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By William H. Spice

The area on which oil and gas development is reported covers 30 counties, which are included in the Texas Railroad Commission's District No. I. This area not only includes the old established Balcones fault-line group of producing fields but also includes the southwest extension of this trend and some of the deeper Wilcox (Eocene) exploratory development. (Fig. J.) In the old Balcones fault-line zone, three new fields were discovered during 1941. These fields are comparatively small, producing from Dale limestone or Austin chalk. No new fields were discovered during the year in the Edwards (Lower Cretaceous) limestone horizon. One new shallow field was discovered in the Reklaw (Eocene) sand horizon and, in the southwestern part of the district, one oil field and one gas field were discovered in the Navarro (Upper Cretaceous) sand horizon. An extremely important extension was made to the one producing Wilcox (Eocene) field of the district in the Washburn Ranch field of La Salle County. The district produced 6,650,357 bbl. during 1941, which was a 12 per cent decrease under production for 1940. Approximately 4,954,000 bbl. of this total production was produced by the three Edwards limestone fields, Luling, Salt Flat and Darst Creek, the remaining production coming from the other 43 active fields in the district. In all, 3694 wells were producing at the end of 1941, compared with 3559 wells at the end of the previous year. During the year, 139 new producing wells were completed and 29 wells were abandoned in the producing fields. The increase in producing wells represents an increase in new wells over abandonments in these fields, together with a decrease in wells temporarily shut down as of the end of 1941. The majority of production drilling was carried on in the following fields; Bee Creek, Chicon Lake, Elm Creek, Gas Ridge, Pearsall and Tenney Creek. Approximately 250 wells were drilled during 1941, of which 110 were exploratory wells completed as failures throughout the district. Considerable exploratory work was continued during 1941 along the Wilcox trend. Geophysical work employing various types of geophysical methods and leasing activity was continued along this trend, particularly by the major companies. The significance of this activity is apparent from the successful extension and development in the Washburn field of La Salle County, where several well-developed gas-and-oil producing horizons have been developed in the lower Wilcox section between 5100 and 5600 ft. as noted in the following paragraphs. Continued exploratory activity along this general trend as far as present conditions will permit is predicted for 1942. New Fields Elgin Field, Bastrop County.—No. I-A Hiram Walker, Marts and Beaven, Inc., discovery well of the Elgin field, was com pleted on Apr. 22, 1941, in broken Austin chalk from 2820 to 2840 ft., pumping 105 bbl. per day, 36.8°A.P.I. gravity. The well apparently is producing from a crevice in

Jan 1, 1942

By Warren B. Weeks

The year 1940 saw an increase of 20 per cent in oil production over the previous year—compared with a 16 per cent increase the previous year. In all, 25,790,380 bbl. were produced, an increase of 4,414,150 bbl, over 1939 and the largest production figure for south Arkansas since 1928. The older settled production continued to decline. Magnolia accounted for most of the increase, with aid from the other recent deep fields. During the year, 169 wells were drilled, 79 fewer than in the previous year. Of 131 wells drilled in proven fields, 18 were dry. Three of the 38 wildcats were pool openers. The drilling depth record was increased from 9028 to 9550 feet. Trend of Prospecting For the first time since 1936, the search for oil in the deep Smackover limestone slackened perceptibly; g dry wildcats ended in Smackover, 2 in. the underlying Eagle Mills; 7 penetrated Paleozoic beds, while 9 ended in Hosston, 2 in Glen Rose, 2 in Paluxy and 4 in Gulf. Geology The wells listed in Table 2 either resulted in the discovery of new oil pools or, because of their depth or location, afforded impor-tant stratigraphic or structural informa-tion. Fig. I is a general columnar and stratigraphic section showing the relation-ship of the strata within the Comanche series. The nomenclature shown was ac-cepted by the Shreveport Geological Society. It was subsequently published by Imlay,l who indicated probable correlations with other areas and presented evidence for the possible Jurassic age of the under-lying Cotton Valley and Smackover formations. New Fields Pouke.—On June 10, 1940, the Louark Producing Co. completed its No. I Sturgis, sec. I, T. 17 S., R. 27 W., in central Miller County, producing between 3583 and 3607 ft. in the upper part of the Paluxy forma-tion. The well flowed I00 bbl. of 3r.4' gravity oil per day through Ns-in. tubing choke. This discovery resulted from seismograph work. Six other wells were drilled in the area, none of which found production in the original sand. One of these wells is producing from a sand 50 ft. deeper in the section. The others were abandoned. No further development is in prospect. Production is from lenticular sands of the upper Paluxy; 45,556 bbl. had been pro-duced by the end of 1940. There is structural closure against a fault to the northwest. McKanzie.—The Atlantic Refining Com-pany's No. I Bodcaw Lumber Co., sec. 29, T. 17 S., R. 23 W., eastern central La-fayette County, was completed June 8, 1940, as the eighth and farthest west of the Smackover (Reynolds o6lite) limestone pools. The well flowed 10 bbl. an hour of 58.6' gravity distillate through an 1 1/64 Ma-in. tubing choke, with a gas-oil ratio of 8400:I.

Jan 1, 1941

By William H. Spice

The area on which oil and gas development is reported covers 30 counties, which are included in the Texas Railroad Commission's District No. I. This area not only includes the old established Balcones fault-line group of producing fields but also includes the southwest extension of this trend and some of the deeper Wilcox (Eocene) exploratory development. (Fig. J.) In the old Balcones fault-line zone, three new fields were discovered during 1941. These fields are comparatively small, producing from Dale limestone or Austin chalk. No new fields were discovered during the year in the Edwards (Lower Cretaceous) limestone horizon. One new shallow field was discovered in the Reklaw (Eocene) sand horizon and, in the southwestern part of the district, one oil field and one gas field were discovered in the Navarro (Upper Cretaceous) sand horizon. An extremely important extension was made to the one producing Wilcox (Eocene) field of the district in the Washburn Ranch field of La Salle County. The district produced 6,650,357 bbl. during 1941, which was a 12 per cent decrease under production for 1940. Approximately 4,954,000 bbl. of this total production was produced by the three Edwards limestone fields, Luling, Salt Flat and Darst Creek, the remaining production coming from the other 43 active fields in the district. In all, 3694 wells were producing at the end of 1941, compared with 3559 wells at the end of the previous year. During the year, 139 new producing wells were completed and 29 wells were abandoned in the producing fields. The increase in producing wells represents an increase in new wells over abandonments in these fields, together with a decrease in wells temporarily shut down as of the end of 1941. The majority of production drilling was carried on in the following fields; Bee Creek, Chicon Lake, Elm Creek, Gas Ridge, Pearsall and Tenney Creek. Approximately 250 wells were drilled during 1941, of which 110 were exploratory wells completed as failures throughout the district. Considerable exploratory work was continued during 1941 along the Wilcox trend. Geophysical work employing various types of geophysical methods and leasing activity was continued along this trend, particularly by the major companies. The significance of this activity is apparent from the successful extension and development in the Washburn field of La Salle County, where several well-developed gas-and-oil producing horizons have been developed in the lower Wilcox section between 5100 and 5600 ft. as noted in the following paragraphs. Continued exploratory activity along this general trend as far as present conditions will permit is predicted for 1942. New Fields Elgin Field, Bastrop County.—No. I-A Hiram Walker, Marts and Beaven, Inc., discovery well of the Elgin field, was com pleted on Apr. 22, 1941, in broken Austin chalk from 2820 to 2840 ft., pumping 105 bbl. per day, 36.8°A.P.I. gravity. The well apparently is producing from a crevice in

Jan 1, 1942

By H. H. Reamer, B. H. Sage

The formation volume and the relative volume of the liquid Phase of mixtures of Condensate and gas from five different parts of a field in the Louisiana area have been established experimentally. These studies included gas-condensate ratios as high as 25.000 cu ft/bbl at pressures up to 5,000 psi. The gravities of the tank condensates were between 53.9° and 63.9° API. The compositions of the condensate and gas samples inves-ligated are presented in tabular form. The formation volume. the relative volume of the liquid phase. and the specific volume of the mixtures are available. A rough correlation of the formation volume as a function of pressure. temperature, and gas-condensate ratio has been presented. This correlation i-considered applicable only to the range of conditions covered in this investigation for systems of similar nature and com-position. INTRODUCTION Often a knowledge of the influence of temperature. Pres sure, and relative quantities of condensate and gas upon the volumetric behavior of fluid*. from a given field has been employed in estimating the Conditions existing in the reservoir. The early work of Beecher and Parkhurst' and the more rrcent Studies of the Dominguez' and San Joaqnin Valley Field;: are examples of experimental studies of this character. Correlation of the volumetric behavior of naturally occurring hydrocarbon mixtures has Proved To be feasible' . at low gas-conden-sate ratios-; for fluids*. from a single geographic area. Progres 5 is being made in the Prediction of the volumetric behavior of distillate systems at high gas-condensate ratios and pressure.. However. the estimation of the retrograde". ' dew-point pressure still remains uncertain and probably can best be established by experiment. For this reason it appears of interest to make available experimental information about the volumetric behavior of mixtures of condensate and gas from five different part.; of a single field. This material shows a rough similarity to data for mixtures of condensate and gas from San Joaqnin ' Valley Fields. In the present paper. 110 attempt has been made to coordinate the available information on tbe volumetric behavior of fluids from condensate fields. It appears hopeful that progress can be realized by the utilization of recently developed equa-tions of state.!' However. the primary problem in any such correlation is the proper identification of the components and constituents of naturally occuring systems. Additional experimental information may be required to permit the determination of the values of the constants of the equation of state for References given at end of paper. Manuscriptt received in the office of the Petroleum Branch June 11. 1951. *For present purposes low gas- condensate ratios will he considered as those below 3,000 cu ft/bbl, and the region of high gas-condensate ratio will be limited to compositions containing more than 5,000 cu ft of pas per bbl of condensate. Mixtures Containing between 3,000 and 5.000 CII ft OF gas per bbl will be considered of intermediate gas-condensate ratio.

Jan 1, 1952

By E. A. Nesbitt

THE important permanent-magnet alloys 15 years ago contained carbon and depended upon it for their permanent- magnet properties. In recent years great, advances have been made in a number of new alloys substantially free of carbon. These include Remalloy,l an alloy of iron, cobalt, and molybdenum, the various iron- nickel-aluminum alloys of the Mishima2 type, and the more recent Alnico V3 in which the best properties are developed by heat-treating in a magnetic field. The Mishima and the Alnico types of alloys are very brittle and after casting must be ground to size. This article describes a permanent-magnet material4 that can be machined as cast, and when handled with some care can be .rolled to thin sheet and drawn to fine wire. Optimum magnetic properties are developed by a simple heat- treatment, and at this time the ductility A of the alloy disappears. If the cast alloy is heat-treated without cold-working the magnetic energy product is about 1.0 X 106. This material is called Vicalloy I (pronounced vicalloy, V for vanadium, I for iron, and C for cobalt). When the alloy is first hot-worked and then considerably reduced in area by cold-swaging, drawing or grooved rolling, it is found that after heat-treatment the magnetic energy product measured in the direction of previous extension can be increased to 2.0 to 3.5 X l06. These higher values have been obtained only after reductions in area of 75 to 95 per cent, and since the material hardens considerably during working, the reduction ordinarily can be accomplished only in fine wires, although larger sizes can be reduced by the use of powerful machinery. When the material has been cold- worked in such a manner as to improve its energy product substantially, it is called Vicalloy II. Commercial use of Vicalloy has been made in the recording of speech. Tape 0.002 by 0.050 in. has been found superior in quality to all others tried, and is now used in the Western Electric Mirrorphone In a variety of forms Vicalloy I or II is useful in many laboratory instruments, and in experiments in which the sizes and shapes required cannot be obtained with the other more brittle permanent-magnet materials. In 1936, during a study of other age- hardening magnetic systems, it occurred to the author that some of the iron-cobalt-vanadium alloys might be suitable for permanent magnets. The proportions of iron, cobalt, and vanadium were varied and a range of alloys of particular interest was found, as shown by the indicated area in Fig. I. The limits of this range of com- position are 30 to 52 per cent iron, 36 to 62 per cent cobalt, and 4 to 16 per cent vanadium. The compositions indicated by points outside this area were also tested. PREPARATION AND PROPERTIES OF VICALLY I The alloys were usually cast in graphite molds into bars ¾ in. in diameter and

Jan 1, 1946

AUGUST began with a reminder that warfare was still in progress in the world, in that the Greeks, still at war with Turkey, threatened Constantinople in spite of the small British and French forces of occupation and opened a vista of international dangers. There was in this, moreover, a recollection that religious questions in India had prevented the British from permitting a real settlement of the Turkish question, wherein the absence of Russia as a great power is missed. Civil warfare also continued in Ireland and China. Even in the military way the world is far from being at peace. Bloody fighting between the Fascisti (anti-communists) and the com-munists in Italy led to several provinces being put under martial law, but after a while these disturbances were quelled. In the latter part of the month the assassination of Michael Collins in Ireland produced a great shock. From China, however, there came rather favorable news, indicating the early reintegration of that country, which sooner or later ought to play an important part in world affairs. Economically, instead of there being any improve-ment, there grew a clearer perception of how bad things really are. Italian politics were in chaos through inability to find anyone to accept the premiership and assume the all but hopeless task of averting national bankruptcy. The French, too, began to see their own position in true colors, and especially to see how in reconstruction they had incurred debts on the strength of what they hoped to collect from Germany, with at last the understanding that the Germans could not pay and that France herself was thereby put in a desper-ate economic position. As for the Germans, them-selves their Reichsbank defaulted on ordinary bills early in August. As the month wore on the value of marks fell more and more and at the end it appeared that Germany was on the verge of economic collapse. On Aug. 7, another international conference (with America again absent) was assembled in London, this being the thirteenth since the war, and there was a general feeling that it would be the last. The prime question was what is to be done about the German reparations, but underlying was the whole subject of the entente. The conference opened like a meeting of importunate creditors, doubtful whether the debtor had any tangible assets. On Aug. 14 this conference broke up without coming to any useful conclusion. Indeed, the acrimony among the premiers was so sharp that even the entente between Great Britain and France was endangered. The international situation was saved only by the Reparations Commission excusing the Germans from the payment of 50,000,000 gold marks that come due on Aug. 15 But although the entente was nominally preserved there is no longer any illusion about the interests of Great Britain and France being different and that henceforth they will play their own hands. The London conference was really an effort to maintain the partnership, and it failed.

Jan 9, 1922

By E. W. Newman

DURING 1943 and 1944, there was an urgent need for certain grades of optical calcite (Iceland spar) for instruments for military uses. To find a supply of this material, prospecting was carried out in Montana, California and Colorado. Although some production was obtained by the work in California, the best results were from prospecting the large calcite veins of south central Montana. The bulk of the optical calcite mined during World War II has come from that area. The Bureau of Mines took an active part in the search for optical calcite in Montana. It examined most of the known calcite veins in the 70-mile distance between Wilsall, on the Shields River, and Absarokee, on the Stillwater River, and conducted exploration on several of the deposits. The Geological Survey also took an active part by mapping many of the veins. Actual mining of the calcite was performed at first by Calcite Operators, Inc., and later by the Metals Reserve Co., through an agent. A sorting plant was established at Clyde Park, where custom material could be sold. These activities stimulated mining by private operators. To be suitable for military uses, the calcite mined had to meet rigid specifications as to both size and quality. Individual crystals had to be clear and transparent and if in the form of rhombs had to measure at least 7/8 in. on each edge. Some color and a few inclusions in the calcite were allowable, but material with incipient or developed cleavages, or showing twinning other than parallel to the base, was unacceptable. HISTORY OF DEPOSITS The existence of large veins of calcite in south central Montana has long been known, and for many years the farmers of this region have used the common vein calcite for producing grit for chicken feed. According to reports, the first optical calcite produced from Montana came from the Cartwright deposit near Greycliff,1 but until recently the mining of optical calcite in Montana has been limited to spasmodic searching for small crystals suitable for making nicol prisms for saccharimeters and microscopes, or for mineral specimens. The possible need of substantial amounts of optical calcite for military uses began to appear late in 1942 and early in 1943, therefore the Polaroid company began searching for a source of supply in Montana and California. Work on the Wade property near Clyde Park was started on a small scale in the fall of 1942, by A. H. Hansen, of Clyde Park. During the winter and spring of 1943, a modest quantity of optical calcite was mined and shipped to the Polaroid Corporation, Cambridge, Mass. Most of this was produced from the "Hansen vug," which was found close to the surface. Early in the summer of 1943, mining on the Wade property was undertaken by Calcite Operators, Inc., a company organized for mining optical calcite from the Montana and California deposits. This com-

Jan 1, 1945

By J. E. Burke, C. W. Mason

In attempting to study precipitation from a tetragonal lattice, using solid solutione of bismuth in tin, it was found that although a Widmanstätten pattern is observed1,4 only a qualitative analysis of the orientation relationships is possible, because of the unusual structural changes that accompany the precipitation process. Microscopical Studies Alloys were made from Chempur tin (Standard samples 42b and 426, National Bureau of Standards), and bismuth (Kahl-baum C.P.) by melting weighed quantities together under palm oil, stirring well, and castilig in a heated graphite mold. The polishing and etching techniques employed largely govern the visibility of the structural changes. The preliminary surfacing operations were similar to those recommended by Villela and Bergekoff,5 through Behr-Manning 3/0 abrasive papers, lubricated by a solution of paraffin in kerosene. A rough metallographic polish was next given, using a thin cotton cloth charged with relevigated alumina (maximum particle size of about 4µ) and soap solution; repeated etching and polishing served to remove disturbed metal. For high-power examination better preparation was necessary. It was found that on such soft metals the threads of the fabric, rather than the abrasive, cause most of the scratching. Cotton outing flannel, which had been brushed so that the nap lay down, was fairly satisfactory, but a heavy grade of silk velvet (not the noncrushable kind) was found to be better, especially after some use. A better procedure was as follows: The metal lap was warmed slightly, and a 4-in. circle of woolen broadcloth was cemented to its center by a thin film of melted paraffin. The broadcloth was then moistened with water, and a 30 to 40 per cent solution of sodium hydroxide heated to about 50°C. was poured over it, allowed to stand for I to 2 min. and then washed off. It was neither necessary nor desirable to remove all the sodium hydroxide from the cloth, since its etching action aided in the removal of the flowed layer from the sample. The cloth was then charged with a paste of the relevigated alumina in water. Since this lap did not remove deep scratches, it was necessary previously to polish the specimen on some material such as the silk velvet. The sodium hydroxide softens and partly gelatinizes the woolen lap covering, permitting a scratch-free polish, but its action continues, and the cloth deterioratcs after about 24 hr. This is not serious, because a new lap can be prepared in about 5 min., and only small pieces of cloth are used. Etching with a strongly acid solution of ferric chloride was found satisfactory for removing the flowed layer. For the final etching, the most satisfactory reagent was that of Tafls,7 the formula for which is: FeC13.6H2O, 2 grams; HC1, 5 c.c.; H2O, 30 c.c.; C2H5OH (95 per cent), 60 C.C. This etchant reveals differences in com-

Jan 1, 1942

By J. E. Burke, C. W. Mason

IN attempting to study precipitation from a tetragonal lattice using solid solutions of bismuth in tin, it was found that although a Widnmanstatten pattern is observed 1 only a qualitative analysis of the orientation relationships is possible, because of the unusual structural changes that accompany the precipitation process MICROSCOPICAL STUDIES Alloys were made from Chempur tin (Standard samples 42b and 42c, National Bureau of Standards), and bismuth (Kahlbaum C P ) by melting neighed quantities together under palm oil, stirring well, and casting in a heated graphite mold The polishing and etching techniques employed largely govern the visibility of the structural changes The preliminary surfacing operations were similar to those recommended by Villela and Bergekoff,5 through BehrManning 3/o abrasive papers, lubricated by a solution of paraffin in kerosene A rough metallographic polish was next given, using a thin cotton cloth charged with relevigated alumina (maximum particle size of about 4µ) and soap solution, repeated etching and polishing served to remove disturbed metal For high-power examination better preparation was necessary It was found that on such soft metals the threads of the fabric, rather than the abrasive, cause most of the scratching Cotton outing flannel, which had been brushed so that the nap lay down, was fairly satisfactory, but a Heavy grade of silk velvet (not the noncrushable kind) was found to be better, especially after some use A better procedure was as follows The metal lap was warmed slightly, and a 4-in circle of woolen broadcloth was cemented to its center by a thin film of melted paraffin The broadcloth was then moistened with water, and a 30 to 40 per cent solution of sodium hydroxide heated to about 50°C was poured over it, allowed to stand for 1 to 2 min and then washed off It was neither necessary nor desirable to remove all the sodium hydroxide from the cloth, since its etching action aided in the removal of the flowed layer from the sample The cloth was then charged with a paste of the relevigated alumina in water Since this lap did not remove deep scratches, it was necessary previously to polish the specimen on some material such as the silk velvet The sodium hydroxide softens and partly gelatinizes the woolen lap covering, permitting a scratch-free polish, but its action continues, and the cloth deteriorates after about 24 hr This is not serious, because a new lap can be prepared in about 5 min, and only small pieces of cloth are used Etching with a strongly acid solution of ferric chloride was found satisfactory for removing the flowed layer For the final etching, the most satisfactory reagent was that of Taffs,7 the formula for which is FeC13 6H20, 2 grams, HC1, 5 c c , H2O, 30 c c , C2H5OH (95 per cent), 60 c c This etchant reveals differences in com-

Jan 1, 1941

By B. G. Reisdorf

This paper describes the microstructural changes that occur when quenched ultrahigh-strength steels containing OA pet C and various amounts of nickel, silicon, and cobalt are tempered. The changes that occur in hardness, yield strength, and martensite diffraction-peak widths when these steels are tempered are related to the precipitation of the carbide phases. An unea$ectedly high silicon content (about 30 pct) was found in the E -carbide phase in a steel containing only 1.5 pct Si. TEMPERED martensitic steels have such wide-spread utility that they have been the subject of numerous investigations, and a sizable amount of literature has developed on this subject.M This investigation, which is a part of a larger program to correlate microstructure with mechanical properties at a variety of strength levels, is limited to the microstructural changes that occur when a quenched 0.40 pct carbon steel (USS Airsteel X-200 steel) is tempered, and to the effects of the alloying elements—nickel, cobalt, and silicon—on these microstructures. Used in this investigation were electron microscopy, electron-diffraction identification of the carbide phases, electron-probe micro-analysis of the carbides, X-ray determinations of retained austenite, and measurements of martensite X-ray diffract ion-peak widths. MATERIALS AND METHODS The chemical analyses of the eight heats examined eats No. 30 through 37) are shown in Table L Heat No. 30 has the chemical com~osition of Airsteel X-200, and the remaining seven heats contain various amounts of nickel, chromium, cobalt, and silicon. The heats were air-melted in an induction furnace and cast into 8 by 8 in. ingots that were subsequently heated to 2300 and rolled to 1-in.-thick plate. Oversize 0.505-in.-diam tensile specimens were rough-machined from the plates and austenitized in air at 1700° F for half an hour and oil-quenched. The specimens were then tempered in air at temperatures of 400° to 1000 for tempering times of 1, 4, and 16 hr, and finish-machined to 0.505-in.-diam tensile specimens. Electron micrographs were prepared from Formvar replicas of the midthickness of tensile-specimen shanks that had been electrolytically polished and etched in nital. Electron-diffraction patterns were obtained from carbon-extraction replicas. The replicas were prepared by etching the sample surface in the same manner as for microscopy, evaporating carbon on the etched surface, and re-etching the sample to free the carbon film and the precipitate particles. Electron-probe microanalysis was performed on some of the extraction replicas. To obtain adequate fluorescent X-ray intensities, several thicknesses of replica were exposed to the electron beam so that the results represent an average composition of the extracted particles rather than an analysis of single precipitate particles. The retained austenite contents of the specimens were determined by an empirical X-ray diffraction

Jan 1, 1963

By J. E. Burke, C. W. Mason

In attempting to study precipitation from a tetragonal lattice, using solid solutione of bismuth in tin, it was found that although a Widmanstätten pattern is observed1,4 only a qualitative analysis of the orientation relationships is possible, because of the unusual structural changes that accompany the precipitation process. Microscopical Studies Alloys were made from Chempur tin (Standard samples 42b and 426, National Bureau of Standards), and bismuth (Kahl-baum C.P.) by melting weighed quantities together under palm oil, stirring well, and castilig in a heated graphite mold. The polishing and etching techniques employed largely govern the visibility of the structural changes. The preliminary surfacing operations were similar to those recommended by Villela and Bergekoff,5 through Behr-Manning 3/0 abrasive papers, lubricated by a solution of paraffin in kerosene. A rough metallographic polish was next given, using a thin cotton cloth charged with relevigated alumina (maximum particle size of about 4µ) and soap solution; repeated etching and polishing served to remove disturbed metal. For high-power examination better preparation was necessary. It was found that on such soft metals the threads of the fabric, rather than the abrasive, cause most of the scratching. Cotton outing flannel, which had been brushed so that the nap lay down, was fairly satisfactory, but a heavy grade of silk velvet (not the noncrushable kind) was found to be better, especially after some use. A better procedure was as follows: The metal lap was warmed slightly, and a 4-in. circle of woolen broadcloth was cemented to its center by a thin film of melted paraffin. The broadcloth was then moistened with water, and a 30 to 40 per cent solution of sodium hydroxide heated to about 50°C. was poured over it, allowed to stand for I to 2 min. and then washed off. It was neither necessary nor desirable to remove all the sodium hydroxide from the cloth, since its etching action aided in the removal of the flowed layer from the sample. The cloth was then charged with a paste of the relevigated alumina in water. Since this lap did not remove deep scratches, it was necessary previously to polish the specimen on some material such as the silk velvet. The sodium hydroxide softens and partly gelatinizes the woolen lap covering, permitting a scratch-free polish, but its action continues, and the cloth deterioratcs after about 24 hr. This is not serious, because a new lap can be prepared in about 5 min., and only small pieces of cloth are used. Etching with a strongly acid solution of ferric chloride was found satisfactory for removing the flowed layer. For the final etching, the most satisfactory reagent was that of Tafls,7 the formula for which is: FeC13.6H2O, 2 grams; HC1, 5 c.c.; H2O, 30 c.c.; C2H5OH (95 per cent), 60 C.C. This etchant reveals differences in com-

Jan 1, 1942

By N. A. Zeigler

GRaphitization phenomena occurring in solid cast iron have principally been studied from the angle of the reactions taking place during annealing of white castings in the manufacturing of malleable iron. The selected bibliography at the end of this paper presents the high spots of the published information in this field. Graph-itization of gray iron upon reheating has received much less attention, primarily because only on rare occasions is this material subjected to any kind of industrial heat-treating. Moreovcr, articles made from gray iron are seldom used commercially at temperatures when any graphitization can take place. When used in such conditions, it is assumed that the articles can be replaced at frequent intervals, which can be afforded because of the low cost of gray iron. However, there is at least one commercial process in which articles made from gray iron, during their manufacturing processing, are subjectcd to rather high temperatures; that is, manufacturing of cast-iron enamelware, which is glazed at about 1600° to 1700°F. (870' to 930°C.) From practical experience, it has been found that one of the convenient and economical compositions of gray iron suitable for enameling is, in round figures, as follows: Si, 2.50 per cent; Mn, 0.35; S, 0.07; P, 0.80; T.C., 3.35; C.C., 0.70. Since this iron usually is cast into thin-walled sections, the percentage of com- bined carbon in it is relatively high. Upon heating in the enameling furnaces, this combined carbon graphitizes, which causes permanent dimensional changes of the articles. Obviously, from practical considerations, it is desirable to maintain these dimensional changes as constant as possible. In the course of experimentation with this iron, two series of experimental heats were prepared in which the manganese to sulphur ratio of the standard cupola metal was offset by ladle additions of: (I) progressively larger amounts of sulphur, and (2) progressively larger amounts of manganese. Each one of these ladle charges was cast into experimental plates 8 by 4 in. and about 5/16 in. thick. All told, 13 ladle charges were thus treated. All of them are listed in Table I, together with their chemical analyses. It may be noted that the manganese to sulphur ratio in these samples ranges between 1.2 and 30.2. Every one of these compositions was subjected to thermal allalysis, using an automatic, self-recording differential dila-tometer. The specimens used in this instrument are 50 mm. long and 4 mm. in diameter. During the dilatometer cycle they are kept under a vacuum of about 3 microns. Each one of them was subjected to a thermal cycle by heating it to I830°F. (1000°C.) in 3 hr. and cooling to room temperaturc in 5 hr. Figs. I, 2 and 3 present three automatically recorded dilatometer curves for irons: Serial No. I (normal composition), Serial No. 6 (high sulphur), and Serial No. 13 (high manganese). All three of these figures are

Jan 1, 1945

By E. E. Schumacher

IN a laboratory devoted to the furtherance of the science of communication, the breadth and variety of the problems encountered are challenging to a metallurgist. In my own long association with the Bell Telephone Laboratories, our metallurgical group has dealt with a vast number of alloys, both ferrous and nonferrous, and with many materials in the border range of metallic properties., The objectives of our design engineers embrace every phase of telephony, and the properties they desire in metals are generally unusual, frequently unique, and often conflicting. Commercial alloys have not always been available with properties to meet a special requirement in the telephone plant, and many alloys have had, therefore, to be custom-made. Anyone who has had the opportunity to observe the results of tests of all types on numerous such alloys, both commercially and specially produced, or who has taken part in the development of an alloy of some necessary, but new or unusual combination of properties, could not fail to be impressed by the frequency with which a desired goal has been reached or adequately approached through the presence of decimal quantities of alloying elements. Nor could One fail to be struck by the occasions when, conversely, of a minute amount Of impurity element has rendered an alloy useful. It is no exaggeration to state that the content be- hind the decimal point often spells success or fail-ure, and the critical content is sometimes far to the right of the decimal point as I shall later illustrate. The great effects of small additions have long been recognized and have, in fact, been described by many investigators. The importance of the minute, however, cannot be overemphasized. Therefore, in this discussion, I propose to illustrate for you some of the startling instances, drawn primarily from our own experiences, wherein small, even vanishingly small, proportions of stranger elements in otherwise common aggregates have com-pletely changed the customary pattern of behavior. No one property has a monopoly as to being dis-proportionately affected by minor elements. Nearly all properties are affected, but there is time here to include only a selected few. I have chosen, there-fore, three of general interest: strength, magnetic, and electrical properties. I shall inquire into both the mechanisms and consequences of these disproportionate effects and try to share with you the fascination and challenge of this field. Strength Properties of Lead and Lead Alloys To illustrate the effect of the minute on strength properties I have selected lead and its alloys, with which we have worked extensively for many years. Lead has the advantages of being available in quantity in a state of high purity and of being fairly easy to melt and fabricate without contamination to any extent detectable by the spectrograph. It has the interesting disadvantages of recovery and recrystallization at room temperature. Whether I

Jan 1, 1951

By D. F. Gibbons

THIS investigation was undertaken in order to gain further information on the mechanism of plastic deformation of iron at temperatures between room temperature and 77.2°K, and also to contribute to our understanding of the low temperature brittleness phenomenon that occurs in both the tensile and impact tests. It was decided to study as pure an iron as possible and to use the tensile test in order to simplify the problem as much as possible. Two series of iron were used throughout the investigation: iron A, obtained from the National Research Corp. and supplied as gas-free, high purity iron; and iron B, obtained from Fast' and produced by melting iron under purified hydrogen. Typical analyses of samples of both irons, after fabrication, are given in Table I. The main difference in composition of these irons is in their nickel and oxygen contents. Nickel has a very large solid solubility in iron. However, oxygen has an extremely small solid solubility. An attempt was made to reduce the oxygen content still further by remelting under purified hydrogen. This was successful in reducing the oxygen content to -0.0006 pct. However, no results on tests of this iron are included, since difficulty was encountered in fabricating the ingot. Wire specimens 1 mm in diameter were used for the investigation. The wires were produced from the ingots, as supplied, by cold rolling and swaging, with intermediate vacuum anneals at 700°C. Care was taken to reduce preferred orientation in the wires to a minimum by keeping the percentage of reduction in area between anneals of 30 to 40 pct. X-ray transmission photographs showed no indication of preferred orientation. The final grain size of iron A was 20 to 24 grains per linear mm and of iron B, 16 to 18 grains per linear mm. All specimens were tested in the decarburized and denitrided condition unless otherwise stated. The procedure was to pass hydrogen, saturated with water vapor at 26oC, over the specimens at 730°C for 2 hr. The specimens were quenched in iced water and then annealed in a vacuum of - 5x10-6 mm Hg for one day at 560°C to remove hydrogen. Higher temperatures were used for the vacuum anneal but this temperature was found to be quite satisfactory in removing hydrogen. The specimens were slow-cooled after the vacuum anneal. Where it is stated that the specimens were carburized, the specimens were given an identical decarburizing treatment and then carburized by passing hydrogen, saturated with pure n-heptane vapor at 0°C, over the specimens at 730°C. The specimens were then homogenized at 730°C for 2 hr in dry hydrogen. After the carburizing treatment the specimens were given the same vacuum anneal as for the decarburized specimens. The carbon content was determined from the maximum value of the internal friction carbon peak.2 Apparatus Fig. 1 shows a diagram of the tensile apparatus, with half the cooling coil removed. The cooling coil enabled temperatures from 200" to 77.2oK to be obtained. The apparatus was designed to fit a standard Tinius Olsen Universal tensile machine. The apparatus consisted of the rigid plate A which carried two carefully machined hooks H. These hooks attached the plate firmly to the moving crosshead of the tensile machine. The lower grip B was rigidly suspended from the plate A by three stainless steel rods. The upper grip C was joined to the upper grip of the tensile machine by the stainless steel rod E. The lower part of the apparatus was surrounded by a Dewar vessel, which was made a sliding fit inside the brass collar D. The specimen was held in a clamp which fitted into the grip, forming a ball and socket joint (see inset a). This was to attain as nearly pure

Jan 1, 1954

By Bernard S. Borie

THE U-A1 binary system has been studied by Kaufmann and Gordon.' They have shown that three intermetallic compounds occur in the system: UAl², UAl², and a third compound tentatively identified as UA15. UA1³ is simple cubic, a, = 4.26A. Its unit cell contains one formula weight, and it is iso-morphous with AuCu³. UA1² is face-centered cubic, a, = 7.72A, with eight formula weights per unit cell. Rundle and Wilson have shown that it is iso-morphous with Cu²Mg.² A Debye-Scherrer pattern of the Al-rich compound indicated a more complex structure than either UA1² or UA1³. The following is a report of an investigation of the crystal structure of this compound and a determination of its stoi-chiometric formula. A melt of uranium (99.9 pct pure) and aluminum (99.9 pct pure) was prepared which contained about 25 pct U by weight. It was cooled from 950" to 650°C at a rate of 500" per hr and then taken from the furnace and air cooled. An X-ray diffraction pattern of the ingot showed only lines of aluminum and the Al-rich compound. Filings from the ingot were reacted with a solution of sodium hydroxide, producing a fine black powder, the diffraction pattern of which showed no traces of aluminum. A comparison of the Debye-Scherrer pattern of our sample with the data published by Kaufmann and Gordon1 showed that it is identical with the Al-rich phase which they reported. Single crystals were obtained by cooling the melt more slowly (about 50°C per hr). After reaction with sodium hydroxide, the crystals appeared as small black needles attached to the ingot surface. Cell Size, Space Group, and Uranium Positions A series of Weissenberg photographs for rotation about two of the crystallographic axes, taken with copper radiation filtered through nickel foil, revealed an orthorhombic cell of dimensions: a = 4.41 ± 0.02A b = 6.27 ± 0.02A c = 13.71 ± 0.03A Reflections of the type hkl were observed only if: h + k + I = 2n, of the type hkO only if: h = 2n and k = 2n, of the type h01 only if: h + 1 = 2n, and of the type Okl only if: k + 1=2n. Hence, the cell is body-centered with an 001 glide plane. The evidence for the existence of the glide plane is the observed extinction of 23 possible re- flections of the type hkO with at least one index odd. There are only two space groups consistent with these data: C"" — I2ma and D28 2h — Imma.³ he possible sets of atomic positions for these space groups are: 12ma: (0 0 0; ½ ½ ½) + 4: (a) x 0 %; x % % (b) x ¼ z; x ¾ Z 8: (c) x y z; x y z; x, ½ + y, Z x, M - y, z Imma: (0 0 0; ½ ½ ½) + 4: (a) 0 0 0; 0 ½ 0 (b) 0 0 ½; 0 ½ ½ (c) ¼ ¼ ¼; ¾ ¼ ¼ (d) ¼ ¾ ¾ ; ¾ ¾ % (e) 0 ¾ Z; 0 ¾ z 8: (f) x 0 0; x 0 0; x 1/2 0; x ½ 0 (g) ¼ Y ¼; ¾ Y ¾; ¾ y ¼; 1 y ¼ (h) 0 y z; 0; ;; 0, ½ + y, z; 0, l/2 - Y, Z (i) x 1/4 z; x ¾ z; ¼ z; x ¾ z 16: (j) xy z; x y z; x y z; x y z; x, ½ + y, Z; x,½ - y, z; x, ½ - y, z; 11 1, + y,Z Though density measurements on different samples were found to vary somewhat, they were all within the range 5.7 * 0.3 g per cu cm. If it is assumed that the unit cell contains four formula weights of UAl,, it is 6.5 g per cu cm. If there were as many as eight uranium atoms per unit cell, the

Jan 1, 1952

By C. Kremer Bain

DURING the past several years of diamond drilling in Washington County, Mo., the St. Joseph Lead Co. has discovered a concentration of commercial lead-zinc ore at four different points within an area of 36 square miles. The largest and to date the most promising group of these orebodies is located in the Indian Creek area. It was considered to be of sufficient value to warrant development. The Indian Creek area is in the center of the northern half of Washington County, 11 miles northwest of Potosi, Mo., the county seat. The location is readily accessible from Potosi by car or truck over the all-weather Missouri State Highway No. 114. The topography is one of rolling relief, varying from an elevation of 700 ft above sea level on Mineral Fork and Indian Creek to a maximum of 1176 ft at High Point Tower. It is divided in equal halves between the drainage to Mineral Fork and to Indian Creek. The shaft site at 1060 elevation is on the divide between the two drainage areas. The Indian Creek side is rough and heavily wooded, with only a few cultivated clearings. The slopes to Mineral Fork are more gentle and rounded, with much of the area cleared for farm land. Most of the surface is covered with Potosi and Eminence formations, which show little evidence of any structure. Ore structure was worked out by extensive diamond core drilling, with holes varying in depth from about 700 to 1300 ft. As of Oct. 1, 1950, 218 prospect holes had been drilled within the 36-square mile area. The ore is disseminated galena with considerable accompanying sphalerite in the Bonne Terre forma-tion in the shape of irregular blanket-type deposits. The main controlling structural feature of the outlined mineral zone is a buried pre-Cambrian rhy-olite-porphyry ridge extending partly through the Bonne Terre formation, which laps against the por phyry and also covers it. The mineralized zone parallels and forms an irregular halo around the porphyry ridge and is concentrated in the Bonne Terre formation where the La Motte sandstone is cut out by the porphyry ridge. This is a very common mineral occurrence in the southeastern Missouri lead belt district. The La Motte sandstone, which normally underlies the Bonne Terre formation, is thus cut out entirely. In this area the Bonne Terre is usually about 275 to 320 ft thick, the La Motte varying in thickness from zero up to 400 ft. Commercial concentrations of ore are indicated at several places, the most notable being at the shaft site where an orebody at least 4000 ft long with widths of 500 to 600 ft has been outlined. The total thickness of mineralized rock reaches 150 ft in some holes, although total ore thickness runs from 8 ft to about 60 ft, often in more than one layer. Preliminary Planning Ore reserves as outlined lend themselves to open-stope mining with trackless haulage and mobile loading machines and drilling equipment. This type of equipment has proved to be very efficient during recent years in the company's lead belt operations. After a study of bids for shaft sinking and an estimation of comparative costs, it was decided that the shaft would be sunk by St. Joseph Lead Co. personnel using company equipment. Since the plant site is about 26 miles from the company's nearest lead belt operations, it was necessary to plan a complete surface plant, including mill, shops, office, change room, and warehousing facilities. Immediately following the filing of an application for a certificate of necessity, a headframe was selected for which detailed drawings were already available. The order was placed for fabrication so that it could be delivered and erected in time to serve for sinking the shaft. This eliminated the expense of a temporary headframe. Drilling was started on two churn drill holes near shaft location, and two 1000-gpm deep well pumps

Jan 1, 1954

By H. M. Otte, A. G. Crocker

SLIP, twinning, stacking faults, and precipitates on well-defined planes in a crystal produce traces that are visible on either a polished or an etched surface. The purpose of this note is to establish the usefulness and limitations of the information obtained from such traces when determining the orientation of single crystals or grains in a polycrystal. Attention will be confined specifically to traces produced by octahedral planes in cubic crystals, though most of the remarks can be taken as more generally valid. The problem of determining the crystal orientation is completely solved in principle' and in particular for the special case under consideration.1'2 Tables are available3 in which the orientations can simply be looked up when given the two or three angles between the traces. Thus a quick and simple method is available for obtaining the orientation of a crystal from surface traces. In this note two examples will be given from recently published papers and will show the use of the method with the aid of the Tables, as well as some of the precautions that should be taken in the procedure. As part of an analysis of X-ray Kossel lines, Peters and Ogilvie 4 determined from them the crystallographic orientation of the specimen. They chose a Cu-5.10 wt pct Si alloy that had been partly transformed from the a (fee) phase to the k (hcp) phase. The latter formed as very straight platelets along the octahedral planes of the a phase, and a photograph (Fig. 7 of Ref. 4) was reproduced in the paper4 of the region for which the orientation had been determined from the Kossel lines. Apart from a very small area (about 0.15 mm diam) near the top center of the photograph, the region shown was clearly all of one orientation. Traces in four different directions were readily identified. Starting with the smallest angle and proceeding counterclockwise, the angles between the traces were measured to be 27° 43', 55° 16', 64 3 43 1, and32"26'. These add up to 1802 08 1, indicating a cumulative error of 8'. The correct values should, of course, be taken from the original glass plates, or at least from prints on distortion-free paper, so the precision of the quoted values is actually greater than their accuracy. The solutions can be looked up in the Tables3 in four ways, depending on how the angles are paired, tion for the minutes of arc is required and the solution obtained will be identical for all the four pairs if the values of the angles are not in error. In a practical situation, such as this one, there are several sources of error, so that the four solutions obtained will all be slightly different. An arithmetic average of the four solutions is mathematically incorrect, but may, in special cases, give an answer close to the correct one. A rigorous procedure for refining the orientation has been described by Mackenzie;5 he gives a least-squares method that can be applied, if necessary, to this type of problem. The orientation thus determined can be compared with the one from the Kosel lines and discrepancies larger than the experimental error assigned to nonor thogonality of the X-ray or electron beam to the specimen. Here the example will only be used to illustrate the general procedure for making a very rapid rough check. From measurements on the stereographic projection, Fig. 9 of the paper,4 we can determine that the surface normal is approximately (0.434, 0.704, 0.562). From the Tables3 we find, using 28°, 55" as a good approximation to the first pair (27°43', 55°16'), that the surface normal is (0.453, 0.678, 0.579).* These two values are within 2 deg of each

Jan 1, 1967

By M. J. Pool, P. J. Spencer, R. V. Miner

The partial molar heat of solution of rhodiunz in liquid lin and Rh-Sn alloys has been measured as a function of rhodium concentration at 700" , 725" , 750" , and 775°K. The values at infinite dilution are very exo thermic, ranging from -29,950 to -28,260 cal per g-atom Rh at 700" and 775"K, respectively. At the solubility limit the heat of solution becomes sharply nzore exothermic and has permitted the liquidus boundary to be accurately established at each temperature. From the measurements in the two-phase region of liquid Plus RhSn, the heat of formation of RhSn,has been determined. A large increase in the heat of formation between 725" and 750°K suggests the possibility of a phase transformation in this compound. V ERY few measurements have been made of the heats of solution of transition metals in liquid tin; yet those values that are available are of great interest because of their very large exothermic nature. For example, the heat of solution at infinite dilution of palladium in tin has been measured as about -26,000 cal per g-atom (625" to 800°~),' while the heat of solution at infinite dilution of platinum is even more exothermic at -28,591 cal per g-atom (914°K).' These values are of the same order of magnitude as the heat of formation of many intermetallic compounds and as such clearly indicate that very strong bonding must exist between the solute and tin atoms in the liquid solutions. Rhodium might be expected to display similar solution characteristics in tin in view of its close electronic resemblance to palladium and platinum. Since no thermodynamic data are available for Rh-Sn alloys, rhodium was chosen as an appropriate solute for further investigation of transition-metal systems with highly exothermic heats of solution at infinite dilution. EXPERIMENTAL The heat of solution of rhodium in dilute Rh-Sn liquid solutions was measured as a functlon of rhodium concentration at 700°, 725", 750°, and 775°K. The liquid-metal solution calorimeter used in this work has been fully described elsewhere. At the start of each series of measurements, the solvent bath consisted of about 0.5 g-atoms of 99.9+ pct pure tin. To this was made a number of small rhodium additions, about 0.0005 g-atoms each, and the heat of solution was measured for each. Rhodium of 99.9+ pct purity in powder form was used in order to promote rapid dissolution in the liquid tin. The powder specimens were contained in tin foil stated to be purified (lead-free). This foil was found to have no measurable heat of solution in pure tin so the effect of any impurities could be neglected. The energy equivalent of the calorimeter was experi- mentally determined by dropping tungsten and/or tin specimens at intervals during each series of rhodium drops. The tungsten and tin used were 99.95 and 99.999+ pct pure, respectively. The only heat effect due to a tungsten drop, or a tin drop at low rhodium concentrations in the bath, is the sensible heat of the specimen. The heat content of these materials is well-established and is presented in the compilation of Hultgren et al. 4 As the rhodium concentration in the tin bath increases a small heat effect arises from the reaction: Sn (liquid, T) — & (soln, T) where T is the temperature of the tin bath. Where necessary, this heat of solution of tin was determined by Gibbs-Duhem integration, and corrections were made to the heat effect of the tin calibration specimens and the tin foil containing the rhodium specimens. RESULTS AND DISCUSSION The calculated values of the heat of solution of rhodium in dilute Rh-Sn alloys as a function of composition are shown graphically in Fig. 1. The values have been corrected for the sensible heat of the specimens, initially at 273"K, and apply to the reaction:

Jan 1, 1969

By R. J. Lloyd

INTRODUCTION The Mount Isa Mine is a large modern underground mine located in North-Western Queensland, Australia. Two ore types are mined and treated separately. Currently silver-lead-zinc ore is mined at the rate of 2.6 million tonnes per annum and copper ore at the rate of 4.6 million tonnes per annum. The silver-lead-zinc orebodies are mined by sub level open stoping and cut and fill methods whilst all copper ore is extracted by various forms of sub level open stoping. The mining operations are highly mechanised and utilise diesel powered load-haul-dump units of various sizes, two and three boom face drilling jumbos, electric-hydraulic rotary-percussive ring drills, in-the-hole hammer drills, rotary blasthole drills, raiseborers, battery/trolley locomotives, a large fleet of rubber tyred service and supply vehicles plus light rockdrills mounted on airlegs, rail mounted overshot shovels and battery and diesel powered locomotives. All stoping production ore is extracted with diesel powered load-haul-dump units. The ore is tipped into orepasses which connect to the main rail haulage levels. On the haulage levels electric battery/trolley locomotives are used to pull rakes of bottom dump or side dump trucks which feed the ore into primary crushers. Following two stage crushing the ore is conveyed to the shaft and hoistod to surface in bottom dump skips. Each ore stream has its own rail transport system, crushing stations and hoisting shaft feeding separate concentrators. This paper will consider some aspects of the role of equipment and machinery in the growth of the mine, will discuss in some detail the machinery and equipment in use today and will conclude with a look at some possible developments in mining equipment for the future, with particular reference to the Mount Isa Mine. A summary of mining equipment in use at Mount Isa is given in the Appendix. THE PAST Silver-lead-zinc ore was discovered at Mount Isa in 1923 and within a very short time many small mines were being developed. However the rich surface ore traces did not continue and by 1928 Mount Isa Mines Limited had acquired sufficient leases to plan for a large scale mine to exploit the low grade orebodies. At this early stage it was recognised that the mine would need to adopt the most mechanised mining techniques then available in order to overcome its twin disadvantages of low graaes and extreme remoteness. The Company introduced bar mounted drifters and overshot shovels to replace hammer and tap and hand shovelling in development work and by 1930 headings were advancing at the rate of 30 metres per week. In keeping with the concept of mechanisation the early engineers designed the Man and Supply shaft with a very large, for those days, cage compartment measuring 3.8 m x 3.4 m. This shaft was the main means of access into the mine for 36 years until the K57 shaft (now R62 shaft) was commissioned in 1966. Man and Supply is still in regular use. Production commenced in 1931 at an annual rate of approximately 660 000 tonnes of silver-lead-zinc ore. The mine was mechanised to an extent which was previously unknown in Australia; whilst the concentrator, smelter and power house utilised the most modern and efficient equipment available. Even so, the mine was very near to closure on several occasions and did not return a dividend to its shareholders for many years. Production levels remained at or slightly below 660 000 tonnes until a separate copper ore streani and mill was commissioned in 1953, doubling the existing production levels. The first underground crushers were installed at this time. Production rates expanded in the years between 1953 and 1973. By 1960 production reached 2740 000 tonnes of ore. In 1965-66 total production was 3650 000 tonnes and in 1973 the production rate plateaued at the current level.

Jan 1, 1981

By E. A. Gulbransen, K. F. Andrew

Thermodynamic information on the solubility of hydrogen in exothermic metals is limited. Thus, the overall solubility decreased as the temperature rose, which suggests the heat of solution of hydrogen in the metal is negative; yet the terminal solubility in the metal phase increased, which suggests an endothermic reaction. A thermodynamic analysis, therefore, was made of the several equilibria involved when hydrogen dissolved in the metal. Equations were derived expressing the solubility, terminal solubility, and decomposition pressures of hydrogen in terms of the heat, entropy, and free energy of solution of hydrogen in the given phase. The relations between the thermodynamic functions for the a-zirconium and 8-hydride phase were developed. The thermodynamic quantities were determined experimentally by the measurement of the decomposition pressures over a broad composition and temperature range. Two new methods of analyzing the experimental data were developed for determination of the terminal solubility. STUDIES', ' of the impact strength of zirconium at room temperature indicated that small quantities of hydrogen, of the order of 10 parts per million, embrittles the metal. Micrographic' and X-ray diffraction' studies showed this embrittlement to result from the precipitation of a second phase upon slow cooling. These studies suggested that the terminal solubility of hydrogen in the metal phase increased with increase of temperature. This behavior appeared to contradict the effect of temperature on exothermic hydrogen occluders such as zirconium. For these metals, the solubility of hydrogen should decrease with increase of temperature. Before these facts could be understood, a thorough analysis of the several equilibria was essential. It was the purpose of this paper to consider the several equilibria involved when hydrogen was reacted with zirconium from both the theoretical and experimental points of view. Since the overall solubility of hydrogen in the metal has been considered by a number of workers, it was proposed to study the composition range 0 to 6 atomic pct H in detail. Literature Schwartz and Mallett' determined the terminal solubilities of hydrogen in the metallic phase from diffusion studies. They extrapolated concentration-penetration curves to the boundary between the solid solution phase and the hydride phase at the surface. Their results showed values of 2.6 atomic pct at 400°C and 5.2 atomic pct at 500°C. Extrapolations of the data to room temperature suggested very low values for the terminal solubilities. This study confirmed the hydrogen embrittlement results and indicated that the terminal solubilities increased as the temperature was raised. The solution of hydrogen in zirconium over the complete concentration range was studied by Hall, Martin, and Rees3 and by others. The results showed that hydrogen was absorbed up to a maximum composition of 66 atomic pct or ZrH This composition represented the t-hydride phase. The maximum amount of hydrogen absorbed increased with pressure and decreased with temperature. Due to this temperature behavior, zirconium was classed as an exothermic occluder." In 1930 Hägg studied the crystal structures of the Zr-H alloys over a broad composition range. Four hydride phases were found. However, the range of homogeneity of the several phases was not studied. Gulbransen and Andrew" recently studied the phase diagram of this system by X-ray diffraction methods and by a thermodynamic method based on decomposition pressure measurements. The results showed that only two hydride phases existed for low temperatures, the 6 and the .-phases of Hagg.' Both phases had broad regions of homogeneity. The lower limit of the two-phase region of a and d-phases suggested a terminal solubility of 4 atomic pct at 500°C. This value was in agreement with the results of Schwartz and Mallett.' To avoid hydrogen embrittlement at low temperatures, it was necessary to heat the metal in high vacuum at elevated temperatures. To choose the conditions of temperature and high vacuum, it was

Jan 1, 1956