Search Documents

By R. I. Jaffee, F. C. Holden, H. R. Ogden

ECENT papers dealing with the properties of unalloyed iodide titanium have been directed primarily at the determination of base-line properties for alloy investigations. Early work was limited to a few tests because of the limited availability of iodide titanium at the time. In the results of papers by Campbell et al.,1 Gonser and Litton,2 Jaffee and Campbell,3 inlay and Snyder,4 and Jaffee, Ogden, and Maykuth, data on mechanical properties are presented for unalloyed iodide titanium in the annealed and cold-worked conditions. Data are presented in this paper which show the effects of heat treatment on the structure and mechanical properties of commercially produced iodide titanium. Correlation is made between microstruc-tural variables and the mechanical properties. Experimental Procedures Melting Stock: The melting stock used was as-deposited iodide titanium, produced by New Jersey Zinc Co. The furnished analysis showed the following range of impurities: N, 0.004 to 0.008 pct; Mn, 0.005 to 0.013; Fe, 0.0035 to 0.025; Al, 0.013 to 0.015; Mo, 0.0015; Pb, 0.0045 to 0.0065; Cu, 0.0015 to 0.002; Sn, 0.001 to 0.01; Mg, 0.0015 to 0.002; and Ni, 0.003. Hydrogen content as determined by vacuum-fusion analysis was 0.0091 wt pct (0.44 atomic pct) after arc melting and fabrication. Nitrogen analysis on the arc-melted and fabricated titanium showed a content of less than 0.002 pct N. The average hardness of the furnished stock was Rf 70, or approximately 85 VHN. Melting Procedure: The as-deposited rods were rolled, sheared, and degreased in preparation for arc melting. The charge was arc-melted with a tungsten electrode in a water-cooled copper crucible under a positive pressure of high purity (99.96 pct) argon. The final ingot was approximately 2 in. in diameter and showed no increase in hardness over that of the initial stock. Fabrication: Heating for fabrication was done in air. It was begun by forging the ingot into a 3/4 in. diam rod, at an initial temperature of 1600°F. Scale was removed by sandblasting. The rod was then swaged to 1/4 in. diam at room temperature through a series of 20 dies, with approximately 10 pct reduction in area between each die. An anneal of 1 hr at 850 °C in air was given after the 1/2 in. die, such that the final cold reduction was 75 pct. Sections cut from this rod were used for test and microstructure specimens. Heat Treatment: Heat treatments were carried out in resistance tube furnaces with stainless-steel linings, under an atmosphere of gettered argon. As further protection against contamination, the specimens were packed in titanium turnings in a titanium sleeve. Control experiments have shown negligible hardness increases with this method, indicating that contamination from oxygen and nitrogen is slight. Three cooling rates were employed in this work; these have been designated as water quenching, argon cooling (to simulate air cooling under a controlled atmosphere), and furnace cooling. The cooling rate for an argon cool is 100°C per min for the first minute, with an average cooling rate of 35°C per min over a 15-min period. A furnace cool requires about 10 hr, with an average cooling rate of 3.6oC per min during the first hour, and an average cooling rate of 1.2°C per min over the 10-hr period. Microimpact Test: The specimen adopted was based on the cylindrical Izod Type Y specimen (ASTM, E23-41T). All dimensions were reduced to half scale, including the notch radius. Specifications are shown in Fig. 1. The specimen is held vertically in an adapter and broken as a cantilever beam. Impact tests were run on a constant-velocity (11.34 ft per sec) Tinius Olsen impact testing machine with a total available energy of 100 in.-lb. Tests were made to determine the correlation between this microimpact and the standard V-notch Charpy impact test. Curves showing impact energy as a function of temperature for both impact tests are plotted in Fig. 2. Transition temperatures, when they occur, are about the same for both impact tests. All three titanium-rich materials have the same conversion factor, 10. Tensile Testing: Tensile tests were conducted on Baldwin-Southwark testing machines using the 600, 2400, or 3000 1b range. Specifications for the test specimen were taken from the 1948 edition of the ASM Metals Handbook, and are shown in Fig. 1. Strain measurements were made using an SR-4 resistance gage (Type A-7) cemented to the reduced section in conjunction with a lever-type extenso-meter. Readings on the SR-4 strain indicator were

Jan 1, 1954

By J. W. Evans

ONE of the most important and frequent calculations that the extractive metallurgist is called upon to make is that of the standard free energy change of a reaction (?F°). For many reactions of metallurgical interest, the lengthy arithmetical calculations have been eliminated by the use of free energy-temperature diagrams which have been constructed by Ellingham,1 Richardson and Jeffes,2 Kellogg,3 and Osborn4 (e.g., for oxides, sulphides, halides) from critical surveys of existing data. The speed and simplicity of making calculations with these graphs make them of great practical value and, this should be stressed, in the majority of cases no greater accuracy is obtained by the individual calculations from specific heat data, entropies, and heats of reaction. With the increasing industrial application of vacuum methods to the winning of metals, notably at present magnesium and the alkaline earth metals, it is necessary to calculate low metal vapor pressures above reaction mixtures. The existing free energy diagrams usually give values where the solid and liquid metals are at unit activity. To obtain the free energy change associated with the reaction Metal (solid or liquid) = Metal (gas) it is customary to calculate this from either vapor pressure equations or from the appropriate free energy functions. This paper presents graphically the free energies of vaporization of a number of metals of economic importance which can be used in conjunction with other free energy diagrams. Certain metals have been excluded on the following grounds: titanium, tungsten, molybdenum, and platinum have very high heats of vaporization and boiling points and the uncertainty of these values arising from difficulties of high temperature measurements makes free energy values of doubtful accuracy; the data for cobalt, vanadium, and zirconium are uncertain; finally, arsenic, antimony, and bismuth could not be conveniently included. because of the presence of mixtures of polyatomic and mona-tomic vapors in the temperature range considered. Free Energy Diagram In Fig. 1, the standard free energies of vaporization per mol (?F°T) have been plotted for the temperature range 0" to 2000°C for the reaction M (solid or liquid) = M (gas) The data have been obtained from the free energy functions — (F-H298)/T for the solid, liquid, and gaseous elements and the heats of vaporization at 298°K, i.e., ?H298 (vapor). The values of these functions have been taken without change from the recent critical survey by Brewer;' the bulk of this data is from Kelley7 with adjustments in the light of more recent work. Values of the function — (F-H298) /T at T = 298°, 500°, 1000°, 1500°, and 2000°K were employed. Where possible, a further independent value was obtained by using the boiling point, i.e., where ?F°T = 0. All calculations are based on the assumption that the metal vapors are monatomic and that the boiling points refer to those temperatures at which the partial pressure of the monatomic vapor above the metal is 760 mm. For the alkali metals, e.g., sodium, potassium, and lithium, diatomic gas molecules are present as minor species; details of these are discussed by Brewer." On the basis of the above values and allowing for the change in slope at the melting point, straight line graphs were constructed and extrapolated to 2000°C. The deviation from a straight line did not exceed ±500 cal, which in all cases appears less than the probable error in the ?F°T values.

Jan 1, 1954

By Marston G. Fleming

E. C. Peterson (Anaconda Copper Mining CO., Darwin, Calif.)—A study of this quite comprehensible and interesting paper by Dr. Fleming brings to mind several observations in the practical application of alkalinity and related factors to the actual practice of lead mineral flotation. Soda ash has long been a widely used and a very helpful alkaline conditioning agent in the flotation of galena from the usual run of lead-zinc ores. Soda ash is one of the common "standard" conditioning agents tried in any laboratory investigation of lead-zinc ores because it has so often proved helpful to galena flotation. However, the use of soda ash in the actual flotation of oxidized lead ores is certainly not widespread. In the flotation of certain lead-zinc ores from the Park City district of Utah, it was found in the usual cyanide-zinc sulphate-xanthate circuit that soda ash had an effect of producing a very condensed and flat froth regardless of the many frothers tried and that substitution of lime for soda ash to produce the same pH (8.0 to 8.4) improved the froth condition. However, the flotation of coarse particles of galena became so critical that some would pass through into the tailing, but caustic soda as a substitute for either soda ash or lime produced a very desirable froth condition in the same pH range and greatly improved the metallurgical outcome. Milling was carried out in typically "hard water" from watersheds of limestone and other calcareous rocks and the ore also apparently contributed magnesium and calcium salts to the pulp. Certain lead-zinc ores of Mexico have shown their greatest flotation response in circuits conditioned with sodium bicarbonate, and such actual mill use was also believed to be related to the water necessarily used in milling. On other lead-zinc ores the optimum has been obtained in actual milling treatment by use of caustic soda in both circuits of the operation. In flotation of oxidized lead ores in which sulphidi-zation is employed by addition of sodium sulphide, very high pH's exist in the flotation circuit. With the usual oxide lead ores, demanding 5 to 15 lb of sodium sulphide per ton of ore, pH's in the circuit (closed and open water-circuits) may range from 9.5 to 12, and for ores that contain much anglesite or a high percentage of iron oxide minerals, sodium sulphide consumption may reach as much as 30 lb per ton of ore and the resultant pH will be correspondingly higher. Yet in such flotation treatment employing either xanthate or oil (high-sulphur crude oil or diesel oils) as the collector, satisfactory to excellent grades of concentrate and lead recovery are obtained. Although there have been great studies and accomplishments in the investigations of flotation fundamentals and flotation theory, and although an investigation to determine the effect of all factors entering into the actual plant flotation of sulphide and oxide ores must become very complicated, as Mr. Fleming has mentioned in his caution regarding the drawing of general conclusions for other ores, it seems that it would be of greater interest if the techniques and investigations could, with time, approach the conditions of actual practice and lead the way to improved and more efficient flotation plant performance. Marston G. Fleming (author's reply)—The gulf between fundamental flotation research and plant operation is, perhaps, less wide than Mr. Peterson suggests. For example, the work described in my paper developed from an extensive investigation of a complex lead-vanadium ore from southwest Africa. This investigation started as a standard ore-testing problem but, at almost every stage, results were obtained which could not be interpreted in terms of previous experience. A program of fundamental research was therefore undertaken and was closely interlocked with the ore testing. This coordinated investigation resulted in a flotation process which has now been proved by two years of successful plant operation, and although the grade and mineralogical constitution of ore as well as smelter requirements have altered more than could have been anticipated, our knowledge of the fundamental character of the problem has made it possible to meet each change in conditions with much more confidence than would have been the case had we neglected this aspect of the investigation.

Jan 1, 1954

By W. J. Taylor, H. J. Mutz, A. F. Brock

THE International Kickel Co. of Canada Ltd. operates five underground mines and an open pit. Four of the mines, the Frood-Stobie, Creighton, Murray, and Garson, are on the south range of the Sudbury Basin, map above, within a radius of 10 miles of the city of Sudbury, Ontario. The fifth mine, the Levack, is on the north range of the Sudbury Basin, 30 miles to the northwest of the city. The open pit is operating on surface ores of the Frood-Stobie orebody. Two pits were opened at the Frood-Stobie mine; the Frood section was started in 1938 and the Stobie section in 1942. To meet the heavy demand for nickel during World War 11, open-pit production was accelerated until it constituted over 40 pct of Inco's total tonnage. As a consequence open-pit ore was depleted considerably alhead of schedule; the Stobie pit was completed in the summer of 1951, and it is expected that mining at the Frood pit will be completed in 1953. The major program launched 10 years ago to develop additional underground production as a replacement of open-pit tonnage thus had to be greatly speeded up. This conversion to all-underground mining will be completed within the next two years, and the underground mines will then have an annual hoisting capacity of 13,000,000 tons. One of the new mines in the underground expansion program, the Murray, was brought into production in 1950. Ore production from the new Stobie section of the Frood-Stobie mine was commenced on a limited scale in 1951 and will be increased as the program progresses. Delivery of ore to the new Creighton mill was started in the summer of 1951 from the caving project launched at Creighton mine. When mining was started in the Sudbury district 65 years ago the ore deposits were opened on a small scale and mining methods conformed to a general pattern of small open cast pits, followed by open stopes as mining was extended below the pits. The open stoping methods used were heading-and-bench and shrinkage. In certain cases a type of cut-and-fill mining was used with drywall tramways and dry-wall chutes in the fill. As the mines were deepened,

Jan 1, 1954

By B. W. Levinger

THE system Ti-CI- has been studied by several investigators." ' Though titanium and chromium are completely miscible at high temperatures, an intermediate phase of the approximate atomic proportions TiCr, has been identified at various compositions between 60 and 68 wt pct Cr. The structure of this phase was established as the cubic C15 (MgCu2) type with 24 atoms per unit cell and a lattice parameter 6.929 kX.2 During a study of the ternary system, Ti-Mo-Cr,5 the existence of a high temperature modification of the TiCr, phase was discovered. In a series of alloys annealed at 1300°C and containing from 60 to 70 wt pct Cr and 5 pct Mo, a new phase was present which did not correspond to either ß solid solution or TiCr,. By trial, the new phase was identified to be of the hexagonal C14 (MgZn2) structure with 12 atoms per unit cell. Further work showed that the hexagonal structure was. in fact, also present in binary Ti-Cr alloys quenched from high temperatures. To make the identification more certain, the intensities of the various reflections were calculated assuming a composition TiCr2 and C14 structure. Table I lists reflection planes, interplanar distances, calculated intensities, and a comparison of these values with the lines of a binary Ti-Cr alloy (66 pct Cr) annealed for 20 min at 1385°C and water quenched. Since high angle lines were more diffuse, the correspondence between visually observed and calculated intensities was not as good at these angles. Lattice parameters were computed to be a = 4.922 kX, c = 7.945, c/a :- 1.614. The corresponding interatomic distances are: titanium to titanium distance, 3.00:, kx, chromium to chromium distance, 2.43, kX, titanium to chromium distance, 2.88,, kX. These compare to 3.00, 2.45, and 2.87 kX in the cubic phase, respectively.' The atomic positions in the C14 structure are as follows: Titanium 1/3, 2/3, Z; 1/3, 2/3, 1/2: 2/3, 1/3, i; 2/3, 1/3, (1/2-z); Chromium 0, 0, 0: 0, 0, 1/2; 2x, 2, 1/4; 232, x, %; X, 22, 1/4; X, 2x, 3/4; x. x, 1/4; x, x, 3/4; The values of x and z were calculated for the alloy mentioned and found as follows: z — 0.061, x = 0.165. The values assumed in the intensity calculations were those for an ideal close-packed lattice or z = 1/16, x = 1/6. Work in the Ti-Mo-Cr system indicates that y2 the hexagonal modification of TiCr2, is the stable phase above 1300°C, while y1 with the cubic structure is stable below 1000°C. X-ray examination of a number of alloys annealed at intermediate temperatures showed that the hexagonal and cubic phases can coexist. Alloys quenched from 1000°C and annealed at 1100" and 1200°C showed small amounts of y2 at the higher temperature. A considerable amount of y, seemed present, however, in cast alloys annealed at 1100°C. It further appears that there is a small but definite solubility range for both phases in the ternary system. Acknowledgment The results of this paper represent work carried out in conjunction with a project sponsored by Watertown Arsenal, Contract No. DA-11-022-ORD-272. References 'M. K. McQuillan: Journal Inst. Metals (1951) 79, p. 379. 2 P. Duwez and J. L. Taylor: Trans. ASM (1952) 44, p. 495. W. J. Van Thyne,. H.. D. Kessler, and M. Hansen: Trans. ASM (1952) 44, p. 974. 1 F. B. Cuff, N. J. Grant, and C. F. Floe: Trans. AIME (1952) 194, p. 848; Journal of Metals (August 1952). Unpublished Research, Armour Research Foundation. "H. J. Wallbaum: Ztsch. Krist. 103, p. 391.

Jan 1, 1954

By M. J. Sinnott, W. R. Kiessel

The creep characteristics of commercially pure titanium sheet in the annealed state, cold-worked state, and cold-worked and recovered state in the temperature range from 75' to 750°F have been determined. Titanium has been found to exhibit strain aging characteristics. The effect of strain aging on creep has been determined. A possible explanation for the poor creep properties of titanium is proposed. THE metal titanium exhibits many desirable properties but results on its creep properties have been somewhat disappointing. The creep strength is low even though the material has a very high melting point.' The present work was undertaken to determine the creep strength of titanium in various conditions; annealed, cold-worked, and cold-worked and recovered and to determine why titanium shows such relatively poor creep properties. The general procedure followed in this research consisted in obtaining the usual mechanical prop- erties such as creep strength, short time tensile strengths, and hardness on materials treated to a controlled degree of internal strain, as determined by X-ray diffraction measurements, and their subsequent interpretation in terms of this internal strain. The material used in this work was sheet stock taken from one heat of commercially pure titanium. As-received, this sheet was 0.060 in. thick. The analysis was given as 0.037 pet C, 0.023 pet Si, 0.50 pct W, 0.063 pct Ni, 0.08 pct Fe, and the remainder titanium. The oxygen and nitrogen were unreported but generally are about 0.2 pct in commercial heats. In order to put the material in a state of minimum internal strain all the sheet was given an anneal in a static argon atmosphere for 1 hr at 1600°F prior to processing and testing. The microstructure of the material after this treatment was essentially a single-phase solid solution of uniform equiaxed grains. For the studies on the cold-worked sheet, the material was reduced by rolling in a two high, 5 in. mill. Rolling was done at room temperature in passes

Jan 1, 1954

By C. E. Schwab

A lead-zinc orebody, in fairly strong quartzite and with a dip of 35" to 60°, is block-caved by use of scrams in a stair-step pattern up the ore footwall. Scram linings to handle coarse muck and permit the use of folding scrapers are developed by the use of end-grain wooden blocks to reduce maintenance and keep operating cost to a minimum. THE Bunker Hill mine, since its discovery in 1885, has steadily produced a high grade of lead-silver-zinc ore. By the end of 1952 over 21,000,000 tons of this high-grade ore had been produced by square-set mining, and reserves in the mine continue to be very satisfactory both as to quantity and grade. For many years prior to 1941, mine production and mill capacity had been 1200 tons of feed per day. Closely adjacent to the mill, and stored behind dikes, coarse jig tailings had been impounded during the time preceding the advent of fine grinding and selective flotation. When manpower became short in 1941 and sink-and-float preconcentration was proved successful, mill capacity was increased to 1800 tons per day to treat these jig tailings economically. By 1946, because the supply of jig tailings was limited, underground exploration was started to discover and prove ore reserves of low-grade material which could be mined by an appropriate bulk mining method. During the years of square-set mining many possible areas of low-grade mineralization had been observed. One chosen for the first exploration work was sufficiently remote from active mining areas so that subsidence, if an ore-body were proved, would cause no problem. Also, old adits and workings were still open and in good enough condition so that exploration in the mineralized zone could be started with a minimum of preparatory work. In 1948 an orebody was proved of sufficient tonnage, of a grade about 2 pct Zn, 0.5 oz Ag, and 1.0 pct Pb. It was decided to use block-caving, the only appropriate mining method by which this grade of ore could be economically recovered. Exploration for additional reserves in other areas of the mine is continuing, but ultimate results are not known at this time. With more sink-and-float capacity, larger ball mills, and more flotation machines, mill capacity was increased to 3000 tons per day, permitting the mining of ore in the square-set area at a maximum rate not usually achieved, because of the scarcity of labor. Increased mill capacity also permits block caving and the mining of jig tailings at variable rates to keep mill feed up to 3000 tons per day. Fortunately the three types of feed are amenable to the same mill circuit and reagents for recovery of Pb and Zn. For example, during the first 10 months of 1952 square sets produced 827 tons per day, block-caving 1421 tons per day, and jig tailings 643 tons per day, an average daily production of 2891 tons for all three products. Exploration had proved the existence of an ore-body 1000 ft long and 165 ft wide in horizontal section, see Fig. 1. Company engineers were concerned only with the vertical extension, about 300 ft, from an old level to the surface. Much of this almost outcropped, Fig. 2. The ore lies in the hanging wall of a major fault of the Bunker Hill mine, standing at 65" in one end of the zone and separated from the fault by a wedge of waste, see Fig. 3. This wedge pinches out near the center of the zone, at which point the ore dips 45", lying nearly on the fault, Fig. 4. The remaining portion lies on the fault and conforms to the fault dip of 35", Fig. 5. Open-pit mining for the top of the ore was considered, but since the ore zone dipped into and under the mountains, adverse waste-to-ore ratios precluded use of this method. The ore occurs in massive quartzite of sufficient strength to support untimbered drifts, crosscuts, and raises. Zones of weakness in the quartzite are bedding, jointing, and small faults or slips. The mineralization, which occurs as small stringers of sphalerite and galena as well as pyrite, creates another line of weakness. The mineral veins or veinlets in themselves are high-grade. Their size and regularity and the amount of barren quartzite by which they are separated determined the limits of mineable ore, which are all assay limits except for the one determined by the major fault. Block 1 Without any background of caving in this type of quartzite, engineers selected the first block on the very steep end of the zone. Compelling reasons prompted this decision. The steep portion of the ore in Block 1 was of the lowest grade, so that if difficulties were encountered no very valuable ore would be lost, while the experience gained might be applied in mining the remaining blocks. A block 200x200 ft was laid out, with four scrams spaced 50 ft apart for drawing and placed at a right angle to the strike. Finger raises were placed in a 25-ft interval grid pattern, with flat undercutting done by crosscuts at the undercut level 25 ft above

Jan 1, 1954

By A. J. Opinsky

MANY investigators, in their discussions, have reasoned that the ductile-brittle transition in iron could be explained by the intrusion of cleavage into the normal slip process. The purpose of this note is to apply the laws of critical normal stress for cleavage and critical shear stress for slip to explain the orientation and temperature dependence of the ductile-brittle transition in body-centered cubic metals. It will be found that within a certain temperature range, single crystals tested in tension will cleave or slip, depending on their orientation. Some data recently appearing in the literature will be analyzed from this standpoint. For a single crystal with [uvw] parallel to the tensile axis, the resolved shear stress on the slip

Jan 1, 1954

By Garth M. Crosby, F. McIntosh Galbraith, Bronson Stringham

THE Hercules mine is located in the northeastern section of the Coeur d'Alene district, approximately 1 1/2 miles north of the town of Burke, Idaho. Surface indications of the ore deposit were first discovered in 1886, but regular mine production was not started until 1902 and was continuous until April 1925, when the known ore had been extracted. Incomplete records show that from 1912 until operations were suspended the mine produced 2 1/2 million tons of ore containing 9.4 pct lead and 7.7 oz of silver per ton, together with an estimated 2 pct zinc, 0.3 pct copper, and 20 pct iron. This operation was the first in. a series of mining enterprises culminating in October 1947 with the consolidation of Day Mines, Inc. In the same year it was decided to unwater the levels below the collar of the Hercules shaft in the hope of finding some indication of a recurrence of ore. The unwatering operation has been described in a. previous paper.' The initial exploration, following recapture of the workings, showed sufficient promise to warrant a detailed study of the mineralogy with modern techniques. The general geo1ogy of the Coeur d'Alene district, including a detailed description of the rock types encountered, has been comprehensively treated by Ransome and Calkins' in their classic paper, and only local background description, therefore, is felt to be appropriate here. The Hercules deposit transects a portion of the trough of a broad south-trending synclinorium which has been greatly complicated by faulting. More locally, it lies within a block of ground bounded on the east; by the O'Neil Gulch fault, a steep north-south overthrust of considerable magnitude, and on the west by a monzonite stock, the outcrop of which is 1/2 mile or more wide and 5 miles long. The country rock is composed of thin to medium-bedded argillites and argillaceous quartz-ites of the Prichard and Burke formations, the oldest members of the Pre-cambrian Belt Series of sediments in the area, believed to be of Algonkian age. The contact between them is a conformable gradation. The argillite is colored gray to tannish-gray and is fine-grained, compact, and generally massive in structure. Under the microscope the unaltered argillite is seen to be composed principally of anhedral quartz and a few feldspar grains which were at one time presumably partly rounded sand grains, but as a result of recrystallization and cementation by silica, the interstices are now almost obliterated and quartz grains show crenulate boundaries. The sizes of these crystals vary from 0.5 mm down to 0.1 mm in greatest dimension. In all specimens sericite comprises 10 to 20 pct of the rock and is present abundantly between most of the grains as flakes or shreds which vary considerably in size. Sometimes they form a fine felt-like mat or aggregate, and sometimes flakes are seen which appear to be good muscovite. In some specimens, separated rhombic-shaped carbonate grains are abundant, and in some instances these have been changed to sericite. Mining operations to date have explored the Hercules vein to a maximum vertical depth of 3600 ft below its outcrop, and along a maximum strike-length of 3600 ft on certain of the lower mine levels. The main orebody is irregular in outline, extending over a variable strike-length of 400 to 1500 ft; and it is intersected by a strong transverse fault that has been traced from the surface to the bottom level. This has been named the Hercules fault, and apart from the vein itself, it is the most prominent structural feature in the mine. There is good evidence that it existed prior to the introduction of ore solutions and may have influenced ore deposition, but it was also the locus of important post-ore displacement and shows a progressive right-handed horizontal component reaching 200 ft on the deeper levels. Its vertical component is not definitely known but may be considerably greater. The fault strikes 20° N to 50° E and dips westerly at angles of 70" to 45", flattening in dip where it crosses the original orebody from east to west between 1000 and 1600 ft below the surface. At about 3000 ft in depth the Hercules fault is joined by a vertical fault of similar strike, and the major post-ore dis-placement below their junction is taken up along this vertical branch of the structure, now called the Mercury fault. Recent work has been concentrated in this vicinity. Another structural feature of special geologic interest, though of little economic importance, is the occurrence of a porphyritic dike in this area. This lies a short distance above the Hercules fault, essentially parallel to it, and is 5 to 15 ft in thickness. It appears at first glance to cut the mineralization, suggesting push-apart relationship, but small stringers of the vein minerals have been observed to penetrate the dike for a matter of inches at several points. The dike is thought to be related to the monzonite intrusion. A vertical longitudinal projection of the mine is shown in Fig. 1, which illustrates most of the features discussed above. The Hercules vein was deposited along the course of a strong, persistent shear zone that now appears as a braided network of gouge seams running through more or less crushed and shattered country rock. It strikes 70° N to 80° W and dips southerly at an average of 75". Barren parts of the structure vary in width from less than 1 ft to more than 15 ft. The width of mineralized segments may be double that. Although the evidence is not conclusive, pre-mineral, normal movement along the zone may be 1000 or 1500 ft. The horizontal component is unknown. Post-ore movement appears to have been

Jan 1, 1954

By N. A. Gokcen, J. Chipman

A revised treatment of the authors' published data eliminates the complex relation previously proposed between concentration of silicon and activity coefficient of oxygen in liquid iron. Revised values of the thermodynamic properties of the liquid solution are presented. IN a recent experimental study of the reaction SiO2 (s) = Si+ 2O; Kf, = [% Si] [% O]² [1] the authors' found a substantially constant equilibrium product in liquid iron at 1600°C of 2.8x10-5 They also reported extensive data on the reactions: SiO2 (s) + 2H2 (8) = Si- + 2H2O (g); K'2= [% Si] (H2O/H2 [2] and H, (g) + 0 = H2O (g); K'3 =( H2 O [31 (H2) [%O] From the results on reaction 3 and earlier data of Dastur² on this same reaction in the absence of silicon, they determined the activity coefficient of oxygen, f0, on the basis of the definition K3 = (H2O)/ (H2)f0 [% 0] where K, is the equilibrium constant and f0, is taken as unity in the pure Fe-0 system. Similarly values of fsi were deduced from results on reaction 2. In a more recent study" of analogous reactions in the system Fe-A1-0, it was found impossible to reconcile the results on reaction 3 with Dastur's data; accordingly the latter were ignored and the equilibrium results were extrapolated to find a value of K, at zero concentration of aluminum. This procedure failed to locate the cause of the discrepancy but it did yield reasonable values of activity coefficients. It also avoided introduction of the complex empirical relation between the oxygen activity coefficient and the concentration of the added element. The same type of discrepancy exists for system Fe-Si-0.' In the earlier paper an attempt was made to fit both sets of data by a single curved line (Fig. 6 of ref. l), the form of which is contrary to the theoretical requirement of a finite slope at infinite dilution. In the light of experience on the Fe-A1-0 system the discrepancy must be recognized as one which can be resolved only by more refined measurements. Accordingly Figs. 6 and 10 are retracted. It is pointed out also that until the discrepancy is resolved Figs. 7, 8, and 11 are subject to some uncertainty. Qualitatively the following conclusions still appear valid: 1—The activity coefficient of oxygen is reduced by addition of silicon. 2—In dilute solutions the activity coefficient of silicon increases with its concentration. 3—With respect to equilibrium in reaction 1, the above effects are approximately compensating. The discussion of K'1 in the previous paper requires no revision. It was pointed out that the constancy of the product [% Si] [% 0]² ndicated a compensating effect of the activity coefficients of silicon and oxygen. Therefore, as a very good approximation, K1 = K'1 and the following average values are suggested both for K, and K', at the temperatures 1550°, 1600°, and 1650", respectively, 1.0x10-", 2.8~10-" and 5.5 ~lo-'. Revision of the thermodynamic treatment is necessitated by the recent appearance of new data, based on a combination of combustion and solution calorimetry,' which yields for the heat of formation of low-cristobalite from the elements, the value —209,330 ±250 cal per mol at 25°C. This is about 4000 cal larger than the value previously accepted. The new value for cristobalite is used, together with Kelley's tables of high-temperature heat contents" and entropies and with Korber and Oelsen's' heat of fusion of silicon to obtain the following equation for the standard free energy of cristobalite in the temperature range 1700" to 2000°K: Si (1) + 02 (g) = Si02 (crist.); ?F° = -217,700 + 47.OT [4] The free energy of solution of 0, in liquid iron is:8 O2 (g) = 20 (in Fe); AF° = -55,860 - 1.14T [5] and these two equations are combined to give: Si (1) + 20 = SiO, (crist.); AF° = -161,840 + 48.14T [6] ?F°1873 = -71,700 cal. From the experimental value of K, = 2.8x10-5, Si + 20 = SiO2 (crist.); ?F°1873 = -39,000 cal. [7] The combination of Eqs. 6 and 7 yields the free energy change when liquid silicon dissolves in iron to form the dilute solution of unit activity (1 pct). Si (1) = Si; ?F°1873 = -32,700 cal. [8] The heat effect in this process according to Korber and Oelsen' is an evolution of 28,500 cal per gram

Jan 1, 1954

By Mason K. Banks

A process has been developed which produces spodumene concentrates assaying 6.0 pct Li2O and 0.45 pct Fe2O3, with 70 to 75 pct recovery of spodumene. Two flotation separations are required: the simultaneous removal of mica, feldspar, and quartz as a froth product using a cationic collector, and the subsequent removal of iron-bearing minerals as a froth product while spodumene is depressed as a tailing. SINCE the close of World War II there have been numerous developments resulting in the increased use of lithium by industry. Notable among these has been the development of an industrial lubricant, based on lithium stearate, which is fluid at low temperatures, stable at high temperature, and insoluble in water. A new bleaching agent, lithium hypo-chlorite, has also been developed recently.' Other well-known uses are listed below: 1—Lithium oxide in ceramics reduces firing time, lowers melting temperatures, lowers thermal expansion, raises refractive index, and improves chemical resistivity. 2—Lithium carbonate and lithium strontium nitrate are used in pyrotechnics for their brilliant red color.' 3—Lithium chlorides and fluorides are used as fluxes for welding aluminum and magnesium.' 4—The affinity of lithium for nitrogen is the basis for a process used in purifying helium." 5— Lithium chlorides and bromides are used in air conditioning for their powers to absorb organic amines, ammonia, and smoke.6-—Lithium hydride has been used as a source of hydrogen to inflate life rafts and balloons used by the Air Forces and Navy.' 7— Lithium metal and lithium hydride are useful in the atomic energy program in connection with the production of the isotopes of hydrogen." During the 1942-45 period of World War 11, Solvay Process Co. operated a flotation plant with a daily capacity of 300 tons of ore for the production of spodumene concentrate near Kings Mountain, North Carolina. The operation was shut down upon reduction of wartime demand for lithium chemicals, and until recently there has been no production from the Carolinas. In April 1950 an investigation of the problem of spodumene flotation from North Carolina ores was begun at North Carolina State College Minerals Research Laboratory at Asheville, N. C. This laboratory, operating under the combined auspices of North Carolina State College, North Carolina Department of Conservation and Development, and the Tennessee Valley Authority, undertook the spodumene project at the request of Foote Mineral Co. of Philadelphia. The work, involving a period of 15 months of intensive batch and pilot plant investigation, was completed in June 1951 and resulted in development of a process for concentration of spodumene by flotation which has been hereto unrecorded in the literature. A similar approach has been used before on iron, ilmenite, and other minerals, but the literature shows no record of its having been applied to spodumene. Parts of the process are now being used on a commercial scale at the Foote Mineral Co. plant near Kings Mountain, N. C., which has been in production since July 1951. It is the purpose of this paper to describe some of the results of the investigation. The Orebodies Spodumene-bearing pegmatites occur in a narrow belt 24.5 miles long and 1.8 miles wide extending southwestward from Lincolnton to Grover, N. C. According to statements judged to be conservative, the tin-spodumene belt of the Carolinas contains an estimated 4,300,000 tons of pegmatite ore averaging 15 pct spodumene. This amounts to "a reserve of at least 650,000 tons of spodumene (more than 20,000 tons of metallic lithium) to a depth of 100 ft."' This figure includes only bodies having an average thickness of 35 ft and length of 550 ft. There are hundreds of pegmatites in the belt, many of which are less than 10 ft wide. The largest pegmatite in the area has a maximum thickness of 395 ft and maximum length of 3250 ft.' These larger pegmatites are composed principally

Jan 1, 1954

By Henry F. Hebley

This paper brings within the compass of one comparatively brief article a general description of the situation concerning the nation's water resources. It touches upon the phenomenal growth in the demand for water supply and emphasizes the problems facing the coal industry both with regard to acid mine water drainage discharged from active and abandoned mines and the suspended solids discharged to the stream system from wet coal preparation plants. IT must always be remembered, with regard to the problem of water-borne industrial wastes, that stream pollution from any cause is just one factor in the comprehensive problem of water supply in modern times. Industries nonexistent 25 years ago are now flourishing, and supplies of water piped to homes and apartments, as well as the greater number of plumbing fixtures per dwelling and per building, have created an ever growing demand on the country's water resources. Indication of this rapid growth in demand is shown in Table I, which is quoted from Abrams. of Texas increased 287% and the water consumption 7000 per cent." The domestic load varies greatly, depending on the extent of the available supply and the habits of the community. According to the report of the President's Water Resources Policy Commission' the United States Public Health Service reported a national average of 127 gal per capita per day, varying from 60 gal in communities of 500 persons to 140 or 150 gal in cities of 10,000 or over. Other critical areas may be cited to illustrate the inter-relation between new industrial processes and the demands for water in the area where the new enterprise is located. Powell and Wilson have pointed out that during World War 11, in the vicinity of Louisville, Ky., a rapid expansion of industry took place, consisting of numerous synthetic rubber plants. The demand for water increased from 37 million gal per day in 1937 to 62 million gal in 1943. These heavy requirements drew down the supply stored in the water-bearing aquifers to such an extent that urgent plans for recharging were considered. Similar situations have developed in the Los Angeles area and in the vicinity of Texas City. Warne4 has drawn attention to the situation in Los Angeles area, where in the West Basin the withdrawal of ground water in 1945 was 90,000 acre-ft, almost double the amount of the natural fresh water recharge. The draw down has been so severe that the level of the ground water is now below sea level, and sea water is invading the West Basin aquifers at rates up to 300 ft per year. In the Report of the Engineers Joint Council it is pointed out that in the area of Texas City the ground water table has been critically lowered. In 1930 the daily withdrawal from the water-bearing aquifer was 0.5 million gal. By 1945 the quantity withdrawn

Jan 1, 1954

By Carville E. Sparks, Rollin Farmin

TRIAL installations of rock bolts, of the slit-rod-and-wedge type, were under way at several units of Day Mines, Inc., when Korean hostilities interrupted the already slow deliveries of steel bars to the Coeur d'Alene district. Factory-made bolts had not yet been put on the local market, so the program was halted for lack of supplies. Interest was revived by a visitor's description of wooden roof bolts. These were said to have been used briefly with apparent success in a coal mine, until apprehension voiced by the U. S. Bureau of Mines caused the practice to be suspended. To make wooden bolts for trial in ground support, Day Mines acquired a second-hand doweling machine equipped with two cutting heads, one to turn out the desired round rods of 2-in. diam, the other to turn out 1-in. rods to be used as powder-tamping sticks. This machine was installed in the all-weather sawmill of the Hercules mine unit at Burke, Idaho, where fabrication of the wooden bolts commenced early in 1951. Most of the mining in the Coeur d'Alene district is along steeply dipping veins in shaly quartzite and argillite of Algonkian age. Ground support commonly is required in zones where the rocks have been sheared, brecciated, and hydrothermally altered. Pressure from the sidewalls is more troublesome than weight overhead, but both increase with the size of the mine opening. Caving may come from a progressive sloughing of irregular rock fragments or from an exfoliation and buckling of the layered wall rocks. The disintegration is thought to develop from an initial elastic expansion of the rock toward the newly-created mine opening, followed by the dilation of many tiny partings in the rock by absorption of water. As the partings widen, masses of rock develop weight and become free to fall. The function of rock bolts is to prevent or retard widening of partings in the rock supported. Wooden Bolts, Wedges and Headboards Bolt assembly used by Day Mines consists of a bolt 4 or 6 ft long, two wedges 16 in. long, and a headboard 30 in. long, Fig. 1. All four pieces are made of local red (Douglas) fir, either green or well-soaked in the mill pond before it enters the sawmill. Bolts are fabricated from cants, 2 1/4 in. sq, cut from relatively straight-grained timber with a minimum of knots and trimmed to 4- and 6-ft lengths. The bolt then is turned in the doweling machine from 21/4 in. sq to 2 in. diam round, except for a 4-in. length at one end which is left full square to provide the striking head and the shoulder that holds the headboard in position for wedging. The foot end of the bolt is slit with a thin saw for a length of about 16 in., thereby making a slot to receive the wedge against which the bolt is driven for anchorage at the bottom of the rock hole. A similar slit, 12 in. long, is made in the opposite (head) end of the bolt to receive the second wedge, which crowds the headboard against the ground at the collar of the rock hole and puts the bolt in tension. The second slot is aligned 90" from the plane of the first slot to avoid Longitudinal splitting and is notched out slightly to allow easier insertion of the collar wedge after the bolt has been driven to bottom. To prevent splitting the headboard by spreading action of the head wedge, this slot is oriented at 90" to the grain of the headboard when the pieces are assembled, Fig. 2. The wedges are similar to standard mine wedges, but more slender; they are cut 1 7/8 in. wide and 1 in. thick at the heel and taper out in 16 in. of length. The headboard, or bearing plate, is not necessary for some types of ground but generally is desirable because it helps the bolt to support an area of loose, friable rock and reduces the tendency for the rock at the collar of the hole to split away from the wedged head by distributing the pressure over a wider rock surface. The headboard may be a 24-to 30-in. length of 3-in. plank, 8 to 12 in. wide, but a similar length of rounded sawmill slab serves equally well at 20 pct of the cost. A hole of 2-in. diam is bored or punched through the center of the headboard, either at 90" or at various high angles to its surface. The bolt is inserted to its shoulder through this hole, then driven into the rock hole. Bolts, wedges, and headboards are given a full timber preservative treatment to inhibit rot. Bundles of each are immersed in a warm saturated solution of Osmose salts in water for 48 hr, removed, dripped dry, and stored in a relatively humid underground depot to cure. Most wooden rock bolts used by Day Mines are 4 ft long. Holes to receive them, about 42 in deep and 2 1/8 in. in diam, are drilled into the rock' to be supported, nearly normal to the periphery of the mine opening. The type of drill used is dictated by convenience: stoper, jackleg, or jumbo-mounted drifter. Correct depth of the hole is assured by use of a measuring stick that has been cut to the proper distance from drill chuck to the ground at the collar of the hole when a standard length drill rod is at the bottom. The bolt is seated to the shoulder through the hole in the headboard, the foot-end wedge is placed in its slot, and the assembly is inserted into the rock hole. Then the bolt is driven until it is seated solidly on the wedge against the bottom of the rock hole. Driving may be by hand with a sledge, or

Jan 1, 1954

By M. J. Sinnott

WITH the advent of nodular iron as an engineering material, considerable interest has been shown in developing this material for various applications. Generally the strength, hardness, or ductility are the more common properties used for design purposes but occasionally applications involving a knowledge of the thermal conductivity of the material is required. A search of the literature showed, rather surprisingly, that relatively little work has been done on this property for all types of cast iron. Insufficient data are available on thermal and electrical conductivities to develop the Weidemann-Franz ratio, or the Lorentz relationship, for estimation purposes. There are no data on nodular irons and the published data on malleable irons are quite sketchy. For these reasons the conductivity of the group of nodular irons listed in Table I were measured. Irons I to IV were made in such a fashion as to maintain the carbon and alloy content essentially the same while varying the silicon content. Test specimens were cut from the mid-section of 4-in. keel castings. Iron V is a commercial casting of nodular iron. The test specimen of this iron was cut from the center of a large cast billet 3x10x26 in. All alloys were tested in the as-cast condition. A microstructural examination showed that each iron had spheroidal graphite but the size and distribution varied with the silicon content of the iron. The spheroid size decreased while the number of graphite nodules increased as the silicon content of the iron was increased. The matrix structures of each iron consisted of pearlite and ferrite with the proportions varying from predominantly pearlite in the low-silicon iron to mostly ferrite in the high-silicon iron. The commercial heat, iron V, was predominantly pearlite probably because of its higher manganese and phosphorus content. Two methods for measuring the thermal conductivity were used. The first was a modification of the techniques described by Powell and Hickman and Van Dusen and Shelton,² the second method was a simpler technique described by Jakob and Hawkins." Since the agreement of both methods as tested on two sets of duplicate samples was excellent, the simpler experimental technique was used. The results of the measurements are given in Table II along with a summary of the microstructural constituents. These conductivity data indicate that as the percentage of silicon increases there is a corresponding decrease in the thermal conductivity even though the structure is changing from pearlitic to ferritic. Such a change in microstructure is usually accompanied by an increase in conductivity. A third factor involved in the behavior of these irons is the size and distribution of the graphite nodules. The relative amounts of graphite do not change greatly but the size and distribution do. Generally graphite improves the conductivity but in the present case such an effect is probably masked by the alloying effect from the silicon and its dispersion through the matrix. The thermal conductivity of the nodular irons studied is less than that of regular foundry irons by some 10 to 30 pct and is less than that of regular malleable irons.' The cause of the decreased conductivity is probably the more highly alloyed fer-rites obtained in these irons and the changed mode of distribution of the graphite as compared to the regular foundry irons. References R. W. Powell and M. J. Hickman: Journal Iron and Steel Inst. (1946) 154, No. 2, p. 99. 'M. S. Van Dusen and S. M. Shelton: U. S. Bur. Standards Journal of Research, RP668 (1934) 12, p. 429. ³M. Jakob and G. A. Hawkins: Elements of Heat Transfer and Insulation. 2nd Ed. (1950) New York. John Wiley and Sons. ' J. W. Donaldson: Journal Iron and Steel Inst. (1933) 128, No. 2, p. 255.

Jan 1, 1954

By R. K. McGeary, B. Lustman

Orientation relationships and rates of annealing of 97 pct cold rolled zirconium have been studied by X-ray techniques, metallography, and by hardness measurements. The process of annealing occurring by the formation of domains, and their subsequent growth without recrystallization, is demonstrated. NUMEROUS investigators1-' have revealed sub-grain formation after annealing cold worked metal single crystals and have generally described the results in terms of a dislocation mechanism of polygonization.5,6 in heavily cold rolled polycrystal-line aluminum the first stages of heating cause an apparently spontaneous subdivision of regions of the deformed matrix into a great number of slightly disoriented domains followed or accompanied by rapid growth of certain domains to form a recrystallization texture.7,8 In the present investigation the isothermal rate of annealing of cold worked polycrystalline zirconium has been studied by X-ray techniques, metallography, and by hardness measurement. It will be shown that, rather than by the usual nucleation and growth mechanism,"12 the process of annealing can best be explained by the formation of domains early in the annealing treatment and the subsequent growth of these domains without recrystallization. Experimental Procedure All the experimental work was performed on an arc-melted ingot of high purity zirconium crystal bar made by Westinghouse in a production scale deBoer unit. The weight percentage of impurities in the zirconium were as follows: C, 0.04; Fe, 0.05; Hf, 0.014; W, 0.01; Ti, Ni, and Al, 0.003; Si and N, 0.002; Cr and Cu, 0.001. Metallographically the zirconium showed only a single phase. The 4 in. diarn ingot was forged at 760°C to a 1 1/2x3 in. plate and was then rolled at 760°C to 0.150 in. thickness and annealed at this temperature for 20 min to produce an equiaxed grain structure of about 0.1 mm average grain diameter. The hot rolled plate was roller-leveled, surface ground to 0.135 in., cold rolled 83 pct reduction in thickness on a two-high mill, and then to a total reduction of 97 pct on a Sendzimir mill. The 0.004 in. strip material so produced received no subsequent mechanical treatment. Specimens % in. square were sheared from the rolled strip and isothermally annealed at 104 mm Hg in an all glass vacuum system equipped with a Vycor furnace tube. The temperature data presented are the average temperatures during the runs and did not vary more than about k3"C. X-ray Diffraction Methods: When zirconium is drastically cold rolled, a high degree of preferred orientation results in which prism poles, {1010}, are perpendicular to the rolling direction. After fully annealing this material an entirely new texture develops which corresponds to a 20" or 40" rotation of the deformation texture about hexagonal axes of

Jan 1, 1954

By E. B. Fitch, E. C. Johnson

The operating behavior of liquid-solid cyclones is outlined, together with the nature and range of the process results obtainable, to serve as a background for engineers wishing to consider application of this new process tool. BY now most engineers are familiar with the liquid-solid or Dutch State Mines cyclone. However, it should be helpful to know exactly what it is that the equipment does and what its limits are. Without going into cyclone theory, this paper will describe the operating characteristics of Dutch State Mines cyclones. These are manufactured under license in this country and sold under the trade-marked name of DorrClone. The physical construction of the liquid-solid cyclone has been covered in many papers,'-' the DorrClone in particular being described in some detail by Weems. Fig. 1 shows the unit in cross-section. The feed enters at C. The coarse, heavy particles are thrown centrifugally to the periphery and make their way down the wall to the apex where their rate of discharge as underflow is controlled by an adjustable rubber apex valve. As the apex diameter is decreased the solids build up behind the valve, producing a denser underflow. Meanwhile the fine particles are swept into the upward flowing vortex stream which exits as overflow through the vortex finder, F. Flexibility to produce the specific result desired in a particular process is achieved by providing means for varying the areas of the entrance, vortex discharge, and apex discharge. The entrance area may be varied by insertion of special shims. Vortex discharge area may be changed by use of different-sized vortex finders which are interchangeable. Similarly, the different sizes of apex valves are interchangeable and in addition each apex valve is variable down to about 60 pct of its maximum diameter. A most significant primary distinction to make is that although liquid-solid cyclones have been sometimes called thickeners, they actually are classifiers, and very potent ones. They are almost never thickeners in the special sense that many metallurgical engineers understand the term. There would be no profit in quibbling over the definition of a word, but when the application of cyclones is considered, it will help to understand the difference be- tween two mechanisms, one of which will be called classification, and the other thickening. In what is called thickening the fine solid particles present in the feed hold together by surface attraction during the sedimentation process. The loose network of particles thus held together constrains all particles to settle at approximately the same rate, the larger ones dragging the smaller ones down. As a result, pulp settles with a sharp line of demarcation between solids and a relatively clear supernatant liquid. Essentially all the solids, regardless of their fineness, pass into the thickened underflow, and a clear overflow is separated. In classification, on the other hand, the interparti-cle forces are relatively insignificant as compared to the settling force on the individual particles, and are insufficient to prevent independent movement of the particles. The coarsest, heaviest particles settle most rapidly through the pulp, passing more slowly settling fines. Particles coarser than the mesh-of-separation essentially all settle into the underflow, but if the feed contains any particles finer than the mesh of separation, at least part of them will appear in the overflow. A clear supernatant or overflow can be obtained only if there are no undersize particles present in the feed. Thus it will be seen that classification is impossible under ideal thickening conditions. The finer particles are pulled down at essentially the same rate as coarser particles, and there is no separation on the basis of particle size. The surface attraction holding the particles together in a thickener is usually feeble. Whenever the sedimentation force on any particle is strong with respect to the interparticle forces, that particle can pass through the tenuous structure and settle independently. There are at least four ways of making the sedimentation force strong, with respect to the interparticle forces, and obtaining classification. First, and most obvious, the particles may be large and heavy. Thus coarse sands settle out in a beaker or Dorr thickener ahead of the rest of the thickening solids. Second, the interparticle forces may be altered by physicochemical means; i.e., it is often necessary to add dispersing agents to destroy the interparticle forces and permit classification to take place. Third, the interparticle forces may be reduced by dilution of pulp. It is well known that to obtain the most efficient separation of

Jan 1, 1954

By C. D. Starr

IT is well known that the martensite reaction can be induced to occur isothermally above the M, temperature by plastic deformation of an alloy in its austenitic state, and also that as the test temperature is increased above the M. temperature, plastic deformation under a given set of conditions merely causes additional slip with a corresponding tendency toward the formation of less martensite per unit of strain. Thus it appears that a maximum temperature exists above which martensite cannot be formed isothermally by plastic deformation. This temperature is commonly designated as the equilibrium temperature Te. Attempts to determine experimentally the equilibrium temperature have indicated that a critical temperature is observed, under a given set of conditions, above which martensite cannot be formed isothermally by plastic deformation. But the observation of a "so called" critical temperature, Te, should not be confused with the equilibrium temperature, Te. In order to clarify this anomaly, true stress-strain curves were obtained for a series of type 304 stainless steel specimens (manufacturer's analysis, 0.08 pct C, 18 to 20 pct Cr, 8 to 10 pct Ni, balance Fe) over the temperature range 67" to 300°K.' Since martensite is magnetic, a quantitative measure of the amount of martensite that was produced by plastic deformation was obtained by determining the magnetic permeability as a function of strain. The results of these tests are given in Fig. 1. They appear to indicate that a plastic critical point does exist at about 240°K for the stainless steel under investigation here. But that 240 °K is not the equilibrium temperature nor even a true plastic critical temperature can be seen from Fig. 2 wherein the permeability of the same material is shown to increase with cold rolling at 293 OK. Consequently the observation of a "so called" plastic critical temperature is dependent on the mode of deformation and has no theoretical significance. Acknowledgment This work was sponsored by the Office of Naval Research. Permission to publish this note is gratefully acknowledged.

Jan 1, 1954

By G. A. Deitz, J. Halpren

The kinetics of dissolution of silver in cyanide solutions under oxygen pressure have been investigated over a wide range of conditions with a view to establishing the reactions involved and the factors which influence the rate. The results indicate that the rate is determined principally by the transport of reactants in solution to the silver surface. The thermodynamic features of the reaction with particular reference to the influence of pH and CN- are also discussed and summarized in the form of potential-pH diagrams. METALLIC silver is readily attacked and dissolved by cyanide solutions in the presence of oxygen. This reaction has long been recognized and extensively applied1 in the well-known cyanide process for the extraction of silver from its ores. While this process has been subjected in the past to a number of investigations2,3 both of a practical and fundamental nature, some features relating to the chemistry of the reactions involved, the role of oxygen, the nature of the rate-controlling step, and the effects of pH and certain reagents such as lime, are still not fully understood. It was felt that this situation justified a further investigation of the reaction, made with a view to obtaining a better understanding of its kinetics and mechanism. In the present investigation rate curves for the dissolution of silver were determined over an extensive range of carefully controlled reaction conditions. By carrying out the reactions in a pressure vessel, the partial pressure of oxygen, and hence its concentration, could be varied widely. The influence on the reaction of other variables including temperature, pH, and the concentrations of cyanide, peroxide, and other salts was also examined. The results of these kinetic studies are presented and discussed in this paper, together with a summary of available thermodynamic information relating to the possible reactions which can accompany the attack on silver by aqueous solutions of cyanide and oxygen. Chemistry and Thermodynamics of the Reaction The chemistry of the reactions of gold and silver with aqueous cyanide solutions has been the subject of several recent reviews.'." It has been proposed' that the following reaction occurs when silver dissolves in cyanide solutions in the presence of oxygen: 4Ag + 8CN- + 0, + 2H.0 -t 4Ag(CN); + 40H- [la] An equation of this form, for the corresponding dissolution of gold, was first suggested by Elsner." Bodlaender5 proposed a similar overall reaction, but suggested that it took place in two steps, 2Ag + 4CN- + O2 + 2H2O ? 2Ag(CN),- + 2OH- + H2O2 [2a] followed by 2Ag + 4CN- + H2O2? 2Ag(CN); + 20H- [3a] On the other hand, Janin- suggested that the dissolution of gold can occur with the liberation of hydrogen, rather than by reduction of oxygen. The corresponding equation for the dissolution of silver is 2Ag + 4CN- + 2H20 -t 2Ag(CN); + 20H + H2 [4a] All these reactions represent oxidation-reduction processes and may be resolved into the corresponding separate oxidation and reduction components. The oxidation step involves the formation of the argentocyanide ion and is the same for all the reactions, i.e., Ag + 2CN? Ag(CN)2 + e [51 However, reactions la, 2a, 3a, and 4a differ in the nature of the reduction steps which are, respectively, O2 + 2H2O + 4e ? 4OH- [lb] O2 + 2H2O + 2e ? H2O2 + 2OH- [2b] H2O2 + 2e ? 2OH- [3b] 2H2O + 2e? 20H- + H2 [4b]

Jan 1, 1954

By H. L. Gilbert, H. A. Johansen, R. G. Nelson

High purity electrolytic chromium plate has been hydrogen-reduced and arc-melted under inert atmosphere to give sound ingots. These ingots may be hot forged to break the as-cast structure and then worked at 500°C to finished form. An intermediate and final high temperature anneal gives best ductility and grain refinement. HE increasing interest in refractory metals for I use in high temperature gas turbines, jets, and rockets has led to great efforts in exploiting the fifth and sixth groups of transition elements. Much of the interest has centered upon production of metals that can be worked and fabricated by normal means to produce various engine parts or components having the high temperature characteristics of oxidation resistance and high creep strength required for such uses. If these pure elements do not exhibit all of the desired characteristics, it may be possible to obtain a high purity alloy that will. Since, in all cases, development of these transition elements has depended to a large extent upon removal of oxygen and nitrogen as a means for producing ductile metal, the hypothesis has been accepted that oxygen is the normal embrittling material in a high grade electrolytic chromium metal. Various methods have been employed in an effort to remove this oxygen by direct or indirect attack.' Many workers have endeavored to produce pure chromium through reduction of the oxide by carbon or active metals, while others have recommended fusion electrolysis of chromium salts or reduction of these salts by active metals, such as sodium or calcium. Hydrogen reduction of the oxide or chloride and thermal dissociation of the iodide have been reported to give high purity metal. Experimental Work The U. S. Bureau of Mines, Northwest Electro-development Laboratory, has systematically re-examined the more promising methods and developed two which produce metal having ductility at temperatures lower than heretofore described. It has been found' that oxide-free chromium chlorides in a NaCl-KCl carrier salt may be mag- nesium-reduced and the byproduct salts distilled off in vacuo to give a high purity chromium sponge. Fusion analysis conducted under the supervision of W. W. Horton of Knolls Atomic Power Laboratory showed the oxygen and nitrogen both to be below 10 parts per million on a selected sample. A small amount of carbon is carried over in the final metal from the chlorination and reduction steps which are carried out in graphite crucibles. This trace of carbon is not detrimental to hot ductility. A more practical method for producing ductile metal is through hydrogen reduction of high purity electrolytic chromium. Normal electrolytic chromium will, if "developed" for a few minutes at 1100°C in high vacuum, be found by the method of Adcock:; to contain about 1 pct chromium sesquioxide (Cr2O3). This small amount of oxygen may be effectively reduced by hydrogen.2, 4 The method employed was to crush electrolytic chromium plate in a gyratory crusher to pass 60-mesh; finer crushing appears to offer no advantage. A nitric acid leach removed the iron picked up during crushing. The leached powder was rinsed until neutral with distilled water and vacuum-dried.

Jan 1, 1954

By R. F. Domagala, M. Hansen, D. J. McPherson

On the basis of metallographic analysis, incipient melting data, thermal analysis work, and X-ray diffraction, phase relationships in the 0 to 50 atomic pct Cr region were carefully resolved. Phase relationships in the 50 to 100 atomic pct region were outlined. A single intermediate phase, ZrCr,, was established in the system. A eutectic and a eutectoid were found in the zirconium-rich region of the system, while a eutectic was located in the chromium-rich region. Limited solubility of chromium in both a and a zirconium was observed. THIS is another in a series of papers on zirconium-base binary phase diagrams based on a program sponsored by the Atomic Energy Commission. The Zr-Sn,' Zr-Si,' and Zr-Mo and Zr-W" systems have already been published. Previous work on the Zr-Cr system includes a partial diagram by Hayes, Roberson, and Davies' and a complete diagram by McQuillan." The phase relationships reported by these authors were determined with magnesium-reduced zirconium, whereas those reported herein are based on iodide metal. Some X-ray work on the intermediate phase in this system was also reported by Hayes et al., as well as by Wallbaum.' Comparisons with these data are made in the appropriate sections. Thermal analysis, metallographic and incipient melting techniques were employed to accurately resolve phase relationships in the 0 to 50 atomic pct Cr region, while the remainder of the diagram is outlined on a basis of cast structures and thermal analysis. A description and analyses of the metals used in the preparation of alloys for this study are included in Table I. A "low-hafnium" zirconium crystal bar (Westinghouse "Grade 3") was used. This material was produced by the decomposition of a volatile iodide onto a hot zirconium filament. The as-received crystal bar was coated with corrosion product from a standard autoclave test by which its grade designation is determined. A sand-blasting and subsequent HF-HNO, pickling treatment was employed to remove this contamination. The bars were cold-rolled to approximately 1/32-in. sheet, pickled again, sheared to 1/4-in. squares, washed with acetone, and stored for use. Ingot chromium metal from National Research Corp. and electrolytic chromium flakes from Johnson, Matthey and Co., Ltd., were available as alloy additions. The ingot chromium was received in granular form. The large granules were sized by crushing, treated for iron removal, rinsed with acetone, and stored. The flakes were broken to approximately 1/8 in. with mortar and pestle, cleaned with acetone, and stored for charging. Experimental Procedure A nonconsumable electrode arc furnace identical to that described by Hansen, Kessler, and McPher-son,' was used in this work. A 400 amp dc welding generator was the source of power. To insure homogeneity, ingots were melted in a water-cooled spun copper crucible, a total of four times without opening the furnace. No difficulties were encountered in the preparation of these binary alloys. Analyzed chromium contents were found to agree very well with the intended content. Melts of pure zirconium were interspersed in the course of preparing the alloys and their hardness was measured to keep a constant check on the melting technique. Vycor and quartz bulbs were used to contain the samples for isothermal annealing treatments. Vycor bulbs were employed for temperatures up to 110O°C, while quartz was used above this temperature. For treatments up to 950°C the bulbs were evacuated before sealing, but for higher temperatures a partial pressure of argon was admitted to the

Jan 1, 1954