Jan 12, 1916

By J. S. Pascover, J. K. Abraham

The influence of the early stages of precipitation on the kinetics and structure of martensite formation in Fe-27Ni and Fe-29.5Ni alloys containing from 0 to 10 pct Ti was examined with X-ray and electron microscopy techniques. The formation of a coherent, ordered preprecipitate had a profound stabilizing effect on the austenite. The Ms was decreased by increased titanium content and aging time up to a critical time. When the critical aging time was exceeded, the Ms was observed to increase markedly. The formation of the clusters was insuppressible and the volume fraction of clusters formed during the quench was a function of the titanium content. Martensite resulting from transformation of the clustered austenite is tetragonal with the c/a ratio increasing with titanium content. A model for the tetragonality is suggested. The morphology and substructure of the m artensite is inter-preted in terms of the above information and the cur-rent models of twinned martensite. ThE ramifications of precipitation in austenite to the properties of austenite have been the subject of numerous investigations. The current research is concerned with the influence of precipitation in austenite on the kinetics and structure of subsequent marten-site formation. In a previous investigation, Abraham et al.1 followed the aging reaction in an Fe-29.5Ni-4.2Ti* (at. pct) alloy using an X-ray diffraction technique. This technique, employing a Guinier camera, provided kinetic measurements through observation of the side band position as a function of aging time. The salient results of this work were: 1) The initiation of precipitation was not suppressed by quenching, i.e., there was a finite cluster zone size at zero aging time; and 2) The hardness of the aged austenite correlated extremely well with the zone size. During the previous work it was noted that the mar-tensite formed after aging was tetragonal, substanti-ating an earlier observation.2 Systematic investiga-tion revealed that the martensite was tetragonal in both the solution-treated then quenched, and the solu-tion-treated, aged, and quenched condition, and, furthermore, that a marked stabilization of the austenite occurred as a function of aging time. The present work is concerned with documenting the tetragonality and the stabilization phenomena as well as the ob- served microstruction with a suggested rationale for the behavior noted. EXPERIMENTAL PROCEDURE The compositions of the alloys are listed in Table I. The analyses were performed after the solution treatment of the strip material. Nickel was determined using the standard dimethy1-glyoxime procedure whereas titanium was determined colorimetrically with hydrogen peroxide and volumetrically by titrating with ferric iron. The materials were melted in a 5-lb vacuum induction furnace, cast into 2-in.-diam ingots, and forged in a temperature range of 950. to 1200°C to 1/2-in. slabs. The three higher titanium containing materials cracked during forging; therefore, to get the alloys into strip form, slices 1/8 in. thick were cut from the slab, homogenized 4 hr at 1150°C, then cold-rolled to a 0.04-in. thickness. The remaining slabs were hot-rolled, homogenized 4 hr at 1065"C, then cold-rolled to a final thickness of 0.03 in. All of the heat treatments were performed under a protective atmosphere of argon. The Ms temperature for most of the alloys is below room temperature; therefore, it was possible to solution treat, quench to room temperature, polish, and then observe the transformation optically on a cold-stage microscope. To determine the effect of aus-tenitizing temperature on Ms, eight of the alloys were treated at two temperatures, 1025" and 1120°C. No measurable variations in Ms were noticed. The remaining alloys were treated at 1025°C. The specimens, : by 5/16 by 0.03 in., were austeni-tized in a vertical tube furnace under a dynamic argon atmosphere. The bottom of the tube was submerged in water for quenching purposes. The question of stabilization that may be operating at room temperature was investigated and found to be negligible. Many of the specimens were held at room

Jan 1, 1970

By H. M. Chance

One hundred and twenty miles of hard travel over steep ridges almost due east from Fayetteville, on the St. Louis and San Francisco Railroad, about 100 miles from Eureka Hot Springs, or 75 miles northwest from Batesville, will bring the traveller to the waters of the Buffalo Fork of the White river, in a wild, thinlysettled, heavily-timbered country, now being prospected quite actively for zinc, and known as the Buffalo or Rush Creek district. Excepting here and there a piece of bottom land, patented before the discovery of zinc, the land is unoccupied Government land, and subject to entry under the United States mineral laws. Claims are now being taken, 600 by 1500 feet, but a movement made this summer, if successful, will largely modify the position of claim-holders. A few claims are now being filed under the Placer Act on the ground that as the zinc occurs as a horizontal, sedimentary deposit, etc., it can only be properly so classified. The zinc occurs in limestone, which is at times so siliceous that

Jan 1, 1890

By S. Shapiro, G. Krauss

We will reply to Dr. Pitsch's discussion by 1) presenting in greater detail the single surface trace analysis which we performed on the reversed austenite plates in a single parent plate of martensite of known orientation, 2) relating the results of our analysis to the conclusions which Dr. Pitsch makes on the basis of our data, and 3) examining the validity of our selection of twenty-nine individual traces from the over 200 austenite plates which were observed in a surface of this single martensite plate. Fig. 7 shows a standard (001) projection of the martensite plate from which the austenite-martensite interface traces were taken. The traces are plotted on the projection as the small solid circles, and the great circles corresponding to the loci of plane normals which could contain each trace or could intersect the surface plane along the measured directions are also plotted. It can be seen that these great circles intersect at a point which corresponds to the normal of the surface plane on which the traces were observed. Also rate which occurred only at particularly low heating rates, see Figs. 1 and 3 in the paper.2 Since in this case the interpretation of Jana and Wayman is plausible and since we have no alternative to this interpretation, we would like to state only that the existence of a diffusion-controlled reversal at low temperatures seems to be not yet proved beyond any doubt. The author wishes to thank Professor G. Krauss for making available his manuscript prior to publication. It is also a pleasure to acknowledge the lively written discussions, which the author has had with Professors G. Krauss and C. M. Wayman prior to this communication. The financial support of the Deutsche For-schungsgemeinschaft for the work on which this communication is based is also gratefully acknowledged. plotted within small dotted circles which represent a i3 deg scatter in each of the twenty-four unit stereo-graphic triangles are our A and B poles7 and the pole P determined by Kessler and itsch.' The data presented in Fig. 7 permit a direct association of the measured traces and the various proposed habit plane poles for the reversed austenite plates in the martensite crystal. If the sample measurements do in fact

Jan 1, 1969

By Malcolm T. Hepworth

RECENT interest in thermoelectric devices has been directed toward studies of the properties of thermoelectric materials of semiconducting solid compounds with little attention given to ionic and semiconducting liquids such as aqueous solutions, fused salts, and mattes. One type of thermoelectric system is the thermocell: a nonisothermal galvanic cell with two identical electrodes at different temperatures connected by an electrolyte bridge. An electromotive force, v, is generated which is a function of the electrode reactions and the properties of the electrolyte according to the Eastman' equation: where S* is the entropy change of the system arising from the electrode reactions and by heat transferred by ion migration and by thermal conduction. The quantity nF is the product of equivalents passed and Faraday's constant. A value of S* of 23.06 cal per "C is equivalent to 1 mv-Faraday per "C. The symbol, a, is used for dV/dT in analog to the See-beck coefficient of solid-state thermoelements. de Bethune2 has calculated the temperature coefficients of the electromotive force of a large number of nonisothermal aqueous cells from measurements on the nonisothermal temperature coefficients of the standard hydrogen electrode, combined with data on the isothermal temperature coefficients of half-cells tabulated in the literature. Values of these coefficients (a) in de Bethune's compilation ranged up to 3 mv per C. In particular he reported a value of +2.059 mv per "C at 25'C for the cell: Fe (aqueous, unit activity) (aqueous, unit activity) written for the hot-electrode reaction. The positive sign indicates that the hot electrode is positive (an "n-type thermocell"). In analog to a solid-state p-n system, it would be possible to couple two thermocells together to form a system in which the figure of merit could be calculated by adding the temperature coefficients according to the relationship described by offee:' where a is the Seebeck coefficient in volts per "C, p is the specific resistivity in ohm-cm, and K is the thermal conductivity in watts per cm "C. Even though ionic systems have rather high electrical resistivities compared with semiconducting and metallic systems, it was felt that a preliminary study of one ionic system should be made to establish some basis for evaluating the possibility of a p-n thermocell for energy conversion. Accordingly the Fe", Fe"' system was studied as a possible component for a p-n system. A glass system was constructed consisting of two vertical water-jacketed tubes connected by a horizontal tube, Fig. 1. Platinum-black electrodes 1 cm by 1 cm in dimension were inserted in each vertical tube with thermometers to register the electrode-compartment temperatures. The temperature of the electrode compartments was controlled by circulating water from thermostatted baths around the electrode compartments. The electromotive force of the cell was then read by a potentiometer for zero current as a function of the temperature of the hotter electrode. Current output of the cell for varying external loads was also measured. The cell resistance was measured by means of a bridge circuit with 10,000 cps signal and oscilloscope. Resistance measurements were converted to specific resistivity by calibrating the cell with a solution of known conductivity.

Jan 1, 1965

By M. S. Seltzer

High temperature steady-state creep rates have been determined jor lead sulfide single crystals whose defect concentrations were fixed by equilibration under controlled sulfur pressure. The activation energy of creep, Qc , for undoped lead sulfide, is a function 01 composilion, decreasing from 2.9 to 2.2 ev as the carrier concentration increases from 9 x 1016 to 8 1018 electrons cm-3 for lead excess crystals, and increasing from 1.7 to 2.3 ev as the concentration of holes increases from 4 x 1017 to 1 x 1018 cm-3 in sulfur excess material. For five different composilions, Qc for undoped and bismuth-doped crystals has been found to be equal to Qpb + Qs, the self-diffusion activation energies for lead and sulfur in PbS. It is well-established1 that high-temperature steady-state creep of pure metals is a diffusion-controlled process, where the activation energy of creep is equal, within experimental error, to the activation energy of self-diffusion. The relationship between the activation energy for steady-state creep and those for self-diffusion in binary compounds is more complicated, however, because two different diffusing species must be considered, and becayse the activation energies may be influenced by compositional variations and by foreign atom additions.2-4 In some cases experimentally determined creep activation energies are correlated with those for self-diffusion of the slower-moving species, but such agreement is by no means universal. Interpretation of experimental results is difficult because few investigations include measurements of creep rates and self-diffusion coefficients of both diffusing species on single crystals of similar composition and foreign atom concentration. The objective of this investigation, therefore, is to determine the influence of stoichiometric defects and foreign atoms on steady-state creep and self-diffusion for a well-characterized binary compound. Lead sulfide, a compound semiconductor which crystallizes in the NaC1-type structure, and whose homogeneity range includes compositions on either side of the 1:l atom ratio, was chosen for study in this investigation. The pressure-temperature-composition relations for PbS are available,5,3 and deviations from stoichiometry may be monitored by electrical measurements.7 Single-crystal specimens are available to allow observation of effects due to bulk phenomena without interference from grain-boundary effects. These crystals have been employed to determine steady-state creep rates under compressive stress for "pure" and bismuth-doped PbS as a function of sulfur pressure and temperature as well as crystal orientation and applied stress in order to establish the relationships between defect concentrations and creep rates. EXPERIMENTAL PROCEDURES Crystal Growth. Lead sulfide crystals, prepared by the Bridgman method, are grown in evacuated quartz crucibles, filled with almost equal atomic proportions of high-purity (99.999 pct) lead and sulfur, and heated to a temperature above the melting point of PbS (about 1127°C) so that the lead and sulfur react to form molten PbS. The crucible and melt are dropped through the hot zone of the crystal-growing furnace at the rate of 1 cm per hr. The maximum melting point of PbS is slightly on the lead-rich side of the 50:50 composition; hence crystals grown from a near stoichiometric melt are usually n-type semiconductors containing excess lead atoms. Typically the lead excess concentration in solid solution with the PbS is 3 x 1018 atoms cm-3. Crystals containing either 1/20 or 1/2 mole pct Bi2S3 were prepared by addition of the foreign atoms prior to crystal synthesis. Preparation of Specimens of Controlled Stoichiom-etry. Since it is difficult to grow crystals of desired composition, the process of crystal growth and control of stoichiometry are separated into two distinct operations. Equilibration of as-grown PbS to a desired composition is most easily accomplished by first annealing the n-type crystals under high sulfur pressure (about 1 atm) at temperatures above 700°C. This process serves to put excess lead precipitates into solution, yielding 0 -type crystals upon quenching to room temperature. Inter diffusion occurs readily in crystals so treated, and the methods described by Bloem may then be employed to obtain crystals of controlled stoi-chiometry. For the creep measurements made in this study, this involves heating crystals in mixtures of H2 and H2S The equilibrium constant for H2S is given by: Thus the sulfur partial pressure is obtained from knowledge of the H2/H2S ratio and Kh2S for the temperature in question. Fig. 1 shows the p-T-x diagram for PbS. It can be seen that, within the stability limits for single-phase lead sulfide, desired compositions may be obtained by equilibrating under a specified sulfur pressure and temperature. Characterization of Crystals. The principal methods for evaluating PbS crystals include measurement of electrical properties and mass-spectrographic analysis. The measured electrical parameters include Hall coefficient, conductivity type, and electrical resistivity Bloem7 has shown that there is a 1:l relation between the defect concentration and carrier concentration obtained. Hence, if the contribution to the carrier con-

Jan 1, 1968

By William L. Fink and

Although age-hardening in an aluminum-base alloy containing magnesium was observed by Alfred Wilml as early as 1911, it was not until 1919 that a theory of the mechanism of age-hardening was proposed. Merica, Waltenberg and Scott12 studying the age-hardening characteristics of Duralumin at the National Bureau of Standards, came to the conclusion that age-hardening of this alloy is caused by the precipitation of CuAl2, which is less soluble at the aging temperature than at the solution heat-treating temperature. It was postulated that the initially precipitated particles were of fine colloidal dimensions but that they gradually grew in size. Maximum hardness was assumed to be attained when the particles reached a critical size. This theory was at first received skeptically, since it was a widely accepted view at that time that the solid solution state should represent the hardest state of an alloy. Shortly thereafter, Jeffries and Archer proposed their well-known slip interference theory.'13 They suggested that age-hardening was accomplished by the precipitated particles acting as keys interfering with slip along crystallographic glide planes. They showed that this mechanical theory led direct,ly to the assumption that maximum hardening would be produced by particles of a critical size, which they suggested would have a diameter approximately 10 times that of the aluminum atom. This contribution amplified and explained so rationally the age-hardening theory of Merica, Waltenberg and Scott that wide acceptance resulted. Objections to Simple Precipitation Theory From time to time certain experimental facts have been cited against the simple precipitation theory. The first of these was the discovery by Fraenkel4 that, although the electrical resistivity of Duralumin decreased during aging at higher temperatures (from 100' to 250' C.), it increased during aging at ordinary temperatures. This was not in accordance

Jan 1, 1940

By William L. Fink and

Although age-hardening in an aluminum-base alloy containing magnesium was observed by Alfred Wilml as early as 1911, it was not until 1919 that a theory of the mechanism of age-hardening was proposed. Merica, Waltenberg and Scott12 studying the age-hardening characteristics of Duralumin at the National Bureau of Standards, came to the conclusion that age-hardening of this alloy is caused by the precipitation of CuAl2, which is less soluble at the aging temperature than at the solution heat-treating temperature. It was postulated that the initially precipitated particles were of fine colloidal dimensions but that they gradually grew in size. Maximum hardness was assumed to be attained when the particles reached a critical size. This theory was at first received skeptically, since it was a widely accepted view at that time that the solid solution state should represent the hardest state of an alloy. Shortly thereafter, Jeffries and Archer proposed their well-known slip interference theory.'13 They suggested that age-hardening was accomplished by the precipitated particles acting as keys interfering with slip along crystallographic glide planes. They showed that this mechanical theory led direct,ly to the assumption that maximum hardening would be produced by particles of a critical size, which they suggested would have a diameter approximately 10 times that of the aluminum atom. This contribution amplified and explained so rationally the age-hardening theory of Merica, Waltenberg and Scott that wide acceptance resulted. Objections to Simple Precipitation Theory From time to time certain experimental facts have been cited against the simple precipitation theory. The first of these was the discovery by Fraenkel4 that, although the electrical resistivity of Duralumin decreased during aging at higher temperatures (from 100' to 250' C.), it increased during aging at ordinary temperatures. This was not in accordance

Jan 1, 1940

By S. E. Craig

Jen Inc., operator of the Cord mine, in the Big Indian district of San Juan County, Utah, has a contract with a milling company that provides a small bonus for proper grading and preparation of uranium ores shipped. To obtain maximum returns on this contract very close grading is required with settlements made on individual lots, which vary from 250 to 300 tons. Another feature of the contract, and one that is rather unique in this country, is that the ore is sold over truck scales at the mine. Grade is determined at the buyer's sample plant. It is necessary to take a moisture sample of each truckload shipped for ac- curate weighing and this is done by the representative of the buyer, using facilities supplied by Jen Inc. The sample is hardly more than a grab sample and includes only the finer and smaller pieces of the ore shipped.

Jan 10, 1958

LIMA (PERU) Established May, 1952 (Official year begins in June) Luncheon meetings third Wednesday monthly Ernesto A Baertl, Chairman Arthur C Hall, Chairman-elect Raymond R Beard, 1st Vice-Chairman Edgardo Portaro, 2nd Vice-Chairman Walter E King, Secretary-Treasurer Av Santa Cruz 331 San Isidro, Lima, Peru Alberto E Brazzini, Asst Treasurer Daniel M Rodriguez, Asst Secretary Robert P Koenig, '56, Section Delegate Arthur C Hall, Alternate Section Delegate

Jan 1, 1955

By B. B. A. Luzzat

ALUMINUM is today the most widely used of the nonferrous metals. The technical literature on the aluminum smelting process is, nevertheless, very meager, so that anyone interested in the subject cannot rely on more than a couple of dozen publications.' The patent literature is equally scarce; most patents refer to the production of alumina from aluminum-bearing ores, while not more than a few score significant patents deal with the electrolytic reduction of alumina, which is the real core of the aluminum smelting industry. The "reduction phase" is, from a technical and a scientific point of view, much more interesting than the "alumina phase", which, in effect, is only a combination of such well-known chemical operations as dissolving, precipitating, filtering, drying, and calcining. The electrolytic reduction of alumina, on the other hand, has features which do not appear in any other metal smelting operation. Some of them are of great technical and scientific interest even for those not directly engaged in the production of aluminum. The purpose of this paper is to describe in some detail the basic facts and developments of the reduction phase of aluminum smelting. Two Aspects of the Electrolytic Process The raw material for the reduction process is alumina (Al2O3) . Its purity in general runs as high as 99.50 pct or more. Small differences in the chemical composition generally do not affect the reduction process.* Of more importance are the physical prop- erties of the alumina, since they affect not only its rate of solution in the molten bath but also its heat insulating power.† In the following pages, un- less otherwise stated, it is assumed that a standard "Bayer" alumina is used. The reduction process, by which alumina is broken down into its components, may be roughly defined as its electrolysis in molten cryolite. The oxygen separates at the anode, and the aluminum at the cathode, which forms the bottom of the electrolytic cell. The electrolytic cell (or pot) where the process is carried out is a strongly reinforced steel box. The

Jan 1, 1951

By Walter Craft, John L. Lamont

Adequate hardenability has long been recognized as one of the first requirements for producing desired mechanical properties in a heat-treated steel. Since the introduction of the Jominy end-quench test' and the development of correlative information to expand its use, industry has had an effective measure of hardenability. Prediction and control of the hardenability have been made possible by Grossmann's principle2 for calculating hardenability from chemical composition; and Field's conversiona from depth of half-martensite hardening to Rockwell C hardness has made the relation more quantitative. These developments have facilitated the design of new steels and the control of standard grades to the extent that it has been possible to establish tentative hardenability bands for some of the more commonly used alloy steels.4 As the depth of hardening of the Jominy test specimen is usually measured by Rockwell C hardness, it was considered that it should be possible to predict the hardness by a more direct calculation. It has been found that this can be accomplished by the addition of Rockwell C units proportional to the carbon and alloy content, grain size, and position in the Jominy test specimen. The calculation has been found to be fairly accurate, and because of its additive character is relatively simple to use. In principle the method of calculation is somewhat similar to the expressions developed by Herty, McBride, and Hollen-back,5 Burns, Moore, and Archer,= and Burns and Riege1.l The calculation is started from a base that includes the effects of carbon content and position in the Jominy test speimen. Rockwell C units are added to the base in proportion to the alloy content and grain size. This sum represents the Rockwell C hardness up to the level at which a disproportionate increase of hardness is caused by the formation of martensite, and above this level an increment for martensite hardening is added. The effects of alloys are directly proportional to the amounts present and are independent of each other, the carbon content, and the position in the specimen. Furthermore, the factors for determining the martensite increment are dependcnt only on carbon content and are independent of cooling rate and alloy content. It is this absence of interrelation between the different factors that makes it possible to calculate the hardness and makes the method of calculation consistent with the principle that the character of the hardening reaction is governed primarily by carbon and that alloys exert their effect chiefly through control of the critical cooling rate. The principle of the calculation, and the effects of alloys on the critical cooling rate,

Jan 1, 1947

By John L. Lamont, Walter Craft

Adequate hardenability has long been recognized as one of the first requirements for producing desired mechanical properties in a heat-treated steel. Since the introduction of the Jominy end-quench test' and the development of correlative information to expand its use, industry has had an effective measure of hardenability. Prediction and control of the hardenability have been made possible by Grossmann's principle2 for calculating hardenability from chemical composition; and Field's conversiona from depth of half-martensite hardening to Rockwell C hardness has made the relation more quantitative. These developments have facilitated the design of new steels and the control of standard grades to the extent that it has been possible to establish tentative hardenability bands for some of the more commonly used alloy steels.4 As the depth of hardening of the Jominy test specimen is usually measured by Rockwell C hardness, it was considered that it should be possible to predict the hardness by a more direct calculation. It has been found that this can be accomplished by the addition of Rockwell C units proportional to the carbon and alloy content, grain size, and position in the Jominy test specimen. The calculation has been found to be fairly accurate, and because of its additive character is relatively simple to use. In principle the method of calculation is somewhat similar to the expressions developed by Herty, McBride, and Hollen-back,5 Burns, Moore, and Archer,= and Burns and Riege1.l The calculation is started from a base that includes the effects of carbon content and position in the Jominy test speimen. Rockwell C units are added to the base in proportion to the alloy content and grain size. This sum represents the Rockwell C hardness up to the level at which a disproportionate increase of hardness is caused by the formation of martensite, and above this level an increment for martensite hardening is added. The effects of alloys are directly proportional to the amounts present and are independent of each other, the carbon content, and the position in the specimen. Furthermore, the factors for determining the martensite increment are dependcnt only on carbon content and are independent of cooling rate and alloy content. It is this absence of interrelation between the different factors that makes it possible to calculate the hardness and makes the method of calculation consistent with the principle that the character of the hardening reaction is governed primarily by carbon and that alloys exert their effect chiefly through control of the critical cooling rate. The principle of the calculation, and the effects of alloys on the critical cooling rate,

Jan 1, 1947

By T. G. R. Rawlins, L. E. Brosselard

Direct platinum carbon replicas have been used to study substrates prior to growth and after initial nu-cleation of the layer. Replicas have been directly stripped and correlations have been made with other replica techniques. Mechanically polished substrates are very flat with occasional areas of "dirt", which is apparently silicon. When such substrates are etched in hydrochloric acid gas, scratches and hexagonal defects (thought to be polishing compound) are revealed, together with areas of apparent redeposition. Chemically polished substrates are much less flat although much more homogeneous in appearance. Heat treat)nents have no effect. Nuclei deposited on these surfaces, using a normal silicon tetrachloride system, have been examined. Nuclei on mechanically polished subsrates occur in random areas only, whereas on chemically polished surfaces they are more uniformly distributed. THE interest in the study of thin films and now their rapidly expanding use in many fields has increased over a period of years. Much of this current interest, particularly in the field of single-crystal or epitaxial thin films, has derived its stimulus not only from possibilities for application but also from fundamental electron-microscope studies which have indicated the manner of growth of such layers from the initial nuclei.1-5 Previous work involving study of growth processes may be divided into three categories. First, vacuum deposition, primarily of metals, on a variety of substrates has been studied by electron microscopy and electron-diffraction techniques. These have shown the three-dimensional aspect of nucleation and the remarkable liquidlike behavior of the growing nuclei which coalesce to form a complete layer. More recently this work has been expanded in two ways: by growth inside the electron microscope this has obvious advantages for kinetic studies; and by growth in ultrahigh vacuum—much of this work has been done on semiconductors.8-11 It is of interest to note that metals, specifically gold deposited on rock salt, will form only polycrystalline layers in ultrahigh vacuum unless the substrate surface is contaminated.12 In general the mode of growth for vacuum-deposited semiconductor films is the same as that for metal films. The second method of growth that has been studied is that of electrodeposition.13,14 The little that has been published suggests that the mode of growth is similar to the vacuum case, except that irregularities may perturb the electric field and disturb the growth process. The third and last primary method of growing epitaxial layers is by use of chemical methods. These techniques have generated much interest and much has been published on them. Considerable electron-microscope work has been done on the defects in the layers; however comparatively little work has been undertaken on the initial nucleation and early stages of growth. Confining ourselves now exclusively to the case of silicon, Charig et a1.15 have considered the growth of silicon on silicon substrates by hydrogen reduction of trichlorosilane, and studied the films by means of replica and transmission techniques. Subsequently they have studied the same system for growth on quartz,16 and with the addition of pyrolysis of silane on quartz and alumina.17 Also Manasevit el al. have studied deposits using silane and silicon tetrachloride on sapphire.18-14 Finally, in this volume studies of deposition on beryllia and sapphire are reported. Although Revesz and Evans20 have examined complete layers, grown by means of the widely used silicon tetrachloride reaction, no detailed examination similar to that published by Charig and Joyce21 for the trichlorosilane system has been given. Therefore this investigation has examined substrate surfaces prior to growth and then nucleation on these surfaces for the silicon tetrachloride system. EXPERIMENTAL In this work the surfaces have been studied by means of standard replica techniques. Because of the very real problems associated with artifacts introduced,22 different replicas and different cleaning

Jan 1, 1967

By H. M. Howe

§ 24. Introduction.—This paper discusses the chief existing data as to the temperature, in iron-carbon alloys, of Ae3, 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. 614). 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. In Part 11. (§§ 29 to 39) I consider the chief causes of error. In Part III. (§§ 40 to 48) I apply certain corrections to some of the existing data, review those data, weight them, and calculate a prob-

Jan 1, 1914

By A. P. Herring, S. F. Ravitz

Manganese dioxide reacts with sulfur dioxide solution in the absence of oxygen to form manganous ion and dithionate ion, together with a small amount of sulfate ion. The effects of SO, concentration, hydrogen ion concentration, stirring speed, and temperature on the rate of the reaction were studied. If it is assumed that undissociated SO2 molecules react rapidly with MnO, at active surface sites and that bisulfite ions react slowly, an equation can be derived that satisfactorily represents the observed reaction rates. For solutions in which the reaction with undissociated SO2 predominates, reaction rates and activation energies estimated from diffusion theory agree well with those found experimentally. Manganese dioxide dissolves readily in aqueous solutions of sulfur dioxide. The nature of the dissolution reaction was first investigated by Gay-Lussac and welter1 in 1819; they identified a new oxysulfur radical, the dithionate ion, S2O6, as one of the reaction products. Since then, the reaction has become a standard method of preparing dithionates in the laboratory and one of the more promising methods of leaching manganese from low-grade ores. In the "dithionate process" developed by the U.S. Bureau of Mines2,3, manganese-dioxide ore is suspended in a solution of calcium dithionate and leached with gas containing sulfur dioxide. The manganese is dissolved and the sulfur dioxide is oxidized according to the reactions:

Jan 1, 1965

By C. E. Shoenfelt, E. W. Krampert

The major oil discovery in 1938 for Wyoming was the General Petroleum Corporation's So. 1 Government, C.NW.SE. of sec. 21-35N-77W, on the Cole Creek structure in central Wyoming, 14 miles northeast of Casper. This well found commercial oil production in basal Cloverly sand (Lakota) at 7978 ft. and was completed on May 28, 1938, at 8019 ft., 3 ft. in Morrison shale. It had an initial produrtion of 10 bbl. of oil an hour but at the end of a 7-day test made 336 bbl. of oil in 24 hr. During 1938, the well produced a total of 23,161 bbl. of oil. It has been agitated about 10 days out of each month to provide fuel for lease and drilling operations, the balance of the time it has been shut in pending the completion of the second well on the structure. The Cole Creek oil is of intermediate base and has an A.P.I. gravity of 32.7". The record of the well contains the "tops" listed in the accompanying tabulation. Tops in General Petroleum Corporation's No. 1 Government Well Feet 2210 Top of the Mesa Verde (Teapot sandstone) 2960 Top Steele shale 4500 Shannon sand; good show of oil and gas 6740 Top Frontier sand; some oil saturation 6840 Halliburton test of Froutier did not show much oil, but at 6878 ft. the oil showing amounted to 50 barrels 6878-7051 Shale 7051-7062 Sand with some oil saturation 7062-7920 Shale (sandy phase of Thermopolis shale 7779 to 7788 ft.) 7920-7926 Sand (Muddy); oil-saturated 7926-7974 Shale 7974-7979 Hard, coarse, limy sand (Dakota); some oil saturation 7979-7997 Soft sand; high oil saturation 7997-8002 Shale with pyrites 8002-8016 Sand (Lakota) 8016-8019 Variegated Morrison shale 5600 Elevation Lance Creek Field.—Important extensions to the Lance Creek field in eastern Wyoming were made in 1938 by the completion of a number of

Jan 1, 1939

By C. E. Shoenfelt, E. W. Krampert

The major oil discovery in 1938 for Wyoming was the General Petroleum Corporation's So. 1 Government, C.NW.SE. of sec. 21-35N-77W, on the Cole Creek structure in central Wyoming, 14 miles northeast of Casper. This well found commercial oil production in basal Cloverly sand (Lakota) at 7978 ft. and was completed on May 28, 1938, at 8019 ft., 3 ft. in Morrison shale. It had an initial produrtion of 10 bbl. of oil an hour but at the end of a 7-day test made 336 bbl. of oil in 24 hr. During 1938, the well produced a total of 23,161 bbl. of oil. It has been agitated about 10 days out of each month to provide fuel for lease and drilling operations, the balance of the time it has been shut in pending the completion of the second well on the structure. The Cole Creek oil is of intermediate base and has an A.P.I. gravity of 32.7". The record of the well contains the "tops" listed in the accompanying tabulation. Tops in General Petroleum Corporation's No. 1 Government Well Feet 2210 Top of the Mesa Verde (Teapot sandstone) 2960 Top Steele shale 4500 Shannon sand; good show of oil and gas 6740 Top Frontier sand; some oil saturation 6840 Halliburton test of Froutier did not show much oil, but at 6878 ft. the oil showing amounted to 50 barrels 6878-7051 Shale 7051-7062 Sand with some oil saturation 7062-7920 Shale (sandy phase of Thermopolis shale 7779 to 7788 ft.) 7920-7926 Sand (Muddy); oil-saturated 7926-7974 Shale 7974-7979 Hard, coarse, limy sand (Dakota); some oil saturation 7979-7997 Soft sand; high oil saturation 7997-8002 Shale with pyrites 8002-8016 Sand (Lakota) 8016-8019 Variegated Morrison shale 5600 Elevation Lance Creek Field.—Important extensions to the Lance Creek field in eastern Wyoming were made in 1938 by the completion of a number of

Jan 1, 1939