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By E. E. Donath

Application of the coal hydrogenation process for the production of chemicals is described. It has been estimated that a plant to produce 31,090 bbl per day of chemicals and fuels would cost $326,- 000,000. These products would consist of 6.1 pct by weight tar acids, 50.8 pct aroma tics, 16.4 pct LPG, and 26.7 pct gasoline. THE coal hydrogenation process is well known as a means for the production of liquid fuels from coal. In this paper the possibilities of the coal hydrogenation process as a source of chemical raw materials will be discussed. The recovery of chemicals from coal hydrogenation products necessitates some modifications and additions to the equipment used for the production of fuels. The conversion of coal into liquid fuels such as gasoline requires two steps: liquid phase and vapor phase hydrogenation. Intermediate oils obtained in the liquid phase contain oxygen and nitrogen compounds, especially aromatic compounds, since the coal itself is composed mainly of cyclic compounds. These oils are the raw material for the separation of high molecular weight aro-matics and of tar acids and tar bases. The relative amounts of heavy and middle oil—boiling above and below, e.g., 325°C—can be influenced by temperature, residence time, and catalyst of the liquid phase hydrogenation. In the vapor phase hydrogenation a solid bed catalyst is used to convert the intermediate oil from the liquid phase operation into hydrocarbons of the gasoline boiling range. Essentially pure hydrocarbons with a low content of sulphur, oxygen, nitrogen, and olefines are obtained. Depending mainly on the catalyst, the high ring compound content of the liquid phase oil can be preserved and gasoline rich in aromatics obtained. However, with other catalysts, these ring compounds can be split into gasoline with a high content of isoparaffins.' Again, depending on the operating conditions, products of varying boiling range can be obtained. Selection of catalyst and operating conditions therefore makes possible the production of different grades of motor fuel and also variations in the relative amounts of benzene, toluene, and xylene when aromatic hydrocarbons are produced. The schematic flowsheet, Fig. 1, shows the main steps of the coal hydrogenation process, and the product streams used for the recovery of chemicals are indicated. In the liquid phase hydrogenation stage, coal is made into a paste with recycle heavy oil. The coal paste is mixed with hydrogen and preheated at a pressure of 300 to 700 atm in heat exchangers and preheaters. The coal paste and hydrogen enter high pressure converters where the liquefaction of coal, conversion of the high boiling liquid materials initially obtained, into intermediate oils is performed at a temperature around 470°C. The reaction products enter the hot catchpot in which lower boiling oil vapors are separated from the residue containing unreacted coal, ash, and heavy oil. This residue, usually called H.O.L.D. (heavy oil let down), is processed to separate solid and liquid material. By thermal treatment of the residue, e.g., a coking process, distillate oil is obtained, which can be recycled as part of the pasting oil. This stream is rich in polynuclear aromatics and can be, and has been, used for the recovery of such material. The oil vapors and hydrogen from the hot catchpot are cooled in heat exchangers and a cooler, and the condensed oil is separated from the recycle hy-

Jan 1, 1953

By T. J. Whalen, S. M. Kaufman

Surface-tension measurements for liquid Fe-C-Co and Fe-C-Ni alloys were performed by the sesszle-drop technique at 1350o and 1425°C. Cobalt was shown to he more effective than nickel in lowering the surface tension of Fe-C alloys A minimum value for surface tension of 1640 dynes per cm was found in the Fe-C-Co system at a concentration of 1.5 pet C and 12pet Co. Analysis of these measurements in terms of adsorption and desorption behavior indicated that cobalt and nickel lower surface tension in Fe-C alloys by replacing carbon at the liquid-vapor interface. Comparison of results to date for Fe-C liquid alloys has shown that most substitutional-type elements having about the same atomic diameter as iron also have relatively the same influence on surface tension when present in dilute amounts. It has been shown previously that surface-adsorption behavior in liquid Fe-C ternary alloys is related to the manner in which the ternary addition affects the activity of carbon in the bulk solution.' Certain ternary additions, such as chromium, tending to decrease carbon activity cause adsorption of carbon and chromium to the liquid-vapor interface. Additions, such as silicon, increase the carbon activity, resulting in a desorption of carbon and an adsorption of silicon. Both cases were shown to cause a decrease in surface tension due to adsorption. It is the object of this paper, as part of the writers' continuing interest in the effect of alloying additions on the surface tension of Fe-C alloys, to present and discuss surface-tension data on solutions in the ternary systems Fe-C-Co and Fe-C-Ni. Available activity measurements for these systems in the solid state indicate a strong increase in carbon activity when either nickel or cobalt is added to Fe-C alloys.2, 3 EXPERIMENTAL PROCEDURE The alloy compositions used are shown in Table I. These alloys were prepared by vacuum melting in stabilized zirconia crucibles and then vacuum casting into cold-steel molds. The nominal analyses for the alloys used in this investigation are given in Table I. Surface tensions and densities were measured by the sessile-drop method4,5 in conjunction with the tables of Bashforth and bdams.' Specimens were prepared by slicing 1/4-in. cubes from the center of the vacuum-cast ingots and grinding the edges of these cubes until their shapes approximated spheres with flat bottoms. Proper handling techniques, including an acetone rinse immediately before use, assured minimum contamination from sources extraneous to the actual melting. For each experimental run a sample was placed on a BeO plaque and positioned and leveled inside a vacuum induction heating apparatus. The sample and plaque arrangement sat inside a molybdenum tube which acted as the susceptor. Diagrams of this apparatus may be found in the literature.= After heating to temperatures just above the liquidus at pressures of the order of 10-4 to 10- 5 mm Hg, photographs of the drop profile were made using its natural thermal radiation as a light source. Some measurements were made with partial pressures (-1 cm Hg) of a mixture of H2 and He gases. The H2-He atmospheres proved to be necessary at higher nickel contents to retard excessive vaporization losses. Chemical analysis for carbon and the ternary addition was performed for each alloy sample after completion of the experimental run.

Jan 1, 1964

By Lane Mitchell

A ceramic product or processed material is a solid composed of materials which have been subjected to heat above 875°F. The raw materials, which are blended together (or in some cases used singly), are selected and utilized for various reasons such as ease of fabrication, aid to processing, to yield desired properties after processing, lack or controllable degree of toxicity or hazard, availability, cost, and perhaps other considerations. Almost all solid inorganic, some organic, and some liquid and gaseous materials have the potential to be used individually in some ceramic product. There are several fundamental functions to be fulfilled in every ceramic product and a number of secondary functions are desirable in specified products. These functions are generally met by the most widely occurring minerals and rocks of the earth and their debris. This fact characterizes ceramics as a field utilizing the raw materials most available to man. Of course, specified products utilize synthetics, organics, and rare inorganics to produce desired results. Any solid nonmetallic product processed by subjection to temperature above a red heat may be called a ceramic product. Widely used construction materials and units, domestic utensils and units, industrial parts to facilitate manufacture, technical components, and aesthetic creations are very often of a ceramic nature because of the durability, inertness, hardness, ease of fabrication, cost, and availability of the ingredients. Often, organics or metals cannot meet desired specifications for some of these products. The rocks and minerals and mineral debris of the earth are largely siliceous. Oxygen and silicon comprise roughly 75% of the earth's crust with aluminum, iron, calcium, and the alkalies following in abundance. Silica ( SiO, ) and silicates can be melted to form glasses. Alumina (A1,0,), present in a mineral com- pound, gives greater durability, hardness, and strength, but lessens the glass-forming property. Iron, calcium, and the other alkalies flux silica and reduce melting points. Thus, sand, which is generally almost pure SiO,, and clay, which is generally hydrated alumina silicate, are the most widely used of all ceramic raw materials-principally because of the glass-forming propensities of silicates. In ceramic formulations, clay is generally a refractory filler or skeletal material, having in the raw state a plasticity derived from its colloidal grain size and its water-loving nature. On the other hand, silica sand is a glass former or nonplastic filler. Clay and silica sand in pure forms are quite refractory, i.e., not easily melted. Clay, although siliceous, is less of a glass former than pure silica and is more refractory. Natural contaminants, such as iron oxide or limestone, adulterate many clays and some sands. These contaminants act as fluxes and reduce the fusion points of the mineral or blends. Glass is made from silica sand by fluxing the sand with strong bases, usually soda ash and limestone. Red building bricks are hard and durable because the sand and clay have been partially fused with help of natural iron oxide serving as a flux. The iron oxide per- forms a dual function, serving as a pigment as well as a flux. In a blend of clay and sand and iron oxide, the sand is more susceptible to fusion than is the clay. Although silica sand and clay are the most widely used raw materials in most ceramic products, many other minerals, and some non- minerals are utilized in products where these materials can produce or aid in achieving desired results. Limestone and dolomite, feldspars, pigmentary minerals, refractory oxides or carbides, and special property producers can

Jan 1, 1975

By A. B. Kinzel

A PREVIOUS study1 of the relations of impact strength to inclusions showed that the dynamic strength of steel is lowered by the presence of visible counted inclusions, but that other factors comprised in the term "body" have a marked influence. The previous work was carried out on selected steels from a single source, so that the body factor was purposely minimized, but even under these conditions it was found that inclusion counting or the use of the commercial inclusion rating is not satisfactory. The tensile-impact test, however, was indicated as a satisfactory measure of dynamic strength. It was further suggested that the tensile-impact test should be so standardized as to be suitable for use in specifications, and that the hardness factor should be worked out over a sufficient range to admit ready commercial use of the tensile-impact test. In accordance with these suggestions, and in view of the fact that the steels reported in the previous paper were selected and treated so as to have a minimum variation in body, hardness and structure, further work has been performed on a variety of steels which are not limited by these conditions. The word "body" is used here for want of a better term. It is simply a convenient expression which comprises the effect of the various unknown factors that modify the dynamic strength of the steel. Thus at our present state of knowledge, the writers have chosen to consider hardness, structure and counted inclusion content as factors not comprised in the term "body," and such factors as raw materials, process of melting, fabricating, etc. as comprised in the term "body." Numerous grades of steels made in several ways have been taken from different sources and have been heat-treated to varying hardness by normalizing and by quenching and drawing. The results, therefore, may be considered to be generally applicable to current engineering steels. A certain limitation with respect to the hardness at which steel should be

Jan 1, 1931

By Charles S. Barrett, Robert F. Mehl

It is generally understood by workers in the field of the crystal structure of metallic alloys that terminal solid solutions are of two types, the substitutional and the interstitial. In reviewing the literature, the work of Weissl on the crystal structure of the alpha copper-tin alloys was encountered, in which a new type of terminal solid solution was proposed. In brief, Weiss' findings showed that the density of the alloys calculated from the side of the unit face-centered cube on the assumption of simple substitution—that is, with four atoms to the unit face-centered cell—was much higher than the density measured directly. It was suggested that the assumption of four atoms to the unit cube is not valid for these alloys, and that each unit cube contained less than four atoms; in other words, that one tin atom replaces more than one copper atom, leaving some atomic positions unoccupied. Such a structure, if verified, would have far-reaching significance in the study of the crystal structure of metallic alloys. It would indicate a complexity in terminal solid solutions not hitherto suspected and might encourage work leading to the discovery of other alloys of the same type, and perhaps to types intermediate between it and the two recognized types. It is of importance, therefore, to reinvestigate these alloys with respect to the type of solid-solution structure obtaining therein. Materials and Experimental Method The alloys were prepared from electrolytic copper cut directly from the cathode and the high-purity tin furnished by the U. S. Bureau of Standards for the calibration of thermocouples. No analyses for impurities of these materials or of the finished alloys were made, since such impurities as might be present could have only a wholly inappreciable effect upon the data obtained and the conclusions drawn. The alloys were made by melting the weighed copper charge in a graphite crucible under a KCl-LiC1 flux with later additions of NaC1, using induction heating. When the copper was melted the weighed portions of tin were

Jan 1, 1930

T. R. HARRISON, Washington, D. C. (written discussion). *-Mr. Kowalke shows that a high resistance millivoltmeter is subject to smaller errors, due to change in resistance of the thermocouple to which it is attached, than is a low-resistance instrument. He uses as examples instruments having resistances of 30 and 2 ohms, respectively. At the Bureau of Standards, resistances above 300 ohms would be considered high and 30 ohms rather low. In the tests on calorized-iron thermocouples, a difference between the first and third calibrations of the couples serves to show changes due to the intermediate heat treatment and only under certain conditions would changes in calibrations due to changes in the wire be detected by ,a recalibration after 1 1/2 in. had been cut from the hot-junction end of the couple and the ends rewelded. The calibration of a couple depends only on the thermoelectric prop-erties of that part of the couple which lies within the region of non-uniform temperature, i.e., the temperature gradient; hence, so long as the temperature gradient falls along wires of similar thermoelectric properties no change in the electromotive force is produced by altering the metals of those parts of the circuit that are at uniform temperature. Usually at the cold-junction end of the circuit, copper leads, brass binding posts, manganin resistance coils, and various other materials form part of the circuit, but so long as all are at a uniform temperature (or if for each junction between unlike metals there is a similar opposing junction at the same temperature) no resultant thermoelectromotive force will be produced thereby. Likewise, if a length of several inches at the hot-junction end of the couple is at uniform temperature, it matters not if this section is unlike other parts of the couple, so long as there is good metallic connection and no source of e.m.f. other than thermoelectric is present. Cutting off part of the hot end of the couple within such a region of uni-form temperature would not alter the e.m.f. of the couple.

Jan 12, 1919

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 P. R. Swann, J. G. Parr

Quenched structures were studied in alloys containing up to 12.5 pct cobalt. The subsequent decomposition of a 10 pct cobalt retained-ß phase alloy was investigated using metallographic and X-ray diffraction methods. Hardness measurements also were made during the decomposition process. Precipitation of Ti2Co is by nucleation and growth; and an activation energy of 50,000 cal per mole was determined. The values of the coefficient ß suggest that the precipitate is pearlitic at temperatures between 450 and 475°C, and spheroidal between 500 and 525°C. THIS paper describes part of a series of invesligations into phase transformations in binary alloys of titanium with transition elements. The general approach is similar to that taken in work on titanium-iron and titanium-nickel alloys.' Previous investigators'' have established the titanium-rich end of the titanium-cobalt phase diagram, reproduced in Fig. 1. Orrell and Fontana' showed that alloys containing more than about 6 pct" cobalt quenched from the ß range, produced 100 pcl retained-p phase. The isothermal decomposition of alloys containing between 0.8 pct Co and 15.5 pct CO was investigated by the same workers in the temperature range 650 to 1000°C. They reported that these alloys transformed into a or Ti,Co depending on the cobalt content, but no quantitative data were given. In the work to be described a series of alloys containing 0.8 pct Co to 12.5 pct Co was examined in the quenched condition. The 10 pct Co alloy (the lowest cobalt content to retain 100 pct ß on quenching) was selected for further work on the tempering kinetics of the ß decomposition. Experimental Procedure Since our own melting equipment was not installed at the outset of this work, the Physical Metallurgy Division of the Department of Mines and Technical Surveys (Ottawa, Canada) prepared the alloys. These were made of Japanese sponge, (which when melted had a value of 103 DPH, using a 1-kg load), and electrolytically prepared cobalt. The al- loys, made up to contain 0.8, 1.6, 3.3, 5.8, 8.3, 10.0 and 12.5 pct Co, were homogenized by swaging into rods at 900°C. Filings were taken from the rods, and any iron chips from the file were separated magnetically. Size fractions of both plus and minus 200 mesh (about 75p) were shown by their constitution, after annealing just below the eutectoid temperature, to contain the same cobalt content. Consequently, it was permissible to use the —200-mesh fraction, knowing it to be representative of the rod composition. Quenching in argon was carried out in a newly designed furnace, whose features include (1) an Inconel furnace tube, (2) a positive pressure of argon maintained at all times in the furnace—even when a sample is removed or inserted. The furnace is shown in Fig. 2 and is described in the Appendix. The tempering processes were carried out on powder samples sealed in evacuated quartz capsules. Since the highest tempering temperature was 525OC, no protection against reaction with the quartz was necessary. (Tests were made on filings of iodide titanium and showed no hardness increase after equivalent heat-treatments.) A thermocouple was attached to the capsule, which was heated to the

Jan 1, 1959

By E. C. IBBOTSON

THIS process was reported upon by the Canadian Commission in 1904, and much detailed information was also given in a paper by Chief Engineer V. Engelhardt.1 Believing that some of the latest particulars of the process will be of interest, I submit the following data. At Gysinge in Sweden during the year ending May 31, 1906, from a fixed furnace giving 1 ton (2,240 lb.) of steel per tap, there were produced 950 tons of tool-steel and special steel ingots. . In carbon and iron tool-steels all the usual tempers were made. The bulk of this steel was made from charges composed of about 80 per cent of Swedish white pig-iron and 20 per cent. of steel-scrap. The percentage of carbon was regulated by the addition of briquettes. Other charges were made from Swedish white iron and steel-scrap. The average time taken per charge, for the year, when adding briquettes, was 7* hr., and the electric energy consumed was 1,128 units (kilowatt-hours) per ton. The average time per charge for white-iron and scrap charges was 5.5 hr., and the electric energy consumed was 886 units per ton. These consumptions include all time and energy lost from various causes, such as bad water-supply, ice, etc. It is quite ordinary practice to complete the charges with briquettes in 6.5 hr., and without briquettes in 5 hr., as shown by the following typical charges White pig-iron, 1,457; steel-scrap, 439; briquettes, 220; ferrosilicon (50 per cent. of silicon), 17 ; ferromanganese (80 per cent. of manganese), 15 lb. ; and aluminum, 1 oz.=

Nov 1, 1906

In the Philippines, where distances are spoken of in terms off fight time, the Sipalay copper mines are two flight hours southeast of Manila on the island of Negros. After landing at the airport in Bacolod, it is then 170 km (106 milers) by surface transportation to Marinduque Mining and Industrial Corp.'s expanding copper operation. While copper deposits were discovered in the area in 1936-and one mine, the Binulig, began operations soon after-it wasn't until 1956 that stripping at Sipalay and construction of a 4000-t/d (4400-stpd) mill began. The mill went into operation in May 1957, and the first shipment of copper concentrate was made three months later.

Jan 8, 1978

By E. P. Klier, Volker Weiss, George Sachs

IT has been shown that the isothermal transformation of austenite in a special steel can be modified by isothermal holding in the high subcritical transformation range.' Since this treatment potentially leads to increased hardenability, limited testing has been completed to determine if the stabilization effects observed with this treatment can be used to advantage in the heat-treating of 4340 steel. As an index of the effects of the several austenitizing treatments on the hardenability of the steel, Jominy-type hardenability tests were completed for specimens 2.5 in. in diameter and 8 in. long. Since the steel studied is to be used at strength levels where notch sensitivity is of major concern, notch sensitivity after selected austenitizing treatments has been evaluated by notch tensile tests for several specimen sizes. The steel composition and the austenitizing treatments are given in Table I. The test specimens are presented in Fig. 1. The hardenability data are given in Fig. 2 and the notch tensile properties are presented in Fig. 3. The hardenability of the steel investigated when determined by use of the standard Jominy test specimen2 as high and remained essentially unchanged for the different austenitizing treatments. For the larger test specimen, as has been shown by other investigations," the characteristic hardenability indexes are changed and it becomes possible to isolate austenitizing treatments which promote maximum hardenability. The stepped austenitizing treatment promotes higher hardenability as is indicated in Fig. 2. The evaluation of notch sensitivity for very high strength steels is best accomplished by means of the notch tensile test. The experimental conditions of the test, however, modify the notch strengths measured, and in the present experimentation an effort was made to achieve a limiting notch condition by fixing the notch root radius at 0.001 in. while the specimen diameter was allowed to increase from 0.3 to 1.1 in.* For this root radius the notch strength, 0.3-in.-diam specimen, and this trend differs from that for the larger specimens. At the highest tempering temperatures the 1.1-ip.-diam specimens yield comparable results for the austenitizing treatments compared. However, as the tempering temperature is progressively lowered below 800°F, em-

Jan 1, 1958

By Robert Gorham Morse

This paper presents the results of an investigation made in the metallurgical laboratory of Columbia University, New York City. The object of the investigation was to determine how the tensile strength, the elastic limit, and the size of the grain, of a pure medium-carbon steel are affected by heating to successive temperatures between 500° and 1300° C., with slow cooling therefrom. Since Dr. Sorby's first investigations into the microstructure of steel, the study of the subject has been continued by Professor Martens, Mr. F. Osmond, Professor Arnold, Professor Howe, Mr. A. Sauveur, Mr. J. E. Stead, and many others. Among many valuable and interesting papers I mention the following as having a special bearing upon this investigation.* " Microstructure of Steel," by Albert Sauveur, Trans., xxii., 546 (1893); Microscopic Metallography," by F. Osmond, Trans., xxii., 243 (1893); "The Microstructure of Steel and the Current Theories of Hardening," by Albert Sauveur, Trans., xxvi., 863 (1896); "The Crystalline Structure of Iron and Steel," by John Edward Stead, J. Iron and Steel Inst., 1898. II.—Statement of Experiments. Through the kindness of Mr. N. Lilienberg, New York City, round rods 3/4 of an inch in diameter were obtained, which had been rolled from one ingot. The analysis of the steel was as follows : C, 0.343; Si, 0.027; Mn, 0.221; I?, 0.0266; S, 0.0037 per cent.

Jan 1, 1900

By J. T. Norton, A. L. Mowry

S. J. SINDEBAND*—(1) Discussing the properties of the powders used, Mr. Rostoker mentioned a silicon powder as being between 150 and 325 mesh. We always had much difficulty in measuring particle size of silicon powder by screen analysis, because of its tendency to agglomerate. I would be interested in the method used to measure these particle sizes. (2) Mr. Rostoker maintains that the measurement of magnetic properties is more accurate in determining complete homogenization of an alloy, than is the X ray diffraction technique. I wonder whether this is really true. Even when diffusion is complete, magnetic properties will change during continuation of the heat treatment, due to change in density and pore shapes, as has been demonstrated by Mr. Rostoker himself. Which effect is faster, the diffusion of the alloy components or the attainment of final density, will, in my opinion, depend very much on initial material and sintering conditions used. For magnetic applications, of course, the magnetic measurements are most suited for determining the point at which equilibrium conditions are reached. (3) I was glad to see that Mr. Rostoker had used sample sizes which are similar to those I had used previously, and I believe that ring samples of about 2 in. od will become more or less standard samples for the determination of magnetic properties of powder metallurgy products. I should like to ask how the density was changed for the samples on which the effect of porosity was investi- gated, and, further, why the sintering temperature used for this series of experiments was so low. It is somewhat surprising that a 24-hr treatment at 850°C acts so much more to spheroidize the pores than a treatment for 1 hr at 1100°C. But the effect seems to be indisputable. I have made an investigation of the influence of sintering temperature for longer times on the maximum permeabilities of iron powder compacts which was presented at the International Powder Metallurgy Conference in Graz, in 1948, and I hope that these results will be published here within a short time. The results of this investigation are confirmed by Mr. Rostoker's findings that the change of time from 1 to 24 hr changes the permeability behavior considerably in the direction as indicated by Polder and Van Santen for spheroidiza-tion of pores. I do not quite understand Mr. Rostoker's explanation of the influ-

Jan 1, 1950

By Don H. Baker

THE need for new or improved refractory materials has caused metal phosphides to be given renewed scrutiny. Some metal phosphides show high-temperature inertness, are exceptionally hard, and exhibit a marked resistance to chemical attack. Various metal phosphides have been prepared for study by direct combination of the elements,'-' by reaction of metal or metal compounds with phosphine or phosphorus trichloride,'"' by thermal decomposition of a metallic phosphate or phosphite,"-'8 and by molten salt electrolysis.19 Electrolytic preparation of phosphides of titanium, manganese, and chromium from their oxides is reported in this paper. An externally heated 3-in.-ID by 6-in.-deep graphite cell, that served as the anode as well as a container for the electrolyte, was used in these investigations, and a suspended, centrally positioned graphite rod served as the cathode. A closely fitting silicon carbide furnace liner minimized atmospheric oxidation of the crucible. Electrolyses were performed for predetermined periods and current settings. Preliminary research had indicated the more efficient current and potential settings that could be used. Upon completion of the deposition period, the deposit was hot-stripped from the cathode. The mass of crystalline deposit, plus occluded and adhering salt, was crushed to minus 10 mesh and hot-leached in dilute hydrochloric acid. The leached crystalline material was water-washed, dried, and sampled for analysis. Products were identified by X-ray diffraction and standard analytical procedures. Electrochemical studies were initiated to establish the optimum conditions necessary to produce manganese phosphide (MnP), titanium phosphide (Tip), and chromium phosphide (CrP). Among the factors studied were the operating temperature, the imposed current, and the electrolyte system. If the temperature, or imposed current, was too high, deposition of phosphorus resulted, and if either were too low, partially reduced lower oxides were deposited. The operating conditions established for repetitive high-quality production of metal phosphides of the MP structure are presented in Table I. The metal phosphide crystals varied in size, but all had a definite metallic appearance. Typical are the crystals of CrP shown in Fig. 1. Evaluation data and analysis of the crystals are presented in Table 11. Efforts to measure resistivity of these three compounds over the temperature ranges of 250o to 400°K were hampered by the small physical size of the crys-

Jan 1, 1968

By P. W. Davies, B. Wilshire

PREVIOUS investigations on the effect of stress changes on the high-temperature creep and fracture behavior of metals have been confined mainly to the testing of complex alloys.172 Most of these alloys are structurally unstable during creep because of such effects as recrystallization, overaging, and so forth, so that the results are of limited application. The only pure metals on which observations have been made appear to be lead3,4 and aluminum5 tested under conditions which allow rapid recovery to take place. The present work describes the effect of a single stress change on the creep and fracture properties of a metal in which recovery is very slow. A Ni 0.1 at. pct Pd alloy was used so that grain growth and recrystallization did not occur during creep testing. Specimens of this material were heat-treated to give a uniform grain size of 10 grains per mm. Creep tests were carried out at 500°C using Denison T.47 machines; details of the creep-testing procedure have been given elsewhere.' All specimens were tested at a constant initial stress of 5 tpsi which gives, in an uninterrupted test, a minimum creep rate of ~10-3 pct per rnin and a life of -7000 min. Specimens were loaded under these standard conditions and after 1500 min, when secondary creep was well-established, the stress was changed to either 8, 7, 6, 4, 2, or 0 tpsi for a period of 180 min. After this time the original load was reapplied and the tests continued to fracture. The results are shown in Fig. 1. No detectable creep occurred during the period of reduced load, even at 4 tpsi, and on reverting to 5 tpsi the creep rate returned to its original value immediately. Increasing the stress to 8, 7, or 6 tpsi resulted in an instantaneous extension followed by a period of transient creep leading to a new steady creep rate. On returning from these higher stresses, the resulting creep rate at 5 tpsi was very low compared with the original value. Furthermore, the higher the stress during the stress change, the lower was the final creep rate. It is significant that the rupture life is comparatively unaffected by any of these stress changes.

Jan 1, 1965

By Orson Shepard

TEXTBOOKS on fire assaying list the following standard methods of assaying sulphide ores: (1) scorification, (2) litharge-niter, (3) soda-iron, (4) roasting, (5) combination wet and fire. The litharge-niter method has proved the most satisfactory, and is the usual method for assaying sulphide ores and concentrates. It gives good results when suitably conducted and when lead buttons of uniform size are produced so that the cupellation temperature can be properly controlled. The main objection to the method is the inconvenience of determining the amount of niter to add to each assay charge to produce lead buttons of suitable size from a set of fusions. For the assay of different materials, the niter requirement varies with the particular sulphide minerals present, the amount of sulphide minerals present, the slag composition, and the rate of heating the charge in the furnace. Except for some materials, so uniform in composition that the same amount of niter can be used in assaying all samples, the amount of niter must be determined for each sample to be assayed. This is done by either: (1) calculation from an estimate of the kind and amount of sul-phide minerals present in the sample, or (2) a preliminary fusion. Some assayers use one method and some the other. The estimation method takes the least time; but much experience is required to obtain close estimates on a wide variety of materials. At best, the sizes of the lead buttons obtained vary considerably. The preliminary fusion method usually gives lead buttons of fairly uniform size, although sometimes there is a variation because the oxidizing power of niter varies a little with the charge. This variation can be eliminated by two preliminary fusions: one to determine the reducing power of the ore, and the other to determine the oxidizing power of niter in the charge. The objection to the prelimi-nary fusion is the extra time and expense involved.

Jan 1, 1939

By J. W. Freeman, R. F. Decker

A microstructural investigation was pursued to establish the mechanism of the pronounced benefits of traces of boron and zirconium on creep properties of a 55 Ni-20 Cr-15 (20-4 MO-3 Ti-3 A1 alloy at 1600°F. The mechanism of improvement of creep properties was found to be a pronounced stabilizing effect of traces of boron and zirconium on the grain boundaries of the alloy. The alloy with low boron and zirconium was subject to rapzd agglomeration of M23 C6 and in the grain boundaries, followed by depletion of y ' and intergranular microcracking at the grain boundaries transverse to applied stress. Brittle fracture then occurred by linking of microcracks. However, additions of zirconium, boron, and boron plus zirconium decreased this tendency in that order, allowing longer creep exposure and higher creep defor.mations before fracture occurred. VERY little information has been published describing the mechanism by which trace amounts of boron or zirconium improve the creep properties of complex nickel-base heat-resistant alloys, although the effect is now well recognized.1-4 Because the phenomenon is so important to properties and the effects are so striking, a study was made of the mechanism in a 55 Ni-20 Cr-15 Co-4 Mo-3 Ti-3 A1 alloy. It was believed that such a mechanistic approach would increase knowledge in theory of alloying and give a more basic understanding of alloy design to resist creep. The basic premise of the study was that boron or zirconium would alter the microstructural characteristics controlling creep and fracture to the extent that the effects could be identified by light and electron microscopy and by electron diffraction techniques. Characteristic of the microstructure of the Ti + Al-bearing nickel-base alloys is the dispersed precipitation of the intermetallic compound Ni,(Al, Ti), the ? ' phase, which is generally con- sidered to be the major source of high creep resistance.5-7 In addition, carbide phases have been identified8-10 and these can alter creep properties markedly.11 Since both the ?' and carbide transformations have been found to control properties, careful attention was paid to the effect of boron and zirconium on these transformations.

Jan 1, 1961

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 B. M. Larsen, W. E. Shenk, T. E. Brower

Shortly after our previous paper on this subject was printed1 we located a source of uncertainty in the results arising from the unexpected fact that hydrogen slowly reduces silica at 1100" C. in presence of iron, even when the iron nowhere touches the silica, although in absence of iron it does not do so. This difficulty has been completely obviated by the use of a small high-frequency furnace, which enables us to heat the specimen for analysis without raising the temperature of the silica vessel to a point at which any appreciable reduction of the silica glass occurs. We now describe this modification of procedure, and present some typical results obtained with it. For any given specimen of steel, the results are entirely definite and reproducible, but their precise significance is still open to some question, as indeed is true of all methods of oxygen determination SO far developed. Further elucidation of this question is to be expected from the cooperative comparison of the several methods now under way under the auspices of the Bureau of Standards at the instance of the Iron and Steel Division of the A.I.M.E. Apparatus The final form of apparatus we have used is identical with that described and illustrated in our previous paper, except for the substitution for the Globar furnace of a small high-frequency furnace actuated by a vacuum tube oscillator2 0f about 1.5 kw. capacity, and for a slight modification of the containing vessel. This transparent silica vessel is illustrated in Fig. 1 of this paper. Its enlarged portion is about 5 cm. in diameter and 13 cm. long. The silica tube for inlet of hydrogen is fused into this bulb and ends beneath the metal "bucket" holding the steel sample. This sample is in the form of fine millings. The "bucket" is suspended by a platinum wire from the cap of Pyrex glass. The high-frequency

Jan 1, 1934

By A. B. Kinzel, Walter Crafts

A PRevioUs study1 of the relations of impact strength to inclusions showed that the dynamic strength of steel is lowered by the presence of visible counted inclusions, but that other factors comprised in the term "body" have a marked influence. The previous work was carried out on selected steels from a single source, so that the body factor was purposely minimized, but even under these conditions it was found that inclusion counting or the use of the commercial inclusion rating is not satisfactory. The tensile-impact test, however, was indicated as a satisfactory measure of dynamic strength. It was further suggested that the tensile-impact test should be so standardized as to be suitable for use in specifications, and that the hardness factor should be worked out over a sufficient range to admit ready commercial use of the tensile-impact test. In accordance with these suggestions, and in view of the fact that the steels reported in the previous paper were selected and treated so as to have a minimum variation in body, hardness and structure, further work has been performed on a variety of steels which are not limited by these conditions. The word "body" is used here for want of a better term. It is simply a convenient expression which comprises the effect, of the various unknown factors that modify the dynamic strength of the steel. Thus at our present state of knowledge, the writers have chosen to consider hardness, structure and counted inclusion content as factors not comprised in the term "body," and such factors as raw materials, process of melting, fabricating, etc., as comprised in the term "body." Numerous grades of steels made in several ways have been taken from different sources and have been heat-treated to varying hardness by normalizing and by quenching and drawing. The results, therefore, may be considered to be generally applicable to current engineering steels. A certain limitation with respect to the hardness at which steel should be tested still seems necessary. The upper limit of this hardness range has

Jan 1, 1931