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By Fred C. Bond

MANY grindability tests have been made in the Allis-Chalmers laboratory since the tabulated results were last published.1 The lists of standard ball-mill and standard rod-mill grindability tests are brought up to date in this paper, and considerable new material is added. This includes a tabulation of open-circuit grinding tests, with impact and compression-crushing tests. The standard ball-mill grindability tests (Table I) were made in a standard laboratory ball mill, 12 by 12 in. inside, running at 70 rpm, with a charge of 285 iron balls ranging from 1 1/2 to 3/4 in. in diameter and weighing 20,125 grams. Seven hundred cubic centimeters of minus 6-mesh stage-crushed dry feed was used, and the circulating load was maintained constant at 250 pct by adjusting the number of mill revolutions for each grinding period. Tests were made at all mesh sizes from 28 to 200, and the grindability is the number of net grams of screen undersize produced per revolution. The table includes 479 tests. It has been calculated that the ball mill does 52.3 joules of useful work on the ore per revolution2 with 93 joules input to the mill. The standard rod-mill grindability tests (Table 2) were made in a laboratory tilting rod mill, 12 in. in diameter by 24 in. long inside, with a wave-type lining, running at 46 rpm. The grinding charge consisted of six 1 1/4-in. diameter and two 1 3/4-in. diameter steel rods, all 21 in. long and weighing 33,380 grams. The mill was rotated level for eight revolutions, then tilted up 5° for one revolution, down 5° for one revolution, and returned to level for eight revolutions. It was discharged by tilting downward at 45° for 30 revolutions. Feed consisted of 1250 cc of minus 1/2-in. stone and the circulating load was maintained constant at 100 pct by adjusting the number of mill revolutions for each grinding period. Tests were made at all mesh sizes from 3 to 65, and the rod-mill grindability is the number of net grams of screen undersize produced per revolution. The table includes 105 tests. The impact and compression-crushing tests (Table 3) are given in a table that is an extension of a previous publication3 in which the method of testing was described in detail. Two equal hammers weighing about 30 lb each were arranged to strike simultaneous blows on opposite sides of the test specimen. Broken pieces of rock passing a 3-in. square and retained on a 2-in. square were set up with the smallest dimension between the hammers, and this distance was measured. The height of the hammers was increased slightly before each blow until the specimen broke, and the foot-pounds per inch of thickness was calculated. Ten pieces

Jan 1, 1947

By H. K. Work, G. H. Enzian

In the manufacture of steel for commercial purposes, the deoxidation practice used, i.e., the method and degree of deoxidation, is an important factor affecting the structure and mechanical properties of the finished steel. Deoxidation practice exerts a pronounced influence not only on the soundness of the ingots but also on the reaction of the steel to a number of mechanical and thermal treatments. The first mentioned effect of deoxidation is more or less obvious and was first demonstrated, though perhaps not fully appreciated, by Robert Mushet when, in 1856, he added speigeleisen to low-carbon bessemer blown metal. In 1861. Bessemer patented the addition of one pound per ton of silicon to his blown metal to "cause the metal to lie quietly in the mold." The second effect of deoxidation-—that is, the effect on the properties and behavior of the steel—is, one might say, more subtle, and certainly not as well understood as the first, although in many cases it is the more important consideration. This paper is limited to a discussion of only the second effect of deoxidation and: in particular, to the effect on the strain-sensitivity of low-carbon steels. General Discussion Originally it was thought that the function of a deoxidizer was to combine with the oxygen present in the steel as iron oxide and prevent its subsequent evolution as a gas. -More recently it has been realized that a deoxidizer does more than this. Frequent reference has been made to the effect of deoxidizers on the nitrogen in the steel, and some attention has also been paid to hydrogen. As a consequence of the above situation any study of deoxidation must be concerned with the gas content of the steel and the effect of the deoxidizer on the gases involved. The term "gas content" as used here refers to gases extracted from steel during melting in vacuum rather than to elements present in steel in the gaseous state. The extracted gases, at least in the case of oxygen and nitrogen, are generally accepted to be products of decomposition of oxides, nitrides, or other more complex compounds. The manner in which deoxidation affects the gas content of steel and the significance of gases in steel have been and still are subjects of considerable speculation. No attempt will be made here to give a complete discussion of the literature on this subject but a few references will be cited for purposes of illustration. N. Hamilton1 found a correlation between the oxygen content of alloy steel and the behavior of the steel during tube piercing. Davenport, Bain, and others associated oxygen with aging properties of steel while Köster5 and a number of others6-lo made similar claims for nitrogen. Daniloff, Mehl, and Hertyll stated that "deoxidation decreases the susceptibility of steels to aging directly

Jan 1, 1945

By G. T. Higgins

PREVIOUS workers1,2 have found evidence of exaggerated grain growth or secondary recrystallization on annealing sponge zirconium at temperatures high in the a, phase field, but no details of the orientation relationship between the secondary grains and "as-recrystallized" matrix were reported. In other hexagonal metals, namely dilute Mg-A13 and Cd-zn4 alloys, secondary recrystallization has been observed in which the secondary grains are related to the primary recrystallized structure by rotations about the c axis. These rotations are thus comparable with the rotations about the (111) axis observed in the secondary recrystallization of fcc metals. In the current work secondary recrystallization has been observed on annealing iodide zirconium at 800°C and the associated changes in crystallographic texture have been examined. The material employed was arc-melted iodide zirconium of the following composition: Impurity O H Fe Hf Pb I Ni C1 A1 ppm by wt 130 5 230 98 23 28 200 39 30 This was received as 0.25-in. plate, and, prior to the annealing studies, was cold-rolled to 0.040 in. Specimens 1 in. sq were chemically polished and annealed for various times at 800°C in a vacuum better than 5x 10-6 Torr. For metallographic examination specimens were first chemically polished and then anodized8 to enhance contrast between the grains when examined under polarized light. Changes in crystallographic orientation associated with the development of secondary grains were followed by (1011) and (0002) pole-figure determinations using a conventional Schulz goniometer in reflection. Filtered Cr Ka radiation was employed and great care was taken to avoid spurious re- sults due to the close proximity of the Bragg angles for the (1011) and (0002) reflections. Figs. 1 and 2 illustrate the change in grain structure on annealing at 800°C. After 24 hr the structure has ceased to be equiaxed due to the development of certain grains in preference to others. It is notable that the secondary grains do not grow to the extent observed in sponge zirconium.1,2 This appears to be due in part to the fact that normal grain growth is inhibited in the less pure sponge zirconium, with the result that the driving force for secondary recrystallization remains high, while at the same time the number of grains able to develop in the presence of the impurities is also smaller. As a consequence, in sponge zirconium those grains that do develop preferentially are able to grow into the fine -grained matrix without impingement, while in iodide zirconium the preferential growth of many grains leads to early impingement. The pole figures determined for specimens annealed for 5 min and 24 hr at 800°C are illustrated respectively in Figs. 3 and 4. These indicate that the dominant feature of the initial recrystallized texture consists of basal planes at an angle of 321/2 deg to the sheet surface, with a (1120) axis lying parallel to the

Jan 1, 1967

By J. Leja, A. Pomianowski

This paper deals with equimolar solutions of xanthate and alkyl trimethyl ammonium bromide adsorption on copper, nickel and sphalerite powders. After an exposition of the experimental methods used and the results obtained, a thorough discussion leads to the conclusion that some molecular association between xanthates and CnTAB's does take place in the bulk of the solution as well as at the air/liquid interface. A spectrophotometric study of xanthate solutions alone and their mixtures with equimolar amounts of alkyl trimethyl ammonium bromide (CnTAB) has established the additivity of ultraviolet spectra (190 to 400 mµ) for potassium ethyl xanthate (KEtX) and C12TAB. No obvious effect of C12TAB addition on the decomposition rate of KEtX was observed, the half life of which was established as 29±3 days at 22°C and pH ~ 6. In mixed solutions of longer xanthate homologues (e.g. hexyl and nonyl) and equimolar CnTAB, colloidal precipitates are gradually formed which contain primarily the corresponding xanthate molecules. The kinetics of collector abstraction by copper, nickel and sphalerite powders were studied in 10-5 to 10"3 M solutions of KEtX alone and in equimolar mixtures of KEtX and CI2TAB. Presence of C12TAB caused a two to three fold increase in the amounts of xanthate (equivalent to many monolayers) abstracted by copper and nickel powders (and in their rates of abstraction) but had no effect on the abstraction of xanthate by unactivated sphalerite (equivalent to less than a monolayer). The adsorption of C12TAB itself from the mixed solutions was very low, at most one monolayer only, and was not influenced by the nature of the solid powder used. A change in the rates of abstraction, observed with copper powder, was interpreted as a completion of a multilayer coating (completely enveloping the grains of powder) following which the rate of reaction between solution and substrate becomes controlled by diffusion through this coating. Work of Buckenham and Schulmanl on molecular associations between different collectors has shown unusual synergistic effects in flotation of individual minerals using mixtures of xanthates and alkyl trimethyl ammonium bromides. The objectives of the present work were: 1) to determine whether these molecular associations between the two types of collectors (indicated by strong surface tension lowering in Buckenham and Schulman's work) take place at the air/liquid interface only or in the bulk of solution as well 2) to establish whether different solids adsorb any species from the mixture of these amphipatic molecules preferentially or as molecular complexes 3) to establish whether there are any differences in the kinetics of adsorption. Metallic copper and sphalerite powder were chosen as adsorbents since they represent two extremes since copper readily adsorbs multilayers of xanthate (and is easily floated with ethyl xanthate) while unactivated sphalerite does not appreciably adsorb xanthate but is known to be readily floated by the amine type collectors. Metallic nickel was included because the infrared spectroscopic work2 on xanthate

Jan 1, 1964

I. PRESIDING OFFICER, At all business meetings of the Institute the President, or, in his absence, the First Vice-President, or, in the absence of both of them, any other Vice-President or Director, chosen by the meeting, shall preside. At all other meetings of the Institute the President, or, in his absence, one of the Vice-presidents shall preside. If none of these be present the meeting shall elect a Chairman. The President shall do and perform such other duties as may from time to time be assigned to him by resolution of the Board of Directors of the Institute. II. ORDER OF BUSINESS. At each business meeting of the Institute the order of business shall be as follows: 1. Reading of minutes of preceding meeting. 2. Report of the President, 3. Report of the Treasurer. 4. Report of the Secretary. 5. Election of Directors. 6, Reports of Standing Committees. 7. Reports of Special Committees. 8. Special Orders. 9. Miscellaneous business. This order of business may be changed at any meeting, by a vote of a majority of the Members and Associates present. At all sessions of the Institute, other than business meetings, the order of proceedings and the time of adjournment shall rest in the discretion of the presiding officer. III. SECRETARY OF THE INSTITUTE. The Secretary shall keep a record of the proceedings of all the meetings of the Institute, He shall be custodian of the corporate seal, of the minute books and of all the legal documents belonging to the Institute. He shall have charge on behalf of the Institute of all correspondence. He shall notify all Officers and Directors and all members of committees of their election and appointment; shall issue notices of all meetings of the Board, and of the annual and other business meetings of the Institute; and shall, in calling special meetings of the Directors, specify the objects of such meetings. He shall act as clerk at all the meetings of the Board of Directors and at all meetings of the Institute, The Secretary shall be custodian of all technical or scientific papers submitted to the Institute for its consideration and shall have general charge and supervision of the editing and proof-reading of all material published by the Institute, and of the distribution thereof. The Secretary shall be the custodian of all back numbers of the Transactions and other publications of the Institute. There shall be kept under his direction an account in ledger form of all such back numbers, He shall on the first day of January of each year submit to the Library Committee a statement of the number of copies of Transactions, magazines and other publications printed during the preceding year, giving the number distributed and remaining undistributed; also a statement covering additions to and withdrawals from the total stock of Institute publications, with the number 'remaining on hand at date of statement,

Jan 1, 1928

By Fred C. Bond

Many grindability tests have been made in the Allis-Chalmers laboratory since the tabulated results were last published.' The lists of standard ball-mill and standard rod-mill grindability tests are brought up to date in this paper, and considerable new material is added. This includes a tabulation of open-circuit grinding tests, with impact and compression-crushing tests. The standard ball-mill grindability tests (Table I) were made in a standard laboratory ball mill, 12 by 12 in. inside, running at 70 rpm, with a charge of 285 iron balls ranging from 1½ to 3/4 in. in diameter and weighing 20,125 grams. Seven hundred cubic centimeters of minus 6-mesh stage-crushed dry feed was used, and the circulating load was maintained constant at 250 pct by adjusting the number of mill revolutions for each grinding period. Tests were made at all mesh sizes from 28 to 200, and the grindability is the number of net grams of screen undersize produced per revolution. The table includes 479 tests. It has been calculated that the ball mill does 52.3 joules of useful work on the ore per revolution2 with 93 joules input to the mill. The standard rod-mill grindability tests (Table 2) were made in a laboratory tilting rod mill, 12 in. in diameter by 24 in. long inside, with a wave-type lining, running at 46 rpm. The grinding charge consisted of six I1/4-in. diameter and two 13/4-in. diameter steel rods, all 21 in. long and weighing 33,380 grams. The mill was rotated level for eight revolutions, then tilted up 5' for one revolution, down 5° for one revolution, and returned to level for eight revolutions. It was discharged by tilting downward at 45° for 30 revolutions. Feed consisted of 1250 cc of minus in. stone and the circulating load was maintained constant at 100 pct by adjusting the number of mill revolutions for each grinding period. Tests were made at all mesh sizes from 3 to 65, and the rod-mill grindability is the number of net grams of screen undersize produced per revolution. The table includes 105 tests. The impact and compression-crushing tests (Table 3) are given in a table that is an extension of a previous publication8 in which the method of testing was described in detail. Two equal hammers weighing about 30 lb each were arranged to strike simultaneous blows on opposite sides of the test specimen. Broken pieces of rock passing a 3-in. square and retained on a 2-in. square were set up with the smallest dimension between the hammers, and this distance was measured. The height of the hammers was increased slightly before each blow until the specimen broke, and the foot-pounds per inch of thickness was calculated. Ten pieces

Jan 1, 1949

By E. A. Gulbransen, W. S. Wysong

THE behavior of tungsten and its surface oxides in oxidizing and reducing atmospheres and in high vacua at elevated temperatures is a question of considerable technical importance. The use of tungsten as a metal or as an important component in alloys in high temperature oxidizing atmospheres has been limited because of the unprotective nature of its oxide film and the volatility of its oxide. This paper will present results of a microbalance study1,2 of the following problems: (I) the oxidation behavior in the temperature range of 25 to 550°C (2) the reduction with pure hydrogen of thin oxide films formed on tungsten, and (3) the volatility of thin oxide films on tungsten. Tungsten is an interesting metal to study for the following reasons: (1) although the oxide to metal volume ratio is greater than one, the oxide is not considered protective, (2) the metal readily oxidizes at temperatures from 300° to 550°C (3) the oxides W02 and WO3 are reduced at temperatures as low as 500°C. by hydrogen, and (4) the oxide W02 is volatile at temperatures from 800 to 1100°C. LITERATURE The oxidation of tungsten in its thin film range has not been studied critically. In the thick film range Dunn3 has made the only systematic study. He found the oxidation rate to obey the parabolic rate law in the temperature range of 700 to 900°C. The temperature variation of the oxidation rate constant was found to follow an exponential law of the Arrhenius type. An inflection was noticed in the temperature plot of the rate law constant at 850 to 900°C. This was attributed to a phase change in the oxides. Scheil4 has studied the oxidation rate at 500 and 700°C over long periods of time and found a linear rate law. This result was interpreted as evidence for the presence of a nonprotective film. Pilling and Bedworth5 analyses of the oxide volume to metal volume ratio would indicate that a compact protective film should form. McAdam and Geil6 have studied the oxidation of tungsten in the thin film range using the interference color method. A parabolic rate law was found. Their curves showed that tungsten oxidizes faster than nickel but more slowly than iron. The lattice structures found in the oxidation of tungsten surfaces have been studied by Hickman and Gulbransen.7 They have reported that W03 is the stable oxide in contact with the metallic substrate up to approximately 600°C while W02 forms first at 700°C. Hägg and Magneli8 have recently reported a study of the lattice structures observed in the tungsten oxides using the X-ray diffraction method. In addition to an a-phase W03 and a d-phase W02, they reported the existence of two new phases. A ß' phase, homogeneous between

Jan 1, 1947

By C. M. Shigley

The record of the largest magnesium plant in the country utilizing sea water as a primary raw material stands as another victory in the struggle for large-scale production of pure chemical elements from the oceans. Bromine was the first element to be economically and commercially recovered when, in 1933, a six million pound per year unit was built on the Atlantic Coast near Wilmington, North Carolina, by the Ethyl-Dow Chemical Co.' The bromine was reacted with ethylene to produce ethylene dibromide, a necessary associate of tetraethyl lead in ethyl antiknock fluid. Within eight years that plant was doubled and redoubled, and another large unit was put into operation at Freeport, Texas, taking bromine from the Gulf of Mexico. In 1940, in fortunate anticipation of the impending demand for magnesium and the limitations of the production from natural brines, the Dow Chemical Co. turned again to the sea, and designed and erected a plant at Freeport to produce 18,000,000 lb. of magnesium per year from sea water.2 In March 1941, two months after the new plant had been put into successful operation, construction of an 18,000,000-lb. Government-financed addition was started. Late in 1941, as a part of the $400,000,000 defense program intended to produce 600,000,000 to 700,000,000 lb. of magnesium per year, Dow was asked to build and operate for the Government a 72,000- ooo-lb. plant near its original plant at Freeport. Within a few days after the Japanese made their attack at Pearl Harbor, preparation of a site was started at Velasco, Texas, for the construction of the Texas plant of the Dow Magnesium Corporation—the largest known magnesium plant utilizing sea water as its raw matcrial. Less than six months after the first piling was driven, urgently needed magnesium was in steady production. Five months later, the plant had exceeded its rated capacity. It remained above rated production until the general magnesium curtailment was applied to Government-owned plants in September 1944. Credit for the construction and operation record of the Dow magnesium plant must be divided among the efforts of a very determined group of men, an extremely favorable location, and a simple process. It is with the two latter aspects of the plant that this article will deal. The site for the new enterprise was chosen near Velasco, Texas, on property bordering the Brazos River at a point approximately 6 miles inland from the original magnesium plant and 7 miles inland from the Freeport Harbor on the Gulf of Mexico. This location was far enough away from the operating units to reduce both interference from construction and the vulnerability of closely bunched manufacturing operations to the then feared air attack. Yet the distance inland was not too great for the economical construction of a barge canal from the harbor to serve both the transportation of raw

Jan 1, 1949

By F. S. McNicholas

IN the writer's opinion the term "block caving" has been rather loosely applied to a general principle of mining, and therefore detailed classification of caving methods and draw, together with the characteristics required for each method, will fill a desired need. Selection of caving method should be made only after a study of all governing conditions, such as size of orebody, lateral and vertical extent of ore-body, attitude, treatment demands, possible resultant pressures, and cost and profit comparison of methods. Successful caving methods can be classified under six main headings: (1) Full-protected block caving, (2) semi-protected block caving, (3) unprotected block caving, (4) full-panel caving, (5) half block-panel caving, (6) block-panel caving. The methods and factors governing choice of method are shown in Table I. Full-protected Block Caving Full-protected block caving consists of develop-ing, undercutting, and drawing to exhaustion a block of ore of predetermined size without coordination of mining or draw with adjoining areas. The block is mined and drawn as an independent unit (Fig. 1). Full-protected block caving demands that mining and draw cannot be done against unconsolidated capping in adjoining caved and exhausted blocks. Two sides of block are against solid. Caved capping must be allowed to consolidate for a suitable period, usually not less than one year. Pillars may be left in lieu of consolidated capping (Fig. 2). The advantages of full-protected block, caving are: (1) A definite area is developed, mined, and drawn as a unit so that all work may be completed, the block drawn to exhaustion in the minimum length of time, and the area then abandoned. (? Production is not restrained because of coordina1, on with adjoining areas. (3) Records of draw and caved reserve of ore are good. Upon abanwnment of the block, accountability for production is closed out with no carry-over to adjoining areas. The disadvantages of full-protected block caving are: (1) Side dilution from the draw adjacent to the consolidated capping may be serious, particularly where capping does not consolidate sufficiently in the allotted time. (2) Boundary weakening is needed on the solid sides of the block except in weak rocks. (3) Maximum cantilever and compression effect to aid caving and fragmentation may not be secured since the draw should proceed from the solid to the consolidated capping to minimize side dilution. However, undercutting from the loose (caved capping) to the solid with a slight initial draw in the same manner will develop cantilever effect. (4) A period of at least one year, more is usually desirable, must be allowed for caved capping ,to consolidate before mining the adjoining block, depending upon the characteristics of the capping. (5) Capping may not consolidate sufficiently in the time that can be allowed. Full-protected block caving is indicated where: (1) The ground is weak and heavy and workings

Jan 1, 1952

By R. W. Gurry

In the course of a series of measurements of the rate of diffusion of carbon in austenite at about 960°C. (1760°F.) and III0°C. (2030°F.), it became necessary to determine carbon concentration when austenite is saturated with graphite, because of indications that the hitherto accepted value of the solubility of graphite in this temperature range is too low. Specimens of carbonyl iron were saturated at temperature in a hydrogen-toluene atmosphere which was in equilibrium with graphite. The carbon conteDt of the steel was measured either by combustion or by the loss of weight after substantially complete decarburization in an atmosphere of hydrogen saturated at room temperature with water vapor. The absence of carbide or graphite as a phase at temperature was demonstrated by microscopic examination of saturated specimens that had been drastically quenched, The mean result of concordant ments-—taeats-is-^that gamma iron saturated with respect to graphite contains 1.39 per cent carbon at 957°C .(i755°F.) and 1.89 per cent at III0°C. (2030°F.). These two values, plotted along with what appears from the literature to be the best value (0.69 per cent) at the iron-graphite eutec-toid temperature (738°C. or I360°F.), yield a curve that is almost linear, and which, continued upward through a short interval, leads to a limiting solubility of 1.98 per cent at the iron-graphite eutectic temperature II35°C. (2075°F.) instead of the commonly accepted value of about 1.7 per cent. Experimental Procedure The samples of carbonyl iron, with the exception of those for microscopic examination, were cylinders 3.8 cm. long, 0.475 cm. in diameter. They were placed in a graphite holder and suspended in a vertical furnace, the temperature of which was controlled precisely by means of the resistance of the platinum winding.' In the empty furnace the range of temperature over a distance of 4 cm. at the heat center was 9°C. (I6°F.) but at a given location the temperature remained within +o.5°C. (o.9°F.); it was measured by inserting a platinum-rhodium couple calibrated at the melting point of palladium, 1555°C. Since the presence of the sample probably improved the uniformity of temperature, it was decided to consider the average temperature of the sample to be 3°C. lower than the maximum measured in the empty furnace with the same setting of the controller. Data were obtained in the vicinity of two temperatures, 960°C. (I760°F.) and III0°C. (2030°F.). The samples for microscopic examination, 2.2 cm. long, 0.475 cm. in diameter, were suspended individually on pure iron wire; for these no temperature correction was applied. The carburizing gas passed into the furnace was dry, oxygen-free hydrogen saturated at room temperature with toluene; this quickly produced on the

Jan 1, 1942

By E. A. Gulbransen, W. S. Wysong

The behavior of tungsten and its surface oxides in oxidizing and reducing atmospheres and in high vacua at elevated temperatures is a question of considerable technical importance. The use of tungsten as a a Or as an important component in alloys in high temperature Oxidizing atmospheres has been limited because of the unprotective nature of its oxide film and the volatility of its oxide. This paper will present results of a micro-balance study of the following problems: (1) the oxidation behavior in the ternperature range of 25 to 550°C (') the reduction with pure hydrogen Of thin Oxide films formed On tungsten, and (3) the volatility Of thin Oxide films On tungsten. Tungsten is an interesting metal to study for the following reasons: (1) although the Oxide to to ratio is greater than one, the oxide is not considered protective, ('1 the meta1 readily Oxidizes at temperatures from 30" to 55o°C (3) the oxides WO² and WO³ are reduced at temperatures as low as 500°C. by hydrogen, and (4) the Oxide WO3 is volatile at temperatures from 800 to 1100°C. Literature The oxidation of tungsten in its thin film range has not been studied critically. In the thick film range Dunn3 has made the only systematic study. He found the oxidation rate to obey the parabolic rate law in the temperature range of 700 to 900°c. The temperature variation of the oxidation rate constant was found to follow an exponential law of the Arrhenius type. An inflection was noticed in the temperature plot of the rate law constant at 850 to 900°C. This was attributed to a phase change in the oxides, Schei14 has studied the oxidation rate at 500 and 700°C over long periods of time and found a linear rate law. This result was interpreted as evidence for the presence of a nonprotective film. Pilling and Bed-worth's5 analyses of the oxide volume to metal volume ratio would indicate that a compact protective film should form. McAdam and Geil6 have studied the oxidation of tungsten in the thin film range using the interference color method. A parabolic rate law was found. Their curves showed that tungsten oxidizes faster than nickel but more slowly than iron. The lattice structures found in the oxidation of tungsten surfaces have been studied by Hickman and Gulbransen.? They have reported that WO3 is the stable oxide in contact with the metallic substrate up to approximately 600°C while wo³ forms first at 7oo°c. Hagg and Magneli8 have recently reported a study of the lattice structures . observed in the tungsten oxidcs using the X-ray diffraction method. In addition to an a-phase WO3 and a '-phase WO2, they reported the existence of two new phases. A 8' phase, homogeneous between

Jan 1, 1949

By R. W. Gurry

In the course of a series of measurements of the rate of diffusion of carbon in austenite at about 960°C. (1760°F.) and III0°C. (2030°F.), it became necessary to determine carbon concentration when austenite is saturated with graphite, because of indications that the hitherto accepted value of the solubility of graphite in this temperature range is too low. Specimens of carbonyl iron were saturated at temperature in a hydrogen-toluene atmosphere which was in equilibrium with graphite. The carbon conteDt of the steel was measured either by combustion or by the loss of weight after substantially complete decarburization in an atmosphere of hydrogen saturated at room temperature with water vapor. The absence of carbide or graphite as a phase at temperature was demonstrated by microscopic examination of saturated specimens that had been drastically quenched, The mean result of concordant ments-—taeats-is-^that gamma iron saturated with respect to graphite contains 1.39 per cent carbon at 957°C .(i755°F.) and 1.89 per cent at III0°C. (2030°F.). These two values, plotted along with what appears from the literature to be the best value (0.69 per cent) at the iron-graphite eutec-toid temperature (738°C. or I360°F.), yield a curve that is almost linear, and which, continued upward through a short interval, leads to a limiting solubility of 1.98 per cent at the iron-graphite eutectic temperature II35°C. (2075°F.) instead of the commonly accepted value of about 1.7 per cent. Experimental Procedure The samples of carbonyl iron, with the exception of those for microscopic examination, were cylinders 3.8 cm. long, 0.475 cm. in diameter. They were placed in a graphite holder and suspended in a vertical furnace, the temperature of which was controlled precisely by means of the resistance of the platinum winding.' In the empty furnace the range of temperature over a distance of 4 cm. at the heat center was 9°C. (I6°F.) but at a given location the temperature remained within +o.5°C. (o.9°F.); it was measured by inserting a platinum-rhodium couple calibrated at the melting point of palladium, 1555°C. Since the presence of the sample probably improved the uniformity of temperature, it was decided to consider the average temperature of the sample to be 3°C. lower than the maximum measured in the empty furnace with the same setting of the controller. Data were obtained in the vicinity of two temperatures, 960°C. (I760°F.) and III0°C. (2030°F.). The samples for microscopic examination, 2.2 cm. long, 0.475 cm. in diameter, were suspended individually on pure iron wire; for these no temperature correction was applied. The carburizing gas passed into the furnace was dry, oxygen-free hydrogen saturated at room temperature with toluene; this quickly produced on the

Jan 1, 1942

By J. C. McDonald

A DDITIONAL experimental data are presented in this note on a phenomenon which has been touched on but lightly in the literature. The common magnesium base rolling alloy (AZ31B) contains about 3 pet A1 and 1 pet Zn. When cold rolled, it hardens until it starts to break up in the rolls at 30 to 50 pet reduction. When it is heated after rolling to full hardness, it softens. However, other magnesium alloys have shown themselves capable of being cold rolled indefinitely, provided the ratio of roll diameter to starting gage is sufficiently high. As measured by the tensile test, these alloys actually soften when the reduction becomes large (60 to 90 pct). A subsequent heating at 300' to 500°F can produce hardening of this metal. Heating at higher temperatures (600' to 800°F) causes recrystalliza-tion and softening. Menzen' has shown that a magnesium base alloy can be cold rolled without intermediate anneals as much as 90 pet. The alloy studied, Mg-1.5 pet Mn, softened considerably between 20 and 90 pet reduction, as measured by tensile properties; a decrease in yield strength of 30 pet, and an increase in elongation from 3.2 to 16.7 pet (longitudinal direction of the sheet). However, Menzen gives no data on the reaction of this metal. to heating. Ansel and Betterton2 and Hurst and Hatch3 report a similar effect in Mg-1.5 pet Mn-0.1 pet Ca. Their data show an initial hardening, followed by softening. The former authors also show that the alloy softened by cold rolling will harden when heated at low temperatures, and that these effects are absent in Mg-3 pet Al-1 pet Zn. In the course of work4, 5 some years ago, the author observed similar effects with alloys containing cerium, thorium, or zirconium; but not with elements like aluminum, silver, or zinc. Table IA contains the results of an experiment which shows these effects rather well. A binary alloy with 0.3 pet total rare earths (Mischmetal* added) was rolled hot to 1/16 in. and then annealed to full softness by heating 30 min at 800°F. Rolling was continued at 1.5 pet per pass to 80 pet total reduction on 8 in. diam rolls. The metal was harder after 20 pet work than initially but, at 80 pet reduction, properties were back to their original values. Heating for 1 hr at 450°F produced about the same hardness whether the reduction was 20 or 80 pet. At intermediate reductions, the metal hardened, but not to as high values. Extensive cold rolling may also be carried out on metal hot rolled at temperatures sufficiently low to produce a semihard temper. Mg-0.6 pet Zr was rolled to 0.1 in. at 700° to 800°F, 30 pet per pass. As shown in Table IB, a further cold reduction of 85 pet, at 1.5 pet per pass, definitely softened the metal.

Jan 1, 1959

By E. Parthe, J. P. Pemsler

TWO references can be found in the literature concerning the ternary system uranium-tantalum -carbon. C. H. Schramm, P. Gordon, and A. R. Kaufmam reported in this Journal1 on the existence of the ternary carbide "UTa10C4." They also report a second face-centered-cubic carbide phase in the system U-Ta-C, which they denote as "white" phase. The publication includes a reproduction of a Debye-Scherrer powder photograph of "UTa10C4" and a list of the sin2 0 values of this compound. H. Nowotny, R. Kieffer, F. Benesovsky, and E. Laube2 report the complete solid solubility between TaC and UC with a B1 structure. Since the ternary phase "UTa10C4" lies very close to the binary system Ta-C, and the established phase Ta2C with a C27 structure had not been mentioned by Schramm et al., it was thought worthwhile to compare the patterns of "UTa10C4" with Ta2C. The strong lines of the given pattern were indexed on a hexagonal unit cell with the approximate cell parameters a = 3.09A and c = 4.93A. These are the values reported for Ta2C in the literature.3 The correspondence between reported and calculated sin2 8 values may be studied in columns 4 and 5 of Table I. The agreement is fair, but there remain weak lines which cannot be assigned to the hexagonal unit cell. The extinctions correspond to those of Ta2C, but a comparison of the calculated and observed intensities of the Ta2C lines (columns 2 and 3) with those of the corresponding lines of "UTa10C4" (column 6) show occasional deviations. To clarify this situation, four new samples were prepared. The compositions of these samples were chosen in such a way as to observe any existing ternary phase in the system TaC-UC-U-Ta. The samples were arc melted in an inert atmosphere and annealed at 1100°C for 36 to 72 hr. Compositions of the samples determined by chemical analysis are given along with the results of X-ray investigations in Table 11. The following conclusions may be drawn from these data: a) No ternary compounds occur in the section TaC-UC-U-Ta of the ternary system Ta-U-C. The "white" phase reported by Schramm et al. corresponds to a solid solution between TaC and UC. Only one three-phase field exists: C27-B1-A2. (Both tantalum and ? uranium have body-centered-cubic A2 structures.) The a uranium observed in sample 4 transformed from the high-temperature ? phase on cooling. b) The phase Ta2C with a C27 structure extends into the ternary system. "UTa10C4" is, therefore, a uranium-enriched Ta2C. Good agreement is ob-

Jan 1, 1960

By P. A. Tucker, C. R. Hudgens, D. E. Etter, D. L. Roesch, D. B. Martin

The equilibrium phase diagram of the Pu-Cd system is presented based on data obtained by differential thermal analysis, metallography, and electron-microprobe X-ray analysis. Liquidus temperatures range from 320° to 934°C. The system contains one congruently melting compound, PuCd, (945°C), and three incongruently melting compounds, PuCd, (800°C), PuCd, (730°C), and PuCd11 (410°C). A liquid-miscibility gap extends from 2 to 60 at. pet Cd with the monotectic reaction isotherm at 910°C. INTEREST in the potential use of plutonium alloys as reactor-fuel materials has prompted investigation of the phase equilibria in plutonium binary systems. A cursory investigation of the phase equilibria in the Pu-Cd binary system was conducted by differential thermal analysis (DTA), metallography, and electron-microprobe X-ray analysis (EMX). Extensive solid solubility of cadmium in both e and 6 plutonium was predicted1 based on atomic radii and electronegativities. Liquid immiscibility between these two elements was also predicted based on Mott's extension of Hildebrand's method. In the only previous investigation of the Pu-Cd system,2 two intermetallic compounds, PuCd11 (incon-gruent melting point 406°C) and PuCd8, were identified. EXPERIMENTAL The plutonium metal used in this work had a total impurity content of 500 ppm; the major impurities were: carbon (215 pprn), silicon (75 ppm), iron (60 ppm), nickel (40 ppm), and aluminum (25 ppm). The cadmium was reagent grade with a purity of 99.99 pet. The DTA technique for the study of plutonium alloys was previously described in detail.3 The alloys to be studied were prepared in tantalum DTA specimen capsules which were sealed by inert-gas welding. The alloys were homogenized in the liquid state in these sealed capsules which prevented the loss of cadmium by vaporization. Only the thermal arrests in the DTA heating curves were used to define the transformation temperatures of the system since supercooling affected many of the results during cooling. After the alloys were analyzed by DTA, the same alloys were used for the metallographic studies. Metallographic examinations were conducted in the manner described for plutonium alloys., No reaction was detected between the alloys and the tantalum capsules. Alloys for EMX analysis were placed in metallographic mounts together with specimens of unalloyed plutonium and cadmium which served as standards. The samples were highly polished but unetched. No protective coatings were applied to the surfaces of these radioactive specimens. Such coatings are detrimental to the excitation conditions and have been found to be unnecessary for the control of radioactive contamination. RESULTS The results of the DTA studies are presented in Table I. The phase diagram, constructed from these data plus the metallographic and EMX results, is presented in Fig. 1. The congruently melting compound, PuCd2, was identified by the occurrence of a maximum melting point (945°C) at 33.3 at. pet Pu-66.7 at. pet Cd and by the presence of a single phase in this composition.

Jan 1, 1965

By C. O. Tarr, G. V. Smith, R. F. Miller

METALLURGISTS have long recognized that the Fe3C type of carbide is not a stable phase in steel and that, given sufficient time, it will decompose with formation of graphite, at least at temperatures below about 2050°F.1 This slow graphitization has never been of much concern to users of hypoeutectoid steels, for in such steels it occurs only during prolonged exposure at elevated temperature. In 1935, Kinzel and Moore2 reported complete graphitization of the carbide of a 0.1 5 per cent carbon steel that had been in senrice for about 26,000 hr. at a temperature of about 1100° to 1200°F. In discussing this paper, both Mathews and Sauveur reported graphitization of slightly hypereutectoid steels. In an extensive investigation of graphitization of high-purity iron-carbon alloys, Wells1 produced graphite at 7o0°C. (1290°F.) in an alloy containing as little as 0.13 per cent carbon, and showed that graphite may precipitate either directly from austenite or from decomposition of Fe3C, also that the rate of graphitization tends to increase with increase of temperature, at least up to a certain point, and with the presence of graphite nuclei. Jenkins, Mellor and Jenkinson,3 studying the structural changes in carbon steels ranging from 0.17 to 1.14 per cent carbon during stress-rupture tests at elevated temperature, obsenred graphite in an aluminum-killed 0.40 per cent carbon steel after fracture in 4340 hr. under a stress of 17,900 lb. per sq. in. at 840°F. and in many of the steels after stress-rupture test at 1200°F. Unstressed samples of 0.60, 0.86 and 1.14 per cent carbon steels graphitized almost completely in 360 hr. at 1200°F., while samples of 0.90 and 1.10 per cent carbon steels were somewhat graphitized, and steels containing 0.24, 0.40 and 0.57 per cent carbon showed no sign of graphite. Their results indicate that graphite precipitates the more readily the higher the carbon content, though this tendency is influenced to some extent by deoxidation practice, and that graphitization is accelerated by plastic deformation. In a recent study of the graphitization of 0.4 and 0.6 per cent carbon steel strip, made by M. A. Hughes,4 it was found that at 1200°F. graphite appeared after 72 hr. in aluminum-killed but not in silicon-killed steel, and that the rate of graphitization was increased by slow cooling from 1600°F. and by cold-working prior to annealing. In creep tests of normalized o. I 5 per cent carbon steel killed with 2.5 lb. of aluminum per ton, at the U. S. Steel Corporation laboratory at Kearny, spheroidization and some graphitization were found after 3000 hr. at 1000°F. under a stress as low as 15m lb. per sq. inch.

Jan 1, 1944

By David B. Burrows, Rlkl Kobayashi, Norman L. Carr

The viscosity of hydrocarbon mixtures, whether in the gas or liquid phase, is a function of pressure, temperature, and phase composition. This paper presents methods for the prediction of the viscosity of the gas or less dense fluid phase over the practical range of pressure, temperature, and phase compositions encountered in surface and subsurface petroleum production operations. The correlation necessary to predict the effect of pressure on viscosities is presented in Part I. Serious discrepancies in high pressure gas viscosity data in the literature are discussed. The application of the correlation to predict absolute viscosities is discussed in Part 11. Auxiliary correlations are presented to enable calculations of viscosities from a knowledge of the pressure, temperature, and gravity of the gas phase. INTRODUCTION A knowledge of the viscosity of hydrocarbon fluids is needed to study the dynamical or flow behavior of these mixtures through pipes, porous media, or more generally wherever transport of momentum occurs in fluid motion. Since flow is predominantly in the laminar region in petroleum reservoirs, the influence of fluid viscosity on this flow is especially important. As early as 1894, Onnes1 and Onnes and de Haas' noted that the viscosities of homologs under corresponding states could be correlated. The theorem of corresponding states has been further developed and applied to the viscosity of pure, nonpolar gases under pressure by Comings, Mayland, and Egly.3 It was demonstrated that the viscosity ratio could be expressed rather closely as a function of reduced pressures and temperatures, 1.e.: µ/µ1 = f( TR2 PR) ........(1) temperature, absolute units where: TR =------------------------------ ------ critical temperature. absolute units _pressure, absolute units critical pressure, absolute units µ = viscosity of gas at reduced temperature TR and reduced pressure PR µ1 =. viscosity of gas at atmospheric pressure and at temperature TR Serious discrepancies in the viscosity of pure hydrocarbon gases at high pressures have been called to Our attention by Comings, and and Egly. They made a careful analysis of the following methods commonly used to measure gas viscosities: 1. Oscillating disc viscometer4,5 2. Rolling ball viscometer6,7 3. Capillary tube viscometer12 On the basis of their analysis of the problem and their experimental data on the viscosities of methane, ethylene, carbon dioxide, and propane, they preferentially selected data obtained by the capillary tube viscometer to develop their viscosity correlation. Since then a need has existed to verify the experimental technique of Comings, Mayland, and Egly for the determination of viscosities at high pressure; to extend the data to mixtures of hydrocarbons; and to extend the range of their correlation to include higher pressures. Using the correlation procedure of Comings, May-land, and Egly, the prediction of gas viscosities is resolved into the correlation of the effect of pressure, temperature, and composition on the viscosity of hydrocarbons and their mixtures and the prediction of viscosities of mixtures of hydrocarbons and other natural gas components at one atmosphere pressure.

Jan 1, 1955

By E. R. Johnson

The copper concentrator of the Braden Copper Co. is at Sewell, Chile, on the westem flank of the main Cordillera of the Andes, at an air distance of approximately 50 miles southeast of Santiago, the capital of Chile. The region is mountainous and space is at a premium because of the rough terrain and the danger of snowslides. The ore, a porphyry copper, is mined by a block-caving method in the El Teniente mine. It is hauled to the crushing plant, a distance of 2.6 miles, through a tunnel because of the severe climatic conditions. The usual large, coarsely set, primary reduction machines found in many ore-treating plants are not required because of the mining method employed and the limiting 12-in. spacing of the grizzlies at the head of each ore pass in the mine. It is the purpose of this paper to describe the numerous improvements made in the crushing section of this large flotation concentrator during the past I5 years to increase the efficiency of the plant and to raise the daily output from around 20,000 to 30,000 tons. The reader should keep in mind that all changes were made within the existing building because of the limited space and the high cost of the heavy mill construction required to withstand the snow loads. The present plant, as well as the former, operates on a 24-hr, 7 days a week basis. The crushing plant commenced operations at its present site in 1921, the main equipment being No. 7½ gyratories, followed by 48-in. horizontal Symons disk crushers. Fines were removed by I-in. stationary grizzlies ahead of each unit. In 1924 a third stage of crushing was provided by the addition of 55½-in. rolls in open circuit. During 1925, the Symons disks were replaced by 73½-in. rolls. All the rolls were changed to closed circuit, with elevators and screens to give a final product of 9 pct plus 3-mesh. The flowsheet of a typical crushing section of this period is shown in Fig I. The ore was withdrawn from a common bill serving the five crushing sections in the plant by means of any number up to six 36-in. wide-apron feeders, which discharged onto a common conveyor belt. This conveyor was equipped with a magnetic head pulley and the crusher attendant was stationed near the discharge end to pick out pieces of mine timber that might be in the ore. The ore was discharged over a 13/4-in. spaced bar grizzly and the oversize of this grizzly was crushed by a No. 7½ McCully gyratory crusher set at 13/4-in. opening on the closed side. The grizzly undersize joined the gyratory discharge and was conveyed to a set of 73½ by 20-in. Garfield rolls set at I in. These rolls operated in closed circuit with a bucket elevator and two vibrating screens placed in parallel.

Jan 1, 1949

By G. A. Colligan, G. L. F. Powell

A new experimental technique has been developed to study nucleation behavior in eutectic alloys. It is somewhat similar to that applied by Sundquist and Mondolfo1 but with the advantages that: 1) bulk samples are undercooled instead of small droplets thus allowing the thermal behavior to be monitored by a thermocouple immersed in the sample, and 2) nucleation behavior is investigated in the same sample on either side of the eutectic composition by adding additional component to the sample under controlled conditions which preclude the addition of nu-cleation contaminants. Sundquist and Mondolfo carried out ]nucleation ex-periments on a large number of eutectic alloy sys-tems and concluded that nonreciprocal nucleation operated. If one phase a was a good nucleant for the other phase 0, then B was a poor nucleant for a. This was determined experinlentally by comparing the nucleation temperatures of 100 to 300 u diameter droplets of hypereutectic and hypoeutectic composition cooled from above the liquidus and from a temperature between the liquidus and the eutectic temperature. Primary phase a was concluded to be an efficient nucleant for the other phase B, if the following experimental result was obtained. Referring to Fig. 1, the temperature TI at which a drop of hypereutectic alloy of composition B froze when cooled from above the B liquidus was noted. This was the nucleation temperature for B in the absence of a. A drop of hypoeutectic alloy of composition A was then frozen from temperature T2 between the a liquidus and the eutectic temperature. The temperature T3 at which the eutectic nucleated in the presence of the primary or proeutec-tic a was noted. If this temperature T3 was higher than the temperature TI at which the B nucleated in a hypereutectic alloy, it was concluded that the primary a had nucleated the 6. This temperature T3, representing a certain undercooling below the equilibrium eutectic temperature Te , was designated ?TB by a> the undercooling below T, for nucleation of 13 by a. If there was no substantial difference in nucleation temperature between the hypereutectic drop cooled from above the /3 liquidus and the hypo-eutectic drop cooled from a temperature between the a liquidus and the eutectic temperature, it was considered that the a nucleated B at an undercooling equal to or greater than that at which P nucleated from a hypereutectic alloy. Sundquist and Mondolfo1 found that faceted primary crystals were good nucle-ants for metals that grow as orthogonal dendrites when present as the primary phase. Jackson2 has questioned Sundquist and Mondolfo's technique and proposed that in Sundquist and Mon-dolfo's samples, such as composition A, primary a retained B in reentrant grooves at their surfaces when heated to a temperature above the eutectic but below the a liquidus. This objection was suggested by experiments with organic eutectics where reten-

Jan 1, 1970

By Morris Muskat

The detailed analogy between flow systems in porous media and the corresponding poten-tiometric model systems is developed under conditions where it may be desirable to take into account variable pay thickness, variable porosity, and permeability, and also the dependence of the fluid density on pressure. It is shown that in such models it is only necessary that the electrolyte thickness be made everywhere proportional to the millidarcy-feet of the formation. In contrast to the iso-vol type model, previously suggested as a basis for the analogy, the porosity does not enter directly in the construction of the model. It is introduced only in translating the electrical voltage gradient measurements into the equivalent fluid travel times. A discussion of this procedure is given. I NTRODUCTION It is now some 50 years since it was pointed out' that on the basis of Darcy's law Laplace's equation must govern the steady state flow of homogeneous fluids through porous media. It is 16 years since the obvious implication of this fact, namely, that such steady state homogeneous flow systems in porous media could be simulated by electrical analogies, was first applied2 to problems of practical interest with respect to oil production. In these initial studies major emphasis was placed on the use of electrolytic models, made of blotting paper, to give a direct and graphic history of the fluid particle motion in regular and infinite well networks. However, it was also noted there that the basic requirement of the model was that it give a potential distribution similar to the pressure distribution in the flow system, and that from the electrical measurement of the potential distribution the fluid particle motion could be graphically or numerically determined. This was demonstrated by application to the five-spot infinite network, for which a conducting metallic sheet was used to establish the equipotential contours. As anticipated, the fluid particle motion computed from these contours agreed well with that given directly by the blotting paper model. For irregular well distributions it was found more convenient to use electrolytic bath analogs rather than metallic sheets. Several investigations,3'4 as applied specifically to cycling well patterns, have been reported with these models, which have become known as "potentiometric models." However, the extremely laborious nature of both the electrical measurements by direct probing and the associated interprctive computations retarded the widespread use of these procedures. The electrical measurements can be accelerated by using a four-probe electrodc,5,6 which provides a means for simultaneously determining the streamline paths along which the fluid particles must move and the voltage gradients along these paths which are proportional to the fluid velocitics. With the increasing frequency of discovery of condensate pools, as drilling depths are becoming greater, the applicability of the potentiometric model to production problems, and especially to the study of well patterns for cycling, has been given a fresh impetus. Although the formal theory for determining the motion of fluid particles in porous

Jan 1, 1949