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By Paul D. Merica, R. G. Waltenberg

Although nickel was discovered and isolated as early as 1750 and its valuable properties recognized, many years passed before it was used commercially for wire, sheet, rods, etc., in the pure form. This was due partly to its high cost at that time and partly to the fact that it was not possible to refine and cast nickel into ingots sufficiently malleable to be amenable to the usual forging, rolling, or drawing processes. So remarkable was this fact, and so different from the experience at that time with metals such as copper and iron, that it has left its impress on the nomenclature within the nickel industry. To this day, furnace-cast nickel produced in such a manner as to be suitable for rolling and forging is called malleable nickel to distinguish it from the ordinary pig and shot nickel of commerce. In 1878, the firm of Jos. Wharton, of Philadelphia (which later became The American Nickel Works, a constituent of The International Nickel Co.) exhibited at the Paris Exhibition specimens of rolled pure nickel strip and of drawn nickel wire. About this time, there was considerable activity in the study of the refining of nickel and several methods were described, some of which were patented, for the production of furnace-cast malleable nickel including the use of manganese (Boed-dicker,1 Selve and Lotter2), the use of potassium permanganate (Berns-dorfer Metallwarenfabrik3) and the use of phosphorus (Garnier4). By far the most efficient method was discovered by Th. Fleitmann in 1879;5 it consisted in adding to the molten nickel, just before pouring the castings, from 0.05 to 0.125 per cent. of metallic magnesium. This soon became the recognized final malleableizing treatment for furnace-cast nickel.

Jan 1, 1925

By Robert Mehl

A STUDY of the structures arising from the decomposition of the a solid solutions in the Cu-Zn and the Cu-Al systems is of peculiar interest in the study of the mechanism of precipitation from solid solutions. It is possible in these alloys, by varying the composition within the ß field, to precipitate from the same basic lattice phases having different lattice structures. It has been rather generally assumed heretofore that the type of structure originating from the decomposition of a solid solution-the Widmanstätten structure-is determined by the lattice structure of the parent solid solution alone. In the first paper of this series1 evidence was advanced which threw doubt upon this hypothesis; but definite proof of the correctness or incorrectness of the hypothesis should be forthcoming from a study of these alloys, for if the structures originating, for example, from the precipitation of the a phase from ß and of the -y phase from the ß in the Cu-Zn system should be shown to be crystallographically different, the hypothesis would necessarily be held as definitely disproved. Furthermore, the newer proposal enunciated in the first paper of this series-that the origin of the Widmanstätten structure lies in a cooperation between the lattice of the parent solid solution and that of the precipitate-which at present seems the only alternative hypothesis, would in such an event be given added weight. The work here reported shows that the Widmanstätten structures originating in the precipitation of the a phase from the a and in the precipitation of the -y phase from the ß in the Cu-Zn system are indeed crystallographically different; and incidentally presents some new descriptive information on the Widmanstätten structure from a more general point of view.

Jan 1, 1931

By Alfred Weiss

Daniel C. Jackling's innovative concept for handling low grade ores ushered in a new philosophy of open pit mining. As one of the greatest minemakers of all times he revolutionized major segments of the industry and helped strengthen US defense efforts during World Wars I and II by making possible the tremendous copper supplies from US mines. Many great mining men have since followed in his footsteps with their discoveries of new orebodies or development of new mines. Their brilliance in leadership can also be traced to the coupling of a new idea to the physical nature of the materials in the earth's crust or to the extractive stages of minerals recovery. The minerals industry is now in another era of change and must again devise techniques to meet the challenge. The task is not only to create new exploration techniques and develop new mining methods, but, I believe, to optimally apply new concepts and tools in daily decision-making.

Jan 11, 1978

By Alfred W. Gauger, George A. Burrell

The senior author of this paper, while in Colorado on other official business, made a trip to the Cripple Creek gold-mining district to get more data than are at present available regarding the composition of the gas that issues from the rock into the mines of the district. This was done at the suggestion of George S. Rice, Chief Mining Engineer of the Bureau of Mines. There are -many questions of interest and importance in connection with the ventilation of the mines in the Cripple Creek district, such as the menace to life and mining of a suffocating gas entering the mines from the rock, the danger due to powder smoke (from blasting operations), and danger of continued inhalation of rock dust by the miners. This report confines itself to the first problem, the gas from the rock, and principally to one phase of this question, the composition of the gas and its effects on men and lights. A more thorough study of this and other ventilation problems is planned. That the rock gas is a real menace is shown by the fact that miners (variously estimated from 25 to 50 by different persons interviewed) have been killed by it in the 25 years that mining has been vigorously carried on at Cripple Creek. Many men have had narrow escapes from death, some of them having been incapacitated for days. In addition, much loss of time results because at certain periods of the year or on certain days it is impossible to enter some workings. At a few mines, fans force air into the workings, thus supplementing the natural ventilation and much improving conditions, but the improvement is not entirely adequate at all times. Origin of the Gas Lindgren and Ransome1 think that the gas found in the rocks of the Cripple Creek mining district represents the last exhalations of the ex-

Jan 1, 1917

By B. M. Blake, R. S. Reppert, A. F. Keiser, E. J. Trinkle

The southern West Virginia coalfield was formed in a rapidly subsiding depositional basin associated with deep-seated growth faults. Subsidence began to the southeast during deposition of the Pocahontas Formation, and then shifted to the northwest during deposition of the New River, Kanawha, and Allegheny Formations. Rocks of all the coal-bearing formations grade into massive sandstones to the northwest. For the No. 3 Pocahontas, Sewell, Campbells Creek, and No. 5 Block coals discussed in this study, the overall sulfur and ash values of each coal seam increase gradually toward the northwest. The thickness of each coal tends to increase toward the southeast. These trends are partly a reflection of the differential subsidence of the coal basin along with varying degrees of peat accumulation and degradation. The northwest side of the coal swamps underwent relatively less subsidence and, thus, more degradation due to increased aerial exposure, with a resulting increase in the sulfur and ash values of the coals, and a decrease in the thickness. The open sea existed to the west of the coal swamps, and this marine environment also contributed to the higher sulfur values to the northwest. Coals of the Pottsville Group in the southern West Virginia coalfield generally have sulfur values between 0.6-1.0% with some as high as 2-3% on the northwest edge of the coal basin.

Jan 1, 1983

By Charles A. Ashburner

The manufacturing and domestic consumers of anthracite are beginning to realize the fact more fully, that the coal purchased for any one year does not seem to burn so freely, does not fire with so little trouble, and does not last so long as that purchased during other years, or vice versa. Where coals of different sizes, or from different districts, are offered to the trade by the same or competing salesmen, the question suggests itself, which shall we buy ? Among housekeepers, who are the most numerous class of consumers, though on the smallest scale, distinction is seldom recognized among these anthracites. By other consumers the coals are grouped into those which, when burned, will produce either a white or a red ash, special qualities being arbitrarily attached to each. Others, again, know only of three varieties : (1) Those from the WYoming and LacKawanna fields, or the coals shipped from the northernmost basins over the railroads running through northeastern Pennsylvania direct to New York—notably, the Delaware. Lackawanna and Western, Delaware and Hudson, and Erie railways; (2) those shipped by the Lehigh Valley Railroad and the Lehigh and Susqaehanna division of the Philadelphia and Reading Railroad down the Lehigh Valley ; and (3) those shipped over the main line of the Philadelphia and Reading Railroad down the Schuylkill Valley. In special localities, where a favorite coal is largely used, the consumer will speak of one class, composed of his favorite coal, which possibly comes from two or three collieries, with a total aggregate annual production of less than a million tons; and of a second class, composed of the coals from all the other collieries in the anthracite

Jan 1, 1886

By Henry J. Miller, Marcella Linderman

During some experiments made by Henry J. Miller, partly in Germany and partly in the United States, in which it was found necessary to melt metals in quantities up to 60 kg. in a vacuum or under low pressures of hydrogen, molybdenum was tried as the resistor in the electric melting furnaces. Molybdenum ribbons 16 by 0.55 mm. and 18 by 0.45 mm. were used as resistors. The furnaces were of the type shown in Fig. 1. About the heating tube, Y, are wound parallel resistors of molybdenum ribbon from the water-cooled electrodes, El, Ez. The whole is within a copper container having outlets for the removal or introduction of gases and a window, W, for observation, the space about the heating tube and electrodes being filled with insulating material. The life of the molybdenum used as the resistor was found to depend very much on the manner of using it, its failure being due in some cases to thinning by evaporation or chemical reaction and in others to hardening, which prevented it from following the expansions and shrinking of the heating tubing without cracking. As such failures are often rather expensive in commercial work, it was thought worth while to determine the causes. The factors influencing the behavior of molybdenum resistors used in this manner may be briefly stated as follows:

By Henry G. Granger

A residence of 14 Sears in the Republic of Colombia, spent . in almost continuous traveling and prospecting-trips, has given me an intimate knowledge of the resources of that wonderful country. The man who best knows Colombia is unquestionably General Rafael Reyes, President of the Republic for the past three years, and with seven years more to serve in his present term. Such is the strength of his personality and the wisdom of his policies that his term of office will no doubt endure as long as he is milling to serve. The vastly improved economic situation and the brilliant outlook for Colombia are so directly due to the influence of President Reyes that a few lines concerning him will not be amiss, if they serve towards a better understanding of his personality. Born of a distinguished ancestry in the mountain~ of Boyaca, he is now 57 years old, just the age of his friend Porfirio Diaz when he began the work which has placed Mexico in the rank of great modern nations. It was Reyes who came to Washington to protest against the action of the government of the United States of America in

Jan 1, 1909

By Cyril Stanley Smith

Somewhat over ten years ago the author described studies1'2 on the constitution of the copper-silicon system. The copper-rich portion of this diagram is shown in Fig. 1. The experimental points freely dotted about the diagram seemed to justify an otherwise unconvincing diagram and for several years the curious reverse bend in the alpha-phase boundary was accepted as substantially correct, even by later investigators3 of the system who introduced changes in the high-silicon phases. The binary diagram has been used as a base for several ternary systems5-9 without any suggested changes. Voce10 suspected the existence of another phase from his study of the cast alloys in the copper-manganese-silicon system, but evidently hesitated to extrapolate this to the binary diagram, particularly in view of the too ingenious explanation that was advanced1' to account for the pools of constituent clearly visible in castings; namely, that they were secondary alpha of twinned orientation deposited from beta. Von Schwarz,12 in 1932, called attention to the fact that this micro-constituent in copper-silicon alloy castings was anisotropic under polarized light and asserted that a new phase, not cubic, should be placed in the diagram .adjacent to alpha. Sautner,l3 on the basis of investigations with the polarizing microscope and with X-rays, introduced this phase into the diagram at about 6 per cent Si. The relevant part of his diagram is shown in Fig. 2. Sautner called the new phase beta, renaming the old beta phase zeta. To avoid confusion, in redrawing Fig. 2 the phases have been renamed in accordance with the terminology adopted in the present paper, in which the new phase is called kappa and the other phases retain the designation given them by Arrhenius and Westgren.4 The thermodynamic impossibility of Sautner's diagram and the paucity of experimental data left the exact location of the new phase field most uncertain, although his work proved beyond doubt that an additional noncubic phase exists. Because of the industrial importance

Jan 1, 1940

By Cyril Stanley Smith

Somewhat over ten years ago the author described studies1'2 on the constitution of the copper-silicon system. The copper-rich portion of this diagram is shown in Fig. 1. The experimental points freely dotted about the diagram seemed to justify an otherwise unconvincing diagram and for several years the curious reverse bend in the alpha-phase boundary was accepted as substantially correct, even by later investigators3 of the system who introduced changes in the high-silicon phases. The binary diagram has been used as a base for several ternary systems5-9 without any suggested changes. Voce10 suspected the existence of another phase from his study of the cast alloys in the copper-manganese-silicon system, but evidently hesitated to extrapolate this to the binary diagram, particularly in view of the too ingenious explanation that was advanced1' to account for the pools of constituent clearly visible in castings; namely, that they were secondary alpha of twinned orientation deposited from beta. Von Schwarz,12 in 1932, called attention to the fact that this micro-constituent in copper-silicon alloy castings was anisotropic under polarized light and asserted that a new phase, not cubic, should be placed in the diagram .adjacent to alpha. Sautner,l3 on the basis of investigations with the polarizing microscope and with X-rays, introduced this phase into the diagram at about 6 per cent Si. The relevant part of his diagram is shown in Fig. 2. Sautner called the new phase beta, renaming the old beta phase zeta. To avoid confusion, in redrawing Fig. 2 the phases have been renamed in accordance with the terminology adopted in the present paper, in which the new phase is called kappa and the other phases retain the designation given them by Arrhenius and Westgren.4 The thermodynamic impossibility of Sautner's diagram and the paucity of experimental data left the exact location of the new phase field most uncertain, although his work proved beyond doubt that an additional noncubic phase exists. Because of the industrial importance

Jan 1, 1940

By John G. H. Crump, E. W. Owen, Peter P. Gregory

.Although oil Production in West Texas in 1939 reached the highest figure for any year since the inauguration of proration, drilling activity continued in the decline that had commerlced the previous year. Production totaled 79,469,341s bbl. of oil during 1939 as compared with 71,257,541s bbl. in 1938 and 75,743,000 in 1937. The number of wells completed in 1939 was 1850, compared with 2045 in 1938 and 2806 ill 1937. Several factors combined to cause the decrease in drilling activity, principally the contiriued increase in the length of time required to obtain a return of invcstment and the scarcity of important new discoveries during the past two years. Of the 1850 completions 1638 resulted in oil wells, 4 were gas wells, 168 were dry holes and 40 were abandoned locations; 1990 new locations were made during the year. The ratio of dry holes to producing wells completed was one dry hole to each 9.75 oil wells, compared with one dry hole to each 7.48 oil wells completed during 1938. This large decrease in dry holes was due to a marked decline in the number of wildcat wells drilled, there having been only 120 wildcat completions during 1939. In addition to the lessened exploration work, the deeline' in activity was largely accounted for by the slowing up of operations in the older pools of Ector, Howard and Winkler Counties. Ector County, which had led West Tcxas in 1938 with 622 new oil wells, furnished only 485 producers in 1939, but was still the leader for the West Texas district. The largest gain in activity was in Yoakum County, whew 350 oil wells were completed in the Denver-Wasson field against 152 during 1938. Most of the older oil fields have been almost completely drilled up, only a few new producers still being completed from time to time in

Jan 1, 1940

By E. W. Owen, John G. H. Crump, Peter P. Gregory

.Although oil Production in West Texas in 1939 reached the highest figure for any year since the inauguration of proration, drilling activity continued in the decline that had commerlced the previous year. Production totaled 79,469,341s bbl. of oil during 1939 as compared with 71,257,541s bbl. in 1938 and 75,743,000 in 1937. The number of wells completed in 1939 was 1850, compared with 2045 in 1938 and 2806 ill 1937. Several factors combined to cause the decrease in drilling activity, principally the contiriued increase in the length of time required to obtain a return of invcstment and the scarcity of important new discoveries during the past two years. Of the 1850 completions 1638 resulted in oil wells, 4 were gas wells, 168 were dry holes and 40 were abandoned locations; 1990 new locations were made during the year. The ratio of dry holes to producing wells completed was one dry hole to each 9.75 oil wells, compared with one dry hole to each 7.48 oil wells completed during 1938. This large decrease in dry holes was due to a marked decline in the number of wildcat wells drilled, there having been only 120 wildcat completions during 1939. In addition to the lessened exploration work, the deeline' in activity was largely accounted for by the slowing up of operations in the older pools of Ector, Howard and Winkler Counties. Ector County, which had led West Tcxas in 1938 with 622 new oil wells, furnished only 485 producers in 1939, but was still the leader for the West Texas district. The largest gain in activity was in Yoakum County, whew 350 oil wells were completed in the Denver-Wasson field against 152 during 1938. Most of the older oil fields have been almost completely drilled up, only a few new producers still being completed from time to time in

Jan 1, 1940

By J. Wesley Pullman

It is stated by Dr. Tuttle in a paper read before the New Jersey Historical Society, that the celebrated Dickerson mine at Succasunna, Morris Co., N. J., yielded ore, about as early as 1710, for use at the Whippany forge, on Rockaway River, between Rockaway and Boonton. The ore was, for some time, free to all who chose to dig it. The tract embracing the Dickerson mine mas taken up, on account of its minerals, in 1713 or 1714, by John Reading, who sold it in 1716 to Joseph Kirkbride. John Jackson built a forge in 1722 on the Rockaway River a mile west of Dover. The ore here worked was probably chiefly from the Dickerson mine, but a portion may have been Hibernia. Hon. E. D. Halsey, of Rockaway, K. J., writes me: It is quite possible that the ore was at first taken from the outcrop of Hibernia by anybody who wanted it. The property first had an owner, May

Jan 1, 1886

By HUBERT O. De

IN December, 1936, several drilling tests were made at the Hubert O. De Beck feldspar mine at Green Mountain, N. C., to determine the most efficient type of hammier-drill bit and drilling method for use at this particular property. This mine is well recognized as having the hardest rock in the Burnsville - Spruce Pine feldspar district and drilling costs always have been high. Local structural deformation has greatly distorted and warped the normal crystalline structure of the feldspar so the rock is much tougher than usual. In studying drilling methods and bit types, available literature was re¬viewed but little specific data could be found on the direct comparison of four-point and six-point drill bits so the following results may be of some interest.

Jan 1, 1937

THE CHAIRMAN (H. W. MORSE, Los Angeles, Cal.).-I would like to open this meeting for a little while to the general subject of leaching. We ought not to hold back if we have any new schemes for the future. I know that those of us who are tangled up with this lei thing work will appreciate any suggestions that will make us work harder and, scheme, harder to pull through these past difficulties on leaching. F. S. SCHIMERKA, Clifton, Ariz.-Under the direction of J. W. Bennie, General Manager of the Shannon Copper Co., Clifton, Ariz., 'it has been my valued privilege to cooperate in the elaboration of a hydrometallurgical process aiming at the recovery of copper in mill tailing resulting from a gravity concentration of a low-grade semi-oxidized sulphide ore occurring in a porphyritic gangue. The experimental work which has been carried on with a 25-ton plant is completed, and the company is building at present a leaching plant on a larger scale, the first unit consisting of a 150-ton roasting furnace and accessories for leaching the calcine.

Jan 12, 1916

By Otto C. Kopp, Thomas B. Crattie, Dennis R. Owen

Whole-rock analyses of limestones, fine-gralned dolostones and coarser-grained dolostones adjacent to mineralized breccias (Coy mine, Mascot-Jefferson City district) were compared with similar lithologies adjacent to apparently non-mineralized breccias at the new Thorn Hill section located approximately 39 km north of the Coy mine. Specimens were analyzed for Ca, Mg, Si, Al, K, Fe, Mn, Sr, Br, C1, S, Ti and P using X-ray fluorescence analysis. The concentrations of the major and most minor elements for Thorn Hill specimens fall within the range of concentrations for Coy mine specimens; however, significant differences (probability < 0.05) were noted for Fe, C1 and Br for fine-grained dolostones and for MgO, Fe and Mn for the coarser-grained dolostones. No significant differences were detected for the limestones.

Jan 1, 1985

By James F. Kemp

Discussion of the paper of D. Foster Hewett, Bulletin To. 27, March, 1909, pp. 291 to 310. JAMES F. KEMP, New York, N. Y.:-Mr. Hewett&apos;s paper is one of exceptional interest, because it not only adds an important contribution regarding one of the rarer, valuable elements, but also because it introduces compounds hitherto unknown and in associations no less novel. While we have occasionally dis¬covered and recorded asphaltite in metalliferous deposits, for example in the Joplin and Granby districts, we have not seen a metallic ore in a deposit essentially asphaltite. The source and method of introduction afford a subject well worth serious reflection. Vanadium was first discovered and recognized as a distinct element in the slags obtained in smelting the titaniferous magnetites at Taberg, Sweden. For a long time, therefore, we looked upon the titaniferous magnetites as its hone. Analyses proved, years ago, that it was present in the ores of this type in New Jersey and in the Adirondacks. It was quite rarely determined, but when looked for it was, I think, invariably found, although the Amount seldom exceeded 0.5 per cent. of V,05., In just what combination it exists in the titaniferous ores is uncertain. One might imagine V2O3 replacing some of the Fe2O3 of magnetite; or, since in the lead series vanadates and phosphates are closely akin, one might wonder if a lime-vanadate could take the place of apatite. Yet no lime-vanadate has been found in nature, and apatite itself is usually rare in the titaniferous ores. When percentage-curves are plotted for a series of analyses of the ores, the line of vanadic oxide shows a curious sympathetic behavior with the line of chromic oxide;&apos; but the data are somewhat limited, and no compound has sug¬gested itself which throws light on the matter. Dr. W. F. Hillebrand has discussed the occurrence and dis-

Oct 1, 1909

By R. I. Jaffee, C. M. Craighead, G. A. Lenning

The a-p type alloys are subject to a loss of tensile ductility with increasing hydrogen content. No hydride phase is visible in embrittled a-B type alloys. The embrittlement encountered appeared to be of the strain-aging type. Both compositional and structural factors are shown to influence the hydrogen tolerance of a-B type alloys. IN previous papers by the authors, the effects of hydrogen on the structure and mechanical properties of high-purity and commercial-purity titanium were described. It was shown that the presence of hydrogen in these materials results in a hydride phase having low solubility at room temperature. This insoluble phase had little effect on the room temperature tensile properties, but did decrease the notch-bar toughness to a large degree. The binary Ti-H systemz indicates that hydrogen is much more soluble in £ than in a-titanium. Hence, it is not expected that the embrittling effects of hydrogen in a-fi alloys will be similar to that found in a alloys. Materials of this type studied in the present investigation included two commercial a-/3 alloys, Ti-8Mn and Ti-4A1-4Mn; three high-purity Ti-Mn alloys containing 3, 6, and 9 pct Mn; and four high-purity Ti-Mo alloys, Ti-SMo, Ti-10.9M0, Ti-13.1 M0, and Ti-20M0, of the a-B and B types. Materials and Fabrication—The high-purity base alloys, composed of iodide titanium and high-purity metals, were prepared by double arc melting under argon in a water-cooled copper crucible, using a water-cooled tungsten electrode. Radiographic examination showed homogeneous Ti-Mo alloys. The analyses of the alloys used in this investigation and their as-fabricated hydrogen content, where determined, are listed in Table I. The two commercial alloys were 1/2 and % in. diam bar stock. No analyses other than hydrogen content were made. In order to maintain the a-B relationship existing in the two commercial alloys, vacuum annealing and hydrogenation were carried out in the B field prior to final fabrication. Fabrication then was done by The three high-purity Ti-Mn alloys were forged to 3/4 in. diam rods at 1600°F, and hot swaged to 1/2 in. diam at 1380°F. Machined and degreased bar stock was vacuum annealed or hydrogenated, fabricated to 1/8 in. diam rod by hot swaging, annealed in argon for 1 hr at 1380°F !75O°C), and water quenched. The six yz lb Ti-Mo ingots were forged to Wi in. diam rods at 1600°F and then hot swaged to % in. diam. Machined and degreased specimens were vacuum annealed or hydrogenated in the /3 field, prior to fabrication, by swaging to Y4 in. rod at 1400°F. After fabrication, the 5 and 10.9 pct Mo alloys were annealed in argon for 16 hr at 1290°F and water quenched to give equiaxed a-B structures. The higher molybdenum content alloys were argon annealed 4 hr at 1470°F and water quenched to give all £ structures.

Jan 1, 1957

By Larry Kaufman, Martin Schatz

The effect of pressure on the extension of the ? loop in the FeSi system has been determined by means of metallogvaphic studies and hardness measurements performed on a series of high-purity Fe-Si alloys containing 7.5, 11.0, and 13.9 at. pct Si, respectively. These mensurements, performed at 42 kbar and temperatures up to 1200oC, indicate that the ? loop is expanded to about 10 at. pct Si at 42 kbar as opposed to a maximum extension of 4 at. pct Si at 1 atm. Comparison of the experimental results with thermodynamic predictions of the pressure shifts yields satisfnctory results. DURING the past few years, several studies have been performed in our laboratory1-&apos; in order to determine the effect of high pressure on phase equilibrium in pure iron and iron-base alloys. The purpose of these studies has been to elucidate the effects of high pressure experimentally and to compare the observed results with predicted pressure effects derived on the basis of known thermody-namic and volumetric data at 1 atm. These studies have included work on pure iron2,5,7 as well as Fe-Ni,1,5 Fe-cr,l,5 and Fe-c4-6 alloys. In addition, Tanner and Kulin3 have reported results of pressure studies on two Fe-Si alloys containing 2.0 and 6.25 at. pct Si. At the time of this latter study, no detailed information was available concerning the difference in volume between the a (bcc) and ? (fcc) phases in the Fe-Si system as a function of silicon content. In order to compare their observations with calculated pressure shifts, Tanner and Kulin were forced to assume that silicon had no effect on the difference in volume between a and ? iron. The resulting discrepancy between their calculation of the a/? phase boundary at 42 kbar and the observed results led them to the conclusion that silicon additions probably decrease the difference in volume between a and ? iron. Recently: Cockett and Davis8,9 have reported de- tailed studies of the lattice parameters of a series of Fe-Si alloys at temperatures ranging from 20" to 1150°C. These measurements, performed on alloys in the bcc and fcc range, show that silicon does indeed decrease the difference in volume between a and ? iron. By correcting the calculations of Tanner and Kulin in line with the observed effect of silicon they were able to show improved agreement between computed and observed pressure shifts.&apos; The present measurements were undertaken to provide additional corroboration of this effect, by extending the range of composition, in addition to exploring a situation where large extensions of a ? loop could result in impingement of the ? field with an ordered bcc phase (based on Feo.75Sio.25). I) EXPERIMENTAL PROCEDURES AND RESULTS The alloys investigated were obtained from Dr. F. Kayser of M.I.T. They were prepared at the Ford Scientific Laboratory by vacuum melting electrolytic iron and high-purity silicon. The melts were poured under an argon atmosphere into hot-topped steel molds. Subsequently the ingots were hot-worked down to 1/2-in.-diam rods. Three alloys containing 7.5, 11.0, and 13.9 pct Si were studied. Carbon, regarded as the principal impurity, analyzed at, or below, 0.001 wt pct for all of the alloys. Prior to pressure-temperature treatment, the rod was annealed for 24 hr in vacuum at 1000°C, water-quenched, and subsequently machined into 0.100-in.-diam by 0.100-in.-long specimens. Subsequent to machining, the specimens were again annealed and then examined metallographically. They were found to exhibit a clear coarse-grained ferrite similar to Figs. 10 and 110 of Ref. 1 and Fig. 2 of Ref. 3. Subsequently, specimens of each alloy were equilibrated at 42 kbar at various temperatures in supported piston apparatus.1,3,4,6 Three specimens, one of each alloy, were wrapped in platinum and exposed simultaneously. The pressure-temperature cycle consisted of increasing the pressure from ambient to 42 kbar at 25oC, heating rapidly to the desired temperature, holding for 15 min, and quenching to 100°C, followed by slower cooling to 25°C and pressure release. The temperature was measured with a Pt/Pt-13 pct Rh thermocouple which was not corrected for pressure effects. Subsequently, specimens were examined metallographically and by

Jan 1, 1964

By John Brownson

Ge-Si N-N heterodiodes hare been built recently which show promise as high-speed logic devices. Low-resistivity germanium is deposited on silicon substrates held at temperatures above the germanium melting point and an alloyed heterojunction formed. The diodes are fabricated from this material using conventional mesa techniques. Over-all device qualify has been greatly improved by the use of epitaxial silicon substrates, that is, a subsirale consisting of a film of thin, high -resistivity silicon on a thicker Piece of low-resistirily silicon crystal. A semimpirical device design equation has been devised which predicts switching performance fairly well within the range of resistivitics and geometries employed. Switching times 01 0.9 ns and PIV &apos;s of —20 v are typical of the better 10-ma diodes. Switching times as low as 0.5 ns have been observed for 10-ma diodes and as low as 2.8 ns for 200-ma diodes. With further development it should be possible to improve switching speed by a factor of four. IN our laboratory, Ge-Si heterodiodes have been built recently which show promise as high-speed logic devices. The diodes have been built using a process reported in some detail in an earlier publication.&apos; The process in short involves alloying a thin film of low-resistivity germanium into a silicon substrate. the germanium having been transported and deposited by the well-known Theuerer halide reduction process.2 This process contrasts with that reported earlier by Oldham who used an essentially conventional direct epitaxial deposition technique.3 Oldham&apos;s process, unlike ours, requires cleavage of the silicon sample inside the reactor furnace the instant prior to deposition. Our process has the advantage of yielding large-area macro-scopically plane heterojunctions. Heterodiodes in general have several interesting properties. Without attempting to summarize the theory of heterojunctions.4 two of these properties which have direct relevance should be mentioned. First, N-.V and P-P heterojunction diodes rectify alternating current. Provided that either the band gap or the electron affinity of the two materials is different (which in general is the case), electronic barriers will exist in the junction band structure. When the device is sufficiently forward-biased, the barriers shift so as to permit current flow, and when it is reverse-biased. the barriers block current flow. Second, for N-N and P-P heterodiodes. the foward-conduction process involves majority carriers only. Consequently. when such a device is turned off. there is no minority-carrier storage and hence the diodes switch on and off quite rapidly. As we have reported earlier. N-P and N-N Ge-Si heterodiodes have been built in this laboratory. As one would predict from theory, the N-P heterodiodes were rather slow in turning off while the N-N&apos;s were quite fast. Similarly, the turn-off time of the N-P&apos;s increased rapidly with forward current while that of the N-N&apos;s was independent of forward current. Both N-N&apos;s and N-P&apos;s were moderately photosensitive. Photocurrents resulting from normal room illumination were as high as 1 µa at 1 v for small-area devices. The most disappointing parameter of the early N-N devices was reverse leakage.&apos; The reverse characteristic was invariably "soft" and leakage at only several volts reverse bias was intolerable. The reverse characteristic was greatly improved by using higher-resistivity silicon substrates. Leakage becomes large at voltages about one third of the avalanche voltage one would expect of a P-N homo-junction formed on silicon of the same resistivity. Thus leakage could be reduced to reasonable limits by using unconventionally high-resistivity silicon. Medium-power diodes formed on 30 ohm-cm substrates leaked typically 15 to 50 µa at 100 v reverse bias. The use of high-resistivity silicon substrate material, however, created a new problem. In order to have an acceptable forward-conductance characteristic. the area of the diodes had to be increased. With this increase in area, the capacitance increased. Switching time for N-N heterodiodes is essentially a linear function of capacitance. Thus when the resistivity was raised. so was the switching time. A SEMIEMPIRICAL HETERODIODE DESIGN EQUATION As a result of our experiments with a limited range of diode geometries and resistivities. a semi-

Jan 1, 1965