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By Joseph C. Platt

IT is not the object of the present paper to give a description of the minerals found on Mine Hill, in Sussex County, N. J., nor even to touch upon all the forms of the ores named, but to place upon record and call to the attention of the Institute some interesting facts concerning them. In May, 1875, after the Dover meeting, some of the members visited this locality, and, no doubt, it is fresh in their memories, being one of the best known mineralogical points in our country. It will be only necessary to describe it very briefly. Mine Hill and Stirling Hill, in Sussex County, N. J., the former being at the village of Franklin Furnace, and the latter near Ogdensburg,-are the only localities in the State where zinc ores are found in workable quantities.* Mine Hill is the more northerly, and mineralogically differs from its neighbor, chiefly in having no hydrated ores to speak of, while at Stirling this deposit is considerable. At both points Franklinite, red oxide, and silicate of zinc occur in large quantities. Mine Hill lies on the east side of the Wallkill River, above which it rises to an extreme elevation of about 150 feet. On the summit the outcrop of the Franklinite vein appears, while the lowest worked points are perhaps 10 or 15 feet above the level of the stream. Corn¬mencing at the northern end, where the Hamburg Road crosses it, this outcrop runs along the northwestern brow of the hill a distance of about 2000 feet, in a general southwest direction, to a point where is a large, cavern-like opening, called the "Southwest Opening." " Double Rock," about the highest point on the hill, lies near the middle of this 2000 feet of outcrop, and over or near it passes a property line, to which allusion will hereafter be made. At the Southwest Opening the vein bends abruptly towards the east,-the angle between the two parts being perhaps 45°,-and this easterly branch continues some 700 feet. From the northern part of the Stirling Hill deposit to the southern part of the Mine Hill deposit is about two miles, and in this interval the vein carrying Franklinite * See New Jersey State Geology, 1868, p. 669.

Jan 1, 1877

By G. Thodos, R. B. Grieves

A method has been developed For predicting the critical temperatures and critical pressures of binary mixtures of carbon dioxide, hydrogen sulfide, nitrogen, hydrogen, carbon monoxide and oxygen with the normal paraffin hydrocarbons. For carbon-dioxide and hydrogen-sulfide systems, relations are presented that take into account the peculiar behavior of mixtures with closely boiling components, such as carbon dioxide-ethane and hydrogen sulfide-propane mixtures which exhibit minimum critical temperature points. For hydrogen, nitrogen and carbon-monoxide systems, the extreme critical behavior caused by wide differences in pure component properties is established In addition, those fixed gas-paraffin systems which resemble paraffin-paraffin systems are also accounted for. For a mixture of known composition, the pure component critical temperatures, critical pressures and normal boiling points are all that are required to determine its critical point. Graphical relations are presented relating Tc and PC , of the mixture to the pure component properties. From the treatment of 12 carbon-dioxide and hydrogen-sulfide systems reported in the literature (74 mixtures), the expected error lor the critical temperature is approximately 1.5 per cent, and for the critical pressure, approximately 2 per cent. From the treatment of six hydrogen, nitrogen and carbon-monoxide systems reported in the literature (30 mixtures), the expected error for both the critical temperature and critical pressure is approximately 2.5 per cent. The relationships, which have been developed with only normal paraffins as the hydrocarbon components, may be extended to those isoparaffins and olefins which fall within the allowable volatility ranges. INTRODUCTION Many of the fixed gases — carbon dioxide, hydrogen sulfide, nitrogen, hydrogen, carbon monoxide and oxygen — occur in natural mixtures with hydrocarbons. Carbon dioxide and hydrogen sulfide are frequent components of the fluids produced from underground petroleum reservoirs. Nitrogen, carbon dioxide and hydrogen sulfide are present in varying quantities in most natural gases and gas-condensate well effluents. Hydrogen mixtures are of considerable interest in many phases of refining processes of petroleum. The determination of the critical temperatures and critical pressures of such mixtures is of value in vapor-liquid equilibrium studies, for the prediction of the characteristics of underground reservoirs, and for reduced-state correlations of PVT, transport and thermodynamic properties. The accurate estimation of the critical point for binary mixtures is an important initial step toward a complete analysis for the establishment of the critical temperatures and pressures of multi-component mixtures. Methods for predicting the critical temperatures and critical pressures of binary hydrocarbon systems have already been presented in the literature.8 It is possible to apply these existing methods to fixed gas-paraffin mixtures, but due to their unusual critical behavior, values calculated deviate considerably from experimental values. For systems containing trace quantities of the fixed gases, these methods are acceptable; however, for systems containing more than 5 mol per cent of the fixed gases, these utterly fail to produce reasonable critical values. Consequently, in this study a method has been developed for handling such binary mixtures over the entire composition range. CARBON-DIOXIDE AND HYDROGEN-SULFIDE SYSTEMS The critical behavior and the vapor pressure behavior of mixtures of carbon dioxide and hydrogen sulfide with paraffinic hydrocarbons may be quite similar or quite dissimilar to that of paraffin-paraffin mixtures, depending on the volatilities of the components involved. The critical temperature and normal boiling point of carbon dioxide are very close to the corresponding values for ethane, while its critical pressure is considerably higher than that of ethane. The normal boiling point of

By Charles R. Keyes

During the past decade the genesis of the lead- and zincdeposits of the Mississippi valley has received special attention from many distinguished observers. But their united egorts, instead of settling all disputed questions, have, in many respects, involl-ed the general problem in greater uncertainty than would be thought possible under the circumstances. In place of the harmony of opinion that might be expected, there is unexpected disagreement, largely due to the fact that, instead of giving attention to a possible multiplicity of ore-producing conditions among the different deposits, the attempt has been made to bring all deposits under a single genetic head. To a new observer of the lead- and zinc-deposits of the Mississippi valley, it appears at the outset that all the deposits cannot possibly have had the same genesis. In fact, different modes of origin have been often asserted for the ore-bodies, but the difficulty has been that each writer has referred them either all to one category or all to another, and no intermediate ground has been considered possible. Such a position now appears to be clearly untenable. The opinion that, in the deposits of the region under consideration, the ore-materials represent original depositions, made at the time the rocks themselves were formed, is no longer held by any authority, and therefore need not be considered here. Of late years, a number of writers have attempted to account for the presence of the lead- and zinc-ores on the hypothesis that the metallic materials arose in heated solutions from the

Jan 1, 1902

By P. M. Robinson, J. S. LI. Leach

The heats of solution oj' indiurrr, tin, lend, nrzd tellurium have been calculated from the measured heat effects when mechanical mixtres of indium and telLuium tin and tellurium, and lead and tellurium were added to liquid bismuth. The results are in good agreement xith publislzed values.s for the separate sollction of each eleltzent in bismuth. The heats oj solution of cadmium and tellurium calculated from the rneasuved heat effects on adding trechanical mixtures of these elements do not ugree zc,itl the published values jbv the separate solution of each element. It is shown that at 623°K Ile interaction between cadmium and tellurium dissolved in liquid bismuth is strong enough to led lo preciPitation of solid CdTc. The heats oj- jor-mation of CdTe at 273" nd 623°K (1)-c crilculated fi-or the measured heat ejlfecls. The calcnlaled az'erage deviation from the Kopp-l\'ez?,zunrz rule fov solid CdTe is less than 0.06 cat per g-atom- C over this lertzperalure range. Tlze importance 0.f these oDserl.ations to the determination of heals of formation hy metal solution calorimetry is considered. LIQUID metal solution calorimetry is a convenient method for determining the heats of formation of solid compounds. In this technique the heat of formation is the difference between the measured heat effects on dissolution of the compounds and of mechanical mixtures of the components in the liquid metal.' The heat of solution of the mechanical mixture may be calculated from the measured heat effect. At infinite dilution of the solutes, this heat of solution is equal to the sum of the heats of solution of the separate components. If the heat of solution of one of the components is known, the value for the other can be derived; if both are known, they may be used to check the accuracy of the calorimetric technique. The heats of formation of the tellurides of cadmium, indium, tin, and lead have recently been measured by metal solution alorimetr. The heats of solution of indium, tin, lead, and tellurium at infinite dilution in liquid bismuth at 623"K, calculated from the measured heat effects on solution of the mechanical mixtures, are in good agreement with the published values. The heats of solution of cadmium and of tellurium calculated from the measured heat effect on solution in bismuth at 623'K of mechanical mixtures of cadmium and tellurium, however, do not agree with values estimated from the literature. 1) EXPERIMENTAL PROCEDURE AND RESULTS The Heats of Solution of Indium, Tin, Lead, and Tellurium in Bismuth. The heat effects were measured when mechanical mixtures corresponding to the compounds In,Te, InTe, In2Te3, In2Te5, SnTe, and PbTe were dissolved in bismuth. The calorimetric procedure and the method of calculation have been described elsewhere.' The heats of solution of the mechanical mixtures were obtained by subtracting the change in heat content per gram-atom of the sample between the addition temperature (273°K) and the bath temperature (623"K), (H623°K - H273°K)S, from the measured heat effects. The calorimeter was calibrated with pure bismuth. The reported values of the measured heat effects are based on (HGoK - ^273oK)Bi = 4.96 kcal per g-atom.3 The measured heat effects are found to be linear functions of the solute concentrations of the bath in the dilute solution range. The values, extrapolated to infinite dilution, are listed in Table I, together with the heats of solution of the mechanical mixtures calculated using the published values of (H 623°K - H273°k)s for indium, tin, lead,3 and tellrium. All the error limits quoted in this work represent the spread of values obtained. The heats of solution in liquid bismuth at 623°K of mechanical mixtures of indium and tellurium in four different proportions were determined. Values of the heats of solution of the two components were then calculated from the resulting four simultaneous equations: The heats of solution at infinite dilution of tin and lead in liquid bismuth at 623°K were calculated from the heats of solution of the mechanical mixtures of tin and tellurium and of lead and tellurium using the heat of solution of tellurium calculated above. These values of the heats of solution are listed in Table I1 together with some published values for comparison.

Jan 1, 1967

By A. H. Larson, L. G. Twidwell

The influence which Au, Ag, Sb, Bi, Sn, and Cu have, both individually and collectively, on the activity coefficient of sulfur in liquid lead at 600"C zuas studied by circulating a H2S-Hz gas wlixture over a specific lead alloy until equilibrium was attained. Subsequently, the H2S concentration in the equilibrium gas mixture and sulfur concentration in the condensed phase were deterruined. The elements gold, silver, and antinzony (above 8 at. pct) increased the activity coefficient of sulfur. Bismuth had no apparent effect. Tin (above 3 at. pct) and copper decreased the coefficient. The influence of an individual element, i, on sulfur is best reported as the interaction parameter, riS, which is defined as The values o these first-order interaction zus are: ESzu = —55.0. These interaction parameters are used to predict the activity coefficient of sulfur in six fouv-component alloys and one seven-component alloy. Comparisons are made with direct experimental determinations. INTERACTIONS in dilute solution have been studied by many investigators. Most of the experimental work has been confined to solute-solvent interactions in simple binary systems and solute-solute interactions in ternary systems. Dealy and pehlke"~ have summarized the available literature on activity coefficients at infinite dilution in nonferrous binary alloys and have calculated from published data the values for interaction parameters in dilute nonferrous alloys. Interaction parameters are a convenient means of summarizing the effect of one solute species on another in a given solvent. Only a few investigators have studied interactions of the nonmetallic element sulfur in a metallic solvent. They are as follows: Rosenqvist,~ sulfur in silver; Rosenqvist and Cox,4 sulfur in steel; chipman, sulfur in alloy steels; Alcock and Richardson,% ulfur in copper alloys; Cheng and Alcock,' sulfur in iron, cobalt, and nickel; Cheng and ~lcock,' sulfur in lead and tin. The only reported work on the Pb-S system in the dilute-solution region is that of Cheng and Alcock.' Their investigation involved a study of the solubility of sulfur in liquid lead over the temperature range 500" to 680°C. The results may be summarized by the following relationship: S (dissolved in lead) + Pb(1) = PbS(s) log at. %S = -3388/T + 3.511 Experimentally, it was found that Henry's law was valid up to the solubility limit of sulfur in lead, i.e., at 600°C up to 0.43 pct. Their investigation did not include the study of sulfur in lead alloys. More accurate calculations could be made in smelting and refining systems if activity coefficients of solute species could be accurately predicted in complex solutions. One of the objectives of this study was to compare the experimental data with the values calculated from the equations derived from models for dilute solutions proposed by wagner9 and Alcock and Richardson. A temperature of 600°C was chosen as the experimental temperature to attain reasonable reaction rates and to minimize volatilization of the condensed phase. EXPERIMENTAL Materials. The Pb, Au, Ag, Sb, Bi, Sn, and Cu used for preparation of the alloys were American Smelting and Refining Co. research-grade materials. All were 99.999+ pct purity except the antimony and tin which were 99.99+ pct. The initial alloys prepared for this study consisted of twenty-one binary alloys, eleven ternary alloys, and one six-component alloy. The constituent elements were mixed for each desired alloy and were placed in a crucible machined from spectrographically pure graphite. The crucible was placed in a vycor tube which was evacuated with a vacuum pump and gettered by titanium sponge at 800°C for 8 to 12 hr. After the gettering was completed, the chamber containing the titanium was sealed and removed. The remaining sample chamber was placed in a tube furnace at 800°C for 2 hr and quenched in cold water. The final operation consisted of homogenization of the alloy for 1 to 2 weeks at a temperature just below the solidus for the individual system. The resulting master alloys were sectioned into small pieces and a random choice made for individual equilibrations. Cobalt sulfide (Cogs8) used to control the gas atmosphere in the circulation system was prepared by passing dried HzS for 24 hr over a Co-S mixture heated to 700°C in a tube furnace. This material was then mixed with cobalt metal to give a two-phase mixture which, when heated in hydrogen to a particular temperature, produced a desired H2S/H2 gas atmosphere in the circulation system. A Cu2S-Cu mixture also used in this study was prepared in a comparable manner. Apparatus for Equilibrium Measurements. The experimental technique of this study required apparatus

Jan 1, 1967

By R. S. Barneyback

Not much more is known about concrete today than was known to the Romans. For all the research only better tools have resulted to measure the quality of the materials that go into it." In this paper "some of the materials for lightweight concrete and their characteristics are considered and effort is made to indicate their effect on the end result — a structure of lightweight concrete." Lightweight concrete had noble beginnings. It is believed that the first specification for lightweight concrete was written by the Roman Emperor Hadrian in the early years of his reign, 117-138 AD. Hadrian, was an engineer by trade and an Emperor by adoption. He took considerable interest in the structures sponsored during his reign, even to the point of working out the structural details and preparing working drawings for some of the more prominent works in the vicinity of Rome. In order to reduce the dead weight of the 140 ft diam dome of the Pantheon he specified that the lightweight structural concrete members supporting this concrete and tile composite dome were to be fabricated from a concrete containing pumice and scoria. Still standing after 18 centuries of abuse, this structure has been described as the master effort of a great structural genius, the ultimate achievement of Roman engineering skill.' The Romans were the first to employ many concrete techniques we think of as modem innovations. Some unnamed superintendent noted that when a carefully measured amount of pigs blood was measured into each batch of concrete during mixing, the concrete was more durable and exhibited much better resistance to freezing and thawing climates. He no doubt, attributed this success to the appeasement of one of the gods who in return provided protection for the building containing this sacrificial offering in its walls. It is known today that the blood-entrained air in the concrete tends to make mixtures more workable, resistant to moisture penetration and more resistant to frost damage.

Jan 1, 1964

By Arthur G. Metcalfe

Arthur G. Metcalfe (SOLAR)—Three explanations to account for mechanical nucleation effects are considered in the paper, viz., theories based on fragmentation, agglomeration, and pressure-wave mechanisms. The authors show that none of these mechanisms will explain the results observed with tin and Sn-Pb alloys. A fourth mechanism of nucleation enhancement was developed during work at Armour Research Foundation on casting of beryllium and, although presented briefly on various occasions, the theory has never been discussed adequately. It is believed that this theory will explain many of the observations. Classical homogeneous nucleation theories assume that embryo nuclei are formed in the melt as a result of compositional and/or thermal fluctuations. Stable nuclei are formed when a critical size is reached such that the decrease in free energy for conversion of this volume of melt to solid offsets the increase of surface, energy. The assumption is made that the average properties of liquid and solid metal can be used. In practice this assumption is invalid and indeed is contrary to the postulation of thermal and compositional fluctuations in the melt. Actually the conditions favoring embryo formation bring the seeds of its own destruction—the thermal and compositional fluctuations leave the embryo surrounded by atoms of higher thermal energies and/or by solute atoms that depress the melting point. Any mechanical method of dispersing this destructive

Jan 1, 1964

By T. Egleston

The treatment of the residues from the manufacture of sulphuric acid which contain small amounts of copper, silver and gold, has attracted considerable attention in Europe. They are successfully treated in several works on the continent, and in as many as twenty establishments in different parts of England. As the process must sooner or later attract attention in this country, I have put together my notes made in three of the most important establishments in Europe. These are the works at Hemixem near Antwerp, of Duisbourg in Westphalia, and of Oker in the Hartz. In the last works only, the ores are produced in the vicinity of the place where they are treated. The works at Duisbourg treat ores which come from the Rio Tinto mines in Spain, which often contain considerable quantities of arsenic. They are roasted in a number of different works along the Rhine for the manufacture of sulphuric acid. They are brought by boat and are landed at the works by steam-cranes. They are carried at once by a double-inclined plane worked by steam to the storagehouses to be kept, until treated. The wagons, after being weighed, are dumped. The ore is assayed at once, the assay-sample being taken from the boat while the ores are being discharged. They are all fine, and contain two to eight per cent. of copper and about sixty per cent. of iron, and a small amount of silver and gold. Their average composition is given below:

Jan 1, 1886

The first mention of the mining and use of coal in the Pittsburgh district refers to the mine under Duquesne Heights that furnished coal for the garrison at the fort at Pittsburgh in 1760. Coal had been dug and used as fuel just outside of Brownsville, Fayette county, in 1759, but this was not a regular mine as the opening was in an outcropping. Maps of Ohio in 1770 showed "Cole Mines" at various points. The Penns purchased all the coal south of Kittanning in southwestern Pennsylvania from the Chiefs of the Six Nations for a reported price of $10,000. During the Revolution, coal from Herron Hill, Mincrsville, and Coal Hill, all within the present city limits, was used in Pittsburgh. There is today one custom pit opened in Coal Hill (Duquesne Heights). The first steam engine was set up in Pittsburgh in 1794 and used coal as fuel. The first mine in the Youghiogheny gas district was opened in 1796. In 1803, the first shipment of coal by water was made from Pittsburgh down the Ohio river and landed at Philadelphia, where it sold for approximately $9.50 per ton. The mines along the Monongahela were naturally the first to be opened. With the completion of locks and dams in 1844, permitting slack-water navigation, the industry began to thrive. The No. 8 field of Ohio and the Fairmont region of northern West Virginia were opened in the period 1840 to 1855. From that time on there has been a continuous development of the coal rcsources of this district, until at present productive capacity is enough to supply 30 per cent. of the country's needs of bituminous coal. The original method of working the Pittsburgh seam was to drive under cover at some easily accessible point on the outcrop with a single entry, usually 1½ yd. wide. Rooms or gangways were turned to the right and left from this entry and ventilation was usually poor and inade-

Jan 1, 1927

By William Glenn

The Ritchie vein, of Ritchie county, W. Va.,* was a straight fissure, about 3600 feet in length, which cut vertically downward across the horizontal beds of shale and of sandstone to a depth not ascertained. It might be described as lying in a. Vertical plane, bearing 12 degrees north of west. The geological horizon is that of the " upper barren coal measures'" of the Appalachian coal-field, being a part of the strata lying above the Pittsburgh bed. The vein matter was declared by Prof.

Jan 1, 1896

By C. H. Loux

This paper deals primarily with the advantages realized from the adoption of methods more suitable than those previously used. The improvements noted include: (1) modification of practice in shrinkage stoping, (2) use of sublevel caving over grizzlies, (3) improved haulage and loading, (4) use of contract wages wherever possible. The Washington mine is on Jonestown Hill, one mile south of Oxford, in northwestern New Jersey. It is producing 16,000 tons of concentrates a month, which are being shipped to the Alan Wood Steel Company's furnaces at Swedeland, Pennsylvania. History The first settlement in this region is reported to have been in 1735, and the magnetite ores were recognized immediately. The first furnace, built in 1741, began operation in 1743. During the Revolutionary War the output was chiefly used for making cannon balls, which, owing to the sympathies of the community, without doubt found their way into the hands of the British. This old furnace is still standing. Several important veins were soon developed, including the Martin, Strayley, McKinley, Adelaide, Welsh and Lanning. Mining was carried to a depth corresponding to the capacity of the pumps available. When these became inadequate, the workings were abandoned, and another vein was opened up. The Washington vein was probably discovered about 1850, and the first shaft started in 1854. In 1879, William H. Scranton made the first complete magnetic survey of the district and serious exploration of the deposit was begun. Rather indifferent success attended the earlier efforts of the many companies that attempted to mine and smelt the ore. In 1929 the property was leased by the Warren Foundry and Pipe Co. to the present operators, and the modification of practice then inaugurated is described in this paper. Geology These veins, like most eastern deposits of magnetite, are formed from, or are contemporaneous with, pegmatite intrusions into a gneissic country rock. The ore therefore follows the banded structure of the gneiss,

Jan 1, 1934

By David H. Browne

One of the most difficult problems in the chemistry of iron-ore, and one, the solution of which, so far as I am aware, has never been attempted, is the distribution, throughout a given vein, of Bessemer ore, and its relation to the formation of the deposit. In those hematite-mines in which both Bessemer and non-Bessemer ore occur, the sorting of the ore as it lies in the deposit becomes a problem of much economic as well as scientific interest. It would seem, from a superficial examination. or, indeed, from any examination not conducted for this especial purpose, as if high- and low-phosphorus ores were mixed in inexplicable confusion ; and a mining-chemist is very apt to fall into a system of adventitious analyses, taking first-class ore wherever he can find it, and overlooking its relation to the formation and position of the vein. I hope that a few notes which I present on this subject may be found worthy of consideration, as throwing a new light upon this obscure topic. During the last three years, while acting as chemist of the Lumberman's Mining Co., I have made some 3000 analyses of iron-ore from the Ludington mine at Iron Mountain, Michigan. These analyses were necessary in order to separate Bessemer and non-Bessemer ore which occurred intermixed in the deposit. During the last year, I attempted in several ways to find some reason or method in the distribution of phosphorus, and have finally become cognizant of the arrangement herein outlined. I have been obliged to confine my attention to our new mine, and, in that, to that portion wherein

Jan 1, 1889

By C. L. Meyers, J. L. Lytton, T. E. Tietz

The recovery of tensile flow stress of 99.995 pct A1 under conditions of elastic strain and plastic creep straining was investigated using a fractional recovery parameter. Tensile straining was conducted at room temperature to a true strain of 0.10, and recovery treatments were made under stress in the temperature range from 80° to 198°C. Whereas elastic strains had no appreciable influence on flow-stress recovery, plastic creep straining was found to accelerate the recovery process. Although higher creep stresses gave greater recovery for a given time and temperature, it was found that lower stresses produced greater recovevy at equal ALTHOUGH many studies have been made to date on the recovery of metals from the cold-worked creep strains above about 0.005. This effect was attributed to the coarser, and therefore weaker, substructure developed during creep at the lower stresses. The activation energy for recovery during creep straining at 2075 psi between 160" and 198°C was found to be 25,000 cal per mole. This value was not significantly greater than the value previously obtained for no-load recovery. The activation energy for creep at 2075 psi between 160" and 198°C was 34,000 cal per mole, a value significantly greater than that for recovery under the same conditions. state, little is known concerning some important aspects of recovery behavior. One such area is the effect concurrent strain has on the recovery process. Since metals in structural applications at high temperatures are under stress, the possible effects of the resulting elastic and plastic strain on recovery may be of significant importance.

Jan 1, 1962

By Howard Willey

MINING operations of the Charcas unit at present are limited to the Tiro General mine at Charcas, in the State of San Luis Potosi, Mexico. The Tiro General mine was first operated during the Spanish occupation of Mexico for rich silver ores in an oxidized zone along the outcrop of the principal vein. In depth the ore is a complex sulfide with widely varying proportions of sphalerite, argentiferous galena and chalcopyrite; and until recent years, it was economically impossible to carry on mining otherwise than irregularly in sections of the veins richest in galena and chalcopyrite. The advent of selective flotation brought the orebody as a whole within the field of economic interest, and a flotation mill of 650 metric tons daily capacity was constructed in the year 1925. The mining of partly worked-out sections of the mine, as well as the very heavy ground in most of the stopes opened in virgin ore, presented an unusually difficult problem. This -paper describes the so-called "filled top slice" stoping method finally adopted as the standard system.

Jan 1, 1930

By R. B. G. Yeo

The effects of alloy additions on the M, and A, temperatures of an Fe-22.5 pct Ni alloy have been determined. Increasing amounts of titanium, colum-bium, vanadium, and silicon raise and then lower M,while raising A, cmtinuously. Cobalt raises both M, and A,. Aluminum has little effect on Ms but raises A,. Chromium md nickel lower M, and A,. It is proposed that elements raise M, in accordance with their effect on the Ae3 temperature of iron until the lattice becomes stiffened against the shear transformation so that M, is then lowered. An anomaly, first pointed out by Zener,1 arises in steels when the addition of elements, such as molybdenum and tungsten, which raise the Ae3 temperature, also lower the M, temperature.2'3 During the development of a series of martensitic precipitation-hardening (maraging) steels, the effect of several elements on the transformation of austenite to martensite was studied. The results show that under suitable conditions several elements which raise Ae3 also raise the M, and A, temperatures. PREPARATION OF MATERIALS STUDIED A series of alloys was made in which cobalt, titanium, columbium, vanadium, silicon, aluminum, molybdenum, chromium, and nickel were added to an iron base containing 22.5 pct Ni. The compositions of the alloys prepared are given in Table I. The residual manganese contents of the heats were in the range of 0.030 to 0.35 pct, silicon 0.05 to 0.1 pct, carbon 0.0008 to 0.009 pct, and nitrogen from 0 to 0.004 uct. The allois were made as 50-lb induction heats starting with electro-iron and electro-nickel, melted in air to oxidize impurities. Additions of silico-manganese and ferro-silicon were made after which the power was turned off to allow the products of deoxidation to rise and be skimmed from the surface of the melt. The furnace chamber was pumped down to a pressure of 5 p and the charge was heated to 2900°F for the addition of other alloying elements. The heats were poured into five 10-lb ingots, making successive alloy additions to each. The ingots were soaked for 2 hr at 2300°F and hot-worked to 3/4-in.-diam bars. This stock was heated to 1500°F for 1

Jan 1, 1963

By J. R. Bell, W. J. Childs, J. H. Bucher, G. A. Wilber

A technique for determining recrystallization times as short as 0.10 sec was developed utilizing the "Gleeble", a commercially available testing system designed for the study of short-time, high-temperaLure themal and mechanical processes. The procedure consisted of heating a small tensile specimen to a given temperature of hot deformation, loading to a given reduction in area, unloading, delaying various intervals at temperature, and then reloading- to failure. The magnitude of the ultimate load obtained upon reloading decreased with delay lime as recrys-lallization proceeded. The technique was applied to austenite recrystallization in AISI 1010 and AISI 1010 uith 0.02 pct Cb steels. For each steel the reduction in area given the specimen on the first pull was mainlairred at 30 ± 5 pct and recrystallization times deterntined at various temperatures. The results indicaled a significantly slower rate of recrystallization for the columbium-modified composition, suggested the presence of- a recovery stage in the softening process , and indicated a greatly increased softening rate at a temperatuve where significant allotropic transformation to a partially ferritic Structure could occur. In recent years increasing attention has been paid to the fact that the process of recrystallization of austenite deformed at elevated temperatures is far from instantaneous at many practical hot-working temperatures.1-3 This realization has given rise to such terms as hot cold-working1 or warm-working,2 These terms generally describe processes where the recrystallization rate at the temperature of deformation is slow enough to have an appreciable effect on mechanical properties despite a relatively high deformation ternperature. The mechanical properties of interest can be either the properties at the deformation temperature as in hot-workability studies4 or the room-temperature properties after cooling as in the many recent studies of various thermomechanical processes172 where heat treatment and deformation are intentionally combined to give a unique set of room-temperature properties. Because of this interest in processes where the austenite recrystallization kinetics can be an important variable, the development of quantitative methods of following the course of short-time, high-temperature recrystallization has received increasing attention.l,3,5 The experimental methods to date have, in general, relied upon rapidly deforming the austenite, holding at temperature for various brief intervals, quenching as G.A.WILBER and W. J. CHILDS, Members AIME,are Research-Fellow and Professor, respectively, Rensselaer Polytechnic Institute, Troy, N. Y. J. R. BELL and J. H. BUCHER, Member AIME, are Research Engineer and Research Supervisor, respectively, Graham Research Laboratory, Jones & Laughlin Steel Co., Pittsburgh, Pa. Manuscript submitted March 13, 1968. IMD. rapidly as possible, and then using room-temperature measurements to follow the recrystallization process. Although such methods can be successfully applied to certain alloy steels, the existence of the allotropic transformation during cooling of plain-carbon or low-alloy steels tends to obscure the results. Thus, such room-temperature measurements as hardness and X-ray line widths do not correlate well with the extent of austenite recrystallization before quenching,5 and results based on room-temperature microstruc-tural observations are dependent upon the success in correlating the observed structure with the prior aus-tenitic grain structure.1,3,5 The purpose of the present work was to develop a quantitative method for the determination of short-time, high-temperature recrystallization rates, based on measurements made at the temperature of deformation. EXPERIMENTAL TECHNIQUE The basic technique consisted of heating a small tensile specimen to a given temperature of hot deformation, loading to a given reduction in area, unloading, delaying various intervals at temperature, and then reloading to failure. The data were obtained in the form of traces of load and elongation as a function of time. Due to the high deformation temperature, the strain hardening introduced during initial loading was progressively annealed out with holding time after unloading and the loads obtained upon reloading decreased as this softening proceeded. Although the value of the second load at any Consistent point On the load-elongation curve could have been used as a measure of the degree of softening, the most convenient to use was the ultimate load. The softening indicated by the decrease in the second ultimate load with time is essentially a process of annealing of cold-worked material at a high deformation temperature. Although some recovery grain growth may contribute to such a softening process, it is generally considered that the major softening which must take place to achieve complete removal of substantial Strain hardening will occur by the formation of new, stress-free grains. As the results of this work indicate that essentially complete removal of strain hardening did in fact occur. the primary softening process will be attributed to recrystallization, and specific reference made where it appears that other mechanisms may be contributing to the total observed softening. It would, of course, be of interest to attempt to correlate the results of this work with the actual austenite fraction recrystallized as determined by other techniques. This was not attempted in the present work because it would have required running a large number of additional specimens and, as discussed previously, there is limited assurance that the results would accurately reflect the prior austenite fraction recrys-

Jan 1, 1969

By J. D. Miller, M. Misra

The processing strategy for the effective separation of bitumen from low grade (<l0 weight percent bitumen) Utah tar sands by a hot water process differs significantly from that used for the processing of high grade (> 10 weight percent bitumen) Utah tar sands. Excellent separations (coefficient of separation = 0.9) can be achieved for high grade Utah tar sands by intense hot water digestion followed by a modified froth flotation step. Such a technique is ineffective for low grade tar sands. In order to change the characteristics of the low grade tar sand an attempt was made to enrich the bitumen content of the feed to greater than 10 weight percent by recycle of bitumen concentrate to the digestion stage. However, the quality of the separation was not improved under these circumstances. Similarly feed enrichment by heat treating the low grade feed with recycled concentrate prior to digestion did not improve the separation. More successful separations of low grade Utah tar sands were finally achieved by modification of the viscosity of the low grade bitumen with controlled addition of diluent. These results of the hot water separation tests and variations in the quality of separation are interpreted in terms of the physical properties of the bitumen and the surface bonding forces operative at the bitumen-sand interface.

Jan 1, 1981

By E. H. Rennhack

THE presence of sufficient quantities of the inter- stitial elements, carbon, oxygen, and nitrogen is known to decrease sienificantly the room-temperature impact resistance of titanium. Hydrogen does not appear to affect impact strength unless present

Jan 1, 1959

By G. W. Tuffnell, S. Floreen

Three Fe-18 pet Ni-base ternary alloys cortaining carbon, molybdenum, or cobalt were aged to pgroduce hardening by carbides, Ni3Mo, or ordering, respectively. Each alloy was tested in rotating-beam fatigue tests after hardening to 195 ksi ultim.ate tensile strength. The fatigue properties of three alloys soere essentially identical. The results suggest that tlze fatigae strength of an igron-base alloy should depend primarily upon the tensile strength, and not iipon the hardening mecaanisrn. THE fatigue strengths of many steels have been found to be directly related to their ultimate tensile strengths. For ultimate strengths below 200 ksi, the fatigue endurance limit at 107 to 10&apos; cycles is approximately half the ultimate strength. Essen- tially all of the steels that have been tested, however, have been hardened by carbon. Thus it is not certain whether the relationship between fatigue and ultimate strengths is a general one that applies for other types of hardening in steels, or whether it applies only for the particular method of hardening by carbon. The recent developments of the martensitic precipitation-hardened stainless steels and the marag-ing steels have shown that it is possible to achieve high strengths in iron-base alloys by other hardening mechanisms than that due to carbon. Therefore, it is now possible to compare the fatigue properties of several iron alloys having the same ultimate strengths but hardened by different mechanisms. For the present study a binary Fe-18 pct Ni martensite was selected as a base material. This particular matrix composition has been found to have deformation characteristics very similar to pure iron.&apos; Three ternary alloys were prepared by adding either 0.23 wt pct C, 5 wt pct Mo, or 20 wt pct Co to this base composition. After suitable heat

Jan 1, 1965

By R. L. Jones, H. Conrad

The effects of gain size on the room-temperature tensile properties of commercial(A- 70)-purity and iodide-purity titanium were investigated by concurrent tensile testing and thin-foil electron transmission studies. The mechanical tests showed that the effect of grain size on the yield, flow, and fracture stresses could be expressed by relations of the Hall-Petch type. The magnitude of the grain size effect on the yield stress was larger for commercial-purity than for high-purity titanium, but in both materials it was intermediate between that typically observed for fcc and for bcc metals. The effect of strain on the gain size sensitivity of the flow stress was found to reflect the grain size dependence of strain hardening. The electron transmission study indicated that the tensile behavior could be accounted for in terms of the dislocation densities and distributions formed during deformation. It was concluded that the effect of grain size on strength could be attributed to a relationship between grain size and the dislocation densities generated in initiating and sustaining plastic flow, the difference in stress levels being due to strain hardening. The relationships between recrystallized grain size, uniaxial tensile properties, and dislocation substructure have not been explored in any detail for a titanium. With titanium and its alloys finding increasing applications in aerospace systems, such information has become essential. The research described in this paper had two objectives: first, to document the effect of grain size on the yield, flow, and fracture stresses of unalloyed a titanium by the tensile testing of recrystalliied specimens at room temperature; second, to attempt an interpretation of the mechanical test behavior in terms of the dislocation structures formed on deformation, as observed by transmission electron microscopy of thin foils prepared from deformed tensile specimens. The observations reported here are restricted to room-temperature deformation; the effect of temperature on the yield and flow stresses of a titanium and the athermal nature of the contribution of grain size to the flow stress have been discussed elsewhere.1"3 EXPERIMENTAL DETAILS Two purity grades of unalloyed titanium have been investigated: Crucible Steel A-70, a typical commer- cial-purity product, and a high-purity iodide grade supplied by the Foote Mineral Co. Chemical analyses for interstitial impurity contents are given in Table I, together with values for the total interstitial atom fractions in terms of oxygen equivalents, which were calculated by the method outlined previously.4 ,5 According to the manufacturer&apos;s nominal analysis, the A-70 grade also contains about 3700 ppm of Fe. The A-70 grade was supplied as 1/4-in.-diam centerless-ground rod. The iodide grade was supplied as crystal bar which was consolidated to approximately 1/4-in.-diam rod by a single, rapid, molten zone pass, using electron beam heating. The 1/4-in. rods were cold-swaged to 0.078-in.-diam wires and 2-in. lengths were recrystallized in a vacuum of -5 x 10-5 torr, giving grain sizes in the range 0.8 to 30 . The thermal treatments and resulting grain sizes are summarized in Table 11. Since there was in no case any obvious sign of a bimodal dis tribution of grain sizes, the grain size values quoted in Table I1 are those obtained from mean linear intercept measurements involving >I00 grains. For the two coarse grain sizes the measurements were made using conventional optical techniques. It was noted during these determinations that the etchants used (10 pct HF; 30 pct HN03; 60 pct H20 and 2 pct HF; 2 pct H202; 96 pct H20 were both tried) etched grain boundaries very nonuniformly and optical polarization effects had to be employed to reveal boundaries which might otherwise have been missed. It was found that this problem became more acute with the finer grain sizes as the usefulness of polarization diminished.

Jan 1, 1970