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GENERAL COMMITTEE GERALD F. G. SHERMAN, Chairman. ARTHUR NOTMAN, Secretary. NORMAN CARMICHAEL, JOHN C. GREENWAY, W. L. CLARK, W. G. McBRIDE, B. BRITTON GOTTSBERGER, FOREST RUTHERFORD. General Committee on Transportation WALTER DOUGLAS, Chairman. CLEVELAND E. DODGE, Secretary. ARTHUR S. DWIGHT, JOHN C. GREENWAY, JULIUS KRUTTSCHNITT, JR. Committee at El Paso W. D. GORDON, ROBERT McCART, JR., W. W. ROSE. Committee at Santa Rita JOHN M. SULLY, Chairman.

Jan 12, 1916

As described in the section on the Palabora twin crushers, the Palabora ore consists of two types: a carbonatite containing a low titanium magnetite, and a foskorite containing high titanium magnetite. As the Palabora pit was widened and deepened, more and more of the foskorite had to be mined. The 25,000 mt expansion of the Palabora plant which went into operation in early 1977 therefore takes its feed from the foskorite section of the orebody. For the expansion, a third 54 in. by 74 in. gyratory crusher was installed to crush feed for two 32 ft by 15 ft (9.75 by 4.6 m), 9000 hp (6710 kw) autogenous single -stage grinding mills. These units are located near the two existing primary crushers, and the ground ore is pumped 5277 ft (1640 m) to the expanded flotation plant by five stages of centrifugal pumps. The new gyratory is installed in a unique Figure-8 shaped enclosure with the crusher in the smaller 27 ft 11 in. (8. 5 m) diameter cylinder and the maintenance area in the 36 ft 1 in. (11 m) diameter cylinder. Cylinder walls are only 23.6 in. (600 mm) thick because their circular design permits all the concrete to be in compression. A rectangular dump pocket which sits on the smaller cylinder contains two manganese steel faced splitters to protect the crusher spider and countersunk water spray headers under the dumping positions for dust suppression. The dump pocket holds 330 st or 300 mt and is also lined with manganese steel. The crusher is mounted on a reinforced concrete diaphragm over the 363 st (400 mt) crushed ore pocket. In the back of the pocket is plastic pipe. Radioactive level control sources are lowered into this pipe from the crusher support floor. The pipe is protected by concrete covered with steel castings. Level control detectors are mounted on the front wall of the pocket. Liner plates on the crushed ore pocket walls are removed and in- stalled by the use of a circular monorail and trolley mounted on the pocket ceiling. The door in the front of the crushed ore pocket is hinged at the top rather than at the sides and is raised by an electric winch. For removal of the eccentric, rails are installed in the pocket and a unique hydraulically operated cart is moved under the eccentric. A platform is raised to receive the eccentric and lowered so that it may be removed. Crushed ore is removed from the pocket by a hydraulically powered, 8 ft

Jan 1, 1978

By Floyd C. Kelley

The literature of the last decade is rich with information relating to the cause and means of control of grain growth in pure metals, but is deficient concerning the role diffusion plays in grain growth, although during this period many new products that depend on diffusion for their properties and success have been developed. Among these are cementation products, produced by calorizing, chromizing, and carbonizing, or by mixing, pressing, and sintering powdered metals such as Syke's iron-molybdenum die material, Genelite, and Elcon Metal (copper, tungsten) etc. This is a fertile field for new developments, but before it can be utilized to the fullest extent there must be a thorough invest,igation of the processes by which diffusion and grain growth take place. Grain growth plays no small part in the process and certainly the physical properties of these products depend largely on the grain size and state of equilibtiuni produced. The field of investigation does not end here, but may be extended to the effect of diffusion on impurities, segregations and dendrites in the broad field of ferrous and non-ferrous metallurgy. A number of years ago the author investigated several of these cases and noted, with striking regularity, the pronounced effect of diffusion in promoting recrystallization and grain growth. An example of this phenomenon is given in his paper on chromizingl which contained photomicrographs of large radial or columnar crystals produced by diffusion of chromium in the solid state. Another manifestation of this effect was discussed by Austen,2 who showed the part hydrogen plays in the decarburization of steel and the effect of diffusion upon the grain structure. Diffusion of Metals in Iron It seems to be a general law, whenever two metals are brought into intimate contact at a temperature at which diffusion takes place, that a comparatively rapid, or abnormal, grain growth results. The grains

By Charles N. Becker

The practice of drying phosphate in Florida is as old as the industry, which began a little more than half a century ago. The methods, however, have changed considerably. At first, the natural process of exposure to the sun and air was used, later supplemented by wood fires beneath open-air stationary dry kilns and drying towers of various designs. It was not until the early nineties that rotary driers came into use, and at first they were of very small design and fired with wood. As the industry grew and tonnage increased, so likewise grew the number and size of rotary driers, until today the largest installations are 6 ft. up to 7 ft. 6 in. in diameter, and 55 to 60 ft. long, fired with crude oil. The reasons for drying phosphate rock are: (1) to eliminate freight on water in the shipment and (2) to facilitate the good grinding qualities required by the buyers in their acidulation. Phosphate pebbles vary materially in natural characteristics and each property has a direct bearing on the processing. In making comparisons of cost and operating conditions, the following are usually taken into consideration: 1. The hard dense pebbles, which contain very little interior moisture and 6 to 8 per cent total moisture, usually produced from the low-grade deposits. 2. The lighter, porous pebbles, which contain 4 to 5 per cent interior moisture and a total moisture ranging from 9 to 15 per cent. 3. The product of recovery operations using oily reagents, containing from 15 to 25 per cent moisture. 4. The size of the pebbles Usually the plus 5-mesh material is considered as "coarse rock"; the minus 5-mesh plus 24-mesh is "fine rock," and the minute particles below 24 mesh are called "concentrate." 5. The amount of moisture allowed in the dried product. The practice is generally to dry down to 1.5 to 2 per cent moisture. There is, however, an actual range in guarantee of from 1 per cent maximum to 3 per cent maximum.

Jan 1, 1938

By Charles N. Becker

The practice of drying phosphate in Florida is as old as the industry, which began a little more than half a century ago. The methods, however, have changed considerably. At first, the natural process of exposure to the sun and air was used, later supplemented by wood fires beneath open-air stationary dry kilns and drying towers of various designs. It was not until the early nineties that rotary driers came into use, and at first they were of very small design and fired with wood. As the industry grew and tonnage increased, so likewise grew the number and size of rotary driers, until today the largest installations are 6 ft. up to 7 ft. 6 in. in diameter, and 55 to 60 ft. long, fired with crude oil. The reasons for drying phosphate rock are: (1) to eliminate freight on water in the shipment and (2) to facilitate the good grinding qualities required by the buyers in their acidulation. Phosphate pebbles vary materially in natural characteristics and each property has a direct bearing on the processing. In making comparisons of cost and operating conditions, the following are usually taken into consideration: 1. The hard dense pebbles, which contain very little interior moisture and 6 to 8 per cent total moisture, usually produced from the low-grade deposits. 2. The lighter, porous pebbles, which contain 4 to 5 per cent interior moisture and a total moisture ranging from 9 to 15 per cent. 3. The product of recovery operations using oily reagents, containing from 15 to 25 per cent moisture. 4. The size of the pebbles Usually the plus 5-mesh material is considered as "coarse rock"; the minus 5-mesh plus 24-mesh is "fine rock," and the minute particles below 24 mesh are called "concentrate." 5. The amount of moisture allowed in the dried product. The practice is generally to dry down to 1.5 to 2 per cent moisture. There is, however, an actual range in guarantee of from 1 per cent maximum to 3 per cent maximum.

Jan 1, 1938

By Don C. Blackmar

The production of non-ferrous secondary metals has become a large and important industry in the United States, and deals with practically cvery type of manufacturing concern. Its business is unique in that it generally buys frorn its customers as well as sells to them, whether they are individuals, cities, corporations, or the United States government. Its operations are of vital importance to the success and prosperity of nlany of the nation's most important manufacturers; yet there are few industries about which less is generally known by those outside it, whether concerning the rliagnitude of its operations or the details of its actual technique. The industry itself is to blame for this meager publicity, because its technical men have made few attempts to openly exchange ideas, in spite of the excellent examples set by the iron and steel or the copper and brass industries. Whether this is due to the ancient shroud of secrecy generally supposed to cover smelting operations, or because its technical men actually felt that the industry was too puny to be interesting, is hard to say. This paper will consider its subject in a general way, attenlpting to show something of the size and importance of the industry, as well as its fitness to do its work well. Attention will be called to the sound economic reasons for the handling of non-ferrous wastes by specialists, and to the often unseen losses of metals and labor which occur when manufacturc~rs rcclairn thrir own metallic wastes. Magnitude of the Modern Industry No particular thought is given to the kitchen accident whereby a ruined saucepan is sorrowfully tossed into the ash can, yet it is a fairly safe guess that within a month this saucepan, together with hundreds of its follows, will again be in service, perhaps in an autonlobile crankcase, or in an electric vacuum sweeper. It is by this conversion of the useless into the useful, whether from home or large manufacturer, that the secondary tonnage is built up.

By Stephen Taber

Introduction.............................. 62 Asbestiform Minerals.......................... 63 Chemical and Mineralogical Relations............... 63 Physical Properties........................ 64 Types of Asbestos............................ 65 Origin of the Fibrous Structure...................... 66 Views of Previous Investigators.................... 66 Discussion of the Evidence.................... 67 Conclusions........................... 69 Origin of Cross-fiber Veins....................... 71 Chrysotile Veins......................... 72 Structural Features of Cross-fiber Veins............... 78 Veins of Crocidolite and Other Fibrous Amphiboles........... 83 Origin of Slip-fiber........................... 84 Origin of Mass-fiber........................... 86 Discussion............................... 87 IntRoduCtion The term asbestos, as commonly used, includes half a dozen minerals all having a well-developed fibrous structure, but differing in chemical composition and in some of their physical properties. In its strict application the name is limited to the fibrous varieties of the monoclinic amphiboles. Commercially, however, the most important of the asbestiform minerals is chrysotile, a fibrous variety of serpentine. About 95 per cent. of the asbestos used in manufacturing is chrysotile, and it commands a much higher price than any of the other fibrous minerals now on the market. Although the production of asbestos has increased rapidly in recent years, comparatively little has been published concerning its origin. The present paper is preliminary in its nature, and therefore does not pretend to exhaust the subject. The ideas herein developed are the result of field investigation, laboratory experiments in the growth of fibrous

Jan 1, 1918

By AIME AIME

THOUGH the Annual Meeting of the Institute-officially numbered 158 on the records was delayed a bit at the start by low steam pressure on the locomotives bringing members to New York, the crowd that finally arrived more than lived up to expectations, and the technical program had few difficulties because of absent authors or lack of competent discussers. The transportation difficulties were occasioned by the fact that Monday, Feb. 15, was the third coldest day in the 72 year history of the New York Weather Bureau, the official temperature being 8 below zero. The New York Central's premier train, the 20th Century, due at 9:30 a.m., arrived about 6:30 p.m., and the Commodore, another crack train from Chicago, was about equally late.

Jan 1, 1943

By R. Laird Auchmuty

A NUMBER of factors, of varying importance, should be considered in assessing mineral land-here specifically coal land -for tax purposes. (1) Is the coal developed or un- developed'! (2) If undeveloped, is it surrounded by active development in adjoining properties? (3) Accessibility of railroad facilities to the property. Sometimes the railroad itself is of importance. (4) Cost of development of the seam under consideration, whether it can be developed by a drift from the outcrop or whether it will require deep and costly shafts or slopes. (5) Is it definitely known that the coal seam being assessed is of minable thickness and quality on the property? (6) Thickness of recoverable coal from the seam. (7) Quality of the coal. (8) Is the seam being assessed likely to be more costly to mine than other seams in the same district? (9) Is there an active market demand for coal from the seam being assessed? (10) Is the coal held only as protection to surface structures and in such location that it can never be mined? (11) Is the coal in a solid piece or is it in pillars that have been standing for some years as a result of incomplete mining in an old operation? (12) Expected percentage of recovery from the seam being assessed as determined by present mining practice in similar properties. (13) Value of the seam as indicated by sales of similar mineral rights in the immediate district. (14) Current royalty rates of leases for coal in the seam under consideration.

Jan 1, 1939

By S. WHINERP

(Cleveland Meeting, October, 1912.) I AM indebted to L. E. Bryant, of Danville, Ky., President of the Virginia Mining Co., operating coal-mines in Scott county, Tenn., for the following information relating to the existence of the Clinton iron-ore under the NW. slope of the Cumberland Plateau in Kentucky and Tennessee. During the past 15 years quite an important oil-field has been developed in a region having Wayne county, Ky., as its center, and a large number of wells have been drilled in that and adjacent territory in the search for oil. Many of' these wells have been carried to considerable depths below the recognized oil-bearing horizon, and one of them was drilled by Mr. Bryant at Pine Knot, a station on the Cincinnati, New Orleans & Texas Pacific railroad, a few miles north of the point where that road crosses the Kentucky-Tennessee State-line. The elevation of the surface at the crossing is about 1,400 ft. above sea-level. The railroad is located on the dividing ridge between the Cumberland river and Big South Fork. At a depth of 1,720 ft. below the surface the drill reached and passed through a formation which the drillers called " red rock," but which Mr. Bryant classified as Clinton iron-ore, as its geological position corresponded to that formation. The ore at this point was 6 ft. thick and appeared to be of uniform quality throughout. An analysis of the drillings gave : Fe, 33; Mn, 0.25; Si02? 3 ; Al203, 2 ; CaO, 13; MgO, 7 ; P,05, 0.333 per cent. ; S, trace. This analysis seems to confirm the belief that the ore is Clinton, and that it is of a quality equal to the average of the deep or unbleached Clinton ores in Tennessee and Alabama. This discovery led Mr. Bryant to make further examinations and inquiries, and he found that the stratum called " red rock " by the drillers had been passed through and noted in the great majority of the wells carried down to the same geological hori-

Oct 1, 1912

By Harry E. Cross

Kiln Products commissioned a Waelz kiln 4 metres in diameter by 75 metres long, in South West Africa in March, 1969, to recover nine in a form suitable for the production of electrolytic zinc. The raw material consists of a mixture of zinc silicate concentrates and zinc rich tailings purchased from an adjacent zinc mine - the mixture containing 20% to 25% zinc. The chemical composition of the ore is tabulated and the initial test results are described. Due to the comparatively low temperature at which the ore starts softening the kiln has certain unusual features to enable the temperature to be controlled within the necessary limits. A detailed description of the kiln, the starting-up problems and present operating conditions and results are presented.

Jan 1, 1970

By Royal Preston Jarvis

The jig, in one form or another, continues to hold a leading place among the machines designed to separate two or more

Jan 1, 1909

By James W. Halley

' FINE-GRAINED " steels have been standard products for many years. This paper describes an investigation of the effects of some of the more common grain-growth; inhibitors used to produce these steels. The properties, response to heat-treatment, and the deoxidation practice necessary to produce "fine-grained" steels have been the subjects of numerous papers. It has been shown that a substantial quantity of' aluminum is necessary to produce this type of steel, and it has been indicated that titanium and zirconium produce a similar result. For some time there was a lively argument between those who felt that aluminum refined the grain and those who felt that aluminum oxide was the effective agent. This argument subsided with an apparent victory for those promoting aluminum oxide. Most of the work on grain size has divided steels into two broad classifications based upon McQuaid and Ehn's original carburizing test at 1700°F. or some similar test at this temperature. If the steel coarsened at this temperature, it was coarse grained, while if it did not it was fine grained. Quantitative data concerning how much a certain amount of aluminum raised the coarsening temperature and affected the properties, all other factors being constant, are very meager. Similar information regarding titanium and zirconium is practically nonexistent. The published information on aluminum yields some quantitative information. Epstein, Nead and Washburn' gave the first quantitative information on the amount of aluminum necessary to prevent grain growth at 1700°F. They showed that the addition of a pound to a pound and a half of aluminum per ton (0.05 to 0.075 per cent) would assure steel that would not .coarsen during a McQuaid-Ehn test at 1700°F. Herty, McBride and Hough2 reported that a steel containing 0.020 per cent acid-soluble aluminum coarsened between 1742° and 1832°F., while steels containing 0.016 per cent and 0.017 per cent acid-soluble aluminum coarsened between 1652~ and 1742°F. compared with similar aluminum-free steels that started to coarsen at 1580°F. Herty3 also showed a marked improvement in low-temperature notched impact resistance with increasing acid-soluble aluminum up to 0.030 per cent. McQuaid4 compared the coarsening of steels containing 0.011 to 0.204 per cent total aluminum and found a maximum coarsening temperature at 0.098 per cent aluminum. He had no samples between 0.015 and 0.098 per cent aluminum. Houdrement5 found a marked decrease in coarsening temperature with aluminum contents above 0.50 per cent. Kinzel, Crafts and Egan6 found that aluminum and zirconium improved thy low-temperature impact resistance of a low-alloy steel, while titanium was detrimental. Sims7 shows that sulphur increases the coarsening temperature and that the maximum coarsening temperature is between 0.04and 0.06 Per cent added aluminum. The

Jan 1, 1946

By Maurice Ewing

THE purpose of this paper is to present the results of the application of the earth-resistivity method of subsurface investigation to the problem of locating seams of anthracite coal beneath a mantle of soil and subsoil. Details are given of the successful use of this method in locating the outcrops of anthracite seams in actual prospecting. The presence of the outcrop of an anthracite seam is indicated at points where electrical resistivity tests showed relatively low readings. The reason for, this is that in some localities the resistivity of anthracite was found to be about 0.0001 megohm-cm. compared to 1 to 200 megohm-cm. for shales and sandstones. For two reasons it is believed that the data sum-marized in this paper should be of particular interest. In the first place, most of the interpretations of the resistivity survey have been checked by subsequent drilling and some by the removal of the overburden and the exposing of the anthracite seams. It is infrequent that the oppor-tunity for checking results so thoroughly is given. In the second place, the fact that recent commentators 1.2.1 on the application of geophysical methods to mining have concluded that direct prospecting for anthracite and other types of coal is not promising makes the good results obtained more significant. So far as the authors can learn, the only previous experiment with electrical methods in the Pennsylvania anthracite field was one made by Sherwin F. Kelly in 1922, when he used the self-potential method at Wilkes-Barre4. The profile he made does not show a very marked correlation with the geologic cross section. Kelly points out that stray currents from electric motors in the mines undoubtedly affected his results, but the experience of the present authors with stray currents from mining machinery suggests the possibility that the potentials measured by Kelly were due almost entirely to this effect.

Jan 1, 1936

By E. S. Machlin, W. R. Yankee

IN a previous study1 of the effect of heating com-mercial titanium in air on its subsequent friction coefficient against other metals, as well as itself, it was found that the friction coefficient markedly decreased from a value of about 0.7 to about 0.3. A tentative explanation was given that surfaces normally produced at room temperature are not contaminated sufficiently to prevent seizing or welding of the titanium to the softer mating metals. The latter tend to cleanse themselves during rubbing over the harder titanium. It was thought that the lack of a contaminant protective film on the titanium was due to the high solubility of titanium for oxygen and nitrogen and hence an inability to form a contaminant oxide or nitride. This explanation requires the ratio of the surface absorption rate to the diffusion rate to become much lower at room temperature than it is at high temperatures. In order to check the phenomenon further, commercial titanium specimens were nitrided or oxidized at 800°C for 20 hr in flows of prepurified N2 and 01, respectively, at about 1/2 in. H2O above atmospheric pressure. Friction runs were made in argon using a freshly cut copper hemisphere (cut in argon) on surfaces cut successively into the diffusion layers in the titanium (cut in argon) using the techniques described in a previous publication.' DPH values (100 gram load) were made as a function of depth into the diffusion layer using a Tukon tester. Also, micrographs were taken at separate cross sections to indicate the diffusion layers. The results obtained are presented in Figs. 1 and 2, which show the "static" friction coefficient vs hardness for the nitrided and oxidized specimens, respectively. A separate measurement of the friction coefficient of clean copper vs iodide titanium also was made. From results reported in the literature' giving the oxygen and nitrogen contents as functions of the hardness, cross plots were made showing the friction coefficients as functions of the amount of interstitial solute. These plots are given in Figs. 3 and 4. From micrographs of the diffusion layers and the phase diagrams, it was deduced that the data in Figs. l through 4 correspond to the single phase a region. The points observed on the compound regions have been excluded from the figures. It is apparent that nitrogen or oxygen in solution in the a titanium markedly affects the friction coefficient against a softer mating metal. Discussion of Results These results are extremely interesting from both a practical and theoretical viewpoint. The theoretical implications will be discussed first. According to Bowden, the friction coefficient should be given to a good approximation by the relation where a is the fraction of contact area that has welded, a is the shear strength of weaker component, and H is the hardness of softer component. Using this relation alone, it is difficult to understand the results because none of the terms should be affected by a variation in the oxygen or nitrogen content of the harder and stronger metal, titanium. Even if the ratio of S/H for titanium is used in Eq. 1, the ratio has been shown to be independent of oxy-gen or nitrogen content.' If a more rigorous equa-tion is used combining Eq. 1 and a result given pre-viously" for the case where welding is absent, then the relation obtained is µ = a S/H + (1-a) a W aß/H where a is constant and Waß is the work of adhesion between the two metals comprising the friction couple. This relation states that if a is less than 1/2 or so, variation in the work of adhesion Waß between copper and the titanium should affect the friction coefficient markedly. It is reasonable to expect that the work of adhesion will depend on the oxygen or nitrogen content of the titanium. Available data4 show that clean metals and oxides have much lower works of adhesion than the same metals against the

Jan 1, 1955

By Nicholas J. Grant, Robert F. Wilde

TAYLOR and Floyd's"" work in establishing phase diagrams based on the elements Ni-Cr-Ti-A1 has led to an understanding of the precipitation hardening mechanism in alloys based on these elements. Nordheim and Grant4 concluded that in simple alloys, and where the aluminum to titanium atomic ratio was such that less than three out of five aluminum atoms were replaced by titanium, the precipitate on aging is the face-centered-cubic Ni 3A 1 phase, called They further found that increasing amounts of hexagonal ? phase, Ni3Ti, precipitated from these alloys when the titanium content exceeded the solid solubility of both matrix and Ni3A1. For alloys of Ni-Cr-Ti-Al, in which the titanium and aluminum contents each ranged from 0 to 4 wt pct, the titanium-rich was superior for strengthening to either pure ?' or 7. It was also noted that the combined titanium plus aluminum content (atomic pct) was a direct measure of the high temperature strength and overaging temperatures for these alloys.4 The present investigation was undertaken to extend existing data on precipitation hardening in the more complex commercial alloys containing higher titanium plus aluminum, and with significant quantities of cobalt, molybdenum, and carbon. Experimental Procedure Reforging of As-Received Bar Stock—The alloys were received as ground, forged bar stock. Chemical analyses and the as-received bar diameters are shown in Table I along with the ASTM grain size after the various treatments. All stock except the Waspaloy was reforged to % in. diam to gain material and to facilitate machining of stress-rupture specimens. Forging was carried out at 2100°F, and discontinued when the bar temperature fell to 1800°F. Heat Treatments—For experixental simplicity it was desirable to heat treat all of the alloys at, the

Jan 1, 1958

Organization Place - Date 1918 American Iron and Steel Institute New York, N. Y. May American Water Works Association :.. St. Paul, Minn. May 20-25 American Institute of Chemical Engineers Berlin, N. H.. June 19-22 American Concrete Institute Atlantic City, N. J. June 24-26 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 5, 1918

By James P. Sloss

WHAT is the likelihood if any-that a real gold mining industry will be developed in the southern Appalachian region? Has the increase in the dollar value of gold from $20.67 to $35 per ounce potency to turn the trick? Suppose it be assumed that the price of gold will, at worst, not recede, and that the cost of digging ore and treating it of which the average level of commodity prices and wages is a fair index-will, at most, not exceed that prevailing in 1926. One may or may not accept these as reasonable assumptions; but one must arbitrarily remove some of the potential variables if one is to get anywhere on a problem like this. As a matter of fact, this article is not going to venture a conclusive answer to the question that has been posed; but it will endeavor to present some of the factors that have a bearing on the problem. The writer spent ten days visiting a dozen properties in Virginia and the Carolinas early in April, 1935, and in doing so got a first-hand slant on mining conditions in the domain of King Cotton.

Jan 1, 1935

By Shiro Ban-ya, John Chipman

Equilibrium in the reaction was investigated at temperatures of 1500°, 1550°, and 1600°C for sulfur concentrations up to 7.2 wt pct. Multisample crucibles contained the liquid alloys in a resistance-heated furnace using a technique especially designed for the study of more complex alloys to be reported separately. Modern free-energy data are used to correct the H2S:H2 ratio for dissociation of H2S and calculalion of the partial pressure of S2. Published data on the equilibrium are similarly corrected. Thermodynanzic treatment of the data employs the composition variable zs = nS/(nFe — nS) and the activity coefficient Gs = as/zs The data at 1500" and 1550°C are fitted by the equation log s = —2.30zs. Within the limits of experimental error the same coefficient is applicable to the data at higher temperatures. Equations are given for the free-energy change in Reaction [I] as well as for the solution of S, gas in the metal. The heat of solution of 1/2 s2 is -32.28 i2.5 kcal. Uncertainty in the free energy is very much smaller. For dilute solutions of interest in steelmaking, the activity coefficient of sulfur is unchanged from that listed in Basic Open Hearth Steel-making. DETERMINATIONS of the thermodynamic properties of sulfur in liquid iron by Morris and williams1 and by Sherman, Elvander, and chipman' provided a basis for control of sulfur in steelmaking processes. From the standpoint of understanding the chemistry of metal plus nonmetal in liquid solution they left several questions unanswered. The activity of sulfur in dilute solution at about 1600°C was well-established but temperature coefficients were uncertain, due at least in part to the use of the optical pyrometer and uncertainty regarding the effect of sulfur on emissivity. It appeared that deviation from Henry's law increased with increasing temperature, a most unusual behavior requiring either confirmation or disproof. These studies were based on experimental determination of equilibrium in the reaction: At high temperatures H2S is partially dissociated so that the gas mixture contains HS, S2, and S in addition to HS. At the time of the earlier studies the free energies of these constituents were unknown and it was therefore impossible to make adequate correction for dissociation. Observations on the effects of alloying elements by Morris and coworkers1, 3 and by Sherman and Chip-man4 enable us to assess the effects of alloying elements on the activity and to make corrections for incidental impurities in the binary liquid. These studies as well as a number of more recent investigations will be reviewed in detail after out own experimental results have been presented. It was our purpose in planning this study to avoid uncertainties regarding the emissivity of alloys and the errors of thermal diffusion which plagued some of the early attempts,5 by using a resistance furnace and thermocouple in preference to induction heating and optical pyrometer. Modern data on free energies of the gaseous species are to be applied to our data and to those of other investigators to obtain corrected values of K1 and of the activity coefficient and ultimately to relate the sulfur content of the bath to the equilibrium partial pressure of S,. Extension of the study to include ternary and complex solutions will be described in a later section. EXPERIMENTAL METHOD a) Preparation and Calibration of H2-H2s Gas Mixture. The source of hydrogen sulfide was a preparer mixture of 43 pct H2S, balance hydrogen, contained in a large aluminum cylinder. This was passed through anhydrone and through a microflowmeter. Hydrogen was passed through platinized asbestos, ascar-ite, and anhydrone, and through a capillary flowmeter. Argon was passed through copper wool at 500°C, then through ascarite, anhydrone, and a flowmeter. The flow rate of hydrogen was kept constant at 200 ml per min, to which an arbitrary amount of the hydrogen-hydrogen sulfide mixture was constantly added and then the prepared gas mixture was introduced into the reaction tube through a gas mixer. In certain experiments 200 ml per min of argon was added to the hydrogen-hydrogen sulfide gas mixture to increase the total flow rate of gas. The ratio of hydrogen-hydrogen sulfide in the inlet gas was checked for each run by chemical analysis. A sample of the gas taken from a bypass was bubbled through zinc and cadmium acetate solution (4 pct zinc acetate, 1 pct cadmium acetate, and 1 pct acetic acid) to remove hydrogen sulfide from the gas mixture, and the flow rate of the remaining hydrogen was measured by a soap bubble method to determine the volume of hydrogen. The amount of hydrogen sulfide absorbed in solution was determined by titration with iodine against sodium thiosulfate, with starch used as the indicator. The ratio of hydrogen sulfide to hydrogen in the inlet gas could be kept within ±2 pct in the range from 10-2 to 5 x 10"4 which corresponds to from 0.2 to 7.0 wt pct sulfur in liquid iron. b) Furnace Arrangement. Fig. 1 shows the furnace arrangement and the shape of the alumina crucible used in this experiment. A vertical-tube silicon carbide electric resistance furnace contained the reaction tube which consisted of two parts, the gas-tight

Jan 1, 1969

By D. T. Peters, S. Floreen

The age hardening behavior of an Fe-8Ni-13Mo alloy was studied after the matrix had been varied to produce either ferrite, cold u~orked ferrite, or nzassive nzartensite. The aging behavior of the cold worked ferrite and murtensite structures were very similar. The martensite aging kinetics were much different from those observed in earlier studies of aging of maraging steels, even though the martensite wzatri.r had the same dislocation structure as those found in maraging steels. The results suggest that the previously observed precipitation kinetics of maraging steels ?nay have been controlled by the nucleation be-haviov, which in turn were dictated by the alloy compositions and the resultant identities of the precipitating phases. IT is well known that the rate of precipitation from solid solution depends not only on the degree of super-saturation, but also on the density and distribution of dislocations in the matrix structure. These imperfections often act as nucleation sites, and may also enhance atomic mobility. 'Thus, the presence of dislocations is important since the type and distribution of precipitates may be determined by them. The precipitate density and morphology in turn affects the mechanical properties of the alloy. A number of studies have been devoted to the precipitation characteristics in various types of maraging steels.'-" These are iron-base alloys containing 10 to 25 pct Ni along with other substitutional elements such as Mo, Ti, Al, and so forth, that are used to produce age hardening. The carbon contents of these steels are quite low, and carbide precipitation is not believed to play any significant role in the aging reactions. After solution annealing and cooling these alloys generally transfclrm to a bcc lath or massive martensite structure characterized by elongated martensite platelets that are separated from each other by low angle boundaries, and that contain a very high dislocation den~it~.~~~~~~~~-~~ Age hardening is then conducted at temperatures on the order of 800" to 1000°F to produce substitutional element precipitation within the massive martensite matrix. Most of the aging studies to date have revealed several common traits in these alloys, regardless of the particular identity of the precipitation elements. Generally hardening has been found to be extremely rapid, with incubation times that approach zero. The agng kinetics, at least up to the time when reversion of the martensite matrix to austenite begins to predominate, frequently follow a AX/~~ = ktn type law, where x is hardness or electrical resistivity, t is the time, and k and n are constants. The values of n are frequently on the order of 0.2 to 0.5, which are well below the idealized values of n based on diffusion controlled precipitate growth models. Finally, the observed activation energy values are typically on the order of 30 kcal per mole, and thus are well below the nominal value of about 60 kcal per mole found for substitutional element diffusion in ferrite. The common explanation of these observations is that the precipitation kinetics are controlled by the massive martensite matrix structure. Thus, the absence of any noticeable incubation time has been attributed, after ~ahn," to the fact that the precipitate nucleation on dislocations may occur without a finite activation energy barrier. The low values of the activation energy are generally assumed to be due to enhanced diffusivity in the highly faulted structure. If this explanation that the precipitation kinetics are dominated by the matrix structure is correct then one should observe a distinct difference in lunetics between aging in a martensitic matrix and aging the same alloy when it has a ferritic matrix. Such a comparison cannot be made with conventional maraging compositions, but could be made with the alloy used in the present study. In addition, the ferritic structure of the present alloy could be cold worked to produce a high dislocation density so that one could determine whether ferrite in this condition would age similarly to martensite. EXPERIMENTAL PROCEDURE The composition of the alloy used in this study was 8.1 pct Ni, 13.0 pct Mo, 0.10 pct Al, 0.13 pct Ti, 0.012 pct C, bal Fe. The alloy was prepared as a 40 lb vacuum induction melt. The heat was homogenized and hot forged at 2100°F to 2 by 2 in. bar, and then hot rolled at 1900°F to $ in. bar stock. The aging lunetics were followed by Rockwell C hardness and electrical resistivity measurements. Samples for hardness testing were prepared as small strips approximately 2 by $ by 4 in. thick. Electrical resistivity was studied on cylindrical samples approximately 2 in. long by 0.1 in. diam. The method for making the alloy either martensitic or ferritic was based on the fact that the alloy showed a closed y loop type of phase diagram. At high temperatures, above approximately 24003F, the alloy was entirely ferritic. Small samples on the order of the dimensions described above remained entirely ferritic after iced-brine quenching from this temperature. In practice, a heat treatment of 1 hr in an inert atmosphere at 2500°F followed by water quenching was used to produce the ferritic microstructure. These samples were quite coarse grained and usually en-

Jan 1, 1970