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By L. S. Darken, H. A. Wriedt

In a previous paper,1 an experimental study of nitrogen dissolved in a cold-rolled ad heat-treated, low-carbon steel at 300° to 450°C yielded the equilibrium solubility relations and the concentrations of the two types of deject sites involved. In this paper, the probable identities of the defects that absorb nitrogen are restricted from the available evidence to screw dislocatioms for B sites, and to either micro crack surfaces or edge In a previous paper.' we reported an experimental study of the excess nitrogen solubility in a low-carbon steel produced by a combination of plastic deformation and nonrecrystallizing heat treatment. The concentrations of the defect sites that absorb the excess nitrogen were measured in terms of their capacities for nitrogen. Also measured were the equilibria of nitrogen distribution among the sites. Several problems and questions arise from these measurements. We should like a physical identifi- dislocations for A sites. The concentrations of these defects in experimental steel specimens are estimated from the concentrations of defect sites. finally, the influence of chemical composition upon the nitrogen-trapping defects—the relative numbers generated in deformation, the relative numbers surviving as temperature is raised, the apparent numbers observed, and the distribution equilibria-is discussed. cation of the defects involved and of the two kinds of nitrogen-absorbing sites, called A and B types, upon those defects; the concentrations of the defects themselves could then be computed. We should also like to know how exclusively the findings apply to the "X steel" used in the experiments and to what extent they apply to cold-rolled steel given no subsequent treatment. By considering the data already given, together with results from a few specific tests which will be reported as they are invoked, we are able to eliminate some interpretations altogether and to secure an acceptable though limited interpretation from among the remaining possibilities.

Jan 1, 1965

By James M. Barker

Sulfur is a nonmetallic element of great physical and economic importance to the world. It is widely but sparingly distributed throughout the hydrosphere, lithosphere, and biosphere. Sulfur is the tenth most abundant element in the universe and eighth most abundant in the sun. In the earth's crust, which is mainly igneous, it ranks 14th, but is eighth or ninth in sediments (Kaplan, 1972; Stanton, 1972). It apparently is very abundant in the core of the earth, because it is a strong chalcophile, and it is fifth in abundance in stony and iron meteorites (Field, 1972) where it occurs as trolite (FeS). In ancient times sulfur was called brimstone, literally "burning stone." Today the term brimstone is used interchangeably with the term elemental sulfur. Shelton (1979) summarized most of the common definitions of terms, grades, and specifications for the sulfur industry as follows (with minor additions): Sources of Sulfur: Combined sulfur-Sulfur that occurs in nature combined with other elements. Cupriferous pyrites-Pyrite containing relatively minor amounts of copper sulfide minerals. Hydrogen sulfide-A toxic gas (H2S) occurring in natural gas and petroleum. Involuntary sulfur-Sulfur produced primarily as a result of legislative or process mandates. Native sulfur-Sulfur that occurs in nature in the elemental (uncombined) form. Nonferrous metal sulfides-Copper, lead, zinc, nickel, and molybdenum sulfides that are processed for their metal content. Organic sulfurs-Complex organic sulfur compounds occurring in petroleum, coal, oil shale, and tar sands. Pyrites-Iron sulfide minerals that include pyrite, marcasite, and pyrrhotite. Sulfate sulfurs-Sulfur in anhydrite and gypsum. Voluntary sulfur-Sulfur produced in response to market forces. Basic Sulfur Products Produced and Marketed: Acid sludge-Contaminated sulfuric acid usually returned to acid plants for reconstitution. Brimstone-Synonymous with crude sulfur. Bright sulfur-Crude sulfur free of discoloring impurities and bright yellow in color. Broken sulfur-Solid crude sulfur crushed to -8 in. Byproduct sulfuric acid--Sulfuric acid produced as a byproduct of a metallurgical or industrial process, generally relating to combined sulfur sources. Crude sulfur-Commercial nomenclature for elemental sulfur. Dark sulfur-Crude sulfur discolored by minor quantities of hydrocarbons ranging up to 0.3 % carbon content. Elemental sulfur-Processed sulfur in the elemental form produced from native sulfur or combined sulfur sources, generally with a minimum sulfur content of 99.5%. Formed sulfur-Elemental sulfur cast or pressed into particular shapes to enhance handling and to suppress dust generation and moisture retention. Frasch sulfur-Elemental sulfur produced from native sulfur sources by the Frasch mining process. Hydrogen sulfide-Associated with natural gas or petroleum and produced at refineries and coke oven plants; used to make sulfuric acid or recovered sulfur. Liquid sulfur-Synonymous with molten sulfur. Liquid sulfur dioxide-Purified sulfur dioxide compressed to the liquid phase. Molten sulfur-Crude sulfur in the molten phase.

Jan 1, 1983

By P. Payson

INTERGRANULAR corrosion in corrosion-resistant chromium-nickel steels has been widely discussed in the last few years. So far as the author knows, nothing has been published which definitely shows that this tendency can be eliminated, although suggestions have been made that a remedy is possible if certain specifications are satisfied. Strauss, Schottky and Hinueber1 suggested an increase in chromium content to an extent that would prevent the impoverishment of chromium on carbide precipitation sufficient to cause impaired corrosion resistance in the matrix. Pilling2 suggested an increase in nickel, so that the stability of the austenite matrix would be increased. Aborn and Bain,3 say that "intergranular attack-may be eliminated by preventing carbide precipitation (e. g., by lowering the carbon content or somehow raising its solubility) or by precipitating it permanently under conditions which will not remove chromium from solid solution so drastically at any points." In a later paper Aborn and Bain4 state that many different metallic elements, tungsten, vanadium, copper, aluminum, molybdenum, titanium and zirconium, have been added in small per-centages to increase the stability of these alloys, but that it has been reported that according to the copper sulfate test these added elements act only to retard the intergranular corrosion, and that increased nickel and chromium contents have similar effects. Newell5 showed that the lower the quenching temperature before reheating, the less severe was the intergranular attack.

Jan 1, 1932

By T. S. Blair

I feel a certain sense of responsibility in bringing before you the subject of the direct process in iron manufacture. I am aware that, in such a body as I have now the honor of addressing, there are few who are not already so well informed upon its past history that it would be a weariness to them to listen to anything else than an account of practical success. Yet, to claim that success involves so much that, if I do not make good my claim, I deservedly expose myself to severe criticism. The whole literature of the art, so far as it relates to the direct process, is, up to this time, but a history of failure. It is safe to say that more money, time, and talent have been fruitlessly spent in the pursuit of this object than in all the other unsuccessful efforts in the whole line of iron metallurgy. A distinguished authority in patent law has remarked that " the invention records of the United States and of foreign countries are filled with the waifs and abandoned relics of these abortive struggles." Dr. Percy, whose great work may be taken as an epitome of all that was worth mention, whether useful or curious, in pig-iron metallurgy, up to the date of its publication (1864), after giving elaborate accounts of various attempts at the direct process, condenses his own opinion of all that had been then effected, into a brief but summary comment upon a pamphlet of one of the sanguine inventors who had said: "It is evident that the present mode of working iron

By J. J. Jonas, G. Gagnon

SHG zinc was extruded in the temperature range 110" to 350°C and the strain rate range 0.05 to 5 sec-1 The strain rate/flow stress/temperature results were analyzed using a power sinh stress relationship. When temperature changes due to the heat of deformation and to heat losses are neglected, the exponent of the sinh function of the stress is 5.6, and the apparent activation energy of deformation is 28 kcal per mole. When these changes are taken into account, the exponent decreases to 4.7 and the activation energy to 23 + 2 kcal per mole. The corrected stress exponent and activation energy are in very good agreement with published values obtained from creep experiments, and suggest that the hot extrusion of zinc is controlled by a mechanism involving self-diffusion. When the extrusion and creep data are compared using a Zener-Hollomon parameter and either a sinh or an exponential stress term, an appreciable offset is observed, which may be due to the difference in impurity content. For a given set of extrusion conditions the ram speed, maximum pressure, and initial temperature can also be correlated using a Zener-Hollomon parameter and a sinh pressure term. THE deformation of metals at temperatures over about one-half the absolute melting temperature has been extensively studied at creep strain rates. By contrast, relatively little work has been carried out on the behavior of metals at hot working strain rates. Most of the latter investigations have been performed using simulative methods, such as hot torsion and hot compression, in which the friction conditions and temperature rise during deformation may differ appreciably from those existing under industrial conditions. Recently, however, Wong and Jonas1 used a scaled-down industrial process to determine the stress and temperature dependence of the strain rate during the extrusion of aluminum. In such tests, the effects of friction and adiabatic heating are closer to those produced in industrial operations. Also, with regard to the testing of materials of limited ductility such as zinc, hot compression and hot torsion do not permit the attainment of true strains as large as the deformations usually applied commercially. The present study was undertaken to investigate the extrusion behavior of Special High Grade (SHG) zinc. The detailed objectives were: 1) to establish the stress and temperature dependence of the strain rate with and without a consideration of adiabatic heating, 2) to study the pressure and temperature dependence of the ram speed, and 3) to investigate the microstruc- tural changes occurring during the deformation. The last aspect of the investigation will be covered in a separate paper. The treatment described below differs from that of Wong and Jonas in that the adiabatic temperature rise during deformation is taken into account, and the calculation of the mean equivalent strain rate is based on the redundant as well as on the homogeneous work. EXPERIMENTAL PROCEDURE Rods from two shipments of continuously cast SHG zinc* were used in the investigation. The composition *Supplied by courtesy of Cominco Ltd. range of the impurities present, as given by the supplier, was: Pb: 0.0013 to 0.0023 pct, Fe: 0.001 pct max Cd: 0.0001 to 0.0006 pct, Cu: 0.0002 to 0.0005 pct, Ti: 0.0001 pct max; thus, by balance, zinc valued from 99.9963 to 99.9966 pct. The as-received rods were machined into billets having a nominal diameter of 1.56 in. and a nominal length of 1½ in.; longer billets up to 4 in. in length, were also used to investigate special aspects. The as-machined rods were annealed at 400°C for 24 hr and slowly cooled. This treatment produced a columnar grain structure, with a grain size of about $ by 2½ cm which was appreciably larger than the as-cast one. A 150-ton, direct extrusion, vertical press was used. Ram displacement and force were recorded continuously against time. A constant flow control valve permitted the maintenance of a range of preselected ram speeds up to in. per sec. The selected speed was held constant, irrespective of the required force, as long as the load developed was below the maximum available. Strain gages were used to determine the force; the gages were calibrated before and after each testing period with a 200,000-lb capacity load cell. Further details of the experimental equipment can be found in Ref. 2. The billets were preheated for 90 min in the extrusion container, which was well insulated so as to minimize temperature gradients. This period was sufficient for the billet to reach a uniform temperature at all temperatures between 110" and 350°C. A square-shoulder die having a 0.290-in. diam central hole was used. The extrusion ratio was 30 to 1. This is equivalent to a reduction in area of 96.7 pct, an elongation of 2900 pct, and a true strain of 3.4. The ram speed was varied over two orders of magnitude from 0.0027 to 0.26 in. per sec. The ram was water-cooled during most of the tests, although some experiments were conducted with a preheated, uncooled ram. All extrusions were run without lubricant, which resulted in conditions of sticking friction. EXPERIMENTAL RESULTS Stress Dependence of the Strain Rate Neglecting Adiabatic Heating. The maximum force required to extrude is given in Table 1 for each of the five initial

Jan 1, 1970

By A. G. Gilbert

Paradoxical is the word. The coal industry, despite reach- ing a 22-year high in production (590 million tons), has been tagged as having its back to the wall vis-a-vis its valiant attempts to quench the nation's still unabated craving for coal. What must be even more reassuring to the industry, infected once with rumors of a uranium takeover, is a nation's almost insatiable appetite for electricity. Between 1967 and the summer of 1970, utility stockpiles were being gobbled up, diminishing to 79% of the January 1968 level.

Jan 1, 1971

By A. J. Boynton

THIS paper is not the result of recent research with regard to any particular feature of iron metallurgy, blast-furnace practice or mechanical engineering. It is rather a series of notes with regard to contemporaneous progress in blast-furnace construction and operation, together with some suggestions as to changes and improvements that seem to be desirable. On April 1, 1930, a committee of the Chicago District Blast Furnace and Coke Association presented to that association a rather ambitious study of blast-furnace equipment, together with recommendations for the design of construction of a complete blast-furnace unit for the production of 1000 tons of pig iron per day. This report represented the result of months of study by members of the committee, all of whom were actively engaged in operation or design of blast-furnace plants. It is natural, therefore, that comments on the present state of the art should take this 1000-tons furnace, as recommended by the Association, as a basis for comparison with corresponding features of construction or design. See Table 1. In looking through this report at the present time, the significant difference is in the nature of the gas-washing equipment that today would be specified. In other respects, the installation would remain generally very much as it was outlined in 1930. The change in furnace dimensions would be very slight and of no especial significance, except with respect to changes in stock-line diameter, of which more will be said hereafter. The high-efficiency stove as developed by various designers is thoroughly described within this report, and few changes have taken place since. Blowing equipment shows refinement and reflects the improvement in steam engineering. Hoisting and charging equipment and ladles for the conveyance of iron and slag remain, in general, as they were in 1930. In accordance with a general tendency

Jan 1, 1935

By Robert Bosworth

THE liability for damages to the surface caused by subsidence is an ever present threat in all underground mining. In ordinary lode mining, this threat rarely materializes into an action, due to the method of mining metalliferous ores, the dip of the veins, and the nature of the ground itself. In the mining of coal, however, this threat is very real. The coal frequently lies close to the surface, in beds underlying large areas of land of which the surface is suitable for agricultural or urban development. Furthermore, the coal is generally mined by the "room and pillar " method and when the pillars of coal are removed, the subjacent support is destroyed. This question of the duty of surface support has now become a very live one in Colorado. What was waste prairie land a few years ago has become valuable agricultural land dotted here and there with growing towns. Frequent references will be made here to Colorado conditions and adjudicated cases, but those conditions and cases and the conclusions to be drawn therefrom are applicable to all coal-mining states. Briefly stated, the question is "Does the owner of the substrata or underlying mineral owe any duty of surface support to the owner of the superjacent strata or surface?" There is no absolute duty of support owed by the mineral owner and this assertion is made with full knowledge of numerous expressions to the contrary by courts of Pennsylvania, Illinois, Colorado and other coal-mining states. Whether or not any duty exists depends upon the circumstances surrounding each case, and since in the nature of things those circumstances are rarely identical, there can be no absolute rule.

Jan 1, 1928

By W. W. Norton

The gradually increasing proportion of sulphide ores which lead smelters of to-day are called upon to handle has caused the roasting problem to become one of ever greater importance. Mines have increased in depth, methods of concentration have improved, competition in the purchase of ores has become more keen and it has been clear that new and modern methods of eliminating sulphur must receive a large share of attention. We may look back a score of years or so and recall the old hand roasters, some of which turned out a finely divided roasted product, and others fashioned with a "fuse-box" wherein the roasted ore was slagged. Then came mechanical furnaces of several types, the Bruckner cylinder, the Brown-O'Harra, the Ropp, and others, all designed to cut out the cumbersome hand labor of the old reverberatories. Roasting costs were thereupon reduced and tonnages stimulated to a gratifying extent. However, it seems to have been early recognized that this very feature of a greater amount of roasted sulphide ore as compared with oxide ore brought with it a train of difficulties at the blast furnaces. The mechanically roasted ore was fine physically, the blast furnaces were choked and the troubles of the smelterman were not at an end. Then the Huntington-Heberlein pot system of roasting appeared upon the scene, and later on the Dwight-Lloyd machines were invented, and inasmuch as both of these processes were designed not only to roast the ore but to agglomerate it as well, it was apparent that distinct steps in advance had been achieved. At the Murray plant, modern up-to-date roasting practice is fully exemplified and there are now in successful operation roasting furnaces or devices of several sorts: namely, Godfrey revolving-hearth furnaces, Wedge multiple-hearth mechanical roasters, Dwight-Lloyd sintering machines, and Huntington-Heberlein pots. Godfrey and Wedge furnaces will properly handle material high in sulphur, say ores with 25, 30, and 35 per cent. of that element; D. & L. machines and H. & H. pots will positively not treat efficiently ores or mixtures containing anywhere near the sulphur content mentioned, but are confined to charges containing in the neighborhood of 15 or 18 per cent. In passing, it may also be explained that, so far as the knowledge of the writer goes, Godfrey and Wedge furnaces do not economically eliminate sulphur to an extent

Jan 1, 1915

By E. Miller, K. L. Komarek

Equatiorzs have been derived which related maximum solid solubilities in semicondcting compounds having retvograde solidus curves with 1iqllidus data. Liquidus curves in Lke Pb-Te, Pb-Se, ard PB-S systetris have been defermined by thertrzal aralyses. Fvotrz expevimental maximum solibilities ia CdTe, PbTe, uxd PbS vetvograde tetrperatures hale beep1 calculated. TIze resllts support the concept that under certaiz conditiots pronounced itjlections in the liquidis curves arc indzcatiz:e of retropade solidus curves and that the tenlperatltre of the lmaximum solid solubility will be close to the temperature of the point of inflection in the liquidus curve. The maximum solid solihility within a gvoup of homologous cottrpoods SeetlLs to increase with increasing flatness ol the liquidus curvres. The phenomenon of retrograde solubility in metals, i.e., maximum solubility in a solid terminal phase in equilibrium with a liquid phase, has been theoretically predicted by Van aar' in his calculations of hypothetical binary phase diagrams. It was not until 1926, however, that retrograde solubility was experimentally verified in the Zn-Cd system.' Since then many sys- tems with retrograde solubility have been found, so that at present approximately fifty binary diagrams with a retrograde solidus curve are known.3 Meijering4 has critically appraised the accumulated data and has presented calculations which alloy predictions as to whether or not a solidus line will be retrograde. Interest in retrograde solubility increased when it was found that the solidus curves of germanium and silicon alloyed with a great many doping elements are retrrade. The problem was treated thermody-namically by odkinson,% d all available data on solid solutions in germanium and silicon were summarized by Trumbore.7 Although it is to be expected that intermetallic compounds will also exhibit retrograde solubility, experimental evidence is much more limited. Until now retrograde solidus curves have been reported for the compounds de,' be, Ps:" ne," SnSe," and SnS.13 All these compounds are semiconductors, and the solidus curves were usually obtained by determining the carrier concentration at room temperature of samples equilibrated at elevated temperatures and then quenched. It has been hown,'' however, that it is not always possible to quench in the equilibrium compositions from above a certain temperature. Theoretical discussions have either explicitly excluded intermetallic compounds4 or not treated them with respect to retrograde slubilit.j In the following a thermodynamic treatment of retrograde solu-

Jan 1, 1967

By T. L. Joseph

The extent to which hot metal from the blast furnace affects open-hearth practice and the quality of steel produced has been discussed widely. Open-hearth operators have attributed difficulties experienced in making satisfactory steel to characteristics of the pig iron not disclosed by ordinary analysis. The commonest criticism of the iron has been that it is "physically cold" or "dirty." Often when the blast furnaces are working irregularly the quality of the iron is questioned. A cold hearth, slipping and hanging, the use in the past of unsintered flue dust, and the use of ores difficult to smelt have been associated with the production of iron of poor quality. The difficulty of the situation is that we have no proven yardstick for quality aside from ordinary analysis. Uniformity in analysis is recognized as being important, but the difficulty of changing the open-hearth practice when the iron analysis varies widely may not always be fully appreciated. Although the problem of correlating the characteristics of steel with those of pig iron is admittedly obscure, the effort of producers of quality steel to investigate all factors that may have a bearing on the final product is justified. This report contains data on the oxides in several hundred casts of basic iron produced in a furnace during the course of normal operation on Lake ores. Incidental to the study of the oxides in the iron, it was desirable to follow closely the temperature of the iron. The effect of temperature of the iron upon the silicon and sulphur present is discussed. A general relation between the basicity of the slag and the sulphur in the metal was developed. The amount and composition of oxides in the hot metal and in the steel bath during various intervals between melt-down and tap are discussed. Heats of rimmed steel, killed steel, and semikilled steel were investigated. The hot metal on individual heats was either all taken from a mixer or consisted partly of direct metal and partly of metal from the mixer. Samples of the iron for oxide determinations were

Jan 1, 1937

By J. Gordon Parr, D. H. Polonis

The formation and subsequent decomposition of metastable phases in Ti-Ni alloys containing up to 11 pet (atomic) Ni have been studied. The decomposition of a completely retained ß phase and of a completely transformed 8 phase in a 6 pet alloy has been followed by X-ray diffraction and metallographic methods and by hardness determinations made during the process. The possible mechanisms of the reactions are discussed. PREVIOUS investigations of the Ti-Ni system have usually been limited to phase diagram studies; but little attention has been given to metastable phases and tempering processes. These are important, however, since equilibrium conditions are rarely achieved—nor, perhaps, are they desired—in practice. Up to the present time the available transformation data for titanium alloys appear to be restricted to isothermal transformation curves for selected binary and ternary systems. No quantitative studies have been made of the mechanism by which equilibrium is approached. Several independent investigations have been carried out to determine the Ti-Ni phase diagram. Early work by Wallbaum' and later by Long et al.' produced tentative phase diagrams which were not representative of true binary conditions, since the alloys were contaminated with oxygen and nitrogen. The most recent diagram (Fig. 1) is due to Margolin et al.," and a slight modification of the a + ß/ß boundary (shown dotted) has been proposed by McQuillan.' The structure of the phase Ti,Ni was shown by Duwez and Taylor" to be face-centered-cubic, with 96 atoms per structure cell. The formation of a martensitic ß phase (close-packed-hexagonal) in Ti-Ni alloys has generally been observed when specimens of low nickel content are rapidly cooled from the 0 (body-centered-cubic) range. Margolin et al. reported an increasing tendency for P to be retained in lump specimens as the nickel content increases. McQuillan' has studied the effect on the microstructure of delay time in quenching, and has reported the formation of pro- eutectoid a precipitate in a quenched hypoeutectoid alloy. In a previous study of Ti-Fe alloys," experiments were made on powder specimens produced by filing alloy ingots. Techniques were devised for the preparation and heat treatment of alloys, and X-ray diffraction methods were used both for structure determinations and phase ratio estimations. A similar approach has been made in this study of Ti-Ni alloys. Experimental Methods Ten alloys ranging from 0.25 pet to 18 pet Ni* * All compositions are in atomic percentages unless otherwise stated. were prepared from iodide titanium bar stock (hardness Rf 72) and Johnson-Matthey spectrographic standard nickel by levitation melting.' As a check

Jan 1, 1957

By M. F. Hawkes

Austenite grain size has long been recognized by metallurgists as an important property of steels because of its influence on toughness, hardenability, ma-chinability and creep strength. Much research has been carried out on wrought steels to develop methods for disclosing austenite grain size, and to, provide knowledge of the grain-size characteristics of steels produced and heat-treated in various ways. Much less work in these fields has been done on steel castings; partly because, owing to the variable and complex microstruc-tures of cast steels, it is frequently very difficult to obtain results that are not questionable. The object of this investigation, therefore, was to establish, for a wide variety of carbon and alloy cast steels, suitable methods for disclosing austenite grain size and some knowledge of the grain-size variations to be expected. The steel foundryman is interested in austenite grain size at two different stages in the manufacture of his products; one is just after the steel is cast, and the other is after any reheating operation carried out above the critical temperature range. In both, it must always be kept in mind that the grain size being sought is actually a previous austenite grain size, and that the austenite no longer exists once the steel has cooled to room temperature. The prob-lem of the investigator is always to use evidence obtained from the structure at room temperature to deduce this previous austenite grain size, which was established the last time the steel existed at a temperature above the critical range. Since most steel castings today are at least annealed or normalized, the measurement of austenite grain size established by heat-treatment will he considered first. More than 50 commercially produced cast steels rcpresenting a wide variety of compositions and melting practices were used in the study. For each steel, grain-size determinations were made after each of three widely varying heat-treating schedules namely, one hour at I550'F, one hour at I700°F, and six hours at 1700 F. The list of steels and results obtained on them will be found in the appendix. (See page 530.) A discussion of the knowledge gained on the applicability of various test methods and on grain-size characteristics of cast steels in general follows. MEASUREMENT OF AUSTENITE GRAIN SIZE ESTABLISHED BY HEAT TREATMENT Methods Suitable foR Determining Austenite Grain Size after Heat-treatment at Ordinary Temperatures and Times It was desired, as one of the results of this investigation, to be able to recommend to steel foundries a method, or methods, of disclosing grain size best suited to accurate

Jan 1, 1948

By M. F. Hawkes

Austenite grain size has long been recognized by metallurgists as an important property of steels because of its influence on toughness, hardenability, ma-chinability and creep strength. Much research has been carried out on wrought steels to develop methods for disclosing austenite grain size, and to, provide knowledge of the grain-size characteristics of steels produced and heat-treated in various ways. Much less work in these fields has been done on steel castings; partly because, owing to the variable and complex microstruc-tures of cast steels, it is frequently very difficult to obtain results that are not questionable. The object of this investigation, therefore, was to establish, for a wide variety of carbon and alloy cast steels, suitable methods for disclosing austenite grain size and some knowledge of the grain-size variations to be expected. The steel foundryman is interested in austenite grain size at two different stages in the manufacture of his products; one is just after the steel is cast, and the other is after any reheating operation carried out above the critical temperature range. In both, it must always be kept in mind that the grain size being sought is actually a previous austenite grain size, and that the austenite no longer exists once the steel has cooled to room temperature. The prob-lem of the investigator is always to use evidence obtained from the structure at room temperature to deduce this previous austenite grain size, which was established the last time the steel existed at a temperature above the critical range. Since most steel castings today are at least annealed or normalized, the measurement of austenite grain size established by heat-treatment will he considered first. More than 50 commercially produced cast steels rcpresenting a wide variety of compositions and melting practices were used in the study. For each steel, grain-size determinations were made after each of three widely varying heat-treating schedules namely, one hour at I550'F, one hour at I700°F, and six hours at 1700 F. The list of steels and results obtained on them will be found in the appendix. (See page 530.) A discussion of the knowledge gained on the applicability of various test methods and on grain-size characteristics of cast steels in general follows. MEASUREMENT OF AUSTENITE GRAIN SIZE ESTABLISHED BY HEAT TREATMENT Methods Suitable foR Determining Austenite Grain Size after Heat-treatment at Ordinary Temperatures and Times It was desired, as one of the results of this investigation, to be able to recommend to steel foundries a method, or methods, of disclosing grain size best suited to accurate

Jan 1, 1948

By Kenneth R. Hancock

Iron oxides are unique in that they are the only significant colored mineral found in a natural state suitable for use as a pigment after being pulverized to pigmentary size. The current world production of iron oxide pigments is estimated by the author to be between 499 and 590 kt (550,000 and 650,000 st) based on 1979 data. The fact that highly colored natural deposits of iron ore are found throughout the world accounts for its use in prehistoric man's artistic cave paintings. These early artists did not realize that they had established man's first paint test fence which now has some 20,000 years of exposure. In addition to abundance, constituting about 7 % of the earth's crust, iron oxides have the advantages of low cost, permanency, and are not toxic. Through the centuries, succeeding civilizations have utilized iron oxides as a major source for decoration and protection when coloring was desired. In the last century the chemical industry has improved on nature by developing a complete range of synthetic iron oxide pigments which surpass the pigments produced from natural iron ores in uniformity, color quality, and chemical purity. In the United States alone, the combined production of natural and synthetic iron oxides produced sales of over $28,000,000 in 1970 (Stipp, 1970) and increasing to $97 million by 1980 (Spinrad, 1980). Nomenclature With the increasing importance of the synthetic iron oxides it is necessary to make a distinction between the natural or mineral pigments and the synthetic pigments. Natural pigments are those products which are derived from selected ores and should not be confused with iron ores mined for steel production. Iron ores that are mined for steel must be capable of being mined and reduced to iron on a commercial basis. These ores are selected on the basis of iron content and processing economics. It is therefore unusual when iron ores for steel production are suitable for use as mineral pigments. Natural pigment ore sources are selected for their special physical-chemical properties and can command a premium price. Synthetic pigments, and in this instance iron oxides, are those pigments produced from basic chemicals. Through chemical synthesis pigmentary sized particles are produced as opposed to comminution, the major procedure common to all natural iron oxide pigments. Classification An important characteristic of a pigment is its color and, therefore, a logical separation can be made on this basis. A. Yellow Iron Oxide Pigments 1. Natural mineral origin a) Goethite b) Lepidocrocite c) Ochres d) Siennas e) Limonite 2. Synthetic pigments a) Goethite B. Red Iron Oxide Pigments 1. Natural mineral origin a) Hematite b) Siderite (calcined) c) Pyrites (calcined) 2. Synthetic pigments a) Hematite C. Brown Iron Oxide Pigments 1. Natural mineral origin a) Umbers b) Limonite (calcined) c) Siderite (calcined) d) Goethite (bog ore or sulfur mud) 2. Synthetic pigments a) Blends of hematite, goethite, and magnetite

Jan 1, 1983

By D. W. Frommer, M. M. Fine

Mineral dressing research showed that iron concentrates of commercial quality could be produced from the Pea Ridge deposit near Sullivan, Mo. Magnetic separation and flotation, on a laboratory scale, yielded concentrates ranging from 60.0 to 71.4 pet Fe at recoveries of 89.9 to 97.6 pct. Early in 1957 St. Joseph Lead Co. announced discovery of three new centers of iron ore deposition in east central Missouri.' The discovery resulted from exploratory drilling in the vicinity of a magnetic anomaly or high. A deep hole, drilled into the Pre-Cambrian porphyry to determine the cause of anomaly, penetrated a magnetite-rich deposit.' The magnetic surveys that revealed the anomalies were begun by the Missouri Geological Survey in 1929 and were continued into the 1930's.3 At that time an area in Crawford County known as the Bourbon magnetic high was located. A second anomaly, similar in size and intensity, was discovered about six miles to the northeast in Franklin County in the vicinity of Sullivan. This area was not studied in detail until the early 1940's. To determine the cause of the anomalies, the USBM drilled four holes at the Bourbon site in 1943-1944.4 The most productive hole penetrated four mineralized zones having a total thickness of 127.5 ft. These zones contained magnetite in rhyo-lite porphyry at depths between 1600 and 2000 ft. Additional iron ore below 2000 ft was considered a possibility at the time. Some years later, the USGS, Missouri Geological Survey, St. Joseph Lead Co., and others cooperated in sponsoring an aeromagnetic survey of the Bourbon-Sullivan area which resulted in discovery of a third high, about eight miles distant at Pea Ridge. This deposit, with an estimated reserve of 50 to 100 million tons of iron ore, is considered the main find, although other orebodies in the same general area are of definite interest.' When this discovery was announced, St. Joseph Lead also revealed plans to exploit the deposit jointly with Bethlehem Steel Co. A new corporation, Meramec Mining Co., was established, and 1962 was set as the target date for completing physical plant.2 Annual production goals of 2 million tons of beneficiated and pelletized iron ore were proposed. Preparation of the site for shaft sinking was begun in June 1957. Orebody and Character of Samples: Drilling to date has established the Pea Ridge orebody as a crescent-shaped pipe about 300 ft wide. Some drillholes were bottomed at 2800 ft in very good iron ore.6 he orebody is predominantly magnetite, although hematite and a mixture of hematite and magnetite occur in the upper areas and peripheral walls. Drillhole cores representing ore from different areas and depths of mineralization were grouped into composites for testing. These composites consisted of: 1) medium grade mixed hematite and magnetite, 2) high grade mixed hematite and magnetite, and 3) high grade magnetite. The medium grade ore came from three holes with depths of i350 to 1900 ft. The high grade mixed hematite and magnetite cores came from the 1790 to 2812-ft interval of one hole. Partial chemical analyses of the three samples, given in Table 1, reveal that all are excessively high in phosphorus and sulfur, and sample 1 is

Jan 1, 1960

By D. C. Lindley, D. H. Gaucher

The displacement of oil by water in a waterflood project is accomplished by the action of transient viscous, gravitational and capillary forces which drive fluid through interconnecting pore spaces toward production wells. The relative importance of each of these forces to the effectiveness of the displacement and the production history depends on properties of the reservoir itself and the manner in which it is operated. There has been considerable discussion'-3 concerning the importance of these factors and the extent to which they control the performance of individual waterflood projects. No data have been presented, however, to demonstrate the effect on waterflood behavior of variations in rock permeability, water-injection rates and mobility ratios in three-dimensional reservoir systems in which viscous, gravitational and capillary forces are allowed to assume the proper relative influence on fluid flow. Much information relevant to water flooding has been gained from the study of field case histories. But, the complexity of the systems involved, the difficulty of defining geometry and obtaining sufficient data, and the fact that the same reservoir is never flooded twice with the same initial conditions, all obscure the role of process variables such as rate. Further, mathematical calculations of waterflood behavior are restricted at this time by available mathematical techniques to highly simplified situations. Scaled models, however, do offer an approach at the present time to evaluation of the effects of the pertinent variables. Several investigators have predicted prototype reservoir behavior from observations of model waterflood performance under a variety of conditions. Two-dimensional aspects of waterflood pattern efficiency have been investigated by Muskat, Aronofsky, Dyes, et al, raig, et al,' and Rapoport, et al. he effects of gravity segregation, viscous fingering and permeability stratification have also been studied in two-dimensional models. Craig, et al," studied the importance of gravitational forces on frontal displacement in three-dimensional models with wells on a five-spot pattern. This work in- vestigates the tendency for water to segregate in homogeneous reservoirs because of gravity and to under-run the oil for a range of water-inject ion rates. The effects of permeability stratifications were investigated by these authors using miscible fluids to simulate water-channeling through permeable strata in systems of negligible capillary force. In this investigation, a three-dimensional model of a five-spot pattern flood was designed to represent typical prototype conditions, and the sand and liquid properties were selected so that capillary, gravitational and viscous pressure gradients were scaled. It was not, however, possible to achieve exact similitude regarding viscous fingering when the more viscous oil was used. The effects of rock stratification on waterflood behavior were studied by changing both the permeability ratio and the position of the more permeable sand stratum in a two-layered, horizontal model. For each type of stratification, constant-rate floods were performed and the rates were varied, in separate experiments, over a tenfold range. To observe the effect of mobility ratio on flood performance, two series of constant-injection-rate floods were performed on the most highly stratified reservoir at a water-oil viscosity ratio of one.

By Robert M. Grogan

Fluorspar is the commercial name for fluorite, which is the mineral having the composition CaF2, calcium fluoride. Its valuable properties are due to its content of fluorine, and it is the only important commercial source of that element. The name is derived from the Latin fluere, to flow, because the mineral melts easily and is a good flux. History The mineral has been known since Greek and Roman times, when it was used for drinking cups and ornamental slabs. Various peoples including the Chinese and the American Indians have carved ornaments from large crystals. Its usefulness as a flux was known to Agricola, who wrote about it in 1546.1 Mining began in England about 1775 15 and at various places in the United States during the period 1820 to 1840.28 Substantial production was achieved first in the period 1888 to 1900 in consequence of the development and widespread adoption of the basic open hearth method of making steel, in which fluorspar is used as a flux. After that, production and usage was stimulated by growth in the steel, aluminum, chemical, and ceramic industries and accelerated by World Wars I and II. The organic fluorides called "Freons" entered the picture in 1931, and the use of anhydrous HF as a catalyst in the manufacture of alkylate for high octane fuel blends began in 1942. The development of the froth flotation process in the late 1920's, a differential flotation scheme for separating fluorspar from galena, sphalerite, and other minerals in the 1930's, and the application of heavy-media concentrating methods to the treatment of low-grade ores in the 1940's were outstanding technological contributions that enabled increased production of fluorspar concentrates. Composition and Properties Fluorite in its purest form contains 51.1 pct calcium and 48.9 pct fluorine. Substitution of small percentages of cerium and yttrium for calcium have been noted.4 Mechanical inclusions of gases and fluids such as petroleum and water, and of other solid minerals such as pyrite, marcasite, and chalcopyrite are common. The fluorspar of commerce contains attached and admixed mineral impurities, chiefly calcite, quartz, barite, celestite, and various sulfides. It is interesting that the purest commercial form in which the mineral is sold, acid grade concentrate, contains a minimum of 97 pct CaF2, and as such is of comparable purity to many reagents used in chemical laboratories. Fluorite has a marked tendency to occur in large, well-formed crystals sometimes six to ten inches on a side. It crystallizes in the isometric system, frequently forming cubic and octahedral crystals or combinations thereof. The mineral also occurs in massive and in earthy forms, and in crusts or globular aggregates with radial fibrous texture. Crystalline fluorspar exhibits a great array of colors, from colorless and water clear to yellow, blue, purple, green, rose, red, bluish and purplish black, and brown. The colors are often arranged in alternating bands parallel to cube faces. They may be altered by exposure to X-rays, heat, ultraviolet light, and pressure, and are caused by a variety of factors including the presence of trace impurities and displaced ions in the lattice. Sometimes the changes induced by X-rays can be reversed by ultraviolet radiation. The mineral has a hardness of 4, and is the model of that hardness on the Mobs scale.

Jan 1, 1960

By G. M. Ault, G. C. Deutsch

The paper reviews the efforts made to utilize powder metallurgy to solve problems encountered when using alloys at high temperatures. The following subjects are discussed: comparison of wrought and sintered super alloys, sintered aluminum powder, porous materials for transpiration cooling, molybdenum, and cermets. TODAY, powder-metallurgy techniques are be-JL coming increasingly important, producing materials which at the present time cannot be made by any other method. Among these materials are high melting-point metals such as tantalum and tungsten, porous metals for filters and lubricant-containing bearings, electrical contacts and electrodes (i.e., tungsten-copper), cutting tools of the cemented carbides, and magnet alloys. In addition, the powder-metallurgy industry has grown because, through the application of its methods, shaped parts, such as gears, can be produced at tremendous rates with a low scrap loss in comparison with manufacture by casting or forging and machining. In the past few years, by utilizing powder metallurgy, several approaches to the problem of high temperature materials have been investigated. In this paper the authors will review some of the studies on application of materials having properties above 1350°F. Since their experience lies in the aeronautical field, possible uses of powder-metallurgy techniques in the production of aircraft en- gines will be emphasized. A large portion of the work is classified, but such a restriction has not eliminated any field from discussion, although limiting the amount of detail it is possible to present. The development of high temperature alloys from powders and porous metals for cooling will be discussed as well as research done on molybdenum and molybdenum alloys, cermets, and intermetallics. Some studies on the utilization of cermets will be considered along with special problems that have been revealed through these investigations. Special interest in certain factors of sintered aluminum powder (SAP) makes it desirable to discuss this material although its use temperature is below the 1350°F limitation set for this paper. High Temperature Alloys from Powders In general, components made from powders for room-temperature application have been investigated with the primary purpose of taking advantage of the high production rates and economies made possible by powder metallurgy. From the standpoint of properties, the ojective of the powder metallurgist has been to obtain a product comparable to the cast or wrought product that is to be replaced. Comparisons of the properties of alloys made by powder-metallurgy methods with those of similar compositions made by casting and forging are reported in the literature.12 In many cases equivalent

Jan 1, 1955

By W. H. Bassett, C. H. Davis

ALTHOUGH brasses and bronzes have been made for ages, a systematic study of their physical properties has been carried out only during the years of the present century. Among these properties may be included those which are to be detected by means of microscopic examination; in other. words by the science of metallography. The earlier workers in this field, both in this country and abroad, gave their attention to steel. When the senior author explored the situation in 1902, there was little encouragement to be found in undertaking the study of the non-ferrous alloys. A start was made, and the metallography of the brasses and bronzes, as well as of the copper-nickel-zinc alloys developed materially under his direction. Annealing experiments were begun in 1902, and in the succeeding years the effect of temperature, and the influence of previous working, on the grain size of brass were studied. The conclusions so well known and widely published today were largely reached during those earlier years. . In 1905 the first complete annealing series were made. By this it is meant that brass and copper sheet, 5 B & S Nos. hard, was machined into tensile test specimens, then annealed under accurate control for 30 min. at temperatures up to the melting point of the material. Various determinations were made, including tensile strength and elongation in 2 in. There rapidly followed similar series on all of the copper-zinc alloys from 100 to 60 per cent. copper, on the bronzes, cupronickels, and on copper-zinc-nickel alloys. At this point there was published by Grard, in October, 1909,1 the very comprehensive and complete work on the tensile properties of cartridge brass, 90-10 copper-zinc, and electrolytic copper. The excellent photomicrographs in that paper illustrated the changes in structure produced by cold rolling as well as by annealing at different temperatures, but where Grard's work was confined to copper and to two alloys, the investigations in this laboratory have been over the entire fields of the commercial copper-zinc alloys, copper-tin alloys, representative copper-nickel and copper-nickel-zinc alloys as well as aluminum bronzes and others of a more special nature.

Jan 1, 1928