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By George Comstock

THESE notes should be considered as a further discussion of Mr. S. W. Miller's paper on "Some Structures in Steel Fusion Welds."1 In that paper and the resulting discussion; several conflicting opinions were expressed as to the identity of the needles or small crystals present in oxyacetylene and electric welds. An interesting specimen of an electric weld examined by the writer seems to afford new evidence regarding the needles, that may be worth presenting at this time. The specimen consisted of a piece of 3/8 -in. (9.5-mm.) steel plate, about 2 ¼ by 1 ¾ in. (5.7 by 4.5 cm.) in size, on which some iron had been deposited by arc-welding to a depth of about 3/16 in. (4.7 mm.). The weld appeared to be a very good one, with no noticeable break or boundary between the plate and the deposited iron. Sections for microscopic examination were cut in three planes at right angles to each other through the deposited metal, two of these sections also extending through the steel base. After polishing in the usual way, the microscope showed that the deposited metal was full of very small, round, gray, oxide spots, while the steel plate contained quite a number of alumina inclusions and a little slag. The sections were etched with nitric acid in ordinary alcohol, and structures similar to those described by Mr. Miller were then displayed. Fig. 1 shows the typical appearance of the deposited metal, which was quite uniform in all three of the planes examined. The round dark-gray spots are oxides, and the pale angular crystals are evidently what, Mr. Miller called cementite and Mr. Jeffries martensite, while Dr. Ruder and Prof. Boylston suggested that they might be nitride. The boundary between this structure and the steel base was sharply defined under the microscope. Fig. 2 shows the structure of the plate just under the weld; this is almost martensitic and resembles a coarse-grained casting. This coarse cast structure soon became finer as the distance from the weld increased, finally, becoming very fine, with numerous small particles of sorbite. This very fine structure, shown in Fig. 3, became coarser in turn and finally merged into the original normal structure of the steel plate, shown

Jan 1, 1919

By Harrison R. Cooper

The key to concentrator automation is practical means for obtaining continuous assay data from concentrator streams. The technique most successfully used is x-ray fluorescence analysis. The practical reality of on-stream x-ray analysis has been achieved through effort over the past twenty years, marked by an occasional breakthrough, but more typically a step-by-step development to which many individuals and organizations have contributed. The net result of this progress is the present capability to install on-stream x-ray analyzer systems on a turn-key basis. It is now possible to provide all components of an x-ray analysis system as a completely engineered unit which can be put into immediate use, minimizing needs for specialized application knowledge to benefit from continuous assaying in process control. The economic factors which influence the choice of system and limitations of the x-ray fluorescence technique for slurry analysis are reviewed.

Jan 1, 1976

By Albert J. Phillips

The effect of impurities on the flowsheet in the smelting and refining circuits for copper, lead and zinc is reviewed and the interflow of by-poduct metals from copper, lead and zinc plants is pointed out. The principal points of separation of all impurities in the circuits are indicated and the additional steps added to these circuits in order to effect impurity separation me shown. In this day and age, when difficult metallurgy is mentioned, one thinks of the extraction of more refractory or possibly the alkaline earth or rare-earth metals. It is true that the extraction of metals having a high affinity for oxygen and deleterious solubility for that element in the liquid metal, affords some of the most difficult extractive metallurgy problems. When this is coupled with an affinity for hydrogen, nitrogen, and carbon a devious approach is required that sometimes rivals the complexity of the metallurgy with which this paper deals. However, in all such cases the aim is for a simple

Jan 1, 1962

By William L. Fink, Kent R. Van Horn

Zinc is one of the effective elements introduced to enhance the strength of aluminum. This strengthening is principally attributable to the high solid solubility of zinc in aluminum and the pronounced variation of solubility with temperature. Consequently an accurate determination of the solid solubility curve is desirable. The solid solubility relations have been studied by numerous investigators. Shepherd1 first established the existence of a solid solution region at the aluminum end of the diagram (-v phase) by specific volume and microscopic determinations. Bauer and Voge12 published a constitutional diagram which showed the limits of solid solubility as determined by thermal and microscopic methods. Hanson and Gayler3 presented the aluminum-zinc diagram which is now most generally accepted (Fig. 1). Chill-cast samples were given thermal treatments designed to obtain equilibrium conditions, quenched, and microscopically examined. The solubility was placed between 15 to 20 per cent at 60" C., 20 to 22 per cent at 140" C. and 36 to 38 per cent at 270" C. Sander and Meissner decidedly modified the limits of the -y phase field of Hanson and Gayler's diagram by using similar methods on chill-cast specimens annealed for a shorter period of time. Tanabe,s utilizing dynamic hard-ness, electrical conductivity and dilatometric measurements of specimens at temperature, obtained values comparable to Hanson and Gayler's at room temperature, but appreciably lower at higher temperatures. Nishimura6 concluded from age-hardening results of aluminum-zinc alloy chill castings, which had been quenched from 400" to 500" C., that the solubility of zinc in aluminum at room temperature is less than 5 * Metallurgical Division, Aluminum Research Laboratories. 1 E. S. Shepherd: Aluminum-Zinc Alloys, Jnl, phys. Chem. (1905) 9, 504. 2 0. Bauer and 0. Vogel: Aluminum-Zinc Alloys, Int. Jn1. Melallog. (1916) 8, 101. 3 D. Hanson and M. V. L. Gayler: A Further Study of the Alloys of Aluminum and Zinc. Jnl. Inst. Met. (1922) 27, 267. 4 W. Sander and K. L. Meissner: ZII~ Kenntnis der Konstitution der Aluminium-Zinklegierungen. Ztsch. f. Metallkunde (1922) 14, 385. 4 T. Tanabe: Studies in the Aluminum-Zinc System, Jnl. Inst. Met. (1924) 32, 415 6 H. Nishimura: On the Age-Hardening of Aluminum-Rich Al-Zn Alloys. Mem. Kyoto Imp. Univ. (1924) 3, 133.

Jan 1, 1932

By Charles Wert

THE diffusion and precipitation of carbon and nitrogen in a iron have previously been investigated using the internal friction as a measuring tool.' Most of this work has been done on rather pure iron; no effect was observed which would indicate that either of these phenomena is affected by the rather small amounts of impurity found in these samples of iron. Fastz observed, however, that both the diffusion rate and the aging properties of nitrogen in iron were sensibly changed by the addition of Vz pet Mn. The diffusion rate at a given temperature is reduced and the nucleation of nitrides is apparently changed somewhat. He observed no such changes for carbon in this alloy. Later Dijkstra and Sladek" extended these observations on nitrogen to other alloys of iron. They found that metals other than manganese also influence the behavior of nitrogen in iron; chromium, molybdenum and especially vanadium affect the diffusion and precipitation of nitrogen even more than manganese does. Their results have been verified in all essential details by this author, who finds in addition that small additions of nickel have about the same effect on the diffusion of nitrogen as the same amount of manganese. The present work was undertaken to study the effect on carbon in iron of these alloying elements. The alloys used had two sources. The material used as a "standard" (designated Fe in this paper) in the measurements was some iron supplied by J. K. Stanley, of Westinghouse Electric Corp., who reported 0.01 pct 0, as the only major impurity. He also made up an alloy of 0.26 pct Ni and one of 0.9 pct Mo using this same iron as a base. They were supplied by him in 2 lb billets, which were sawed into rods and cold formed into 0.030 in. wires for measurement. The alloys of chromium, manganese, and vanadium were prepared by the metallurgy section of the Institute for the Study of Metals, University of Chicago, by adding these metals in turn to vacuum melts of National Research Corp. iron. The small castings prepared in this way were also cold formed into 0.030 in. wires. After these wires had been prepared they were decarburized for 30 min at 730°C in wet Hz. After this treatment, no trace of carbon (as measured by internal friction) could be found. All specimens were then carburized for about 15 min at 710°C and water quenched. By this treatment the internal friction at 40°C was raised to a Q-' ~ 0.015. The diffusion of carbon in these alloys was studied by observing the shape and position of the internal friction peak at 0.9 cycles per sec. These measurements were made using a torsional pendulum in a manner described earlier.' The data are plotted in Fig. 1. It is seen that there is no apparent difference in internal friction between the various alloys. This is in marked distinction to the broadening and shift-

Jan 1, 1953

Cortez Gold Mines operated a conventional 2,100 mtpd (2, 300 stpd) cyanidation plant until the 5 million ton ore body was worked out in 1973. (See Gold and Silver Cyanidation Plant Practice by F. W. McQuiston, Jr. and R. S. Shoemaker, Society of Mining Engineers, AIME 1975.) Sub-grade material was dump leached at the mine -mill location in 1971, and the resulting pregnant solutions were added to the feed in the plant's Merrill-Crowe precipitation unit for gold recovery. In early 1973, however, Cortez put into operation their Gold Acres mine which was located about 13 krn (8 miles) to the west of the 'Cortez mine. Economics at that time dictated the heap leaching of the lower grade portion of the ore body with the higher grade being trucked to the Cortez plant for milling. Leach ore was moved directly from the open pits to prepared leach pads located on a gently sloping terrain of 570 grade. Preliminary pad preparation at the leach site included removal of vegetation which was composed of sagebrush and grading of the base. Pads were comprised of mostly minus 74 micron (200 mesh) materials and were made of clay-silt or slime tailings spread on the pad area in thin 50 to 75 mm (2 to 3 in. ) layers, compacted with a vibrating roller compactor to a depth of about 380 mm (15 in.). This was followed with a 100 mrn (4 in.) layer of coarse rock to prevent erosion on the pad and to allow solutions to move laterally under the heaps. Leach solutions normally traveled the length of the heaps and were collected in plastic-lined ditches from which they flowed by gravity to the pregnant solution storage pond. Both pregnant and barren ponds were constructed in the same manner as the leach pads - being lined with compacted tailings or clay silts. The Gold Acres facility required pregnant solution storage of 6 million liters (1.6 million gal) and barren storage of 3.8 million liters (1.0 million gal) designed to handle two to three days of heap drainage or to retain run-off from a major rainfall. Various heap heights were tried including 3, 6, and 9 meters (10, 20, and 30 ft), with a 6 m (20 ft) height selected. Ore was dumped by trucks in a single 6 m (20 ft) lift using a D8 Caterpillar dozer for

Jan 1, 1981

Division of Geology, State of Tennessee, 401 Seventh Ave, North, Nashville, Tenn. Walter F. Pond, State Geologist A selected list of Bulletins available: Bulletin 1(B), Bibliography of Tennessee geology (1911); 2(A) Outline introduction to mineral resources (1910), 2(D) Marbles (1911); 2(G) Zinc deposits (1910), 16, Red iron ores of east Tennessee (1913), 22, Geology and natural resources of Rutherford County (1920), 24(A) Geology and oil possibilities of parts of Overton, Clay, Pickett and Fentress counties (1920); 24(B) Oil and gas resources of northeastern Sumner County (1920), 26, Mineral resources of Waynesboro Quadrangle (1921); 28, Marble deposits of East Tennessee (1923), 29, Magnetic iron ores of east Tennessee (1923), 31, Zinc deposits of east Tennessee (1923), 33, Tennessee coal fields, 37, Geology and mineral resources of Hardin County, 38, Stratigraphy of the Central Basin (in press), 39, Brown iron ores of the Eastern Highland Rim (in press) From 1911 to 1919, inclusive, volumes were issued annually on The Resources of Tennessee Only a few of the separate papers contained in those volumes are now available Vol. 2 (1911): No 1, Explosions of coal dust in mines, and other papers, No. 4, Lignite and lignitic clays in west Tennessee, and other papers; 5, The growth of knowledge of Tennessee geol¬ogy; 9, The valley and mountain iron ores of east Tennessee, 10, The iron industry of Lawrence and Wayne counties, and other papers; 11, Barite deposits in the Sweetwater district, and other papers, 12, The iron ore deposits in the Tuckalioe district, and another paper Various oil maps (15 to 40 cents each) and traverse maps of counties (25 cents and 31 each) can be had, as well as pertinent U. S topographic maps.

Jan 1, 1933

By J. C. Mertz

ACCURATE knowledge of the solid solubilities of the elements that dissolve in the important base metals is needed for guidance in the preparation and heat-treatment of the alloys derived from these compo-nents. While there is still difference of opinion concerning the merits of the X-ray and microscopic methods of determining such solubilities, it is certainly true that the recent extensive use of X-ray diffraction to review the existing constitutional data has revealed many glaring inaccu-racies and has brought about a much improved knowledge of phase-boundary locations, which will inevitably come to include all of the important alloy systems. When the work is done with all necessary precautions it appears that in the majority of cases where the solubilities extend beyond a few tenths of a per cent the X-ray back-reflection technique is capable of furnishing the best of information in this field. For the most prolonged and thorough studies it is obviously advisable to combine the results of several methods, in particular, to obtain an agreement between X-ray and microscopic data. This paper reviews the work previously done on the solubilities of phosphorus, arsenic, antimony and bismuth in copper and, in considera-tion of the uncertainties thus made apparent, presents, new X-ray data obtained with the first three members of this group.

Jan 1, 1936

By David P. Shoemaker, Clara Brink Shoemaker

The I phase was discovered by Bardos, Malik, Spiegel, and Beck1 in the V-Ni-Si system at 1100°C and in the Mn-Co-Si and Mn-Ni-Si systems at 1000°C. Kuzma and Hladyshevskii2 and Kuzma, Hladyshevskii, and cherkashin3 have reported a new phase, which they named the S phase, in the Mn-Co-Si and the Mn-Ni-Si systems at 800°C at approximately the I phase compositions. The powder diffraction diagrams of the I and S phases, compared by Bardos el al.,1 are related but show distinct differences in relative intensities. Professor Paul A. Beck kindly sent us a specimen of the (v-Ni-Si) I phase for single-crystal study. Precession and Weissenberg diagrams taken with a tiny single-crystal fragment showed that the structure is monoclinic with a large unit cell. The cell dimensions were refined from a powder diffraction diagram taken with CrKa radiation in a 57.3-mm camera with our computer program LSCELP4 using only the indices of those reflections that were observed on Weissenberg diagrams (hnl, with n = 0 through 9 and n = 12) and precession diagrams (Okl, lkl, Izk0, hkl, hk2). Table I shows the agreement obtained between the l/d values calculated with the final values for the cell dimensions and the l/d values observed by Bardos et al .1 for I(V42Ni33Si25), by US for I(V41Ni36Si23), and by Kuzma and Hladyshevskii2 for S(MnpCoSi). The powder patterns contain many broad and diffuse lines. In fact practically all powder lines observed are near-superpositions of several reflections. The refinement program is not set up to handle several reflections contributing to one observed line: the position of each line is refined with the aid of one set of indices only. The final values for the cell dimensions were obtained from the lines of strong or medium intensity with the indices indicated by asterisks in Table I: a0 = 13.403(6), bo = 23.336(15), co = 9.129(6)A ß = 99.11(6) deg The standard deviations (given in parentheses) are those calculated by the refinement program from least-squares theory and do not take into account that the lines included in the refinement may not have been correctly indexed in every case or that the position of a line may also be partly determined by the overlapping reflections. The agreement between the calculated and observed I phase patterns is fairly good, although some discrepancies occur. Not all observed lines could be indexed with the incomplete set of sin-

Jan 1, 1968

By A. T. Sweet, C. E. Plummer, H. W. St. Clair, S. F. Ravitz

The ammonium sulphate process for recovering alumina from clays was proposed by Rinman, Buchner, and others many years ago, and more recently various modifications have been investigated both here arid abroad.l-Is The process, as it is being investigated by the Bureau of Mines, involves the following essential steps: (I) sulphating the alumina in the clay by baking with ammonium sulphate at approximately 4m°C., (2) leaching with water to extract aluminum sulphate and ammonium sulphate, (3) crystallization of ammonium alum, (4) conversion of the alum to aluminum hydroxide by the ammonia gases given off during the baking, and (5) calcining the aluminum hydroxide to alumina. The over-all reaction between kaolinite (the most important alumina mineral in most clays) and ammonium sulphate during the baking step may be expressed as follows: Al2O8.2SiO2.2H2O + 4(NH4)2SO4 = (NH4)2SO4.A12(SO4)3 + 6NH3(g) + SH2O(g) + 2SiO2 [i] There is definite evidence. as is shown later. that the aluminum occurs in the baked product as anhydrous ammonium alum rather than as aluminum sulphate, provided the baking temperature is not much above 4o0°C. It is probable that the reaction takes place in the following steps: (NH4)2SO4 = NH3 -(- NH4HSO4 [2] Al2O3.2SiO2.2H2O + ;}NH4HSO4 = A12(SO4)3 + 3NH3 + 5H2O + 2SiO2 [3] A12(SO4)3 + (NH4)2SO4 = (NH4)2SO4.A12(SO4)3 [4] In onc modification of the process, the ammonium sulphate is first decomposed according to Eq. z, and the clay is treated with the resultant ammonium acid sulphate. Reaction I is highly endothermic. On the basis of the best available data, the following values have been estimated for the changes in heat content and free energy in calories per mol: -AH = 331,040 - 34T -AF = 331~040 - 78.3T log T - 671.8T The heat required' at 25OC is 320,900 cal. per mol, or 5650 B.t.u. per pound of alumina. The theoretical equilibcium pressure of NHa, based on the free-energy equation given above, increases very rapidly as the temperature rises above 3o0°C., and reaches one atmosphere at 43s°C. Ammonium alum solutions are almost ideal for crystallization. A saturated solution of ammonium alum contains 126. grams of AlzOa per 1000 grams of water at 90°C. and only 16.5 at 20 C. Hence most of the alum crystallizes out when the

Jan 1, 1944

By R. W. Heckel, R. L. DeGregorio

The DeHoff method of determining the size distribution of ellipsoid-shaped, second-phase particles has been applied to the spheroidization of cementite in a eutectoid steel. The surface area of Precipitates determined from the various size fractions in the distribution was correlated with surface-area measurements based on the number of intersected interfaces on a random lest line. The precipitate particles were found to be oblate ellipsoids with an axial ratio of about 0.90. The size distributions were found to be log-normal. A method is proposed whereby the shrinkage of small particles and growth of large ones can be determined from the experimental data. The experimental data are compared to previously proposed mathematical models describing diffusion-controlled kinetics and various types of interface-controlled kinetics. The experimental growth and shrinkage rates are considerably slower than those predicted by diffusion-controlled kinetics. The best fit is obtained for a model describing interface-controlled kinetics limited by the rate of formation of cementite at the growing interfaces where the interfacial reaction rate is proportional to the solute thermodynamic activity gradient across the surface. THE subject of spheroidization of second-phase particles has been considered previously by other investigators. Livingston1 has studied the precipitation of the cobalt-rich phase from copper alloys containing 0.7 to 3.2 wt pet Co. His results indicate that the average particle size increases as the cube root of the heat treatment time in accord with diffusion-controlled kinetics.'-' Komatsu and rant' in their studies of the growth of SiO2 in a dispersion-strengthened copper-silica alloy found that the initial growth of SiO2 proceeded by diffusion-controlled growth and later stages were limited by interface-controlled growth. The values of the activation energy obtained for the interface- controlled process led them to the conclusion that the process was limited by the dissociation of SiO2 at the shrinking interface. The transition from diffusion-controlled growth to interface-controlled growth was characterized by a particle size which varied with the heat-treatment temperature. It is also interesting to note that the particle-size distribution as found by Komatsu and Grant exhibits log-normal behavior when replotted on log-probability coordinates. Dromsky, Lenel, and Ansell9 have observed the growth of Al2O3 particles having a mean free path of about 1.5 to 13 µ. Their photomicrographs indicate that the Al2O3 particle sizes were larger than those observed by Komatsu and Grant. Dromsky, Lenel, and Ansell concluded that the Al2O3 coarsened by an interface-controlled growth mechanism limited by the solution of A12O3 at the shrinking interfaces. Bannyh, Modin, and Modin10 have studied the spheroidization of a eutectoid steel (0.83 wt pet C). Their spheroidization (tempering) treatments were carried out in the range from 210o to 700°C for times between 1.5 sec and 20 hr. Measurements of mean particle size as a function of time indicated a cube root of time dependence of size at 700°C, in agreement with previous analyses of diffusion-controlled kinetics.2°7 At lower temperatures, the time dependence was less than the one-third power. It is important to note that, although mathematical models of growth* considering particle-size distribution have been available, measurements of only mean particle size have been carried out. DeHoff11 has presented a quantitative metallography technique which is applicable to the determination of the size distribution of ellipsoids of constant shape. This method is applicable to both oblate and prolate ellipsoids of all ratios of minor to major axis and is based upon an extension of Saltykov's analysis12 of the distribution of spheres of varying size. DeHoff's analysis is based upon measurements of the minor axis of the particles on a random plane of polish in a unit area. This method provides a measure of the number of ellipsoids in various size ranges per unit area. As pointed out by DeHoff, such measurements may be used to obtain surface area and total precipitate volume data. Thus, the accuracy of the distribution analysis may be checked by comparison of the surface and volume

Jan 1, 1965

By O. P. Arora, M. Metzger, G. R. Ramagopal

The rates of grain boundary and general corrosion were surveyed by an approximate method. Quantitative differences between their variations with the strength or cupric ion content of the acid yielded large variations in their ratio, highly selective intergranular attack being observed only under specific chemical conditions. The boundary corrosion rate increased with the copper content of the aluminum; this was attributed to an autocatalytic effect similar to the one shown for general corrosion. High- purity aluminum in hydrochloric acid exhibits striking intergranular corrosion and other structure-dependent corrosion phenomena of fundamental interest. The behavior is highly sensitive to the metallurgical and chemical conditions, the significance of many of which has not been established. The features of the intergranular-corrosion phenomenon, first described by Rohrman,l are summarized in the remainder of this paragraph. Strong attack normally occurs only at high-angle grain boundaries.' Usually 15 to 25 pctHCl is used to obtain a high rate, but this has also been obtained with weaker (7 to 15 pct) acid either by adding cupric or ferric ion to the acid3-5 or by passing an anodic current (-0.1 ma per sq cm).2,3,5,6 The two latter corrosion conditions produce strong attack of low-angle boundaries after certain heat treatments 2-4,5,7 The susceptibility of high-angle boundaries is influenced by the grain-boundary segregation of iron atoms; this increases the slow (µ per month) attack in 10 pct HCl8 but diminishes the rapid (mm per month) attack in 20 pct Hc14 (the present and most previous investigations deal with rapid attack). That segregation of elements other than iron affects intergranular corrosion has not been demonstrated, although analysis of data for iron alloys indicated that at least one other element must be considered.9 Intergranular attack occurs over a wide range of purity although it begins to become obscured above several hundred parts per million (ppm) total im- purities by the severe general corrosion which accompanies the higher iron contents and which is associated with the presence of a second phase or an inhomogeneous distribution of the dissolved iron.4,6,10 The variation of intergranular-corrosion rate with heat treatment1'3-6'"10 can be explained in some cases in terms of the distribution of the iron impurity but is not in general adequately understood. The present work dealt with two questions not previously considered in detail. The first proceeded from the view that the extent to which a special behavior is associated with the boundaries is indicated not by the intergranular corrosion rate alone but by the ratio of the intergranular to the general corrosion rate. A comparison of the two rates was therefore made for one lot of aluminum in acids of varying strength and metallic ion content. The second question was the effect of the copper content of the aluminum. For general corrosion, it has long been known that copper ions introduced into the acid by corrosion of the solid solution are reduced on the aluminum as patches of elemental copper which enhance the corrosion rate by providing cathodes of lower hydrogen overvoltage than were originally present.''-'3 Since the copper patches remain themselves unchanged, their action is "catalytic", and since they are products of corrosion, the effect is "autocatalytic." This phenomenon is significant at copper levels much lower than previously suspected, even at those typical of high-purity aluminum, as the authors have shown in a previous paper.l4 The present work shows that copper content affects intergranular corrosion. With polycrystalline specimens, truly quantitative rate measurernents are not readily made for intergranular corrosion or for general corrosion in the presence of rapid intergranular attack, and previous work in this field has tended to be qualitative. The present study made use of a simple procedure which provided fair approximations to the quantitative corrosion rates and fitted the purpose of surveying the behavior over % wide range of conditions and displaying certain large effects. The approximations involved in this work were usually outweighed by the experimental scatter, which tends to be substantial in a system as sensitive as this one. I) EXPERIMENTAL A. Material. The material procured, Table I, represented three low copper (1 to 3 ppm) lots, two of "normal" copper content (21 and 22 ppm), and two

Jan 1, 1962

By E. A. Holbrook

AS A whole, engineering schools have not awakened A to the fact that the workmen compensation laws passed in most of our states between 1914 and 1917 effected a quiet but none the less real revolution in. the relations between labor and management; no longer are industrial accidents unfortunate or careless happenings over which we feel a humanitarian interest and sorrow, they are a cost of the process and the finished product, as vital as improved design and increased efficiency. Last year the writer and others made a committee report to. the American Institute of Mining and Metallurgical Engineers on the cost of accidents in the coal industry of Pennsylvania. Comparatively the accident record in Pennsylvania coal industry is not high, yet the direct compensation cost plus the interference with operation cost of accidents was over 5 per cent. of the total cost of producing the coal. This stands out more vividly -if you realize that about 70 per cent. of the' cost of producing the coal is for payment of labor, wages that are fixed and over which engineering efficiency and management skill have little or no direct effect. This leaves 30 per cent. of the cost chargeable .to hoisting, haulage, overhead 'and other items subject to engineering control. One sixth of this is due to cost of accidents. Surely a direct place 'for an engineering attack.

Jan 1, 1925

By P. K. Lucke

ONE of the interesting features connected with the great continental uplift, which formed the table land of Mexico, is the great depth to which oxidation and secondary enrichment of orebOdies occurred. This table land lies at altitudes ranging from 4000 to. 7000 ft. (1219 to 2133 m.) above sea level. Several cases could be cited of oxidized zones in copper and lead mines which reached depths of upward of 1500 ft. (457 m.) below the surface, and it is universally admitted that the oxidized zone in a mine is limited by the permanent water level. FIG. 1. Mexico, however, like many other countries in which deserts occur, is visited at rare intervals by tremendous floods, which sometimes cause variable water levels over long periods. The following cases bear out the idea, and lead to interesting conclusions of commercial value. My paper demonstrates that carbonates of ores may occur below water level and sulphides above, and I will endeavor to explain the causes of the phenomena in certain specific instances.

Jan 6, 1918

By E. L. Kamen, H. D. Kessler, M. Hansen, D. J. McPherson

The highly reactive Ti-Mo and Ti-Cb alloys were prepared and heat treated under protective conditions. Phase diagrams were established based on micrographic and X-ray diffraction analysis and detection of incipient melting. ß titanium forms a continuous series of solid solutions with both molybdenum and columbium, whereas these metals are only slightly soluble in the a titanium modification. PREVIOUS work on the Ti-Mo and Ti-Cb systems was very limited and is discussed in succeeding sections of this paper relating to the respective phase diagrams. The diagrams in the present work were determined principally by micrographic analysis, because other methods such as thermal analysis and dilatometry are not suitable, due to the low diffusion rates of these alloys in the transformation range. X-ray analysis was believed less useful than micrographic analysis because: 1—On quenching certain high titanium alloys from above their transformation range, the body-centered cubic ß phase decomposes into acicular a (hexagonal close-packed) which room temperature X-ray diffraction techniques cannot differentiate from isothermal a. 2— High temperature X-ray techniques might be used, but are difficult to apply and are subject to error because of the high reactivity of titanium with gases such as oxygen and nitrogen. Although metallo-graphic study was the basic method used, X-ray diffraction analysis was applied to a limited extent, to further substantiate the findings. The transformation ranges on the titanium side of the Ti-Cb and Ti-Mo systems were studied both with DuPont Process A (magnesium-reduced) titanium alloys and with iodide titanium alloys. The Process A metal was used chiefly to bracket the transformation range in order to reduce the number of alloys given a particular treatment for the more accurate final study with iodide titanium alloys. Experimental Procedure The analyses of the metals used in the preparation of alloys for this study are presented in Table I. Melting Practice: Early in the work, a consumable electrode, arc melting furnace was used in the preparation of the Process A Ti-base Mo and Cb alloys. This type of furnace has been described by other investigators.', ' One of the major difficulties of the consumable electrode melting process was the prep- aration of homogeneous electrodes (with the mixture of coarse titanium sponge and fine powder alloying addition) which would give homogeneous ingots. Composition gradients encountered may have been due to a tendency for powdered alloying metals to drop away from the electrode in handling. This difficulty in the preparation of homogeneous alloys was overcome by the use of a nonconsumable electrode furnace for later work. This furnace is similar to the one used by Mc-Pherson and Fontana a Ohio State University. A diagram of the nonconsumable electrode arc furnace is given elsewhere.' The source of power was a 400 amp dc welding generator. Electrode tips of tungsten (% in. in diam) were used for all columbium melts and for a limited number of molybdenum melts. Molybdenum tips were used for the majority of molybdenum alloy melts. Columbium tipped electrodes were tried, but disintegrated rapidly at currents above 300 amp. In the Process A titanium melting practice the metals were charged into the water-cooled spun copper crucible in the following forms: l—titanium: sponge (—4 + 16 mesh); 2—molybdenum: sections of 0.003 in. sheet (approximately ½ in. sq); and 3— columbium: powder compacts (? in. lumps broken from large section). After alternately evacuating and purging the furnace several times with argon or helium, the arc was struck against the metal charge,

Jan 1, 1952

By W. E. Ruder

It has been pointed out by Stead1 that grains of considerable coarseness may be developed in steels containing from 3 to 5 per cent. of silicon, and in a previous paper2 the present author has shown that under the proper conditions of annealing single grains having an area of 50 sq. cm. may be obtained. It is the purpose of this paper to discuss in more detail the conditions promoting the growth of these grains, in the hope that the experiments described may throw some additional light upon the general problem of grain growth in metals. These silicon steels lend themselves particularly' well to such experiments because of the ease with which the change in structure may be followed and because of the fact that the effect of the carbon present is largely obliterated by the high percentage of silicon. This forms a solid solution with the iron, which acts very much like a pure metal. This alloy has been found to have but one critical point, viz., Ar2. This point, determined by Roberts-Austen for Hadfield's 4 per cent. Si alloy, was found to lie at 703" C. Vigouroux3, in working with pure Fe-Si alloys, finds this point to rise from 750" C. for 0.5 per cent. Si to 860" for 6 per cent. alloy, with a flat region in the curve from 3 to 4 per cent. Si. No accurate determination of this point has been undertaken by the present author, but it has been roughly determined to lie between 730" and 750:. In the preliminary experiments, some of which have been described in a previous paper, it was found that practically all of these steels, when annealed to 1,200" C. or higher, showed grains of comparatively large size. These grains varied in size, however, from about 4 sq. mm. to 50 sq. cm. (see Figs. 1 and 2) under the same conditions of anneal, and it was for the purpose of determining the cause of this difference in size that the experiments herein described were undertaken. From a preliminary study of the chemical composition of the specimens

Jan 1, 1914

By C. Norman Cochran

The pllnse diagvam for the NaF-AlF3 system was used to calcutate an ionic model for the NaF-AlF3 system. Assuming an ideal solution,a series of simultaneous equations expressing equilibria be-tween solid and liquid phases at the euleclic, perilec-tic, and melting points were solved for the activities of the ionic species, the dissociation constants, and the entropies and heats of fusion. The calculations suggest the existence of A13F1415 ions in addition to the F-1+AlF6-3 , and AlF4-4 ions previously proposed by others. The calculaled valnes give better agreement with vapor pressures than the previous model without Al3Fl14-5. Additional possible vefinements of the model are proposed. CRYOSCOPIC1 investigations and density data2 for the NaF-A1F3 system have previously been used to study the dissociation mechanism of Na3A1F6 and to derive equilibrium constants for its dissociation to NaF and NaAlF,. Depending primarily on the heat of fusion assumed for cryolite, the dissociation constants ranged between 0.02 and 0.18 from cryoscopic studies, and from 0.09 at 1273°K to 0.16 at 1363°K from density data. In most cases the values were unable to reproduce satisfactorily the experimental liquidus lines very far on the A1F3 side of the Na3A1Fe composition. This suggested the existence of at least one other ionized compound in the melt besides NaA1F4 in the Na3A1F6-A1F3 side of the system. This is assumed to be liquid Na&13F14 (chiolite), which is already established as a stable solid in phase studies of this system. MODEL FOR THE MELT The melt is assumed to be an ideal solution with ion activities equal to anion fractions. The only cation in the model is sodium so that Temkin and simple anionic activities are identical. Although the compounds are completely ionized to Na' and the respective anion in the melt, molecular rather than ionic notation is used throughout this work. The Na3A1Fe is assumed to dissociate to NaA1F4 and NaF as in the former model, and Na&13F14 to dissociate to Na3A1Fe and NaA1F4. Other valid dissociation equilibria can be written involving these four compounds, but all of these can be obtained by combinations of the two described dissociation reactions and, thus, are automatically considered in these calculations. The model allows for no free AlF3 so that compositions for NAIF3 > 0.5 (mole fraction A1F3 on the NaF-A1F3 basis) cannot be treated. The question of the existence of free AlF3 in the melt will be discussed again later. The constants in the model were evaluated from points along the entire known liquidus line of the NaF-A1F3 system. Previous work employed only the liquidus line or densi- ties near the Na3A1F, composition. The liquidus line compositions used in the solution of the model are from unpublished work by Mr. P. A. Foster, Jr., for compositions between the Na3A1F6 melting point and the Na&13F14-A1F3 eutectic, and from the published works of Grjotheim,1 Phillips,3 and Foster4 for the remainder of the system. The relationships used in solving for the desired dissociation constants and heats and entropies of fusion are listed in Table I, and the points along the liquidus line at which each apply are indicated to the right of the relationships. The mole fractions of each of the separate species in the melt are symbolized by N. Relationships [I] and [2] are the respective dissocia-ation constants, Kl and K2, of Na3AIF6 and Na5A13F14 for this model. For simplicity, these constants will be assumed to be independent of temperature. Relationship [3] follows from the assumption of the ideal solution. The expression relating the values of N to the experimental values of NAIf3, is given in Relationship (41. Relationships [5], [6], and [7] each state the equilibrium between a compound in the melt and its pure solid phase for the portion of the liquidus lines where it precipitates. The heats of melting, AH,, and entropies of melting, AS,, used in [5], [6], and [7] are assumed to be independent of temperature. The compositions and temperatures of all five invariant points (two melting points, two eutectics, and one peritectic) along the liquidus lines from NAIF3 = 0 to NAIF3 = 0.5 were employed in the solution. The eutectic and peritectic compositions were particularly useful because each of these is involved in one more equation than other points along the liquidus lines and thus reduces the number of points required to solve for the constants. Also, their use assures that the inflection points in the derived liquidus line will correspond exactly with those on the experimental liquidus line. The total number of equations is 5k1 — 1, where n is the number of experimental composition points used. The number of unknowns is 4n + 5 (4n- 3 values of N, 3 values each of AH, and AS,, and 2 values of K). Thus, six points must be used in the solution to obtain an equal number of equations and unknowns. The one additional required experimental composition was taken on the liquidus line between the Na3A1Fe melting point and the Na3A1F6-Na5A13F14 peritectic. Previous work indicated this was a difficult portion of the curve to fit. The temperature used for the point was 1161°K, the same as for the NaF-Na3A1Fe eutectic. This choice of temperature gave two points with identical NNa3AIF6 values which simplifies the algebraic solution. The second point at this temperature is denoted 1161°'K. PROCEDURE FOR SOLUTION OF EQUATIONS Values were assumed for NNa,AIF and NNaF at the NaF-Na3A1F6 eutectic at 1161°k. By an iterative procedure, the corresponding values for NNa5A13F14 and NNaAlF4 at 1161°K were determined from 131 and 141. A value was assumed for NNaAlF4 at 1161°'K and

Jan 1, 1968

By Davis M. Lapham

Ore bodies at Cornwall, Pennsylvania, have been mined since 1742 principally for iron from magnetite, but also for copper (in chalcopyrite), silver (in chalcopyrite), gold (in chalcopyrite), cobalt (in pyrite), sulfur, and crushed limestone aggregate. Metallization occurs as a limestone replacement above the essentially conformable, south dipping portion of a discordant saucershaped diabase sheet. Pre-Triassic and Triassic faulting have emplaced host Cambrian limestone and two Ordovician(?) hornfels units, now for the most part resting above diabase. Thermal metamorphism of carbonate-bearing country rocks largely to calc-silicates, is ubiquitous. Metasomatism, particularly of potassium, is unique to ore zones. Associated magnetite- actinolite mineralization replaces, in a preferential sequence, all earlier metamorphic and metasomatic minerals and rarely diabase chilled margin. Mineralogical (diopside, actinolite, mica, sulfides, oxides) and chemical (Fe, Cu, S, Co) zoning of the eastern ore body is focused down dip, near its western edge, along a major vertical fault through diabase. This zoning is spatially related to magnetite veins in diabase, to an ore body within diabase, and to a shear zone that probably extends through the sheet.

Jan 1, 1968

By J. W. Spretnak, D. A. Chatfield, G. W. Powell, J. R. Eifert

In nzost cases, the driving force for a lattice transformation is produced by supercooling below the equilibriunz transformation temperature. The interfnce reaction in isothermally annealed, multiphase diffusion couples may involve a luttice transformation which also requires a driving force. Direct experinzental evidence has been obtained for the existence of the driring force in the form of a supersaturated phase at the aocc)-0@cc) interface in Cu:Cu-12.5 ult pct A1 couples; the super saturation is equivalent to an excess free energy of approximately 3 cal per mol at 905. A tentatiue interpretation of the dynanzic situation a1 the interface based on the free energy-composition diagram is proposed. THE presently accepted theory of diffusion in multiphase couples1 states that there will be a phase layer in the diffusion zone for every region which has three degrees of freedom and which is crossed by the diffusion path in the equilibrium phase diagram. For binary systems, this restriction excludes all but single-phase fields and, for ternary systems, only one- and two-phase fields are included. In addition, Rhines"~ as well as other investigators3 6 have reported that the compositions of the various phases adjacent to the interfaces are, for all practical purposes, the compositions given by the intersections of the diffusion path with the solubility limits of the single-phase fields of the equilibrium phase diagram. Some studies of the rate of thickening of these intermediate diffusion layers indicate that the thickness of the layer changes para-bolically with time, or: where x is the position of the interface relative to an origin xo, t is the diffusion time, and k is a temperature-dependent factor. crank7 shows mathematically that, if the compositions at an interface are independent of time and the motion of the interface is controlled by the diffusion of the elements to and from the interface, then the segments of the concentration penetration curve for a semi-infinite step-function couple will be described by an equation of the form: hence, Eq. [l] follows from Eq. (21 if the interface compositions are fixed and if the motion of the interface is diffusion-controlled. Although the concept of local equilibrium being attained at interfaces has assumed a prominent role in the theory of diffusion in multiphase couples, experimental evidence and theoretical discussions which challenge the general validity of this concept have been reported in the literature. arkeen' has stated that strict obedience to the conditions set by the equilibrium phase diagram cannot be expected in any system in which diffusion is occurring because diffusion takes place only in the presence of an activity gradient. Darken also noted that it is usually assumed that equilibrium is attained locally at the interface although the system as a whole is not at equilibrium, the implication being that the transformation at the interface is rapid in comparison with the rate of supply of the elements by diffusion. ISirkaldy3 indicates agreement with Darken in that he believes the concept of local equilibrium is at best an approximation because the motion of the phase boundary requires that there be a free-energy difference and, hence, a departure from the equilibrium composition at the interface. Seebold and Birks9 have stated that diffusion couples cannot be in true equilibrium, but the results obtained are often in good agreement with the phase diagram. The initial deviation from equilibrium in a diffusion couple will be quite large because alloys of significantly different compositions are usually joined together. Kirkaldy feels that the transition time for the attainment of constant interface compositions (essentially the equilibrium values) will be small, although in some cases finite. Castleman and sieglelo observed such transition times in multiphase A1-Ni couples, but at low annealing temperatures these times were quite long. Similarly, ~asing" found departures, which persisted for more than 20 hr, at phase interfaces in Au-Ni and Fe-Mo diffusion couples. Braun and Powell's12 measurements of the solubility limits of the intermediate phases in the Au-In system as determined by microprobe analysis of diffusion couples do not agree with the limits reported by Hiscocks and Hume-Rothery13 who used equilibrated samples. Finally, Borovskii and ~archukova'~ have stated that the determination of the solubility limits of phase diagrams using high-resolution micro-analyzer measurements at the interfaces of multiphase couples is not an accurate technique because of deviations from the equilibrium compositions at a moving interface; diffusion couples may be used to map out the phase boundaries in the equilibrium diagram, but the final determination of the solubility iimits should be made with equilibrated samples. The purpose of this work was to investigate the conditions prevailing at an interface in a multiphase diffusion couple and to compare the interface compositions with those associated with true thermodynamic equilibrium between the two phases. Microanalyzer techniques were used to measure interface compositions in two-phase Cu-A1 diffusion couples annealed at 80@, 905", and 1000°C for various times.

Jan 1, 1969

THE man who forgot to mail the letters his wife gave him was for once justified at Tulsa, for envelopes, scratch paper and tablecloths were all in demand and through the two days of the meeting of the Petroleum Division, pencils were busy everywhere sketching out diagrams, drawing curves, figuring, or just taking notes. Those attending took the serious papers seriously, and discussion was wide-ranging but pointed. Despite the highly technical character of the papers presented, the chairmen had never to call for discussion; it was only necessary to say the paper was open for it. Both days the meetings lasted until after five in the afternoon, and it was enthusiastically voted to advance the meeting hour on Friday, in order to give more time. In all, ten papers, abstracts of which appeared in MINING AND METALLURGY for October, and copies of all but two of which were available in print, were presented in the two days, and no more could have been handled to advantage in that time. All but one of these dealt with problems of production engineering. That, the opening paper, was a general review of demand, supply and price in 1928, by Campbell Osborn, in which he argued for the price control of production and showed how the economic conditions determined development. J. Elmer Thomas presented a carefully prepared review of the same data, but came to somewhat different conclusions as to trend, and J. E. Pogue pointed out that in recent years it has been the manufacturing rather than the producing industries that have been notably profitable. These and other discussions were too long to be reported here, but will be printed in full later.

Jan 1, 1928