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By John Rogers

The goal of a detailed quantitative understanding of the variables insulfide flotation in terms of established, or new, scientific principles is still distant, although there has been a good beginning in the past 50 years with more rapid progress since 1930. Advances have paralleled closely those in other branches of surface chemistry and the development of a series of experimental techniques such as contact angle, surface area measurement, radioactive tracers, infrared spectra, electron diffraction, monolayer, and electro- chemical methods of investigation. The second editions of books by Sutherland and Warkl ( 1955) and Gaudin2 ( 19571, are detailed accounts of this progress. The complexity of sulfide mineral flotation systems is indicated by Sutherland and Warkl who list 32 variables of flotation, of which only 22 can usually be controlled by the metallurgist. A consequence of this multiplicity of variables, many of which may be specific to each particular ore, is that ways of floating sulfide minerals from new ores are still developed empirically. How- ever, this review will try to show how the chemistry of the function of frothers, collectors, depressants, and activators in sulfide flotation is being steadily unravelled. Chiefly, it will be concerned with the interaction of pure soluble compounds with individual sulfide minerals, the surfaces of which are often not stoichiometric for several reasons discussed by Plaksin.3 As a result, for example, a freshly cleaved galena surface has cathodic and anodic areas which have different degrees of oxidation and different reactivity to- wards collectors like xanthate. Such complicating considerations should be remembered in the subsequent discussion of pure minerals. THE NEED FOR FLOTATION REAGENTS After considerable controversy it has been established with a few exceptions that unoxidized, uncontaminated sulfides will not float. Moreover all flotation plants recovering sulfide minerals use collectors which are removed from the circuit with the sulfides. Gaudin, Miaw, and Spedden4 have discussed the relation between the crystal structure of solids and the native floatability of the exceptions mentioned above. A second question which has been much explored is the nature of the surface on which a collector like xanthate is adsorbed or reacts. Is this the un- changed surface of the sulfide mineral, or does the adsorption depend on the initial oxidation of the sulfide surface ? Sutherland and Warkl and Gaudin2 discuss the work of Taggart5 and others on this question without reaching any other conclusion than that oxygen was important.

Jan 1, 1962

By W. G. Woolf, E. R. Crutcher

The electrolytic zinc plant of the Sullivan Mining Co. is in Government Gulch, at Silver King, Shoshone County, Idaho, in the Coeur d'Alene mining district, about one mile from the Bunker Hill smelter and about three miles from Kellogg. The Sullivan Mining Co., which owns both the zinc plant and the Star mine, is itself owned jointly by the Bunker Hill & Sullivan Mining & Concentrating Co, and the Hecla Mining Company. The Tainton high-density, high-acid process is used at this plant, therefore some parts of its flowsheet differ markedly from those of electrolytic plants using the low-density process. While it is a custom plant and has treated a variety of zinc concentrates originating from various sources in a number of states, it has obtained its main supply of zinc concentrates chiefly from the zinc-bearing ores of the Coeur d'A1ene mining district, of which the principal important sources have been the Bunker Hill and Star mines. Thus the main feed has been zinc concentrates obtained from complex lead-zinc-silver ores. For the year of 1935 the concentrates had the following composition: water, 9.5 per cent; Zn, 50.6; Pb, 3.3; Fe, 9.4; S, 31.0; Cu, 0.2; insoluble, 2.9. Flowsheet The concentrates are delivered to the plant in railroad cars, which discharge into storage bins directly under the track. Bottom-dump cars are dropped directly into the bins while a slip scraper, pulled by an air tugger hoist, is used to empty box cars. There are five storage bins for concentrates, each of approximately 300 tons capacity. At the bottom of each bin there are individual belt feeders that discharge onto a common conveyor belt, which in turn discharges to another belt that carries the concentrate onto a weightometer belt for weighing. Immediately after the weighing, the crushed oversize return from the roasters is added to the load on the belt and then the ground-up sweepings, lumps and roaster cleanings. An electromagnet at the end of this conveyor removes tramp iron from the feed. The belt discharges to a set of 30 by 12-in. rolls, which break up lumps or frozen chunks of concentrate, etc. Beneath the rolls there is a screw conveyor, which conveys the roll discharge to a

Jan 1, 1937

By William Marsh Baldwin

TWO of the most useful and important equations available to the metallurgist for the study of plastic deformation of metals are the Huber-von Mises-Henckyl-~ and the St. Venant7-10 equations. Huber-von Mises-Hengky Equation The Huber-von Mises-Hencky equation answers the question: When does plastic flow occur in metal that is subjected to a multi-axial stress? It occurs, according to this equation, when the three principal stresses,t UI, u2, and u3 satisfy the equation: (<ri - <r2)2 + (<r2 - <rsY + (ff! - <r3)* = 2Ki [i] Here K is the yield strength of the material as determined in an ordinary tensile test. If the quantities ul, 52, andas are assigned to the coordinates of a Cartesian three-dimensional system, this expression describes a cylinder whose axis of symmetry is inclined at equal angles to the three coordinate axes4s6 (Fig. I). The radius of this cylinder is .\/%K. For the purpose of simplicity, it is sometimes advantageous to ascribe the values al/K = sl, az/K = s2, UD/K = SJ to the three coordinate axes instead of the principal stress alone. In this case, Eq. I becomes (*i - s*)1 + (s2 - S3)2 + (si - SiY = 2 [2] and the radius of the cylinder becomes \/%. In the latter method of representation, a point lying inside the cylinder indicates that the metal will react elasti-cally, whereas a point lying on the cylindrical surface indicates that the metal will behave plastically. Some of the geometric features of this cylinder are worthy of study. Let us inquire first as to what interpretation may be placed upon what we will choose to call the "circles of latitude" of the cylinder (L in Fig. I) and the "meridians" of the cylinder (M in Fig. I). Circles of Latitude Circles of latitude are formed by allowing a plane, passing perpendicular to the cylinder axis, to intersect with the cylinder. Any point, P, on this circle is presumed to have the coordinates sl, SZ, and s3. The coordinates of the point resulting from the intersection of the plane and the cylinder axis will be a, a, and a (since the cylinder axis is equally inclined to the three coordinate axes). L?t US now pass a line through the point on the circle and the point on the axis.

Jan 1, 1946

By William Marsh Baldwin

TWO of the most useful and important equations available to the metallurgist for the study of plastic deformation of metals are the Huber-von Mises-Henckyl-~ and the St. Venant7-10 equations. Huber-von Mises-Hengky Equation The Huber-von Mises-Hencky equation answers the question: When does plastic flow occur in metal that is subjected to a multi-axial stress? It occurs, according to this equation, when the three principal stresses,t UI, u2, and u3 satisfy the equation: (<ri - <r2)2 + (<r2 - <rsY + (ff! - <r3)* = 2Ki [i] Here K is the yield strength of the material as determined in an ordinary tensile test. If the quantities ul, 52, andas are assigned to the coordinates of a Cartesian three-dimensional system, this expression describes a cylinder whose axis of symmetry is inclined at equal angles to the three coordinate axes4s6 (Fig. I). The radius of this cylinder is .\/%K. For the purpose of simplicity, it is sometimes advantageous to ascribe the values al/K = sl, az/K = s2, UD/K = SJ to the three coordinate axes instead of the principal stress alone. In this case, Eq. I becomes (*i - s*)1 + (s2 - S3)2 + (si - SiY = 2 [2] and the radius of the cylinder becomes \/%. In the latter method of representation, a point lying inside the cylinder indicates that the metal will react elasti-cally, whereas a point lying on the cylindrical surface indicates that the metal will behave plastically. Some of the geometric features of this cylinder are worthy of study. Let us inquire first as to what interpretation may be placed upon what we will choose to call the "circles of latitude" of the cylinder (L in Fig. I) and the "meridians" of the cylinder (M in Fig. I). Circles of Latitude Circles of latitude are formed by allowing a plane, passing perpendicular to the cylinder axis, to intersect with the cylinder. Any point, P, on this circle is presumed to have the coordinates sl, SZ, and s3. The coordinates of the point resulting from the intersection of the plane and the cylinder axis will be a, a, and a (since the cylinder axis is equally inclined to the three coordinate axes). L?t US now pass a line through the point on the circle and the point on the axis.

Jan 1, 1946

By John H. Holloman

In recent papers, O&apos;Neill,&apos; Vivian, and Zener and Hollomon3 have reviewed some of the information concerning the relations between stress and strain during plastic deformation. Since further information has been obtained since these reviews were published, this paper attempts to further coordinate and amplify the knowledge concerning the plastic deformation of metals in simple tension. Ordinarily the results of tensile tests of metals are presented as graphs in which the load divided by the original area is plotted as a function of the percentage of elongation measured over some specified gauge length. The interpretation of graphs of this sort is limited, since the stress required to deform the metal at any stage of the deformation is actually the load divided by the instantaneous rather than the original area. Furthermore, each increment of the deformation is performed on metal that has been previously deformed, and, as pointed out by Ludwik,4 the strain could be more effectively defined: where e is the strain and AO and A are, respectively, the original and instantaneous areas. The results of the tensile tests can be more effectively presented and interpreted if the stress* (load divided by actual area) is .lotted as a function of the strain as defined above. A schematic curve of this type is presented as Fig. I. In a previous paper,6 the concept of Ludwik7 concerning the flow and fracture of metals was successfully employed to explain some of the puzzling results of notched-bar impact tests of steel. It appears that the use of this concept ii; very fruitful and should be kept in mind in any study of the deformation charactcristics of metals. Ludwik considered that a flow stress-strain curve of a metal was essentially a locus of points that described the stress required for plastic flow of an infinite numbcr of specimens, each with a different strain history determined by the preceding part of the flow curve Each of these specimens can also be considered to have a fracture strength. Uniortunately (or fortunately depending upon the point of view), all the specimens, except the one deformed to the fracture strain, flow and do not fracture. Even though the metals do not fracture, the concept of a fracture-strength curve seems

Jan 1, 1945

By Richard Moldenke

One of the little-known characteristics of cast iron, which nevertheless has an important bearing on results where accuracy in machining is essential, is the ability of this material to ease up internal strains when allowed to remain quiescent for a more or less extended period of time. It seems as if the molecules in such a casting, by virtueof their "mobility," can adjust their relative positions to an extent sufficient to overcome some of the existing stresses. The following instance will perhaps give a fair idea of the condition a casting may be in when just shaken out of the sand. A very large sheave-wheel, after shaking out, was taken outdoors to be cleaned and made ready for turning up. It was leaned against the side of the building, but before much could be done an arm tore apart with a loud report. Investigation showed that the sun had been shining on the upper rim, thus adding a slight strain to those already existing within the arm and thus overbalancing the strength of the metal in tension. Had this sheave been kept under cover for a while, or at least until machined, the strains would have eased off sufficiently to allow the sun to look upon it without disaster. It will not be necessary to multiply examples. Every engineer knows the danger of water-hammer in pipe lines, particularly if the latter are of cast iron. Every mechanic knows, or should know, that it is not good to strike a fitting that is under steam pressure. It will be necessary to say a few words on the "internal strains" in castings—the so-called "casting strains" we hear so much about. We all know that to get a casting reasonably true to the dimensions wanted requires a slightly larger pattern. The usual allowance for gray iron is 1/8 in. to the foot (1 cm. per meter) and 1/4 in. to the foot (2 cm. per meter) for white iron (all dimensions). This reduction in length, breadth and thickness in a casting is erroneously called "shrinkage." It should be called "contraction," as for practical purposes it is simply the difference in dimensions of the casting red-hot and cold. The real "shrinkage" covers an entirely different situation. When a

Jan 1, 1917

Discussion of the paper of Edward Keller, presented at the Butte meeting, August, 1913, and printed in Bulletin No. 80, August, 1913, pp. 2093 to 2115. GEORGE L. HEATH, Hubbell, Mich.:-In the admirable paper quoted, is mentioned the date when the 5-g. assay was first proposed is a standard for refined metal. The author omitted, however, to mention a later paper,1 which contains a proposal for the use of a single " stock solution " of mixed acids, which has been adopted by the American Brass Co. and others. The suggestion is made that such a scheme would save time and manipulation with converter metal. Unless the low current of 0.5 ampere and the large excess of nitric acid, recommended by Mr. Keller, have been proved necessary to hold up antimony-and selenium, the use of the mixed solution which we have adopted will permit the use of 1 ampere of current per square decimeter of cathode surface, until the solutions have become colorless. At this point, we wash the covers and reduce to 0.5 ampere to prevent oxidation or contamination. The ordinary split electrodes have been used. With strong current, at least, the use of an excess of nitric acid tends to the neutralization of the solution before the end of the period, from the formation of too much ammonia., and this is detrimental. Antimony deposits more easily than arsenic, and tends to drag the latter dorm with it. There must, be some such explanation for the fact. that we have made hundreds of deposits of pure cathodes from Lake material containing no antimony, but as. high as 0.5 per cent. of arsenic. By placing an assay beaker in the Frary solenoid, or rotary device, a cathode deposit with less than 0.01 per cent. of impurity is easily obtained in one operation from 3 g. of whitneyite, carrying from 7 to 10 per cent. of arsenic. In such a case, it is necessary to test several times for end point and remove the plate as soon as no brown tint appears (at once) when hydrogen sulphide water is added to the test portion on the spot plate. Edward Keller&apos;s proportion,, of solvent figure out as 14 cc. of strong nitric to 11.4 cc. of sulphuric acid (1.84).

Jan 11, 1913

By E. A. Calnan, B. E. Williams

IN the development of a new treatment for the prediction of deformation textures,&apos;-&apos; it was noted that for no metals are there experimentally determined tension textures with which the predictions may be compared. There is a considerable knowledge of drawing textures and previous workers have been content to consider these as equivalent to tension textures for the purposes of comparison. It is shown, however, in the new treatment that the tension and drawing textures are not necessarily identical, the radial compression exerted by the dies in the drawing operation producing some modification of the tension texture. In particular for the face-centered cubic metals it is predicted that for drawing the final texture should be [1ll] with a spread towards [211] (a more detailed derivation of this texture has been made by Calnan3). This has been amply confirmed by experiment, see Hibbard.6 For the pure tension case, however, the treatment predicts intermediate [1ll] and [loo] textures leading to a [211] end-point, while all previous treatments have predicted the final texture as [1ll] with in some cases an additional [loo] component. Thus evidence that the pure tension end-point is the [211], or at least that [1ll] and [l00] are not the final textures, should provide a valuable test of the new treatment. Accordingly some experiments were made on aluminum. Three aluminum specimens were examined in detail, one of cold-rolled high purity rod (99.99 pct), specimen A, and two of commercial extruded rod of purity 99.4 pct, specimens B and C. The initial annealing treatments were: A, 1½ hr at 400°C; B, 2 hr at 400°C; C, 1½ hr at 650°C. The principal difficulty is that of obtaining sufficient elongation before fracture occurs. This was overcome to some extent by giving a softening heat treatment, 1 hr at 300°C, after each 15 pct of extension. Vickers hardness measurements gave values before and after the softening treatment of about 30 and 28, respectively, in comparison with the initial value of about 19 corresponding to fully annealed material. From recent observations in this laboratory it is concluded that this small recovery corresponds to a polygonization process rather than recrystallization proper and consequently the preferred orientation is unaffected. At the higher extensions, however, some slight necking of the specimens took place and it was necessary to turn them down to a uniform cross-section before

Jan 1, 1953

By T. Wasson

Midland and Isabella counties have been the centers of activities for the year 1932. The major part of the 6,967,000 bbl. produced during the year was obtained from the old Mt. Pleasant field and the Eastern Extension field. The total production to the end of 1932 for Michigan, from all fields since discovery, is 20,679,600 bbl. Production in the Eastern Extension field was obtained from Dundee limestone of Devonian age, at a depth of about 3600 ft. As a result of the year&apos;s activity in this area, the limits of the Eastern Extension have been defined. No new fields have been discovered. A number of prospective areas have been drilled and condemned by dry holes. Probably the most outstanding development of the year was the discovery of oil on the Yost farm, in sec. 35 of Greendale Township, Midland County, by the Pure Oil Co., in the early part of December. Production is from the Dundee limestone similar to that in the Eastern Extension but is 4 miles south of that area. The first well has averaged about 500 bbl. per day since completion. It is near the center of a solid block held by the Pure Oil Co., so that rapid development due to competitive drilling is not expected. During the early part of the year the Midland-Isabella area was under proration, but on May 17 proration restrictions were discontinued and remained so until the end of the year. While the Eastern Extension saw the principal activity, some work was done in other fields of Midland and Isabella counties, but very little new production was added. The Vernon field on the north showed a slight increase in production over 1931. The Leaton field decreased. The well in Porter Township, Midland County, is still kept in the production ranks but very little drilling was done in that area. The old Saginaw field, Saginaw County, still remains the only spot in the state where commercial production is obtained from the Berea sand. It showed a slight decline over 1931 with no new producers for the year. The Muskegon field on the west side of the state showed a considerable decline over 1931, but owing to the rejuvenation of some wells by the use of acid this drop was not as great as might have been expected. Only two new producers were drilled in that area.

Jan 1, 1933

By S. J. Leach

The possible solution of some of the problems raised in H. L. Hartman&apos;s article "Determining Ventilation Requirements for Continuous Miners," which appeared in the March 1962 issue of MINING ENGINEERING, is offered by recent investigative work done at the Safety in Mines Research Establishment, Ministry of Power, Sheffield, England. Highlights of this research are outlined here. Accumulations and layers of methane form in a mine roadway because it is difficult to mix methane with air beneath it by turbulent diffusion. Such mixing involves work contrary to buoyancy forces. In specifying requirements for good ventilation it is not, therefore, sufficient to state that the airflow must be turbulent in the absence of methane. Fundamental work at SMRE on the behavior of methane roof layers has led to the formulation of rules for controlling methane roof layers which specify the ventilation velocity needed to ensure adequate mixing in terms of the rate of flow of methane into the layer (V = cu ft per min) and the airway width (D = ft). A "layering number" for methane and air has been defined by [U37/V/D] where U is the mean ventilation velocity in ft/min in the upper half of the airway. In a horizontal airway there is no mixing by turbulent diffusion for values of the layering number less than about 2, resulting in extensive roof layers. But with a layering number of 5, the layer is "brought under control"-i.e., a further increase in the layering number will shorten the length of the layer only slightly, and a small decrease in the layering number will cause only a small increase in the length of the layer. In a sloping roadway with uphill ventilation, higher values of the layering number are needed to achieve this "controlled" condition; the values range from about 5 at small slopes to about 8 at a slope of 1: 10. In downhill ventilation it is possible for layers to "back" against the ventilation, i.e., to flow uphill. The critical condition for preventing backing can also be expressed in terms of the layering number. Backing will be prevented if layering numbers are about 3 for small slopes and about 4.5 for large slopes; these values for downhill ventilation also give good control of the layer.

Jan 10, 1962

By H. G. Botset

A KNOWLEDGE of the water content of producing sands is becoming of increasing importance to the petroleum industry. It is now a generally accepted fact that practically all oil sands contain some free water. Recent experiments1 have shown that an appreciable fraction of the pore space of a sand may be filled with water while oil production from this sand is water-free. Crowther and Haines,2 in experiments on electro-endosmosis in soils, reported that there was no endosmotic flow of water when the moisture content of the soil was 14 per cent or less, indicating that the moisture content of the soil below 14 per cent was held by dif-ferent forces than the water content above this value. This result is confirmed qualitatively by Dunlap,1 who found that "as the volume of water in the voids exceeds approximately 15 per cent of the pore volume, the permeability of the core to kerosene is markedly reduced." The author3 has also found in other experiments that the gas flow through a water-saturated sand reaches essentially 100 per cent when the pores of the sand still contain from 10 to 15 per cent water. The velocities of the flowing fluid in the experiments cited were comparatively high, so that in practice one may expect, at lower fluid velocities, an even higher moisture content of the sands with water-free oil or gas production. Thus a knowledge of the water content of oil-field sands becomes of con-siderable importance in estimating petroleum and gas reserves, and effi-ciency of fluid recoveries from depleted reservoirs. Rapid and reasonably accurate methods of measuring the water content of sand cores have not been described so far in any literature that has come to our attention.4 The method described below is devel-oped from methods that have been used for some time to measure the water content of alcohols.5,6,7 It is an application of the fact that in the presence of certain organic liquids such as kerosene, carbon tetrachloride, xylol, etc., water and alcohol are only partly miscible. This relation-ship has been used for some time in the study of gasoline-alcohol mixtures where the presence of small quantities of water affect the solubility of

Jan 1, 1938

The Telfer Project, one of the world&apos;s newest gold mines, is located about 300 km (190 miles) northeast of the Mt. Newman iron ore project in the northern part of Western Australia. The first mineral claims were staked in 1972; and by mid-1975 ore reserves of 3. 8 million mt (4. 19 million st) of 9.6 g per mt (0. 28 oz per st) ore had been indicated. It is interesting to note that Newmont spent more than 10 years and A$10 million in Australia for extensive mineral exploration before finding the Telfer deposit, and then spent approximately A$3 million in exploration and feasibility engineering on Telfer. Including this A$3 million, a total of A$27 million was spent to complete construction of the mine, village, gold treatment plant and associated roads, airport, water and services. Over 50% of the capital cost is in the metallurgical facility, or approximately A$10, 000 per ton per day. All economically significant gold mineralization at Telfer occurs in a series of layered quartz-limonite reefs in which the former pyrite has been oxidized to limonite to a depth of 100 m (330 ft). The most important gold reef occurs at the base of the siltstone-shale horizon within the enclosing sandstone dome -like structure. At the Main Dome structure the dipping ore horizons will be mined to a vertical depth of about 60 m (200 ft) by open-cut methods. The waste-to-ore ratio is approximately 12:1. Eventually 44 million mt (48. 5 million st) of ore and waste will be mined. Mining of the waste is by contract; however, the ore and a thin layer of waste is company-mined. Dilution from mining the geological ore reserve is about 10%. The ore is completely oxidized and the gold occurs free within the reef, material as discrete particles of varying but mainly fine grain size. Most of the gold is "free milling"; that is, over 50% of the gold is coarse enough to be recoverable by gravity concentration. Two duplex mineral jigs receive the two cyclone underflows from the grinding circuit. The rougher jig concentrate is up-graded on a continuous strake from which the concentrate is tabled to produce a final free gold product. Jig tailings are returned to the ball mill and the concentrates are amalgamated. Gold amalgam is pressed, retorted, and melted into gold bars. The gravity gold recovery circuit is the same as was used in many of the gold mills in California in the 1930s.

Jan 1, 1981

By Ralph Hultgren, Bernard York, David W. Mitchell

It is a well-known fact that magnesium-alloy castings are apt to be coarse grained if the melt is not superheated several hundred degrees above the melting point before casting. (The casting temperature varies according to the shape of the mold. A typical casting temperature is perhaps 1400°F.) British practice is to heat to 900°C. (1650°F.) for 15 min., cool rapidly to casting temperature, and cast.&apos; In Germany superheating is carried out at 850&apos; to 900°C. (1560° to I650°F.) depending on the amount of scrap used. It is stated that further refinement will be obtained by prolonging the period of superheating or by increasing the superheat temperature to 950°C. (I740°F.).2 In the United States superheating is carried out at 1600&apos; to 1700°F. (871&apos; to 927°C.), perhaps even higher in some places. It is stated that superheating effects are found as low as 1500°F. (816°C.), but several hours are required.3 These commercial treatments lead to grain sizes in sand castings that may vary from 4 to 8 grains per sq. mm.! in heavy sections and from 60 to IOO in 1/2-in. sections to perhaps 380 in thin sections. It is also generally known that the refining effect of superheating is lost if the melt is held for some time at lower temperatures before casting. Aside from these very qualitative statements, there is little to be found in the literature as to the effect of temperature and time of superheat on the final grain size. Because of the uncertainty of these factors, the Office of Production Research and Development of the War Production Board placed a research contract with the University of California, supervised by the War Metallurgy Committee. This research, which was done under the "Restricted" Project NRC-550, is the basis of this paper, which has been released for publication by the O.P.R.D. The material studied was an alloy prepared from carbothermic magnesium. The temperatures required for grain refinement proved to be widely different from those used in practice, as described in the statements in the first paragraph. This difference is attributed to the fact that the magnesium in the specimens was of carbothermic origin instead of the electrolytic magnesium in common use. Materials and Methods The magnesium alloy studied was one of the most popular sand-casting alloys, with a nominal composition of 9 Per cent aluminum, 2 per cent zinc, and 0.1 per cent (minimum) manganese and the balance magnesium. This is designated

Jan 1, 1945

By Ralph Hultgren, Bernard York, David W. Mitchell

It is a well-known fact that magnesium-alloy castings are apt to be coarse grained if the melt is not superheated several hundred degrees above the melting point before casting. (The casting temperature varies according to the shape of the mold. A typical casting temperature is perhaps 1400°F.) British practice is to heat to 900°C. (1650°°F.) for 15 min., cool rapidly to casting temperature, and cast.1 In Germany superheating is carried out at 850° to 900°C. (1560° to 1650°F.) depending on the amount of scrap used. It is stated that further refinement will be obtained by prolonging the period of superheating or by increasing the superheat temperature to 950°C. (1740°F.).2 In the United States superheating is carried out at i600° to 1700°F. (871° to 927°C.), perhaps even higher in some places. It is stated that superheating effects are found as low as 1500°F. (816°C.), but several hours are required.3 These commercial treatments lead to grain sizes in sand castings that may vary from 4 to 8 grains per sq. mm.§ in heavy sections and from 60 to l00 in 3-in sections to perhaps 380 in thin sections. It is also generally known that the refining effect of superheating is lost if the melt is held for some time at lower temperatures before casting. Aside from these very qualitative statements, there is little to be found in the literature as to the effect of temperature and time of superheat on the final grain size. Because of the uncertainty of these factors, the Office of Production Research and Development of the War Production Board placed a research contract with the University of California, supervised by the War Metallurgy Committee. This research, which was done under the "Restricted" Project NRC-550, is the basis of this paper, which has been released for publication by the O.P.R.D. The material studied was an alloy prepared from carbothermic magnesium. The temperatures required for grain refinement proved to be widely different from those used in practice, as described in the statements in the first paragraph. This difference is attributed to the fact that the magnesium in the specimens was of carbothermic origin instead of the electrolytic magnesium in common use. MATERIALS AND METHODS The magnesium alloy studied was one of the most popular sand-casting alloys, with a nominal composition of 9 per cent aluminum, 2 per cent zinc, and 0.r per cent (minimum) manganese and the balance magnesium. This is designated

Jan 1, 1945

By Robert E. Green, P. W. Kingman

Application of a constant geometry compression test to single crystals of aluminum of selected diameters from 1/4 to 1/64 in. showed the presence of a diameter-dependmt size effect. The most pronounced effects were found in those crystals oriented for single slip, while for specimens possessing orientations in the comers of the standard stereographic triangle virtually no size effect was exhibited. The yield stress of the crystals oriented for single slip was found to increase with decrease in specimen diameter, while the strain-hardening rate was found to be lower for the smaller specimens. The experimental results are in general agreement with those of other investigators obtained from lensile tests on copper and aluminum crystals. THE earliest systematic investigation of a possible size effect on the plasticity of metals was that of no,&apos; who in 1926 performed tensile tests on cylindrical aluminum single crystals with diameters of 3 to 8 mm. Ono concluded that the gross stress-strain curve did not show a diameter dependence, but that the resistance to slip for strains of 0.1 pet and less appeared higher for 3-mm-diam crystals than for larger sizes. Later studies of aluminum by Maddin et al2 tentatively concluded that a size effect exists, but the conclusions were again open to question because of inconsistencies in the experimental data. Wu and Smoluchowski3 had previously shown that the slip system activated in a single-crystal sheet specimen of aluminum is a function of the specimen cross section in the slip direction, but no stress-strain data were obtained. Subsequently Fleischer and Chalmers4 studied the effect of the length of the slip direction of the primary-slip system on the stress-strain curve by testing aluminum crystals with geometrically dissimilar cross sections. In the course of this investigation a size effect was indicated in rather large crystals; however, the number of these tests was small. Other investigators have indicated that a size effect in aluminum is appreciable only for diameters of 0.5 mm or less.5, 6 Size-effect studies have also been carried out on copper crystals, the most detailed being that of Suzuki et a1.7 who performed tensile tests on specimens of many diameters ranging from 2 to 0.12 mm. Suzuki found a strong size dependence in the easy-glide region, both the extent of the easy glide and the hardening rate in easy glide were size-dependent, and the size effect was found to be orientation-dependent. Suzuki&apos;s results are in agreement with the less extensive observations of Pater-sonB and those of Garstone et al.9 A size effect was found by Rebstock using tubular copper crystals.&apos;0 Size effects have also been noted in a brass,6, 11 in cadmium,12&apos;19 and in hexagonal crystals.14 All the previously cited works have been entirely concerned with the variation of specimen cross section. The effects of specimen length and the change of specimen geometry which results from using progressively thinner specimens while maintaining the same specimen length have been largely ignored. A theoretical discussion of the effects of specimen length and geometry has been given by Hauser and Jackson,15 who predict a grip effect on easy glide as a function of specimen geometry provided that the specimen dimensions are large compared with the spacing between the slip bands, and by Fleischer and Chalmers,18 whose analysis of grip effects resulting from lattice rotation predicts an increase in easy glide with an increase in specimen length. A study of size and geometry effects in aluminum crystals by Kitajima and shimba17 indicated increasing amounts of easy glide in specimens of increasing length and identical cross section, and nearly identical stress-strain curves for specimens of different sizes having constant length-to-diameter ratios. Since the present study is primarily concerned with diameter dependence, the following factors were taken into account: specimen material, specimen geometry, testing method, range of sizes to be tested, and possible influence of surface and volume effects. Aluminum was chosen because of the present lack of conclusive results and the seeming possibility of size effects at relatively large diameters, the

Jan 1, 1964

By J. C. Shyne, T. D. Gulden

The steady-state creep behavior, in compression, of indium containing a dispersion of atomized glass particles was studzed over a range of temperature, stress, and composition. The observed behavior was not consistent with a simple model of dislocation climb over dispersed particles. From room temperature to about 100°C the temperature dependence could be described by an activation energy about one and a half times that of self-dijfusion in indium while at higher temperatures a much higher ternperature dependence was observed. THE value of dispersion-hardened and precipitation-hardened alloys has long been recognized. The mechanism of hardening, however, is not completely understood, especially at elevated temperatures where dispersed particles increase creep resistance. Following the suggestion of Schoeck1 that the rate of creep in dispersion-hardened materials is controlled by dislocation climb over second-phase particles, Ansel and weertman2 derived steady-state creep equations for dispersion-hardened materials. Their derivation was based on dislocation climb over non-deformable spherical particles in a metallic matrix. For low stresses they predicted a linear relation between applied stress and steady-state creep rate. For stresses large enough to cause dislocations to pinch off around the precipitate particles, the theoretical creep rate was shown to be proportional to the fourth power of stress. For very high stresses an exponential stress dependence was predicted. In all cases the theoretical creep rate is linearly proportional to the diffusion coefficient. This provided the primary temperature-dependent factor. Subsequently, Ansel and Lenel3 reported some experimental data on SAP, a composite of aluminum and aluminum oxide, that was in good qualitative agreement with the above theories. Their experimental creep rates, however, were four orders of magnitude less than the theory predicts. This was attributed to a low density of active dislocation sources in the material; somehow the dispersed particles inactivated the dislocation sources instead of merely interferring with dislocation motion. Meyers and sherby4 have recently reported on the creep behavior of SAP. Their results were inconsistent with a simple dispersion-strengthening model and led them to conclude that a continuous network of oxide controls the high-temperature mechanical characteristics of SAP. Because of the rather complex mechanical behavior of SAP and the lack of agreement about the morphology of its oxide phase, it appeared desirable to study the creep of a dispersion-strengthened material of controlled morphology. For the present work a dispersion of spherical glass particles imbedded in a matrix of indium was chosen. The microstructure of this material was similar to the idealized uniform dispersion of hard spheres in a deforming matrix assumed by Ansel and Weertman in their theoretical treatment. SPECIMEN PREPARATION For experimental convenience, it was decided to use a low melting-point metal in this investigation. It was necessary that the metal not be oxidized readily up to its melting temperature and that it wet the second-phase particles. It was desired that the material chosen for the dispersed phase be available as a fine powder with closely controlled size and shape. The material chosen to satisfy these requirements consisted of a matrix of indium metal containing a dispersion of atomized particles of a soft soda-lime-silica glass ranging from 5 to 30 µ in diam. The glass particles had a highly regular spherical shape. The composite was made by stirring the glass powder into liquid indium maintained at a temperature just above the melting point of indium, 156°C. The creep specimens were prepared by a hot pressing operation. Five to ten g of the mixture were placed in a steel die and pressed at 125°C for 5 min under a pressure of 30,000 psi. The resulting specimens were cylinders about 3/8 in. in diam and ranged from 0.4 to 0.7 in. high. By following this procedure a uniform dispersion was obtained in the creep specimens. Typical microstructures of specimens containing twenty and forty volume percent glass powder are shown in Figs. 1 and 2. Unfortunately, grain size could not be determined by the metallo-graphic techniques used. CREEP TESTING PROCEDURE Creep tests were performed in compression under constant stress. The specimens were placed in

Jan 1, 1963

E. A. Loria (Product Metallurgical Engineer, Crucible Steel Co. of America, Pittsburgh)—In this interesting paper, our introductory work was quoted. We would like to call attention to our sequel paper on the experimental determination of oxygen in cupola-melted cast iron,20 which was not mentioned. Vacuum-fusion oxygen values (as well as hydrogen and nitrogen) were reported for nine heats of cast iron melted in the Battelle 10-in. cupola under normal operating practice and under oxidizing conditions. The oxygen analyses ranged from 12 to 68 pprn compared to the author&apos;s computed range of 10 to 80 ppm. The average amount of oxygen found in our irons was about 20 pprn and changes in the silicon content of the iron from 1.32 to 2.35 pct had no consistent effect on the oxygen content of the iron. The gas determination specimens were poured in split steel molds that produced a clean pin, 3/8 in. diam and 2 in. long. Because freezing was almost instantaneous, the pins were entirely white iron (nongraphitic). In the early stages of the investigation, the pins were transferred to a mercury-filled trap system immediately after pouring. This was done to collect gas evolved between pouring and analysis. However, it was found that during storage for 4 weeks gas evolution was negligible. Because the vacuum-fusion analysis was usually completed within 4 days of pouring, pins from later heats were not stored in the mercury-trap system. We found some evidence that cast iron picks up oxygen during long storage, because of rusting. Earlier work by the British Cast Iron Research Association has shown that cast irons may be stored for a long time without significant change in their oxygen content. The practical significance of this study (and our own) would be in the improvement of cast-iron quality. Has the author investigated this aspect and reached any conclusions on the effect of oxygen on the mechanical properties of cast iron? The second phase of our study was to determine the properties of the test bars poured simultaneously with the gas analysis specimens. We realize that there may be complicating factors attendant in this procedure.21 Results from many test specimens measuring chill depth, transverse flexure and deflection strength, spiral fluidity, and sensitivity to hardness of gray irons ranging from 12 to 68 pprn oxygen showed that the lowering of transverse strength was the only significant undesirable effect of high oxygen content. A statistical study of the chill test results21 showed that the iron containing 22 to 46 pprn oxygen had forced chill depths that were 2/32 in. below the expected value from their composition, and irons containing less than 16 ppm oxygen had forced chill depths averaging 1/32 in. greater than the expected chill depth. Higher oxygen contents, within the range of 12 to 68 pprn did not increase forced chill depth. With the wedge tests, there was a good linear relationship between carbon equivalent of the irons and their chill depth. The results indicated that oxygen contents below 50 ppm in the iron did not affect chill depth. With 50 to 70 ppm oxygen in the iron, oxygen appeared to have a slight graphitizing tendency. These results are in disagreement with the common belief in gray iron foundries that "oxidized irons" produce high chill depths. It would be appreciated if the author would comment on this subject. Gustaf Ostberg (author&apos;s reply)—In Fig. 1 the legend of line I should read 2 pct C, 1 pct Si. The author wishes to thank Mr. Loria for calling attention to his later work, which was published after the present paper was concluded. The range of oxygen contents quoted seems to agree well with the author&apos;s values. The lack of response to variations in silicon content is probably due to the fact that the oxygen content in most cases was below the saturation level. The absence of temperature dependence, even in the case of saturation, is understandable if the difficulty in formation and escape of the deoxidation products is taken into account.

Jan 1, 1960

By Donald B. Evans, Robert D. Pehlke

The solubility of nitrogen in liquid Fe-B alloys has been measured up to the solubility limit for the formation of boron nitride. The activity coefficient of nitrogen increases with increasing boron content in the range 0 to 7 wt pct B. From experimen -tal data, values have been calculated for the B-N interaction parameter e3 at temperatures in the range 1550" to 1750°C. A value of 0.038 has been estimated for the boron self-interaction parameter eg at 1550°C. The standard free energy of decomposition of boron nitride into the elements dissolved in liquid iron has been determined to be: ?F° = 45,900 -21.25T in the range from 1550° to 1750°C. The nitride is assumed to be of composition BN. BORON nitride has an unusual combination of properties which make it appear attractive in a wide range of engineering applications. Some of its more important and most recent applications are in the nuclear area, particularly in connection with the liquid-metal cooled reactor concept now receiving considerable emphasis. Boron nitride has a high degree of stability at elevated temperatures. It also has excellent ma-chinability and the ease with which its crystals deform suggests applications as a lubricant. These properties stem from a hexagonal layer-type structure similar to the structure of graphite. One of its primary uses to date has been for seals in liquid-metal pumping systems. It is also used in nuclear reactors as an insulating layer to separate two solid metals which are not themselves compatible under the conditions of temperature and atmosphere in which they are used. Its inertness to liquid metals has also suggested use as a mold-release agent in casting processes. In addition to its excellent machinability and reported inertness to liquid metals such as iron, silicon, aluminum, copper, and zinc, boron nitride has high thermal conductivity and excellent thermal shock resistance. This combination of properties would make it appear ideal as a refractory crucible material for refining of high-purity liquid metals, for example high-quality steels. However, since it is known that concentrations of boron as low as 50 ppm can have a marked effect on the physical properties of certain steels,&apos; in particular on the creep and stress-rupture properties, an investigation was undertaken to define accurately the chemical equilibrium among boron, nitrogen, and liquid iron in the range of steelmaking temperatures. EXPERIMENTAL PROCEDURE Two experimental approaches to this problem were employed: a Sieverts&apos; method and a quenching method. In the first method, the Sieverts&apos; technique was used to measure the equilibrium nitrogen solubility in liquid Fe-B alloys of 0 to 7 pct B as a function of nitrogen gas pressure over the melt. The solubility limit of the boron nitride phase formed was determined by the point of departure of the nitrogen absorption from Sieverts&apos; Law. This technique has been applied to liquid Fe-Ti alloys by Rao and parlee,&apos; to liquid Fe-A1 alloys by Evans and Pehlke,3 and to solid Fe-V alloys by Fountain and Chipman.4 In the second method a melt of liquid iron was held in a crucible of boron nitride under a known partial pressure of nitrogen gas. After thermodynamic equilibrium was attained, the melt was quenched in a stream of helium and then analyzed by wet-chemical methods for boron and nitrogen. The Sieverts&apos; apparatus used in the first method was essentially of the same design as the one described by Pehlke and Elliott.5 The charge materials were vacuum-melted high-purity iron (Ferro-vac E) supplied by the Crucible Steel Co. and -325 mesh boron powder supplied by Cooper Metallurgical Associates of Cleveland, Ohio. The boron contained less than 0.02 wt pct O, according to supplier&apos;s analysis. Recrystallized alumina crucibles were used to contain the melt. Examination of solidified melts showed these crucibles to be satisfactory with no evidence of any reaction or physical penetration of the crucible wall by the melt. The melt temperature was measured by a disappearing filament-type optical pyrometer sighted vertically downward on the melt surface through a 1/4-in.-diam sight hole in the crucible lid. The pyrometer was calibrated against the melting point of pure iron in the same apparatus, taking the emissivity of

Jan 1, 1964

By R. M. N. Pelloux

This study of aluminum-copper alloys had two aims: 1) To determine the effect of the amount and distribution of a second phase, CuAl2, on the creep-rupture strength, ductility, and fracture characteristics of the alloys. The work of Gemmell and grant&apos; on single-phase aluminum-copper alloys provided a basis for the present study. 2) To attempt to provide a relation between the microstructure and strength of two-phase alloys deformed at comparatively high temperatures (greater than 0.45 T,). The creep behavior of the two-phase magnesium alloys Mg;Ce and Mg-A1, has been treated by Roberts. 9 In work reported by Sully and Hardy4 and by Underwood, Marsh, and Manning~ on A1-Cu two-phase alloys, and also in a portion of the work of Gemmell and grant,&apos; aging took place during the creep tests. &apos;In the present work, overaged aluminum-copper alloys were subjected to creep deformation at two temperatures, 500 and 700OF. The overaging treatments to produce the precipitate dispersions were performed prior to the test, at temperatures which were the same as the ultimate respective test temperatures. Hence, the present study is concerned with the creep behavior of stable (in contrast to "underaged") two-phase A1-Cu alloys, i.e., alloys in which no depletion of the solid-solution matrix occurred during: creep. MATERIALS AND PROCEDURE A 2 and a 3 pct Cu alloy, supplied by Alcoa, were studied; Table I shows the compositions. The grain size of the specimens, 0.9 to 1.0 mm, was achieved by annealing the machined test bars for 2 hr at 1000°F, followed by furnace-cooling to 900°F, and homogenizing for 4 hr. Both compositions are in the single-phase condition at 900°F. Two types of overaged dispersions, termed "over-aged I" and "overaged 11" were prepared after the grain size and the homogenization anneals. The overaged I alloys were prepared by quenching to room temperature after homogenization, aging at either 500&apos; or 700°F for 72 hr, and air-cooling to room temperature. The overaged I1 alloys were prepared by furnace-cooling after homogenization, to either 500&apos; or 700°F, and holding at the necessary temperature for 72 hr. The times for furnace-cooling from 900°F to 700° and 500°F were, respectively, about 2 and 3.5 hr. The structures of the A1-2 pct Cu alloys are shown in Fig. 1 (overaged I) and in Fig. 2 (overaged 11). A comparison of Figs. 1 and 2 shows that in the overaged I alloys the precipitate particles along the grain boundaries are much more closely spaced and the grain boundaries are straighter than they are in the overaged I1 alloys. Further, the particle size and spacing in the grains are smaller than in the overaged I1 alloys. Microstructures of the A1-3 pct Cu alloys have not been shown; the structures of these alloys differed from those of the A1-2 pct Cu alloys only in that the distribution density of the particles was greater. The creep specimens had a gage section 1 in. long with a diameter of 0.155 to 0.195 in. Before testing, specimens were electropolished in a solution of 100 cc glacial acetic acid, and 30 cc of 60 pct perchloric acid, at 40&apos; to 50°F, at 24 v. The specimens were kept refrigerated prior to testing to avoid precipitation at room temperature. Constant stress creep tests were conducted; the load was applied 75 min after heating of the specimens to test temperature had begun. EXPERIMENTAL RESULTS Creep-Rupture—Fig. 3 shows the log stress-log rupture life plotfor the overaged alloys studied, and also for the underaged A1-2 pct Cu alloy.&apos; At 700°F, the stress-rupture life relationship is nearly independent of both the amount of precipitate (i.e., composition) and of the type of overaging treatment (i.e., precipitate dispersion). At 500°F it is apparent that the increase in rupture life that was ex-

Jan 1, 1960

By R. Taggart, D. H. Polonis, W. C. Gallaugher

In the Ti-Cu system, the a&apos; phase can be produced over a wide range of alloy composition witJwut the retention of measurable amounts of the ß or ? phases. This paper reports on the decomposition of this hexagonal martensite phase front the standpoint of solute corzcentratiorz, tempering temperature, and coherency strain condition. The mechanism of precipitation during tempering comprises localized precipitation which is followed by discontinuous precipitation if sufficient coherency strains are present. The localized precipitation process in hypoeutectoid alloys is described by the generalized Johnson-hiehl equation and an activation energy of 46,000 cal per mole. In hypereutectoid alloys the corresponcEing activation energy is 51,000 cal per mole. The rate-controlling process has been proposed as the difision of copper along a&apos; platelet interfnces. SEVERAL investigations have been reported concerning the kinetics of decomposition of the mar-tensitic a&apos; phase in titanium binary alloys.&apos; In the Ti-Mo system,&apos; two modes of a&apos; decomposition have been observed in the presence of /3 phase; one of these involves the precipitation of fine a from a&apos;, and the other involves diffusion across the a&apos;-ß interface. In studies of the Ti-Cr system, Rostoker2 did not detect the formation of TiCr2 during tempering. In Ti-Ni alloys,3 the intermediate phase Ti2Ni has been found to precipitate directly from a&apos; along the interfaces between plates. With the exception of the study of Ti-Ni alloys the previous investigations of tempering phenomena in substitutional martensites are mainly qualitative and do not present a detailed description of the precipitation processes. The following limitations restrict the correlation of the microstruc-tural processes and reaction kinetics during tempering in most binary-alloy systems. 1) A mixture of at least two phases characterizes the constitution of quenched alloys. 2) Difficulties have been encountered in obtaining uniform structures throughout quenched samples. 3) The reaction products, and in particular their morphology. have not been clearly resolved. 4) The martensitic a&apos; phase forms over only a limited composition range for most titanium-base binary alloys. Gomez and polonis4 showed that the Ti-Cu system provides an excellent basis for investigating the tempering of a&apos; over a range of composition without the complication of retained P or the transition w phase. In the present work the effects of solute concentration, tempering temperature, and coherency strain conditions are considered with reference to the over-all precipitation process in quenched alloys of the Ti-Cu system. Both microstructural observations and kinetic data are correlated to define the rate-controlling processes which govern the observed localized and discontinuous precipitation reactions. An earlier paper5 was devoted to a discussion of the modes of heterogeneous nucleation of Ti2Cu from the martensitic a&apos; structure. The present paper will therefore emphasize the progress of the tempering reaction beyond the initial stages. EXPERIMENTAL METHODS The Ti-Cu alloys for this study were prepared by conventional arc-melting procedures. Chemical analysis revealed that the alloy buttons contained approximately 0.02 wt pct 0, 0.04 wt pct N, and within 0.1 wt pct of the intended copper concentration. The progress of the tempering reaction was followed by means of electrical-resistance measurements utilizing a Kelvin double bridge, microhard-ness readings with a 400-g load, and X-ray dif-fractometry patterns to reveal line-broadening effects. Metallographic specimens examined at magnifications greater than X1000 were shadowed with germanium to reveal fine structural details. Direct carbon replicas were prepared for the electron-microscopy studies. EXPERIMENTAL RESULTS Property Changes. The changes of microhardness that accompany the precipitation of Ti2Cu from a&apos; are shown in Figs. 1 and 2. As the solute concentration increases the peak hardness, for a given tempering temperature, increases. In alloys of given composition the time to reach the peak hardness agreed with the time to attain maximum X-ray diffraction peak breadth, as shown in Fig. 3. The maximum hardness and the maximum line breadth increased with lower tempering temperatures, and the time to reach the maximum also increased. The a&apos; peaks broadened during the initial stages of tem-

Jan 1, 1965