Search Documents

By R. P. Smith

Iron-carbon alloys containing a single-phase austenite region and a two-phase azcstenite + cementite region at the desired temperature were prepared by partial carburization of iron or partial decarburization of carburized iron. Each sample was held at a fixed temperature until equilibrium was achieved. Analysis of the austenite for carbon then gave the solubility of cementite in austenite. Solubility measzcrements were made for the temperature range 734° to 1012°C. These values together with other data give 7560 cal for the mean heat of solution of cementite in austenite, and 0.765 pct C for the eutectoid composition of austenite. They also indicate that graphite is the stable phase at all temperatures between the eutectoid and eutectic temperature. Measurements of the solubility of cementite in austenite at 927oand 1011 "C, using a method based on the equilibration of iron with boro-cementites, are reported. The solubility of cementite in austenite (?-iron) has been computed by Darken and Gurry1 from the observed solubility of graphite in austenite, and the thermodynamic properties of pure iron and of iron-carbon alloys. They have shown that the solubility of cementite is greater than that of graphite in the temperature range between the eutectoid and eutectic, and thus that cementite is metastable with respect to graphite and austenite saturated therewith. Since their computation is not in accord with the earlier experimental work of Mehl and wells,' the present direct determination of the solubility of cementite in austenite was undertaken. EXPERIMENTAL PROCEDURE Each iron rod about 1/2 in. O.D. by 4 in. was first carburized at a temperature and with a H2-CH4 gas mixture such that the carbon content would be greater than that corresponding to the solubility of cementite in austenite at the desired (lower) temperature; sufficient carburizing time was allowed that the carbon content became substantially uniform, as illustrated by Curve A, Fig. 1. The sample was then partially decarburized with a hydrogen-water vapor mixture, giving a carbon distribution as schematically illustrated by Curve B. The sample was then held in a helium atmosphere at the temperature at which the solubility was to be determined until the decarburized portion of the sample came to equilibrium with that containing cementite. Curve C of Fig. 1 represents schematically the final carbon distribution; the horizontal portion corresponds to the carbon content of austenite saturated with cementite. To bring the sample to room temperature without change in the carbon distribution and in machinable condition, it was first quenched in a salt pot at 480°C, then in water at room temperature. Successive layers were machined from the center 2 in. of the sample and analyzed for carbon by the usual

Jan 1, 1960

L. D. GODSHALL, Everett, Washington: This very interesting paper cannot fail to command the attention of every one who has ever had experience in the amalgamation of gold-ores. I wish to call attention to three very important facts brought out very prominently by the paper, namely: 1. The extent of accumulation of amalgam on copper plates in the form of scale, not removable in the ordinary manner; 2. The change in the relative quantity of the two metals in the amalgam as we. recede from the battery-discharge; 3. The difference in fineness of the bullion obtained from the above-mentioned scale as compared with the bullion from the daily clean-ups. From Mr. Bayliss's figures we find that during the life of the plate in question 14,942 tons of ore were crushed, yielding amalgam of the value of $5.03 per ton, or a total value of $75,158.26. The amalgam accumulating on the plate during this time as scale, we find to have had a value of $8340.54, or $0.558 per ton of ore treated, representing 11.09 per cent. of the total amount of amalgam saved in the ordinary clean-up; or, taking the amalgam saved by daily clean-up plus the amalgam-scale as representing the total saved on this plate, or 100 per cent., we find that the daily clean-up saved 90.01 per cent., while the scale represented 9.99 per cent. The above figures do not include some additional amalgam still adhering to the plate after scale had been removed. We are told that this was not an exceptional case at the Drum Lummon, but that other plates have even yielded a third more than the one in question. The interesting query now comes up, whether this experience at the Drum Lummon is exceptional or universal at all mills; and another question arises, as to how long such an accumulation might continue,

Jan 1, 1897

By A. T. Goldbeck

THE use of stone as a building material in relatively large blocks is recorded in ancient historical records but only within the past 200 years has broken stone in small sizes begun to have extensive use, principally in highway construction. Tresaguet, in 1764, describing his method for highway construction in France, required the top surface to be built of stone about the size of a walnut, broken by the use of a hammer. It is said that the Romans, in the top layer of their rather massive roads, used large stones bonded together with lime mortar and bedded in small stones mixed with mortar. Much of the early macadam as built by McAdam around 1815 in England was made with hand-sledged broken stone. In 1858, the use of crushed or broken stone received a great impetus from the invention in that year by Eli Whitney Blake of what is said to be the world's first stone crusher. As a consequence of that invention, stone could be crushed to small sizes with considerable ease and, as a natural result, the use of crushed stone in macadam roads and as railroad ballast increased at a great rate. Also, as portland cement came into use, machine-produced crushed stone furnished readily available aggregate. Rapidly, other uses developed, such as for fluxstone in the production of pig iron and for other metallurgical operations and chemical utilizations. These utilizations made for the rapid growth of the crushed-stone industry and this growth is still proceeding with the growth of population and the development of new uses, notably the employment of limestone for the improvement of soils for agricultural purposes. The industries of which the production of crushed stone is a part have a tonnage second only to that of mineral fuel in the mineral industries of this country.

Jan 1, 1949

Jan 1, 1923

Jan 1, 1923

By Zay Jeffries

THE object of the present paper is to enlarge somewhat on the general principles advanced in my discussion 1 of Mathewson and Phillips' article on. The Recrystallization of Cold-Worked Alpha Brass on Annealing.2 It will also serve as an acknowledgment of Prof. Howe's3 most important remarks on my contribution. In this paper the writer has adopted Prof. Howe's suggestion to substitute the term "germinative temperature" for "critical temperature for grain growth." Instead of being an exact or certain temperature it should be considered that the germinative temperature phenomenon exists throughout a small temperature range. Factors Influencing Fast Growth Phenomena The development of grains of macroscopic size at the germinative temperature should be considered the extreme condition of a general rule. When considered in this light it is not strange that the development of these large grains should be the exception and not the rule. The principal factors influencing the operation of the laws of fast growth temperature are as follows: 1. Rate of heating.

Jan 10, 1916

By W. C. Ellis

NONFERROUS alloys upon which desirable properties can be conferred by heat treatment are becoming of increasing industrial importance. The alloys of copper with a constituent which has a solubility varying with temperature are materials of this character. Some of the constituents which are effective in producing a change in the mechanical properties of these alloys upon heat treatment are, according to Corson,1 nickel and silicon, iron and silicon, cobalt and silicon, and chromium and silicon. In addition to these elements, Gregg2 states that the combination of beryllium and silicon is effective in producing age-hardening characteristics in copper. The effect of these elements, however, as dispersion-hardening constituents in the copper alpha solid solutions does not seem to have been studied in any considerable detail. This paper deals with the heat treatment and properties of three alpha brasses containing 3 per cent. of nickel plus silicon in the proportion necessary to form the compound nickel silicide, Ni2Si. Some information of a preliminary nature in regard to the hardening by heat treatment of phosphor bronze containing the same percentages of nickel and silicon is included. The method of hardening the alloys, which is effective in increasing the tensile strength and proportional limit, is similar to that used in, the case of duralumin type aluminum alloys. It consists of a quench from a temperature at which the hardening constituent is in solid solution, followed by an aging at a lower temperature to precipitate the dissolved constituent in a dispersed condition. This results in an increased resistance of the alloy to deformation with an attendant improvement in the tensile properties.

Jan 1, 1929

SULPHUR is a very well known mineral and apparently is produced in many places. It is engendered from an unctuous earthy and powerfully hot substance so that it is considered among experienced workers to bear a resemblance to the element of fire. This is called by these same men the masculine seed and the prime agent of Nature in the composition of metals. Because of its great dryness and heat it has, as experience shows, affinity with fire, which is easily introduced in it when brought near. And once introduced the fire is quenched only with difficulty before its unctuousness is wholly consumed. Although it shows itself to us of such a hot and dry nature, we must not think that sulphur is a substance so pure that it can stand by itself or that in order to attain its form it has no need of its portion and part of moisture like every other mixture. This is shown to us by its easy fusion, in which it resembles the metals. This thing is found in many places and in many varieties of color; some are white, others yellow and orange, and some others between gray and black. They also say that some red is found. It does not occur in that arrangement of veins like other minerals, but most liberal Nature makes whole mountains of it as is seen in the Aeolian islands, [26] near Sicily, in Etna or Moncibello which is the island of Sicily, at Pozzuoli, in the territory of Rome, in the Sienese domain at San Filippo, and in many other similar places. It is a substance that has a very strong odor and is most unpleasant to smell. It is very fixed in its substance so that it is never corrupted by time, by boiling, or by the moisture of water. For although it may stand in water a long time it never becomes soft nor does it ever decrease or increase in weight. It is brittle and easily crushed very fine. It is said that a trace of garlic rubbed on the mortar helps anyone who wishes to reduce it to impalpability. Its ores have a form more like earth than like stone although they some¬times have the color of a certain soft rock. The places where it is found are easily recognized by the great odor that they give out and by the very hot baths that often spring forth near it. What I have already told you about quicksilver that is contrary to the

Jan 1, 1942

By M. S. Klima, P. T. Luckie

An evaluation of the operating performance of a recently designed pneumatic centrifugal classifier is presented. This classifier has been modified from a separate air and feed input design to an entrained solids in air feed input. The evaluation first required determining the size distributions for the three streams (feed, fine, and coarse). Using size distribution data and mass flow rates, a size selectivity curve was calculated for each operating condition tested. This curve, in turn, was characterized by appropriate selectivity parameters (i.e., the equiprobable or cut size, the sharpness index, and the apparent bypass values). The variation of these parameters with classifier operating conditions was examined. From these evaluations, the "best" operating conditions for the classifier were then determined.

Jan 1, 1985

Jan 1, 1963

By R. C. Earlougher, F. G. Miller, T. D. Mueller, H. J. Ramey

There are many studies of flow in radial systems that can be used to interpret unsteady rerervoir flow problems. Although solutions for systems of infinite extent can be used to generate solutions fur finite ow systems by superposition, application is tedious. In this paper a step is made toward simplifying calcu1ations of such solutions for finite flow systems. Superposition is used to produce a tabulu-lion of the dimension1e.s.s pressure drop function at several locations within a bounded square that has a well at its center. The square system provides a useful building block that may be used to generate flow behavior for any rectangular shape whose sides are in integral ratios. Values of the tabulated dimensionless pressure drop function are simply added to obtain the dimensionless pressure drop function for the desired rectangulm system. The rectangular system may contain any number of wells producing at any rates. Furthermore, the outer boundaries of the rectangular system may be closed (no-flow) or they may he at constant pressure. Mixed conditions also may be conyidered. Tables of the dimensionless pressure drop function for the square system are presented and various applications of the technique are illustrated. Introduction In 1945, van Everdingen and Hurst' published solutions for the problem of water influx into a cylindrical reservoir. Since this problem is mathematically identical with the depletion of a cylindrical reservoir with a well at the origin, the van Everdingen-Hurst solution may be used to study the depletion problem. In their analysis, they assumed that the fluid had a small, constant compressibility such that flow was governed by the diffusivity equation For a constant production rate q starting at time zero, van Everdingen and Hurst showed that the unsteady pressurc distribution for both finite and infinite systems could be expressed in terms of a dimensionless pressure 'Sabulations of the dimensionless pressure drop for a unit value of r, were provided by van Everdingen and Hurst,' and later by Chatas.' Others also presented values in graphical or tabular form." If the radius of the well becomes vanishingly small, r,+ O, the line source solution may be used for Eq. 2 when infinite systems are considered. Eqs. 5 and 6 are excellent approximations for Eq. 2 under certain conditions: In 1954, Matthews, Brons and HazebroekV emonstrated that solutions such as Eq. 5 can be superposed to generate the behavior of bounded geometric shapes; i.e., the behavior of a bounded single-well system can be calculated by adding together the pressure disturbances caused by the appropriate array of an infinite number of wells producing from an infinite system. These wells are referred to as image wells. Matthews, Brons and Hazebroek considered systems containing a single well producing at a constant rate. This superposition can be represented analytically as

Jan 1, 1969

Jan 1, 1961

By Mayumi Someno, Kazuhiro Goto, Masahiro Kawakami

The apparent rates of decarburization of liquid alloys of Fe-C, Fe-C-S, Ni-C, and Co-C systems and the rate of oxidation of solid graphite with pure carbon dioxide gas and with gas mixtures of carbon monoxide and carbon dioxide have been measured in the temperature range of 1000° to 1600°C. The cotnposition of carbon dioxide and carbon monoxide gas at the reaction surface has been measured by oxygen concentration cells with the ZrO,-CaO solid electrolyte. 1) The apparent rates of the carbon removal are essentially the same for all the cases of solid graphite, Fe-C, Fe-C-S, Ni-C, and Co-C systems under the same experimental conditions. 2) The apparent rates are independent of the carbon content in the high carbon concentration range but very much affected by the flow rate and the gas composition of the CO-CO2 reactant gas mixture. The ratio of the gas consumed by the reaction to the total quantity of the supplied gas is very large under the present experi~nental conditions. 3) There is a concentration gradient of' carbon dioxide in the vicinity of the reaction surface and the content of CO, becomes extremely small at the reaction surface. 4) A large time fluc-tuation of the gas composition was observed. This jluctuation implies the presence of unstable flow in the gas phase in the vicinity of the reaction surface. THE decarburization of molten steel by an oxidizing gas or by slag may be one of the most important chemical reactions in steelmaking processes. Nevertheless, the kinetics of this heterogeneous chemical reaction do not seem to be well-solved even with the previous studies. Although the conditions for the reaction in steelmaking processes are quite different from those in the laboratory scale, some critical experiments may give information on the mechanism of the decarburization. From the previous work,'-' it is known that the rate of the decarburization is independent of the carbon content in liquid iron with more than about 0.2 wt pct C when the oxidizing gases are supplied to the surface of liquid Fe-C alloys on a laboratory scale. Two rate-controlling steps have been proposed for the decarburization of liquid iron with the high carbon content: one is the surface reaction control proposed by Swisher and Turkdogan;' the other is that the rate is controlled by the gaseous diffusion through the gaseous stagnant layer. proposed by Baker. Warner, and Jenkins.7 and also by .Ito and Sano.2 In the present study, some experiments have been carried out for the evaluation of these rate-controlling steps in the decarburization of liquid iron with high carbon content. The apparent rate of decarburization of liquid iron has been compared with the rates of carbon removal of liquid Ni-C, Co-C, and solid graphite under the same experimental conditions. The composition of carbon dioxide and carbon monoxide gas at the reaction surface has been measured by oxygen concentration cells. I) EXPERIMENTAL PROCEDURE Fig. 1 shows the schematic diagram of the reaction chamber. Solid graphite and liquid metals were contained in an alumina or magnesia crucible of 32 mm ID and 35 mm in height. The samples were heated by high-frequency induction and the temperature was measured by the calibrated optical pyrometer. The temperature was held constant to within 10°C. The re-actant gases were supplied to the surface of the samples through the quartz tube of 8.0 mm ID. The distance from the end of the quartz tube to the surface was 20 mm. The block of high-purity graphite was cut and shaped to the inner profile of the crucible. The height of the shaped graphite was 18 mm, which corresponded to the depth of the liquid iron of 100 g. About 100 g of Fe-C alloy (4.20 to 4.40 pct C), Ni-C alloy (1.84 pct C), Co-C alloy (1.85 pct C), and Fe-C-s alloy (4.35 pct c, 0.5 or 1.0 pct S) were melted in the crucible. The reactant gases were pure CO, and gas mixtures of CO-CO,: the flow rates were controlled by capillary flowmeters with bleeders.

Jan 1, 1970

By CHARLES W. BENTON

THE following paragraphs comprise such information as the Secretary has been able to obtain concerning the members and associates whose deaths have been reported. Further particulars or corrections of errors, and biographical data concerning deceased members or associates not already noticed in this way, are solicited. Charles IV. Benton was born at Kezar Falls, Maine, Nov. 12, 1843. We have no accurate knowledge concerning the early part of his career. In 1871 he engaged with the N. Y. Honduras Rosario Mining Co., at San Juancinto, Honduras, C. A., and later was employed at the Monserrat mine at Yuscaran, and at Santa Lucia, Honduras, with the Tenero Mining Milling Co. of Pennsylvania. In 1897 he became a member of the Institute. At the time he was stricken with his last sickness he was employed at the Paymaster mine at Tucson, Ariz. He died at Fairmount, Denver, Colo., Sept. 9, 1907. William R. Boggs, Jr.-The notice in the Bulletin for January was incorrect in saying that the murder of Mr. Boggs occurred while he was employed as metallurgical. manager by Mr. W. B. A. Dingwall, at La Maroma, San Luis Potosi, Mex. Mr. Dingwall writes that in March, 1907, Mr. Boggs left him, to return to his home at Winston, N. C., whence he. subsequently went to Durango, Mex., to take, with the Topia Mining Co., a position which he occupied at the tine of his death, Nov. 17, 1907. Mr. Dingwall says that, while in his service, Mr. Boggs never had any trouble with the workmen, but was esteemed and liked by them, as by all who knew him ; and adds, injustice to the State of San Luis Potosi, that the population, even in the mining-camps of that State, is orderly and law-abiding, and that the authorities are vigilant and just. Our

Mar 1, 1908

By T. D. Teimann, R. L. Stone

The rate of extraction of silica from certain Wisconsin and Minnesota taconites was investigated by autoclave digestion in sodium hydroxide solutions over the temperature range from 296° to 416°F. Rates obtained were from 7 to 254 g mol per cm2 per sec giving activation energies from 15,000 to 19.000 cal per mol. Activation energy was found to increase with increase of sodium hydroxide concentration. Digestion of different forms of quartz indicated the rate of extraction to be solely a function of surface area under similar conditions of digestion. The results of an experimental investigation on the caustic extraction of silica from certain Wisconsin and Minnesota taconites were presented in a recent publication.' It was shown that residual concentrates containing as much as 65% iron can be produced by this method. The occurrence of silica as a micro-crystalline variety of quartz with high specific surface area gave correspondingly high mean rates of extraction in solutions of sodium hydroxide. The present paper extends this previous work by presenting the results of a study of the specific rates of extraction of silica from these ores as related to temperature, sodium hydroxide concentration and variety of quartz. Calculated activation energies for the dissolution of silica are presented and some possible mechanisms are discussed. TACONITES The low-grade siliceous iron ores investigated included taconite from the Wisconsin Gogebic range and a semi-taconite2 from the Minnesota Mesabi range. These are adequately described in the former paper1 and by the U. S. Bureau of Mines. The principal iron minerals are hematite (Fe2O3) and goethite (Fe2O3 . H2O), while the gangue is essentially a microcrystalline variety of quartz. Minor amounts of other minerals are present. Typical analyses show the Wisconsin taconite to contain approximately 28% Fe and 54% SiO2 and the Minnesota semi-taconite 39% Fe and 39% SiO2. Analyses of the actual samples used are given in Table I. The taconite samples were prepared for digestion by reducing the original ore to minus 200 mesh in a Braun pulverizer. QUARTZ Three varieties of quartz were studied in the investigation: Ottawa sand, chert and chalcedony. The Ottawa sand was obtained from the Ottawa Silica Co. The chert and chalcedony came from Wards Natural Science Establishment. A minus 200 plus 400 mesh fraction of the Ottawa sand, used as a surface area standard, was repeatedly washed in hot concentrated hydrochloric acid followed by distilled water before autoclaving. The other two varieties were used directly after grinding through 200 mesh in a laboratory hammer mill. Analyses of these samples appear in Table 11. Microscopic examination of the silica samples by the oil immersion method showed that the Ottawa sand consisted of clean, uniform spheres of quartz with little deviation in size from a mean diameter of 82µ determined by a distribution count. The other two varieties consisted almost entirely of microcrystalline aggregates of quartz crystals; the aggregates ranged from 10 to 70µ. The individual crystals in the chert aggregates were estimated to be of the order of

Jan 1, 1964

The Bougainville ore body was discovered in 1964 by a partnership of Conzinc Rio Tinto of Australia and New Broken Hill Consolidated Limited. The ore body is a porphyry copper in a fine-grained quartz diorite, which intrudes andesite volcanics and is located at an elevation of about 2, 000 ft in the Crown Prince Range of Bougainville in the Solomon Islands. Mineralization is predominantly chalcopyrite with some bornite and some gold and silver present. Rainfall in the area amounts to 200 in. (5. 08 m) per year. An active volcano is situated only 24 miles (38.4 km) from the mine, and all structures were designed to resist seismic shocks. An interesting and unique feature of the Bougainville operation was that the overburden was stripped with hydraulic monitors. Bougainville Copper, at 90,000 tpd, is the largest copper concentrator to be designed and constructed at one time; and besides the twin 54 in. by 74 in. Allis-Chalmers gyratories, it features seven 7 ft (2. 13 m) standard and fourteen 7 ft shorthead crushers, in addition to nine 18 ft diameter by 21 ft long (5. 5 m by 6. 4 m), 4250 hp, single -stage ball mills. During the design stage of the Bougainville primary crushing plant, several alternates were studied because the ore was expected to break with the production of large amounts of small-sized particles but with a minimum of fines. These alternates included two 54 in. by 74 in. gyratories with grizzlies, two 60 in. by 89 in. gyratories, and one 72 in. by 96 in. gyratory, the latter two installations without grizzlies. The two 54 in. units with grizzlies were finally selected as giving good reliability and the ability to handle the large amounts of small material in the feed. As originally installed, grizzly bars were set at 8 in. (203 mm); but, in an effort to perform more interparticle crushing in the primary and less rock-on-steel crushing in the secondaries and tertiaries, a test is underway (1976) to determine the effect of using 6 in. (152 mm) grizzly spacings (see write -up on Anaconda's crusher at Butte). The Bougainville ore is mined with 17 cu yd (13 cu m) shovels and hauled in 105, 170, and 210 st trucks to the crushers, which are equipped for two-side dumping. Up to 40% of the ore passes the grizzlies, which are equipped with splitters; and additional horizontal splitter bars are located directly above the spider caps. Because of the grizzlies, the crushers are supported by unique U-shaped enclosures, which are in turn supported by the end and center walls of the installation.

Jan 1, 1978

By J. T. Norton, N. J. Grant, I. S., Servi

Coarse grained high purity aluminum was tested in creep at temperatures of 400° to 1200°F to develop subgrain structures. Measurements of subgrain size, distribution, and rotation were made from X-ray diffraction patterns. Subgrain size and distribution were checked metallographically and the size was compared with average slip band spacing. The slip family was determined for several specimens. THE interest and research recently evident abroad in the role of subgrain formation and polygon-ization as a contribution to the creep of metals at elevated temperatures is deserving of greater attention in this country. Such metallic subgrains can be defined as macroblocks existing within the grains. The general observation has been that the macro-blocks which belong to the same grain have a maximum difference in orientation of a few degrees. In spite of the considerable amount of work that has been done since Jenkins and Mellorl observed the "division of existing crystals into smaller units when deformation occurs at an annealing temperature," the subject of subgrain formation is only now receiving truly active discussion and investigation. The existence of subgrains has been revealed by metallographic methods, as in the work of Jenkins and Mellor,1 and by X-ray methods, first applied to this problem by Homes.' Hirst3 and Calnan and Burns4 applied the back-reflection Laue technique to the study of coarse grained specimens. Wood et al.5 and Greenough and Smith' examined the ring obtained with a back-reflection camera for the study of fine grained specimens. In addition to the above, the transmission technique was used by Wood.6 A special technique was developed by Guinier and Tennevin8 in order to improve the resolution. Metallographically, the subgrains have been observed directly on the surface of deformed specimens by Wood et al.,3 or have been made evident on repolished surfaces by applying a suitable etching reagent. The latter technique, first suggested by Lacombe and Beaujard,9 was then improved by Wyon and Crussard.10 Subgrains can be formed in single crystals after small amounts of bending followed by heating after this cold work, or during deformation at elevated temperatures. The first phenomenon was analyzed by Cahn11 for the simple case of pure bending followed by annealing. Cahn suggested a mechanism of subgrain formation based on the dislocation theory and called this phenomenon "polygonization." He extended this mechanism to the more complex case of local bending, such as the bending which may occur when a polycrystalline specimen is deformed in tension. Cahn's suggestion was later found quite consistent with the results obtained by Dunn and Daniels." An explanation has been presented recently regarding the formation of subgrains during deformation at elevated temperatures by Chang and Grant.'" In general, there are two schools of thought on the subject. One, according to Wood et al.,5 is that subgrain formation is a mechanism of deformation which is operative under certain conditions in the same way that the slip process is the mechanism of deformation which is operative under other conditions. The boundaries between the subgrains undergo a viscous flow which contributes substantially to the deformation of the material. The second, according to Cahn,13 Wyon and Crussard,10 and Chang and Grant,18 is that subgrain formation is the effect of simultaneous deformation and annealing and is,

Jan 1, 1953

By F. H. Wilson, E. W. Palmer

The solid solubility of iron in 2 to 10 pct cupro-nickels increases with temperature and nickel content. Property changes accompanying various heat treatments indicate typical precipitation hardening behavior. Iron content also affects softening temperature and sub-scale formation. These factors, as well as impingement corrosion resistance, influence the optimum iron content of commercial alloys. FOR many years Cu-Ni alloys have been used extensively in the form of tubes, pipes, and plates for the construction of salt-water lines and surface condensers on shipboard and in tidewater power stations. The 30 pct Ni alloy has been considered more resistant to rapidly flowing sea water than alloys of lower nickel content, and has been standard on ships of the U. S. Navy. Some ten years ago, the still better corrosion resistance obtained by modifying the 30 pct Ni alloy with approximately 0.5 pct Fe was recognized, and the iron-bearing alloy rapidly superseded the plain alloy as the standard material for severe service. In 1945, Tracy and Hungerford1 published a study of the effect of iron on the corrosion of various cupro-nickels in sea-salt solutions, and their data indicated that the 10 pct Ni alloy containing about 0.75 pct Fe was equivalent to the 30 pct Ni alloy containing 0.5 pct Fe. This was confirmed by LaQue in discussion of the above paper, and by results in an experimental condenser set up at the Kure Beach marine test station of The International Nickel Co., reported by Freeman and Tracy.' The 10 pct Ni iron-bearing alloy is now being very widely used in applications where the 30 pct Ni iron-bearing alloy was formerly considered standard. While this "substitution" has undoubtedly been stimulated by the present extreme shortage of nickel, it must be emphasized that it involves no loss of service performance, and would have occurred anyway in the course of time, for economic reasons. In view of the increasing use of the 10 pct alloy, it seems desirable to make generally available the results of several investigations of Cu-Ni-Fe alloys carried out in the Metallurgical Research Laboratory of The American Brass Co. in recent years. The present paper, deals with the constitution of these alloys in the copper-rich corner of the system, and with the variations in hardness and tensile properties resulting from the heat treatment of alloys containing various amounts of iron. Most of this work is concerned with alloys containing 10 pct Ni. With over about 0.75 pct fe, the 10 pct Ni alloy is suscep- Alloys Several series of cupro-nickel alloys containing iron were used in these investigations. Most of them were prepared in the laboratory, but two samples of commercially fabricated alloys were included. Series A—Nominally 2 and 5 pct Ni, each with 0 to 1.5 pct Fe. Series B—Nominally 10 pct Ni with 0.1 to 0.4 pct Fe. Series C—Nominally 1.0 pct Ni with 0 to 2 pct Fe. Series D—Nominally 10 pct Ni with 3 to 5 pct Fe. Series E—Nominally 10 pct Ni with 1 and 1.5 pct Fe.

Jan 1, 1953

By D. E. Thomas

Oxidation rate constants were determined for Cu-Pd and Cu-Pt alloys as a function of alloy composition and temperature. Reaction products were identified. Relationship between oxidation rate constants and diffusion constants in the reaction zones is discussed. THE mechanism of oxidation of alloys is consider--'¦ ably more complex and not so well understood as that of pure metals. The oxidation of a one-phase binary alloy of which one component is a noble metal should logically be the simplest case of alloy oxidation, for in this case one is concerned presumably only with the oxidation of the base metal and the diffusion process by which it reaches the reaction site. This had led a number of investigators to study such systems. Probably the earliest work was that of Tammann and Rienacker' on the tarnishing of Cu-Au alloys at temperatures up to 300°C. These alloys oxidize according to the logarithmic law, that is, the film thickness is proportional to the logarithm of the time. The rate of film formation was found to decrease with increasing gold content. Raub and Engel² investigated the oxidation of Au-Cu, Cu-Pd, Au-Ag-Cu, Au-Pd-Cu, and Ag-Pd-Cu alloys at 750°C in air. These alloy systems form a continuous series of solid solutions at the temperature of oxidation with the exception of those containing silver. Au-Cu alloys oxidize parabolically, the rate constant decreasing slowly with increasing gold content up to about 15 atomic pct* Au, and more rapidly thereafter. An alloy with 14 pct Cu forms only a very thin layer of CuO on the surface and probably also a subscale.† Alloys containing more than 14 pct Cu have scales consisting of CuO and subscales of Cu,O embedded in nearly pure gold. The Cu-Pd alloys obey the parabolic law except for slight deviations for alloys containing 53 and 84 pct Cu. The overall oxidation rate decreases rather smoothly with increasing palladium content. A scale consisting of a thin layer of CuO and a thick layer of Cu²O and a subscale of Cu²O embedded in nearly pure palladium was observed for alloys containing 84, 53, and 30 pct Cu. An alloy with 19 pct Cu formed only a subscale of CuO embedded in nearly pure palladium, and an 8 pct Cu alloy formed only a thin film which was presumed to be PdO. The ternary alloys considered by Raub and Engel oxidized in much the same way as did the binaries. Wagner and Grunewald³ found that Ni-Au alloys, oxidized at 900°C in oxygen, formed a scale of NiO and a subscale containing NiO and gold. The overall oxidation rate increases with increasing gold content, passes through a maximum and then decreases to zero for pure gold. The fact that gold increases the oxidation rate was attributed to "pores" in the scale. Kubaschewski' investigated the air oxidation of alloys of platinum or gold with up to 10 pct Cu or Ni at temperatures in the range 300" to 1550°C. Parabolic behavior was noted for all alloys except Au-Ni, with rates decreasing in the order Au-Cu, Au-Ni, Pt-Ni, Pt-Cu. The diffusion coefficients for the latter three systems are known, and they decrease in the same order. However, activation energies for the oxidation of these alloys do not agree with the activation energies for diffusion in the respective alloy systems. Kubaschewski and Goldbeck7 nvestigated the oxidation of Ni-Pt alloys in air at temperatures of 600"

Jan 1, 1952

By F. M. d’Heurle

Films of molybdenum have been prepared by sputtering onto oxidized silicon substrates. The resistivity. lattice parameter, orientation, and grain size were studied as a function of substrate temperature and substrate bias. Under normal sputtering conditions, the resistivity of the films was found to be quite high (600 x 10 ohm-crn). However, with the use of the negative substrate bias of 100 v and a substrate temperature of 350°C, films weve produced with a resistivity of ahout twice that of bulk molybdenum. The lattice parameters measured in a direction nornzal to the surface of the films weve found to be gveatev than the bulk value. This was interpreted as being at least partly due to the presence of compressive stresses. The effects of annealing in an Ar-H atmosphere were studied in terms of diffraction line width, lattice parameter, and resistivity. BECAUSE of its relatively low bulk resistivity (5.6 x 106 ohm-cm)' molybdenum is potentially interesting as a thin-film conductor in integrated circuits. An additional feature which makes it attractive for this purpose is its low coefficient of expansion (5.6 x KT6 per "c),' which is fairly well matched to that of silicon (3.2 x 10 per c). It is possible to deposit molybdenum films by evaporation but generally films produced in this manner have a high resistivity. In order to achieve resistivities close to bulk value, Holmwood and Glang found it necessary to operate in a vacuum of about 107 Torr and to maintain the substrates at 600 C during film deposition. Sputtered molybdenum films have been examined by Belser et a1.7 and, recently, by Glang et al.' This paper describes the results of an attempt to extend some of that work and examine the effects of annealing and getter sputtering on the physical and structural properties of the films produced. SPUTTERING APPARATUS AND PROCEDURE The apparatus used for most of the film sputtering work described here consisted of two "fingers" serving as anode and cathode, respectively, which were mounted within an 18-in.-diam glass chamber. A liquid nitrogen-trapped 6-in. diffusion-pump system was used to achieve a vacuum of about 1 x 107 Torr within the chamber prior to sputtering. The essential features of the equipment are shown in Fig. 1. Cathode and anode fingers are stainless-steel tubes isolated from the top and bottom plates by Teflon collars. In order to limit the discharge to the space between anode and cathode, each finger is surrounded by an aluminum hield, at ground potential, having an internal diameter 18 in. larger than the outside diameter of the finger. The cathode and anode fingers are 6 and 4 in. in diam, respectively. A 116-in.-thick sheet of molybdenum is brazed with a 10 pct Pd, 58 pct Ag, 32 pct Cu alloy to a copper disc which is mounted by means of screws and a large 0 ring onto the lower end of the cathode finger. The disc is cooled during sputtering by water circulation inside the finger. The use of several feet of plastic tubing for the water input and outputg reduces leakage to ground to less than 1 ma when the cathode potential is raised to 5 kv. The upper end of the anode finger is terminated by a brazed-on copper block. A variety of specimen holders can be easily mounted on the upper face of this block. Substrate heating or cooling is achieved by use of an appropriate unit attached to the lower face of the same block. Heating is achieved by means of cartridge-type heaters and cooling by copper coils fed with forming gas under pressure. The inner chamber of the specimen finger constitutes a small vacuum chamber of its own which is evacuated by an auxiliary mechanical pump in order to limit heating element oxidation and heat transfer by convection currents. An advantage of the finger arrangement is the absence of cooling and heating coils and wires within the main chamber. The stain less-steel shutter is useful to establish a discharge for cleaning the cathode at the beginning of each sputtering run. Water cooling of the shutter reduces heating and the out-gassing of impurities which might condense on the nearby substrates. Unless otherwise specified, the substrates used in these experiments were 1-in.-diam oxidized silicon wafe:s, 0.007 in. thick, having an oxide thickness of 6000A. The substrate holders were large copper discs onto the surface of which a number of molybdenum discs, 116 in. thick and 78 in. in diam, were brazed. The wafers were clamped to the molybdenum discs

Jan 1, 1967