Search Documents

By E. T. Turkdogan, L. S. Darken

Calcium ferrite melts were equilibrated with sulfur and oxygen-bearing gases at temperatures within the range 1290°C to 1620°C. The results show that at oxygen partial pressures below 10-4 atm the sulfide-reaction occurs and at higher oxygen pressures the sulfur dissolves in the melt principally as sulfate ion. It is also observed that when the product increases, sulfate ions are converted to pyrosulfate ions and the results permit the evaluation of the pyrosulfate/sulfate ratio. It is shown that the ratio y CaSO,/rCaO increases with decreasing concentration of calcium oxide in calcium ferrite, silicate and aluminate melts. Indications are that oxy-acids, e.g. silica, alumina and ferric oxide, increase yCaS0,. A few experiments were carried out within the sul-tide range and the results are in accord with those obtained by other investigators on aluminate and silicate melts. BECAUSE of the industrial importance and theoretical interest, many investigators have studied the reactions between molten oxides, silicates or alumi-nates, and gases containing oxygen and sulfur. The early work reviewed by Schenckl and studies made by Bardenheuer and Geller2 indicates that solution of gaseous sulfur in an oxide melt resulted in the replacement of the oxide ions by the sulfide ions. Measurements made by Grant and Chipman3 on the equilibrium partition of sulfur between molten iron and complex silicate melts also demonstrated that, for a given temperature and silicate composition, the distribution of sulfur between slag and metal increased with decreasing oxygen content of the metal. Fincham and Richardson4 studied the effects of temperature and partial pressures of sulfur and oxygen on the solubility of sulfur in simple silicate and alumino-silicate melts. They observed that at oxygen partial pressures below about 10-5 atm sulfur in the gas dissolved in the melt as sulfide ions, replacing an equal number of oxide ions of the melt. At oxygen partial pressures higher than 10-3 atm, sulfur entered the melt as sulfate ions. Similar studies were made by St. Pierre and Chipman5 using calcium ferrite and calcium silico-ferrite melts. The experimental data presented in this paper were obtained in this Laboratory about 10 years ago; this is the first formal presentation although a preliminary report was given previously.6 In each of these experiments, a pure synthetic CaO-Fe2O3 melt in a platinum crucible was equilibrated with a gas mixture (SO2-O2, SO,-air, SO2-CO, or SO2-CO2-CO) at a temperature ranging from 1296°to 1620°C. The experimental technique was essentially the same as that reported by Darken and Gurry,7 the main difference being that the atmosphere in the reaction chamber contained sulfur dioxide together with oxygen, or carbon dioxide-carbon monoxide

Jan 1, 1962

By Fred C. Bond

The process of comminution by grinding is properly classified as an art, rather than as a science. Like most other operations concerned in ore dressing, or in the treatment of nonmetallic minerals, the mathematical relationships of rock breaking are still obscure, and much disputed. If some basic formula exists, comparable for instance to E = RI in electricity, it has not yet been placed in common use. The absence of such a comprehensive mathematical background undoubtedly is the cause of many inefficient designs and installations, as well as of much poorly oriented experimental work. On the other hand, the mathematical immaturity of the process constitutes an opportunity for a real contribution on the part of those who enjoy mental pioneering. Some of the statements made in any such exploratory work may be little more than opinions, and it is to be expected that some will later be proved untrue; but such an evolutionary development is necessary if we are ever to arrive at the fundamental laws, the discovery of which can change the empirical art into a mathematically exact science. The most significant principle of comminution that we possess is probably Rittinger's law, which states that the work done in crushing or grinding is proportional to the area of the new surface produced. There is an alternative theory, known as Kick's law, which formerly was preferred to Rittinger's but which now is rather discredited. According to Kick, the work done in comminution is proportional to the volume, or weight, of the pieces broken, or to the cube of their diameters, while according to Rittinger it is proportional to the square of the diameters. Careful determinations of size distribution below the limit of sieve sizes1 indicate strongly that under ordinary grinding conditions the amount of new surface area produced is directly proportional to the net power input. Changes in the size ratio between the balls and the particles cause important differences in the proportion of the product that passes a given mesh size, but do not affect the total amount of new surface area; they merely change the distribution of the surface among mesh sizes. The principle of constant surface area is the logical result of Rittinger's law, and it may well have an important bearing on the comminution theories of the future. Formula for Ball Wear Grinding tests have been made in the Allis-Chalmers laboratory for more than 9 years, using a standard charge of mixed balls of different sizes; and a continuous record has been kept of the rates of wear of each size. These results have been combined and plotted in various ways in order to discover the relationship that exists

Jan 1, 1943

By Fred C. Bond

The process of comminution by grinding is properly classified as an art, rather than as a science. Like most other operations concerned in ore dressing, or in the treatment of nonmetallic minerals, the mathematical relationships of rock breaking are still obscure, and much disputed. If some basic formula exists, comparable for instance to E = RI in electricity, it has not yet been placed in common use. The absence of such a comprehensive mathematical background undoubtedly is the cause of many inefficient designs and installations, as well as of much poorly oriented experimental work. On the other hand, the mathematical immaturity of the process constitutes an opportunity for a real contribution on the part of those who enjoy mental pioneering. Some of the statements made in any such exploratory work may be little more than opinions, and it is to be expected that some will later be proved untrue; but such an evolutionary development is necessary if we are ever to arrive at the fundamental laws, the discovery of which can change the empirical art into a mathematically exact science. The most significant principle of comminution that we possess is probably Rittinger's law, which states that the work done in crushing or grinding is proportional to the area of the new surface produced. There is an alternative theory, known as Kick's law, which formerly was preferred to Rittinger's but which now is rather discredited. According to Kick, the work done in comminution is proportional to the volume, or weight, of the pieces broken, or to the cube of their diameters, while according to Rittinger it is proportional to the square of the diameters. Careful determinations of size distribution below the limit of sieve sizes1 indicate strongly that under ordinary grinding conditions the amount of new surface area produced is directly proportional to the net power input. Changes in the size ratio between the balls and the particles cause important differences in the proportion of the product that passes a given mesh size, but do not affect the total amount of new surface area; they merely change the distribution of the surface among mesh sizes. The principle of constant surface area is the logical result of Rittinger's law, and it may well have an important bearing on the comminution theories of the future. Formula for Ball Wear Grinding tests have been made in the Allis-Chalmers laboratory for more than 9 years, using a standard charge of mixed balls of different sizes; and a continuous record has been kept of the rates of wear of each size. These results have been combined and plotted in various ways in order to discover the relationship that exists

Jan 1, 1943

By Carl J. McHargue

Rods of 99.99 + pct Al which had initial orientatzons of <001>, <118>, <115>, <111>, and random were swaged at room temperature. Changes in orientation as a function of deformation were studied on axis distribution charts. The <001> orientation appeared to be relatively stable due to the inhomogeneity of the deformation process. near the <100> zone were quickly reoriented towards <001>. Orientations on the <110> zone between <118> and <115> appeared to be stable to reductions of about 50 pct, then were reoriented toward <001>. At very high reductzotzs. movement away from the <111> orientation was observed. the requirement that a circular cross section be maintained. In addition to these mechanical factors, there are grain-boundary effects in poly crystalline materials which are not yet understood. Hartmann and Macherauch conclude, for example, that multiple slip occurs for all orientations in fine-grained aluminum and copper and that the choice of operative slip systems has no simple relationship to orientation.? Many investigators have attempted to avoid problems of interpretation caused by an initial texture by treating the starting material to obtain as ran- IT has been generally accepted that the deformation texture obtained at high reductions, e.g. 90 pct, will not be noticeably affected by a prior texture; whereas, that obtained at reductions of 40 to 50 pct may be significantly influenced by the specimen history.&apos; Some recent studies, however, have been interpreted as showing that an initial texture strongly influenced the deformation textures in rods at reductions greater than 90 pct. Freda and Cullity suggested that the <001> texture in a heavily cold-worked copper rod was due to a <001> texture in the original casting. McHargue, Jetter? and Ogle concluded that the <001> component in an aluminum rod extruded at liquid nitrogen temperature was remanent from a <001> texture in the cast extrusion billet.3 Most of the published work on the effect of initial orientation on deformation textures has been for cold-rolled or compressed single crystals,4-6 The primary interest in these studies was to examine various orientations with regard to their stability under flow? thus determining the possibility of such orientations being stable end orientations. There appears to be no published studies on the effect of initial orientation on fiber textures in polycrystalline specimens. A recent study, however, is concerned with the reorientation of individual grains in polycrystalline specimens pulled in tension.? Although the reorientation of single crystals loaded in simple tension is well known, the movements in the forming of wires and rods would be expected to be different due to the circular array of radial-compressive stresses exerted by the die walls or the rolls, and to

Jan 1, 1962

By D. M. Davidson

THE drill sampling and evaluation of the Piney River ilmenite property was carried out during the early part of 1944 by E. J. Longyear Co., using the company&apos;s standard core-drill outfits to complete 44 holes to an average depth of 110 ft., from which were collected 1100 samples. The Piney River ilmenite-apatite lode is 25 miles north of Lynchburg, in Nelson and Amherst Counties, Virginia (Fig. I). Its elevation is about 900 ft. above sea level and it lies in the old pre-Cambrian complex of crystalline rocks that make up the Piedmont physiographic province lying east of the Blue Ridge Mountains. The terrain is gently rolling and well watered, and is drained by the Piney and Tye Rivers, which are tributary to the James. GEOLOGY The Piney River ore body comprises the upper, weathered part of a tabular basic rock, which occurs in a large area of granite-gneiss. The section containing profitable ore is about 3000 ft. long. It is separated naturally by thinning, into northeastern and southwestern segments with widths of 300 and 100 ft. respectively. The dip averages 45° southeast but steepens locally (Figs. 2 and 3). The unaltered rock is an even, granular mixture of feldspar, ilmenite, and apatite, to which Watson1 gave the name Nelsonite. The decomposed ore body, which is now being exploited by open cut, is a yellowish clay material in which black ilmenite and glassy apatite are the only conspicuous minerals. An economically important structural feature of the deposit is a banding of minerals coinciding with the dip and strike of the dike. This is more promounced in the footwall of the northeastern part of the intrusive, where there is also a higher than average concentration of ilmenite. According to Watson,1 the Ti02 content of the Nelsonites of this region ranges from 10 to 42 per cent, while P205 varies from 4 to 15 per cent. It is inexpedient at present to disclose exact metal content of the Piney River ore body; suffice it to say that the average tenor lies well within the extremes noted by Watson. SAMPLING METHODS AND PROCEDURE During a preliminary inspection of the ore body, Longyear engineers surmised that because of its soft, clayey character, drill sampling would yield little core, therefore they made all possible preparations to procure accurate samples of the drill cuttings, or sludge. The first requisite in obtaining representative drill cuttings is to secure their full recovery. Only under certain conditions, and by employing a most careful and rigid sampling technique, is this possible. There must be no loss of the water circulating in the hole, and the velocity

Jan 1, 1946

Discussion of the paper of WALTHER MATHESIUS, presented at the New York meeting, February, 1915, and printed in Bulletin No. 99, March, 1915, pp. 539 to 555. JOSEPH W. RICHARDS, So. Bethlehem, Pa.-This paper answers. partly the difficult questions which have come up as to why it is not economical to use higher blast temperatures in the smelting of Mesaba ores, such as the high temperatures used in European practices, and the answer is very plain that the ores will not stand the higher temperature. But the paper does not go into detail as to what special difficulties were found with the higher temperature of blast, and I would ask the author to kindly specify them. W. A. FORBES, New York, N. Y.-A large part of the troubles that furnace men experienced in using high-blast heats in smelting Mesaba ores in the early days of using Mesaba ores, was clue to the attempt to use these soft ores on furnaces having the same lines as the furnaces used in smelting the hard Old Range ores. As the result of observation and study, the dimensions of the lower part of the blast furnaces have been changed and the difficulties of the blast-furnace men in operating with a large percentage of Mesaba ore and high-blast temperatures have been largely overcome. The changes I refer to in particular are: (1) steepening the angle of the bosh; (2), decreasing the height of the bosh; (3) increasing the diameter of the hearth. JOSEPH W. RICHARDS.-Mr. Forbes&apos;s answer is quite satisfactory, and the moral which it points is that when the furnace is run with a higher temperature in the smelting zone, the furnace lines which were adapted for the lower temperatures are not necessarily those best suited for the higher hearth temperatures. If. enriched blast were used in a furnace, and higher temperatures run, it would be found necessary to further modify the lines of the furnace to meet the new conditions and to get the maximum output with economy. J. E. JOHNSON, JR., New York, N. Y.-It seems to me this is one of the few papers which could well have been a little longer. The data which Mr. Mathesius has given us, I think should be considered in connection with the paper which Mr. Brassert read before the American Iron and Steel Institute last spring, in which he described how they had obtained remarkable results with furnaces with steep but very short boshes; the angles have been raised to 80°, and the boshes made so short that they no longer appear as a conspicuous part of the shape of the furnace.

Jan 5, 1915

By D. M. Davidson

The drill sampling and evaluation of the Piney River ilmenite property was carried out during the early part of 1944 by E. J. Longyear Co., using the company&apos;s standard core-drill outfits to complete 44 holes to an average depth of IIO ft., from which were collected 1100 samples. The Piney River ilmenite-apatite lode is 25 miles north of Lynchburg, in Nelson and Amherst Counties, Virginia (Fig. I). Its elevation is about 900 ft. above sea level and it lies in the old pre-Cambrian complex of crystalline rocks that make up the Piedmont physiographic province lying east of the Blue Ridge Mountains. The terrain is gently rolling and well watered and is drained by the Piney and Tye Rivers, which are tributary to the James. Geology The Piney River ore body comprises the upper, weathered part of a tabular basic rock, which occurs in a large area of granite-gneiss. The section containing profitable ore is about 3000 ft. long. It is separated naturally by thinning, into northeastern and southwestern segments with widths of 300 and 100 ft. respectively. The dip averages 4.5° southeast but steepens locally (Figs. 2 and 3). The unaltered rock is an even, granular mixture of feldspar, ilmenite, and apatite, to which Watson1 gave the name Nelson-ite. The decomposed ore body, which is now being exploited by open cut, is a yellowish clay material in which black ilmenite and glassy apatite are the only conspicuous minerals. An economically important structural feature of the deposit is a banding of minerals coinciding with the dip and strike of the dike. This is more pronounced in the footwall of the northeastern part of the intrusive, where there is also a higher than average concentration of ilmenite. According to Watson,&apos; the TiO2 content of the Nelsonites of this region ranges from 10 to 42 per cent, while P205 varies from 4 to 15 per cent. It is inexpedient at present to disclose exact metal content of the Piney River ore body; suffice it to say that the average tenor lies well within the extremes noted by Watson. Sampling Methods and Procedure During a preliminary inspection of the ore body, Longyear engineers surmised that because of its soft, clayey character, drill sampling would yield little core, therefore they made all possible preparations to procure accurate samples of the drill cuttings, or sludge. The first requisite in obtaining representative drill cuttings is to secure their full recovery. Only under certain conditions, and by employing a most careful and rigid sampling technique, is this pos sible. There must be no loss of the water circulating in the hole, and the velocity

Jan 1, 1949

By D. M. Davidson

The drill sampling and evaluation of the Piney River ilmenite property was carried out during the early part of 1944 by E. J. Longyear Co., using the company&apos;s standard core-drill outfits to complete 44 holes to an average depth of IIO ft., from which were collected 1100 samples. The Piney River ilmenite-apatite lode is 25 miles north of Lynchburg, in Nelson and Amherst Counties, Virginia (Fig. I). Its elevation is about 900 ft. above sea level and it lies in the old pre-Cambrian complex of crystalline rocks that make up the Piedmont physiographic province lying east of the Blue Ridge Mountains. The terrain is gently rolling and well watered and is drained by the Piney and Tye Rivers, which are tributary to the James. Geology The Piney River ore body comprises the upper, weathered part of a tabular basic rock, which occurs in a large area of granite-gneiss. The section containing profitable ore is about 3000 ft. long. It is separated naturally by thinning, into northeastern and southwestern segments with widths of 300 and 100 ft. respectively. The dip averages 4.5° southeast but steepens locally (Figs. 2 and 3). The unaltered rock is an even, granular mixture of feldspar, ilmenite, and apatite, to which Watson1 gave the name Nelson-ite. The decomposed ore body, which is now being exploited by open cut, is a yellowish clay material in which black ilmenite and glassy apatite are the only conspicuous minerals. An economically important structural feature of the deposit is a banding of minerals coinciding with the dip and strike of the dike. This is more pronounced in the footwall of the northeastern part of the intrusive, where there is also a higher than average concentration of ilmenite. According to Watson,&apos; the TiO2 content of the Nelsonites of this region ranges from 10 to 42 per cent, while P205 varies from 4 to 15 per cent. It is inexpedient at present to disclose exact metal content of the Piney River ore body; suffice it to say that the average tenor lies well within the extremes noted by Watson. Sampling Methods and Procedure During a preliminary inspection of the ore body, Longyear engineers surmised that because of its soft, clayey character, drill sampling would yield little core, therefore they made all possible preparations to procure accurate samples of the drill cuttings, or sludge. The first requisite in obtaining representative drill cuttings is to secure their full recovery. Only under certain conditions, and by employing a most careful and rigid sampling technique, is this pos sible. There must be no loss of the water circulating in the hole, and the velocity

Jan 1, 1949

By W. E. Hall

The Darwin mining district of California, 160 miles north of Los Angeles, has yielded an estimated $45 million in lead, silver, zinc, and copper since 1875. The deposits are in silicated limestone of Penn-sylvanian and Permian age close to a stock of horn-blende-biotite-quartz monzonite. Steep left-lateral strike-slip faults that strike N 50o 70o E served as feeder channels for the ore solutions, and minor folds, favorable beds, and faults close to the feeder channels localized the orebodies. The orebodies are irregular, steep, pipe-like replacements that cut across bedding, bedding replacements, and fissure fillings in a calc-silicate country rock consisting mainly of wollastonite, grossularite-andradite garnet, idocrase, and diop-side. Near surface the ore consists of a soft, crumbly mass of cerussite, hemimorphite, jarosite, limonite, and some secondary copper minerals. The primary ore consists of galena, sphalerite, pyrite, pyrrhotite, and chalcopyrite with smaller amounts of andorite, matildite, scheelite, tetrahedrite, and a high silver-lead-bismuth-selenium-bearing galena. Preliminary X-ray fluorescence study of the primary ore has indicated unusually high concentrations of bismuth, selenium, and silver in galena from certain parts of the mine. One phase of this study concerns the distribution of these elements. Twenty-two samples of galena and thirty of sphal- erite have been purified and analyzed or are being analyzed. The selenium in 21 samples of galena ranges from 0.0045 to 2.11 pct; four contain more than 1 pct. These four samples were collected from the Essex orebody, where most of the selenium is concentrated. Three are from high-grade, near-surface ore, and one is from the 700 level. Four of the seven analyzed galena samples from the Thompson workings immediately north of the Essex orebody contain 0.29 to 0.74 pct Se; the others show less than 0.05 pct. Galena from the Defiance workings about 2000 ft south of the Essex has less than 0.03 pct Se. The selenium-bearing galena also contains concentrations of bismuth and silver. Preliminary spectographic analyses indicate as much as 3 pct Bi and more than 1 pct Ag in galena with high selenium content. Antimony is the only other minor element present in galena in amounts greater than 0.02 pct; most galena contains between 0.1 and 0.2 pct and the maximum is 0.72 pct. A second phase of the study is an attempt to determine the temperature range of the formation of the ore. The iron content of sphalerite deposited in equilibrium with pyrrhotite is being used as a geologic thermometer as it is a function of the temperature of deposition of the ore.&apos; Preliminary results indicate temperature range from 430°C in replacement orebodies in the Defiance workings to 180°C in shallow fissure fillings.

Jan 1, 1960

By Fred C. Bond

THE process of comminution by grinding is properly classified as an art, rather than as a science. Like most other operations concerned in ore dressing, or in the treatment of nonmetallic minerals, the mathematical relationships of rock breaking are still obscure, and much disputed. If some basic formula exists, comparable for instance to E = RI in electricity, it has not yet been placed in, common use. The absence of such a comprehensive mathematical background undoubtedly is the cause of many inefficient designs and installations, as well as of much poorly oriented experimental work. On the other hand, the mathematical immaturity of the process constitutes an opportunity for a real contribution on the part of those who enjoy mental pioneering. Some of the statements made in any such exploratory work may be little more than opinions, and it is to be expected that some will later be proved untrue; but such an evolutionary development is necessary if we are ever to arrive at the fundamental laws, the discovery of which can change the empirical art into a mathematically exact science. The most significant principle of comminution that we possess is probably Rittinger&apos;s law, which states that the work done in crushing or grinding is proportional to the area of the new surface produced. There is an alternative theory, known as Kick&apos;s law, which formerly was preferred to Rittinger&apos;s but which now is rather discredited. According to Kick, the work done in comminution is proportional to the volume, or weight, of the pieces broken, or to the cube of their diameters, while according to Rittinger it is proportional to the square of the diameters. Careful determinations of size distribution below the limit of sieve sizes1 indicate strongly that under ordinary grinding conditions the amount of new surface area produced is directly proportional to the net power input. Changes in the size ratio between the balls and the particles cause important differences in the proportion of the product that passes a given mesh size, but do not affect the total amount of new surface area; they merely change the distribution of the surface among mesh sizes. The principle of constant surface area is the logical result of Rittinger&apos;s law, and it may well have an important bearing on the comminution theories of the future. FORMULA FOR BALL WEAR Grinding tests have been made in the Allis-Chalmers laboratory for more than 9 years, using a standard charge of mixed balls of different sizes; and a continuous record has been kept of the rates of wear of each size. These results have been combined and plotted in various ways in order to discover the relationship that exists

Jan 1, 1940

By M. E. Wadsworth, W. H. Dresher, W. M. Fassell

HIGH temperature-high pressure techniques have long been used to great advantage in the organic chemical industry, the petroleum industry, and the paper industry. Only recently, however, have these methods been used to extract metals from their ores on a commercial scale. The Chemical Construction Corp., together with interested producers of nickel and cobalt, has done much to develop methods of producing nickel and cobalt powders by the use of high temperature-high pressure techniques.&apos; The Howe Sound Co. is currently operating a plant near Salt Lake City in which the new Chemical Construction Corp. technique is applied to cobalt-arsenic sulfide concentrates. In this method the concentrates are leached in a dilute solution of sulfuric acid under air pressure at a high temperature. Near Edmonton, in Alberta, Canada, the Sherritt Gordon Co. is also using the new method in conjunction with its ammoniacal leach process.&apos; National Lead Co., at Fredricktown, Mo., is operating a process similar to that of Howe Sound. In spite of the rapid growth of high temperature-high pressure hydrometallurgical processes, there has been very little work done on fundamental principles involved in this type of process. Conse- quently the literature lacks any significant data in this field. Oxidation of pyrite,3 sphalerite,4 galena," and recently molybdenite" in alkaline solutions has been reported to some extent. This investigation was initiated, therefore, to broaden the application of high temperature-high pressure hydrometallurgy and also to contribute some insight into the basic mechanisms of oxidation in an aqueous medium under these conditions. In addition to the immediate consequences of these processes much valuable information remains to be learned about fundamental reactions when they are carried out at temperatures and pressures slightly higher than those normally encountered. Leaching of molybdenite by alkaline solutions under oxygen pressure has recently been reported in the Russian literature by E. S. Usataya,6 ho found that leaching rate increased with an increase in the pH of the solution—the strongest effects being observed at a pH of 10—and also with an increase in temperature. Usataya also has reported the formation of a protective film on the surface of the molybdenite when the leaching solution was weakly alkaline, neutral, or acidic. He believes that this oxidation process explains the migration of Mo++ in the oxidation zones of molybdenite ore deposits and the subsequent impoverishment of the ores. Equipment: The high temperature-high pressure reaction unit used in this work was especially designed for kinetic studies of this nature, emphasis being placed on accuracy of measurement and precision of control. As details of the unit&apos;s construction and operation have been discussed elsewhere,&apos; only basic features and principles of operation will be discussed at this point.

Jan 1, 1957

By B. W. Levinger

THE lattice parameter of the ß form of pure titanium has been measured at elevated temperature.&apos;, &apos; No attempt was made, however, to correct the parameter obtained to room temperature. In the course of phase diagram studies at Armour Research Foundation and elsewhere, the variation of ß-phase lattice parameter with composition has been established in a number of binary and ternary systems involving titanium. It was possible to extrapolate in these instances to 100 pct Ti to find the apparent lattice parameter of ß titanium at room temperature. Table I lists the results thus obtained. The suggested value for the lattice parameter of ß titanium is the average of the extrapolated values 3.276 ±0.003 kX. This suggested value gives an interatomic distance in ± titanium of 2.837 kX and hence a Goldschmidt atomic diameter (coordination number 12) of 2.925 kX. The latter agrees closely with the value of 2.93 given by Hume-Rothery." From the data of Adenstedt and coworkers&apos; it was possible to determine by extrapolation the mean coefficient of linear expansion for /3 titanium in the range from room temperature to 1000°C. This value, 10.1x10-8 per degree C, compares with about 11x10-8 for a titanium in a similar range." It was thus possible to calculate the parameter at 900 °C. The value of 3.305 kX agrees well with 3.3065 given by Eppel-sheimer.&apos; The majority of values reported in the literature7-&apos;, &apos; were given as Angstroms. In at least one case, ref. 8, it was shown that they actually represented kX units. The source of this confusion appears to be that a large number of tables of X-ray emission spectra list wavelengths as Angstroms and give values in kX units. The accepted conversion factor for kX units to Angstroms (10.&apos; cm) is 1.00202. Thus the parameter of ß titanium suggested corresponds to 3.282A. References J. H. de Boer, W. G. Burgers, and J. D. Fast: Proc. Acad. Amsterdam (1936) 39, p. 515. 2D. S. Eppelsheimer and R. R. Penman: Nature (Dec. 2, 1950) 166, p. 960. 3 W. Hume-Rothery: The Structure of Metals and Alloys (1945) London. Inst. Metals. 4 H. K. Adenstedt, J. R. Pequignot, and J. M. Raymer: Trans. ASM (1952) 44, p. 990. 5 Gmelins Handbuch der Anorganischen Chemie. Titan, Verlag Chemie, Weinhein (1951). 8 P. Pietrokowsky and P. Duwez: Trans. AIME (1952) 194, p. 627; Journal of Metals (June 1952). 7 P. Duwez and J. L. Taylor: Trans. ASM (1952) 44. D. 495. 8 M. Hansen, E. L. Kamen, H. D. Kessler, and D. J. McPherson: Trans. AIME (1951) 191, p, 881; Journal of Metals (October 1951). 8 Unpublished Research, Armour Research Foundation.

Jan 1, 1954

By Benjamin Lustman, Robert F. Mehl

The study of the high-temperature oxidation of pure metals, intensively pursued experimentally since the pioneer work of Pilling and Bedworth1 and supplemented by the recent theoretical work of Wagner2 is now well advanced. The important field of low-temperature oxidation—i.e., oxidation extending only through the temper color range of thicknesses with the formation of thin oxide layers in the range from 0 to 1000-2000 ?ngstroms—has not, however, reached so satisfactory a state, owing largely to the experimental difficulties that attend the formation and study of thin films; most of the work has been performed on abraded specimens whose surface irregularities approximated the thickness of the films formed. It has been pointed out that the rates of oxidation of different crystal faces are different and that the difierence may be related to the orientation relationships that obtain between the metal crystal and the superimposed oxide crystal; it has also been suggested that this orientation dependence should manifest itself in rates of oxidation and perhaps also of corrosion in aggregates bearing preferred orientations.3&apos;4 An attempt to measure the rates of oxidation of different crystal faces of alpha iron demonstrated this difference in rate,4 but the dependence of rate on orientation was not simple; the method of measuring thickness, consisting of a color comparison with barium stearate multi-films of known thickness, was not wholly satisfactory. For these reasons it was felt that a study of the rate of oxidation of single crystals prepared with surfaces as smooth as possible, using a sensitive method giving true film thickness, should be profitable. Copper was chosen because of the ease of reduction of the primary oxide film and because the orientation relationships between metal and oxide and the composition of the oxide films formed at low temperatures are known; for thin films formed at low temperatures, Cu2O alone occurs.22-24 Experimental Procedure Various methods of surface preparation were attempted in order to obtain a surface that would oxidize uniformly and repro-ducibly. Electrolytic polishing by the method of Jacquet5 and electrolytic and mechanical polishing followed by annealing in vacuum and in purified hydrogen at various temperatures were tested. The procedure finally adopted consisted in a fine metallographic polish followed by an anneal in purified hydrogen at temperatures of 900° to 1000°C. for 12 hr. or more. The surface so produced was very bright and smooth, with no trace of specular etching (though some grain-boundary etching was observed); indeed, fine scratches produced by the final polish were entirely removed by the high-temperature anneal. After this treatment, the specimens were cooled in hydrogen to room temperature and placed in the oxidation furnace, where

Jan 1, 1941

By Benjamin Lustman, Robert F. Mehl

The study of the high-temperature oxidation of pure metals, intensively pursued experimentally since the pioneer work of Pilling and Bedworth1 and supplemented by the recent theoretical work of Wagner2 is now well advanced. The important field of low-temperature oxidation—i.e., oxidation extending only through the temper color range of thicknesses with the formation of thin oxide layers in the range from 0 to 1000-2000 ?ngstroms—has not, however, reached so satisfactory a state, owing largely to the experimental difficulties that attend the formation and study of thin films; most of the work has been performed on abraded specimens whose surface irregularities approximated the thickness of the films formed. It has been pointed out that the rates of oxidation of different crystal faces are different and that the difierence may be related to the orientation relationships that obtain between the metal crystal and the superimposed oxide crystal; it has also been suggested that this orientation dependence should manifest itself in rates of oxidation and perhaps also of corrosion in aggregates bearing preferred orientations.3&apos;4 An attempt to measure the rates of oxidation of different crystal faces of alpha iron demonstrated this difference in rate,4 but the dependence of rate on orientation was not simple; the method of measuring thickness, consisting of a color comparison with barium stearate multi-films of known thickness, was not wholly satisfactory. For these reasons it was felt that a study of the rate of oxidation of single crystals prepared with surfaces as smooth as possible, using a sensitive method giving true film thickness, should be profitable. Copper was chosen because of the ease of reduction of the primary oxide film and because the orientation relationships between metal and oxide and the composition of the oxide films formed at low temperatures are known; for thin films formed at low temperatures, Cu2O alone occurs.22-24 Experimental Procedure Various methods of surface preparation were attempted in order to obtain a surface that would oxidize uniformly and repro-ducibly. Electrolytic polishing by the method of Jacquet5 and electrolytic and mechanical polishing followed by annealing in vacuum and in purified hydrogen at various temperatures were tested. The procedure finally adopted consisted in a fine metallographic polish followed by an anneal in purified hydrogen at temperatures of 900° to 1000°C. for 12 hr. or more. The surface so produced was very bright and smooth, with no trace of specular etching (though some grain-boundary etching was observed); indeed, fine scratches produced by the final polish were entirely removed by the high-temperature anneal. After this treatment, the specimens were cooled in hydrogen to room temperature and placed in the oxidation furnace, where

Jan 1, 1941

By C. E. Siebenthal

produce attractive and consequently more salable products. It would seem, however, that if solder and babbitt were cast in closed molds, just as good practical results would be obtained by the user, without his being able to give preference to solders of unnecessarily higher grade on account of their appearance. It would be hopeless for any one. manufacturer of solder to undertake a change of this kind, but if all manufacturers of solder agreed upon it, they would be able, in my opinion, to get the users of solder to take, and to approve by their practical tests, metals containing less tin than they have been accustomed to. The same is true with regard to babbitt metals. An illustration of how, in the use of an alloy, appearance sometimes is deceptive, is to be found in the case of what may be called intermediate grades of babbitt. I am thoroughly convinced that high-tin or high-lead babbitts are better than those containing both lead and tin with relatively high percentages of each. A high-tin babbitt should not contain more than about 10 per cent. of lead, and a high-lead babbitt should not contain more than 10 per cent. of tin, unless the percentage of antimony can be correspondingly increased. The intermediate babbitts, such as those that contain from 30 to 70 per cent. of lead or tin, may give nice appearing castings that flow easily, but they have not the serviceability of the high-lead or high-tin babbitts. Their hardness diminishes very rapidly as the temperature rises, and they have a relatively low softening point due to the eutectic components present. The Cadmium Supply of the united States* C. E. Siebenthal, † Washington., D. C.—From being one of the most maligned of metals—a veritable bugaboo—cadmium has almost overnight become respectable, though its slender claim to respectability rests almost wholly on the possibility of its substitution for tin. Preliminary to any campaign for such substitution, particularly for enforced substitution, the possible supply of cadmium should be determined as closely as possible; for that reason the statistical inquiry of which this paper embodies the results was undertaken. Production Cadmium is marketed in two forms, as metallic cadmium, in sticks or bars, and as cadmium sulfide, the pigment. The metal has found its greatest field of use in this country as a component of an easily fusible alloy that is used in automatic fire extinguishers. The sulfide is used to some extent in paints but chiefly to give color and luster to glass and porcelain. The metal was first made in this country by the Grasselli Chemical

Jan 1, 1919

By D. B. Carson, D. L. Katz

Natural gases under pressure form crystalline hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methanc-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbon-rich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. Introduction Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural-gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villardl and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Dcaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on tem-peraturcs and pressures of hydrate forma. tion for pure methane, ethane, propane, n-butane, methane-ethane mixtures, meth-ane-propane mixtures, methane-butane mixtures, and some Is natural gases, all- in the Presence of excess water. However, up to the Present time no method has been available for predicting the temperature at given pressures or the pressure at given at at which natural gases will form hydrates if hydrates with water. &apos;This Paper Presents data on the methane-propane-water, methane-pentane-water and methane-hex-""e water systems in four phases, one of which is the hydrate. he application of the phase rule to the methane-~ro~ane-water data Proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid. equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1942

By D. B. Carson, D. L. Katz

Natural gases under pressure form crystalline hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methanc-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbon-rich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. Introduction Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural-gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villardl and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Dcaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on tem-peraturcs and pressures of hydrate forma. tion for pure methane, ethane, propane, n-butane, methane-ethane mixtures, meth-ane-propane mixtures, methane-butane mixtures, and some Is natural gases, all- in the Presence of excess water. However, up to the Present time no method has been available for predicting the temperature at given pressures or the pressure at given at at which natural gases will form hydrates if hydrates with water. &apos;This Paper Presents data on the methane-propane-water, methane-pentane-water and methane-hex-""e water systems in four phases, one of which is the hydrate. he application of the phase rule to the methane-~ro~ane-water data Proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid. equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1942

By Walter Miller

BY the beginning of 1945 the output of petroleum products for war had reached a volume and a rate of growth which practically assured all requirements so long as war continued. The programs for making gasoline, lubricating oils of required quality, toluene for T.N.T., and chemicals for manufacture of synthetic rubber, as well as numerous other lesser petroleum products, were all well in hand, and unless catastrophic developments occurred there was no doubt of the ability of the industry to meet all demands. The end of the fighting found the refining industry working at top capacity on war commodities, but also in position to convert quickly into peacetime civilian production. 100-octane Aviation Gasoline Production of the vital 100-octane aviation gasoline, starting with approximately 44,000- bbl. daily capacity at our entry into the war, reached a top of 525,000 bbl. a day in the United States by the end of hostilities. With 75,- bbl. from other Allied sources, the grand total was 600,000 bbl., or 25,000,000 gal. each 24 hr. available to the armed forces had fighting continued. At times it was a close race between requirements and production, but never were any important military operations involving the use of high-octane aviation gasoline held up or delayed for lack of sufficient output of such material. The undivided effort of the entire refining industry in full cooperation with the Government made this record possible. Little diminution in output followed the German surrender on May 7. Plans called for a correspondingly greater activity for the Japanese war and possibly for well into 1946. But when the Japanese sued for peace on Aug. 10 most contracts were quickly canceled. Substantial stocks, reputed to be somewhere between 20,000,000 to 30,000,000 bbl., built up largely between V-E and V-J day pending organization of the larger Japanese war program envisaged after Germany gave up, were in the Government&apos;s hands in this country, in addition to working stocks in the war areas. Toluene and Lubricating Oil Requirements for toluene for T.N.T. increased rapidly as bombing speeded UP with increasing control of the air by the Allies in Europe and Asia. Production in excess of T.N.T. requirements which had been going into 1000-Octane aviation fuel blending during 1943 and 1944 was again drawn into explosive manufacture early in 1945. In anticipation of the war continuing into 1946, two new plants were ordered constructed, the decision being announced in April, plans calling for one of them to get into production about the end of 1945, the other in the first quarter of 1946. Both of these projects were later canceled as victory made it evident that the additional supplies would not be needed. Production was

Jan 1, 1946

For his achievement in building the Panama Canal, Major-Gen. George W. Goethals was presented, on May 22, the John Fritz medal, the highest mark of distinction in the engineering profession. In the absence, in Europe, of Clemens Herschel, chairman of the Board of Award, Charles F. Rand presided over the meeting. Col. John J. Carty, who was chairman of the Board of Award at the time the medal was awarded to Gen. Goethals, and who ordinarily would have presented the medal, was detained in Paris by Government work, so the presentation was made by Ambrose Swasey. When calling the assembly to order, the Chairman said: This medal has been awarded by a Board representing four of the National Engineering Societies: American Institute of Mining and Metallurgical Engineers, American Society of Civil Engineers, American Society of Mechanical Engineers, and American Institute of Electrical Engineers. The medal was established in 1902, in honor of that great American engineer, John Fritz, and has never been awarded except to very distinguished men. In. 1902, the first award was made to John Fritz for scientific and industrial achievement. In 1905, to Lord Kelvin for his work in cable telegraphy and other scientific attainments. In 1906, to George Westinghouse for the invention and development of the air brake. In 1907, to Alexander Graham Bell for the invention and introduction of the telephone. In 1908, to Thomas A. Edison for the invention of the duplex and quadruplex telegraph, the phonograph, the development of a commercially practical incandescent lamp, the development of a complete system of electric lighting, including dynamos, regulating devices, underground system protective devices and meters. In 1909, to Charles T. Porter for his work in advancing the knowledge of steam engineering and in improvements in engine construction. In 1910, to Alfred Noble for notable achievements as a civil engineer. In 1911, to Sir William H. White for notable achievements in naval architecture. In 1912, to Robert W. Hunt for his contributions to the early development of the Bessemer process. In 1914, to Professor John E. Sweet for his achievements in machine design. In 1915, to Dr. James Douglas for notable achievement in mining, metallurgy, education, and industrial welfare. In 1916, to Dr. Elihu Thomson for achievement in electrical invention, in electrical engineering and industrial development, and in scientific research. In. 1917, to Dr. Henry M. Howe for his investigations in metallurgy, especially in the metallography of iron and steel. In 1918, to J. Waldo Smith for achievement as engineer in providing the City of New York with a supply of water. And now to General Goethals for achievement as the builder of the Panama Canal_

Jan 7, 1919

By T. G. Richardson, F. M. Perkins

In the recent paper of Richardson and Perkins entitled "A Laboratory Investigation of the Effect of Rate on Recovery of Oil by Water Flooding,"&apos; the authors found very little appzrent effect on oil recovery of having free gas saturation present prior to water flooding in unconsolidated sands. We agree that the effect in this particular system was small but do not feel that the data presented should be regarded as disproving work of others which has shown an appreciable effect. The authors do not make such a claim, but neither do they advance an explanation of the difference. In our experience the following factors must be carefully considered when studying the relation between residual oil saturation after water flooding and initial free gas saturation: (1) the magnitude of the inherent residual oil saturation, i.e., the residual oil saturation with no free gas; (2) the increase in oil-water viscosity ratio with pressure lowering if the gas saturation is obtained by solution gas drive; and (3) the oil shrinkage which occurs with pressure lowering and gas evolution. The system studied by Richardson and Perkins gave residual oil saturations as low as 20 per cent without free gas present, and one should perhaps not expect much further lowering. As an illustration of the magnitude of the effect when the residual oil saturation is inherently higher we submit the accompanying figure. These data were obtained on an unconsolidated sand under elevated pressure in a system similar to the one described by Richardson and Perkins. Gas saturation was established by gas drive before water flooding. The viscosity ratio was 600:1 under the conditions of the displacement. Here the gas was extremely effective in reducing residual oil saturation. This fact was also indicated by Kyte, et al.2 Their plots of residual oil saturation vs initial gas saturation show trends of greater free gas effect with higher oil viscosities. The pressure-dependent effects were not discussed by Richardson and Perkins. They should be separated from the free gas effect if the objective of the study is a correlation of residual oil saturation vs initial free gas saturation. The increase in oil viscosity when gas is released from solution tends to increase residual oil saturation. This effect is rather small in the viscosity range of kerosene. A Buckley-Leverett calculation, assuming an increase in viscosity ratio from 1.2 to 1.8, indicates an increase in residual oil saturation of about 1 per cent of pore volume. Thus, one would expect this system, if operated at constant viscosity ratio, to show a slightly greater free gas effect. As Dyes- as shown, oil shrinkage can offset the beneficial effect of free gas on waterflood oil recovery, if the gas saturation is established by depletion. Since

Jan 1, 1958