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By J. W. Dougherty

THE Hollinger gold mine is in the Porcupine mining division, District of Cochrane, in the northern part of the Province of Ontario. The adjacent town of Timmins, with a population of 25,119, lies 490 miles by railway north of the city of Toronto. GEOLOGY The property is situated on the northwest limb of a major syncline, which pitches northeast at approximately 50°. The principal rocks of the Hollinger area are of pre-Cambrian age and consist of altered, schistose, Keewatin lava flows intruded by stocks of schistose, quartz-feldspar porphyry generally assigned to the Algoman period. The structure of the Keewatin series is extremely complex as a result of close folding and some faulting. The schistosity, trending north 70° east and dipping steeply to the southeast, is most highly developed along a subsidiary anticline in which the major porphyry bodies occur. The ore bodies, which exhibit three principal structures, consist of quartz veins and associated pyritized wall rock. Some lodes are com-posed of en echelon veins, others exhibit a main quartz body with branch-ing stringers and a third consists of a single definite lead. Gold, in a coarse visible form, may be confined to quartz in some ore bodies but in others it is finely divided and is found not only in quartz but also asso-ciated with pyrite in the adjacent wall rock. In many veins the dis-tribution of gold is such that there are several ore sections, separated by areas of low-grade material, in the same vein although its physical appearance remains unchanged.

Jan 1, 1940

By C. D. Gilpin, Franklin Moeller

The application of electric power for driving mine hoists handling heavy loads at high speeds has recently been extended by the installation of what is probably the largest electrically driven hoist in this country at the Granite Mountain shaft of the North Butte Mining Co., Butte, Mont. While the weight of rock which is hoisted by this machine is not the largest now being handled by electric mine hoists, the speed of hoisting is so, and the combination of the high speed with the heavy load has resulted in a machine of considerable interest to all those actively engaged in mining. Aside from mere considcration of size, this installation deserves attention because of the careful attention given, not only to the question of economy of operation, but to the details of construction and installation of the entire equipment. The conditions to be met in this installation were as follows: Weight of rock to be raised per trip, 7 gross tons........... 15,680 1b. Weight of skip.......................................... 8,000 1b. Weight of cage.......................................... 1,800 1b. Maximum depth of hoisting.............................. 4,000 ft. Diameter of rope.......................................... 15/8 Total weight suspended on one rope from drum............. 42,000 1b. Normal hoisting speed.................................... 2,700 ft. per minute. Maximum hoisting speed.................................. 3,000 ft. per minute. Desired capacity-200 tons per hour from 4,000 ft. depth. The ore is mined in several levels and hoisting is carried on from the 800-ft. level down to the 2,700-ft., which is at present the maximum depth from which the ore is raised regularly. Development is proceeding and a depth of 2,900 ft. has already been reached. The rock is handled underground in cars holding % ton, and about 10 cars are the usual load for a skip. All of the ore is dumped into underground bins, which are of diffcrent capacities varying up to 250 tons. From the bins the ore is fed into the skips without passing into measuring pockets. At the surface the

Jan 1, 1916

Discussion of the paper of ALBERT SAUVEUR, presented at the Pittsburgh meeting, October, 1914, and printed in Bulletin No. 93, September, 1914, pp. 2439 to 2449 G. K. BURGESS, Washington, D. C.-This very instructive contribution by Professor Sauveur to our knowledge of that puzzling substance, Hadfield's manganese steel, should not only be read in connection with the paper of Messrs. Hopkinson and Hadfield referred to by Professor Sauveur (Bulletin No. 87, pp. 513 to 530, March, 1914); but one should also have in mind, as throwing much additional light upon the questions raised, two papers recently presented before the Iron and Steel Institute, the one by Sir Robert Hadfield (Journal of the Iron and Steel Institute No. II, 1913) on Heating and Cooling Curves of Manganese Steel, the other by Messrs. Hadfield and Hopkinson (ibid., No. I, 1914) treating of the Magnetic and Mechanical Properties of Manganese Steel. We then have brought together for this substance, the thermal, magnetic, and mechanical properties as well as the resulting microstructure, for the definite heat treatments described, and in particular after long annealing between 500° and 700° C. Sir Robert Hadfield and Professor Hopkinson see in the properties found for manganese steel (of C = 1.25 and Mn = 12.5 per cent.) a demonstration of the untenableness of the allotropic theory of iron, whereas Professor Sauveur reaches the contrary conclusion, that some of the facts observed can be explained only in terms of the existence of beta iron in steel of this composition. There is another possible hypothesis: namely, that these several series of experiments shed no light on the subject of the allotropy of iron, or at least as regards the existence of beta iron. However heretical it may sound, I am inclined to this last belief.

Jan 4, 1915

By John A. THOMPSON, Pazcl D. Torrey, Frank Breayster

DISCOVERY of natural gas in the Dundee field of New York in February, 1930, and the subsequent discovery in Tioga in September of that year, focused the attention of the natural-gas industry on the enormous possibilities of production and distribution in - the most populous area of the United States-New York and New England. Prior to 1926 the natural-gas industry in New York State had settled into a definite and limited policy, with the distributing companies controlling the output from its discovery to the ultimate consumer. Production amounted to between G and 7 thousand mil- lion cubic feet a year, with another 10,000 million feet imported from Pennsylvania for distribution in New York State. This gas was primarily from the Medina sand stone in. the western part of the state.

Jan 1, 1932

By V. Pasupathi, R. E. Hummel, J. W. Koger

Specimens of P1 brass were plastically deformed at room temperature to various degrees of deformation and subsequently cooled in order to transform them to low-temperature martensite. Deformation shifts Ms. A, , and the temperature of minimum resistivity to lower temperatures, and also decreases the temperature coefficient of electrical resistivity. These properties change rapidly up to about 15 pct reduction but vary very little with higher deformation. The possible relationships between martensite formed by deformation and the M, temperature of low-temperature martensite are discussed. Evidence is given that deformation martensite delays the formation of low-temperature martensite. BETA' brass undergoes at least two different types of martensitic transformations. One of these transformations (B1- B2) was first observed by Kaminski and ~urdjumov' and occurs when 81 brass with a zinc content between 38 and 42 wt pct (quenched from the single-phase region) is cooled below room temperature. Jollev and Hull' determined the structure of 0" from X-ray and electron-diffraction data as ortho-rhombic. Kunze came to the conclusion that the super-lattice cell of 0" is one-sided face-centered triclinic (pseudomonoclinic). The second martensitic transformation (B1-A1) occurs when the specimens are deformed at or somewhat above room temperature. This type of martensite will be called deformation martensite. Horn-bogen, Segmuller, and Wassermann4 determined the structure of deformation martensite to be bct. (An intermediate phase, az, occurs before the final phase appears.) At deformations higher than 70 pct, a, transforms into a.4 A critical temperature Md exists above which no transformation occurs during deformation and is estimated to be around 400°C in P1 brass.5 This martensite has elastic properties.6 When the sample is stressed, martensitic plates appear; when the stress is released, the plates disappear. The present paper studies the effect of deformation martensite on the formation of low-temperature martensite. The experiments involved samples of 8, brass which were plastically deformed by various amounts and were subsequently cooled below the transformation temperature. EXPERIMENTAL PROCEDURE The 13 brass investigated was made from 99.999 pct pure copper and 99.9999 pct pure zinc and contained 38.8 wt pct Zn. The specimens, consisting of foils 0.1 mm in thickness, were heat-treated at 8'70°C for 15 min in an argon atmosphere and then quenched into ice water. They were then deformed by cold rolling and subsequently cooled at a rate of 1°C per min. The martensitic transformation that occurred during cooling was followed by electrical resistivity measurements. The resistance measurement technique and its accuracy have been described in a previous paper. Because the transformation 81 —-8" occurs below room temperature, the samples were placed in a cryo-stat which contained isopentane as a cooling medium. The isopentane was cooled by liquid nitrogen pumped under pressure through a 15-ft coil of copper tubing which was immersed in the isopentane. The nitrogen flow was regulated by a temperature controller using two thermistors in the cooling medium. The cryogenic liquid could be heated with an immersion heater. The useful temperature range with this device was from +25° to approximately -155~C. EXPERIMENTAL RESULTS Resistivity Measurements. The following abbreviations are used in this paper to label the characteristic temperatures during the martensitic transformation. M, is the starting point of the martensitic transformation and is defined as that temperature where the resistivity vs temperature curve on cooling first deviates from a straight line. Mf is the temperature at which the martensitic transformation is completed. On reheating, the transformation from martensite to the parent phase starts at a temperature A, and ceases at a temperature Af. Fig. 1 presents five different resistivity vs temperature curves corresponding to the transformation of brass from Dl to 8" after different degrees of reduction in thickness. The following observations can be made from these curves. 1) With increasing degree of deformation the Ms temperature is shifted to lower temperatures. This shift ranges up to 35°C compared to the undeformed state. This is also indicated in Fig. 2, where AM, (the shift of Ms, compared to the undeformed state) is plotted vs the degree of deformation. AM, increases rapidly until a reduction of about 15 pct is reached. With higher deformations, no additional increase in AM, was found. 2) With increasing degree of deformation the temperature of minimum resistivity (M) is also shifted to lower temperatures. The shift, attains a maximum of about 61°C compared to the undeformed state. In Fig. 3, AM is plotted as a function of deformation. It can be seen that, as in 1 above, AM increases rapidly and no further shift of M occurs for deformations greater than 15 pct. 3) The temperature coefficient of resistivity, is given by the slopes (dp/dT) of the linear portions of

Jan 1, 1969

By C. A. Heberlein

The present war in Europe seems to have stimulated the demand for quicksilver. In July last, the price ranged around $35 per flask of 75 Ib., while to-day it seems to fluctuate between $47.50 and $50. The use of quicksilver in the form of fulminate, containing 70 per cent., and as corrosive sublimate, containing 73.8 per cent., must be extensive and a further market advance may be expected. With such an advance, some revival in quicksilver mining may be looked for, particularly in California, where many abandoned properties exist. What can be done with low-grade quicksilver ores under favorable conditions, particularly with low mining cost, may be seen from the following description of the Oceanic mine, near San Luis Obispo, Cal. Its operations date back to 1876, when rich sand ores were discovered. In three years 7,400 flasks of quicksilver were produced, but since then the deposit has been worked only sporadically . Until two years ago various attempts had been made by the Oceanic Quicksilver Co. to mine the more refractory "mud rock," which was encountered lying beyond the " sand rock." Mud and sand rock in varying quantities were treated together, with poor results, but operations were successful with sand rock of fair percentage. About two years ago, when all the sand rock had been exhausted, Murray Innes purchased the Oceanic mine. He found large quantities of low-grade mud rock, varying from 6 to 8 Ib. of quicksilver per ton, which at the prevailing low price of quicksilver demanded very cheap mining costs, in conjunction with high but cheap metallurgical extraction. At that time the extraction of quicksilver from mud rock ranged between 40 and 50 per cent., as far as I am able to learn. Mining The low cost of mining was the principal consideration, since, with mercury at 50c. per pound, the total gross value of the ore did not exceed

Jan 1, 1915

Organization Place Date 1918 National Society of Naval Architects New York, N. Y. Nov. 14-15 American Society of Mechanical Engineers New York, N. Y. Dec. 3-6 Geological Society of America Boston, Mass. Dec. 28-31 American Association for the Advancement of Science Boston, Mass. Dec. 27¬ Jan. 2. 1919 American Society of Civil Engineers New York, N. Y. Jan. 15-16 American Wood Preservers Association St. Louis, Mo. Jan. 28-30 American Society of Heating and Ventilating Engi¬ neers New York, N. Y. Jan. 28-30

Jan 11, 1918

By Frederic Benard

This paper constitutes a preliminary report on experimental work done to date on the anode-furnace treatment of blister copper containing relatively high percentages of nickel. The investigation has not been completed but results obtained to date are considered of sufficient interest to warrant publication. Blister copper treated by the Ontario Refining Co. originates from the Copper Cliff smelter of The International Nickel Company of Canada, of which the former is a wholly-owned subsidiary. The blister as received contains from 0.50 to 1.50 per cent Ni, and in this respect differs from that treated by other refineries on this continent. During the anode-furnace treatment, only a portion of the nickel content is removed, and of the amount remaining in the anodes a varying percentage is found in the anode slimes. This necessitates a more extensive treatment than ordinary nickel-free material. Sometimes it is necessary to repeat roasting and leaching operations several times before the nickel colltent is low enough to permit the slimes to proceed to the dorè furnace. This, besides increasing treatment charges, causes greater selenium stack losses and involves a longer tie-up of precious-metal values. Therefore this investigation was undertaken with the aim of determining the factors influencing the diversion of nickel into the anode sludge. From experience it was known that by keeping the nickel content of anodes at 0.55 to 0.60 per cent maximum a relatively satisfartory slime resulted. One avenue of attack therefore was developing improved elimination in the anode-furnace treatment so that the anode content mentioned above was not exceeded. Another angle was to improve the solubility, during electrolysis, of the nickel constituent in the anodes, thus decreasing the percentage diverted to slimes. . It may be mentioned here that nickel dissolving electrochemically and entering the electolyte presents no difficulty from a treatment standpoint. Both of these approaches were studied and are discussed separately below.

Jan 1, 1943

By Frederic Benard

This paper constitutes a preliminary report on experimental work done to date on the anode-furnace treatment of blister copper containing relatively high percentages of nickel. The investigation has not been completed but results obtained to date are considered of sufficient interest to warrant publication. Blister copper treated by the Ontario Refining Co. originates from the Copper Cliff smelter of The International Nickel Company of Canada, of which the former is a wholly-owned subsidiary. The blister as received contains from 0.50 to 1.50 per cent Ni, and in this respect differs from that treated by other refineries on this continent. During the anode-furnace treatment, only a portion of the nickel content is removed, and of the amount remaining in the anodes a varying percentage is found in the anode slimes. This necessitates a more extensive treatment than ordinary nickel-free material. Sometimes it is necessary to repeat roasting and leaching operations several times before the nickel colltent is low enough to permit the slimes to proceed to the dorè furnace. This, besides increasing treatment charges, causes greater selenium stack losses and involves a longer tie-up of precious-metal values. Therefore this investigation was undertaken with the aim of determining the factors influencing the diversion of nickel into the anode sludge. From experience it was known that by keeping the nickel content of anodes at 0.55 to 0.60 per cent maximum a relatively satisfartory slime resulted. One avenue of attack therefore was developing improved elimination in the anode-furnace treatment so that the anode content mentioned above was not exceeded. Another angle was to improve the solubility, during electrolysis, of the nickel constituent in the anodes, thus decreasing the percentage diverted to slimes. . It may be mentioned here that nickel dissolving electrochemically and entering the electolyte presents no difficulty from a treatment standpoint. Both of these approaches were studied and are discussed separately below.

Jan 1, 1943

By V. C. Rogers

ALTHOUGH surveying at mining properties is fundamentally the same regardless of the method of mining, at Climax, due to the nature of the ground, the policy of advance development work, and extremes in climatic conditions, surveying practice has had to be revised to meet the specialized conditions of this particular type of mining operation. The company's mine is one of the largest underground properties in the United States. It has proved ore reserves of 275,000,000 tons, 60,000,000 tons of which have been broken. To date, 109,000 ft. of development drifting have been driven, as well as 40,926 ft. of development raising, 10,000 ft. of ventilation drifting and raising, 16,000 ft. of exploration drifting, and 206,000 ft. of diamond drilling. Normal production varies between 1.2,000 and 15,000 tons daily. Development work proceeds at a rate of 11/2 tons developed for every ton milled and with a development of 18,000 to 20,000 tons per day, the following crew is required to take care of mine and surface engineering

Jan 1, 1946

By E. J. Freeh, W. E. Horst, R. C. Kellner

A technique useful in the important area of process-model building is described. The procedure is illustrated in the development of a mathematical model to describe the unsteady-state process of batch ball-mill grinding. The influence of certain assumptions relative to model structure are quantitatively evaluated and reviewed.

Jan 1, 1969

By Robert C. Bates

Is the value of rock sealant on radon control destroyed by changes in barometric pressure? While an article by Dr. Gerald Schroeder in the June 1977 issue of MINING ENGINEERING suggests this, it should be noted this is not necessarily true as the ensuing discussion reveals. Before analyzing the data leading to Dr. Schroeder's conclusions, some comments on their source are needed. The figures were collected during a 1973 US Bureau of Mines test of radon barrier coatings in the Dakota uranium mine near Grants, N.M. Results of that test were reported by Franklin, et al 3,4 in 1975. The mine is essentially dry and ore occurrence is within a lightly cemented, porous medium-to coarse-grained sandstone of high permeability and radon emanation rate.

Jan 12, 1977

Organization Place Date 1918 American Institute of Architects Washington, D. C. April American Iron and Steel Institute New York, N. Y. May American Institute of Chemical Engineers : Berlin, N. H. June 19-22 American Society for Testing Materials Atlantic City, N. J. June 25-28 New York Electrical Society New York, N. Y. June National Association of Stationary Engineers Cincinnati, 0. Sept. 9-13 National Exposition of Chemical Industries New York, N. Y. Sept. 23-28 American Chemical Society Cleveland, 0. Sept. National Petroleum Association Atlantic City, N.. J. Sept.

Jan 4, 1918

Marius R. Campbell, Washington, D. C. (Communication to the Secretary): Having spent considerable time in a systematic study of this field,'both as regards the details of its structure and stratigraphy and the broader question of its relation to the Appalachian basin, I wish to add a word concerning the correlations made by Mr. Hodge in his paper. From A commercial standpoint, the question of correlation, even along the strike, is of little or no importance, for the variability is such that each opening should be tested individually, regardless of the horizon at which it appears; but these correlations assume an entirely different aspect when their scientific bearing is considered; they then become of vital importance, and, before being accepted, should be subjected to the most rigid scrutiny and severe tests. Mr. Hedge states positively that the Imboden seam of coal is equivalent to the Elkhorn coal of Pike and Letcher counties, Kentucky. In the writer's opinion, such equivalency is, at the utmost, only a possibility. This correlation has been generally adopted by the geologists of the Kentucky Geological Survey, but the writer has been unable to find on what grounds they base the statement. The evidence of identity seems to be in the character of the coal, as both seams furnish fine coking coal; also, in the similarity of the interval between them aid the " Bee Rock," or top of the great conglomerate. It is probably an easy matter to determine the thickness of this interval on Elkhorn creek, and we will assume that the measure of 300 to 350 feet is correct. In the Big Stone Gap field, the question of measuring the interval between the Imboden and the " Bee Rock " is exceedingly difficult. The line of outcrop of this mass of strata is along the northern base of Stone mountain, and, in the uprising of the great arch, the strata on its flanks have been thrown into many minor folds, and, in places, have been broken by local faults. This complicated structure, together with the absence of ally well-marked stratum, renders it exceedingly difficult to obtain a correct measure of the intervening sandstones and shales. The interval of 300 to 350 feet, assigned by Mr. Hodge, is mani-

Jan 1, 1893

By L. H. Sjodahl, J. B. Conway

of each particle on grain boundary movement is proportional to the area it occupies on the grain boundary and this increases with the square of the particle radius. In contrast to the impression gained by Tiwari the effectiveness of a particle, as a grain boundary obstacle, increases rapidly as the particle size increases. The counterbalancing factor in a dispersion of constant volume (e.g., those considered by Zener) is of course the rapidly diminishing number of particles, a situation which does not exist in thoria dispersed materials where the volume fraction of thoria remains constant. Although it has been assumed that the Zener approach is valid for the sake of the above argument, it is open to the following objections: 1) It assumes that the effect of many small particles along a grain boundary is cumulative and does not take into account the possibility of each small particle being overcome separately. In this case the boundary will not be able to move forward until the largest particle on the boundary has been overcome. This means that the rate controlling factor will be the rate at which a few relatively large particles are overcome with the remaining small particles playing a negligible role. 2) When the dispersion consists of very small particles the interparticle spacing is usually small compared to the grain size and most particles are located away from grain boundaries where they can play no part. The most efficient dispersion, from a purely geometrical viewpoint, is one where the particle spacing is equal to the grain size so that all the particles are on grain boundaries. Tiwari's second point that voids cannot prevent re-crystallization seems to be unfounded as several workes20-23 have shown that voids alone can retard grain boundary movement and recrystallization. To further convince Tiwari, Fig. 17 shows a void in deformed TD Nichrome holding back a recrystallization interface. Tiwari's explanation for the effect of voids on recrystallization, i.e., they reduce local strain energy and hence lower the driving force for recrystallization may be valid in itself but is irrelevant to the present case where even complete recrystallization after ONE of the more recently proposed expressions for describing stress-strain behavior is that due to Voce.1,2 This equation is usually written: s =s8 ?(s8?so)e??/?c [l] where s is the true stress, ? is true strain, cC is a constant called the characteristic strain, s8 is the asymptotic stress approached at high strain values, and so is the threshold stress at which the plastic deformation begins. While this expression has not been universally accepted as yet it does contain certain features which are consistent with experimental stress-strain behavior. In a more recent publication Hsu, Davies, and Royles3 employed the concept of generalized strain proposed by seth4 and identified a method for linearizing the stress-strain plot. In this approach the generalized strain was given by: where 7 is the generalized strain, 1 is the instantaneous length, 1, the datum length, and n is a constant called the "coefficient of strain measure". A value of n was said to exist which would yield the linearity: s —s+ S[.-(tf] [3] In recent studies of both these approaches, it has been found that while the Voce equation and the gen-

Jan 1, 1970

By Nicholas J. Grant, Chih-Chung Wang

TO phase of the Ti-0 system has the structure of NaCl and has a wide range of solid solubility.' In the course of studying the Ti-Cr-0 ternary system, binary alloys were made of iodide titanium and high purity TiO,. It was found from X-ray studies of the binary alloys that a transformation of the TiO appears to take place at a temperature near 925°C. Evidence of this phase change is best seen in Fig. 1. Fig. 1A shows the X-ray spectrometer pattern (CUKa radiation) of an alloy of 25 wt pct 0 corresponding to the stoichiometric composition of TiO.

Jan 1, 1957

By C. S. Duncan, S. Scuro, D. R. Muss

Work is vepurted which was aimed at accentuating the pec14liar attributes of the GaAs laser diode, namely its sutzull size and its high efficiency. This has been done by reducing- transport losses in the bulk p and n regions of the diode and combining many of. these diodes into series stacks with common optical cazlities. The result of this effort is a nearly monochromati source at about 8450A With a luminous areu 0.05 by The GaAs laser diode is an attractive pulsed light source in the near ir because of its ability to emit very large pulse powers and its small size. In addition to this, the device is efficient; and the higher the 0.05 cm emitting peak pulse po we rs at greater than 300 LC at repetition rates below 200 pps into a cone about 0.01 steradians when operated at 77°K. The results of nzeasuvetnents of peak optical power and spectra frorr~ these stacks are reported and some conclusions are drawn about the vole the individual diodes play in the stacked operation. peak output power, the more efficient it is. The limit for the amount of power that these diodes can emit is the transient and average dissipation associated with the pumping pulse. This power dissipation arises primarily from transport across the bulk regions of the diode; this fact, along with the relatively low thermal conductivity of the GaAs, led us to the conclusion that higher power

Jan 1, 1968

By D. M. Hausen

This study identifies and describes various crystalline phases of the V205-Na20 system, and relates their properties to metallurgical aspects of vanadium production. Phase equilibria and stability ranges of sodium vanadate phases of varying molar ratios of Na20/V205 were investigated in a variety of plant products, ranging from fused "black cakes" (V20 melts) to "salt roast" calcines. Crystalline compounds, Including vanadium pentoxide, V205; sodium vanadyl vanadate, 6 phase, Na2O.V2O5.5V2O5; sodium vanadyl vanadate, y phase, 5Na20.V204.12V205; sodium metavanadate, Na20 .V 05; sodium pyrovanadate , 2Na20 .V205; and sodium orthovanadate, 4Na20.~2~5, have been characterized with the aid of X-ray diffraction patterns, infrared spectra, and optical properties in addition to chemical analyses, as a guide to mineralogical "troubleshooting" of plant problems and processes in vanadium pyro- and hydrometallurgy.

Jan 1, 1984

By P. J. Burkhardt, L. V. Gregor

The oxidation kinetics of single-crystal silicon has been investigated using extremely dry oxygen as the oxidant. Two techniques were used. The first involved a flow system with which incremental thickness measurements were made. This sytem provided an oxygen ambient at atmospheric pressure which had a moisture content of less than 0.1 ppm of water. The second technique involved measuring the change in volume of oxygen with time in a closed system. A temperature range of 900O to 1200 "C and a pressure range of 20 to 760 Tory were covered. Both techniques showed that a simple parabolic rate law holds only at the higher temperatures. At lower temperatures, the data up to 5000Å can be fitted well to a linear-parabolic equation. The two constants in this rate equation are examined in terms of a physical model. The parabolic portion of the low-temperature oxidatLon fits along the high-temperature curve of an Arrhenius plot. The parabolic rate constant for the flow-system technique can be expressed by k = 2 x 10-9 exp (L 31 kcalRT) sq cm per sec. The manostatic technique gave k = 1 x 10-exp (- 23 kcalRT) sq cm per sec. By extending the thickness range to over 104. a rate law of X = At seems to fit all of the data better than the linear-Pavabolic law. Here the exponent n increases from 0.518 at 1150 V to 0.637 at 900°C. PASSIVATION of silicon planar devices through thermal oxidation is of such great importance that considerable effort has been devoted to the study of the process.17 Much of this work involves hydrothermal oxidation, in which H2O is the oxidant: whereby H2 is produced. It has been proposed that the reaction proceeds by the formation of Si-OH groups and hydroxyl diffusion through the film to react with the silicon surface. Thus, the silicon oxide layer probably contains residual hydrogen in some form after oxidation in H2O and it has already been established that hydrogen has a marked effect on the electronic properties of oxide-passivated silicon surfaces. Silicon is oxidized by oxygen at elevated temperatures; but the rate of oxide formation is considerably lower than that for 0." By using dry O2 as the sole oxidant, the presence of residual hydrogen is presumably avoided. At present, the mechanism of thermal oxidation by dry O2 is a matter for conjecture, and the presence of small amounts of H2O was reported to have a marked effect on the rate of oxide formation10 (perhaps on the electronic properties of the surface, as well). Hence, this study of the kinetics of silicon oxide growth in 0, was undertaken: 1) to determine the oxidation rate at atmospheric pressure in a system designed to exclude rigorously all traces of H2O in the ambient 0,; 2) to obtain oxidation-rate data in situ in dry O2 by means of a continuous monitoring of the amount of 0, consumed during oxide growth. These objectives are complementary—the first assesses what effects (if any) are obtained by excluding H2O from the reaction, and the second expands this information while at the same time avoiding the uncertainty inherent in relying upon incremental measurements of oxide growth to furnish kinetic data. EXPERIMENTAL PROCEDURE The conventional silica open tube in a resistance-heated oxidation furnace is subject to sources of trace H2O, even after the input O2 is thoroughly dried and the outlet gas stream is passed through a trap to prevent

Jan 1, 1967

By R. A. Wood, R. I. Jaffee, H. R. Ogden, D. N. Williams

The tensile properties, creep resistance. and thermal stability of highly alloyed Ti-Al-Zr alloys were examined. On the basis of these studies, the Ti-7Al-1ZZr composition was selected for more complete evaluation. The alloy was found to be weldable and free from excessive directionality. In addition, it developed maximum properties without requiring heat treatment other than an annealing operation in the alpha field. The alloy was recommended for scale up and is presently being investigated on a production-level basis. One of the more attractive properties of titanium alloys is their ability to withstand stress at moderately high temperatures, and a considerable amount of effort has been devoted to increasing the maximum service temperature of titanium alloys. This work has suggested that the optimum alloys for high-temperature service will be single-phase a (close-packed hexagonal) alloys containing significant amounts of aluminum. However, the maximum amount of aluminum which can be alloyed with titanium is between 6 and 8 pct,l since at high-aluminum contents an embrittlement reaction occurs in the anticipated service temperature range, 800" to 1100°F. It has been shown that the embrittlement reaction involves decomposition of the high-aluminum a phase to one or more new phases.' Since this reaction does not occur at intermediate or low-aluminum contents, it was felt that intermediate Ti-A1 alloys might be strengthened by a-soluble ternary additions without inducing the embrittlement reaction. The first alloying addition considered was tin, which shows extensive solubility in a titanium and has moderate strengthening tendencies. Unfortunately, it was soon apparent that tin also promoted the embrittlement reaction, and that to obtain a stable alloy, the aluminum content had to be reduced as the tin content was increased. The second alloying addition considered was zirconium, which is similar to tin in its effects on titanium. This element did not contribute to the embrittlement reaction and, in fact, appeared to increase the maximum amount of aluminum which could be alloyed with titanium without inducing instability. This paper describes an investigation of the Ti-A1-Zr a alloy region. Alloys containing from 4 to 12 pct A1 and from 6 to 15 pct Zr were examined. The properties of these alloys are described and the bases for selecting an optimum composition is outlined. This composition, Ti-7A1-12Zr, is presently being scaled up in tonnage quantities, and is being evaluated extensively throughout the industry. In addition to presenting the basis for its selection, this paper presents a description of the properties developed in laboratory material as determined during the alloy investigation. These properties suggest that this alloy can fill an important position in applications requiring light weight, fabrica-bility, weldability, and strength to 1000oF or higher. EXPERIMENTAL PROCEDURES Titanium alloy ingots were prepared by inert electrode arc melting under an argon atmosphere. Alloying elements used were 110 Bhn titanium sponge, high-purity aluminum, and reactor-grade zirconium. Pancake-shaped ingots were prepared weighing approximately 300 g. The composition of the ingots was checked by weight measurements before and after melting. The pancake ingots were forged at 2000°F to approximately half their original thickness to give a flat plate roughly 1/2 in. thick. This plate was then rolled at 1800' to 1600°F to 0.250 in. thick. All of the alloys examined fabricated well. However, alloys containing 15 pct Zr tended to overheat due to exothermic oxidation, and scaling was excessive. As might be anticipated from its effect in decreasing the ß transus, increased zirconium appeared to improve fabricability somewhat, especially during rolling at lower temperatures. Except for a limited study of heat-treatment response, all alloys were examined in the a-annealed condition. Prior to heat treatment the a and ß tran-sus temperatures were determined by metallo-graphic examination of samples quenched after annealing at 50-deg intervals in the transformation region. These data are shown in Fig. 1. Recrystal-lization appeared to occur in about 1 hr in the range 1300º to 1500ºF. Therefore, alloys were annealed for 1 hr at 1550ºF (4 and 5 pct Al), 1600ºF (6 through 7-1/2 pct Al), or 1650°F (8 or more pct Al). This produced an equiaxed a grain structure. In most alloys, a "ghost" structure was visible after the a-annealing treatment, as shown in Fig. 2. This structure apparently resulted from the acicular

Jan 1, 1963