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By Walter R. Hibbard, Cyril Stanley Smith

IN 1929 one of the authors1 determined the constitution of copper-silicon-manganese alloys contailling over go per cent copper. Through a combination of circumstances the presence of the copper-silicon kappa phase was overlooked in both binary and ternary systems. In the binary system the omission has already been rectified.2,3 To establish the limits of this phase in the ternary system, the samples that had been heat-treated at the time of the original research have now been re-examined, using more careful technique. Full details of the compositions used and the temperatures and times of heat-treatment are to be found in the earlier paper.2 The etching reagent now used to distinguish the kappa phase had the following composition: hydrogen peroxide (30 vol.), 2o c.c.; water, 25 c.c.; 20 per cent potassium hydroxide solution, 5 c.c.; ammonium hydroxide (0.90 sp. gr.), 50 c.c. 'I'able I lists the newly observed structures. In virtually every case the constituents are the same as those previously recorded, except where kappa is now shown to be present as a result of the improved etching technique. X few other changes will be noted (No. 138 at 450°C., No. 147 at 550°C., Nos. 153 and 149 at 75o°C.). The change from liquid to beta in equilibrium with kappa in No. 137 at 800°C. is based upon newly heat-treated samples. The alloy is very near the solidus at 800°C. and probably there was a slight error in the old heat-treatment temperature. The isothermal phase diagrams shown in Figs. I to 6 were reconstructed on the basis of the new studies. The presence of manganese does not greatly change the composition limits of the kappa phase or cause the K-a + Y change to occur at a markedly different temperature. There is some uncertainty regarding the range of existence of beta, for alloys were not spaced very closely in composition. The proposed diagrams, however, are in accordance with the available experimental data and with the dictates of the phase rule. Theoretically necessary fields with no experimental points are delineated by dotted lines. The alpha boundaries at all temperatures are shown together in Fig. 7. This includes also some additional points on the alpha boundary at 300' and 350°C., which were obtained as a result of electrical-conductivity measurements. Two series of seven alloys with increasing manganese content but with silicon constant at 1.90 + 0.03 per cent or 2.42 ±. 0.05 per cent were cast in ingots of 3-in: diameter. These were hot-rolled, homogenized and drawn to wire, finished at 0.08-in. diameter with a 61 per cent reduction of area following annealing at 700°C. Conductivity determinations were made before and after annealing for 30 days at 300°C. or 21 days at 350°C. Figs. 8 and 9 show the change of conductivity produced by this annealing, plotted against manganese

Jan 1, 1942

By John Wulff

In a previous paper Burwell and Wulff1 have shown by electron diffraction studies that allotropic transformations can be induced in 18-8 stainless steel by polishing to a depth of about 5 X 10-5 cm. The development of a successful etching technique, which removes accountable amounts of metal from the surface without pitting and without changing the root-mean-square profile as measured with an Abbot pro-filometer, led to the application of the whole technique and material to an investigation of various mechanical methods of surface preparation, such as grinding, lapping, superfinishing and cold-rolling. Ideally suited to such a study is 18-8 of low carbon and nitrogen content. The material can be heat-treated to produce a coarse-grained single-phase structure. On cold deformation there occurs not only a reduction in grain size but, at regions of maximum stress, a change of face-centered material to body-centered material, provided the metal is worked below about 200°C. When worked between 200"about and 415°C., diffraction studies evidence a reduction in grain size without the appearance of any new body-centered ferrite. Ferrite, which can be referred also to strains induced by carbide precipitation, is evident when the material is worked at temperatures between 4150 and 800°C. Stainless steel is advantageous because the usual surface-finishing operations do not readily oxidize it to any appreciable depth. In order to produce detectable oxide films on the surface of austenitic 18-8 in a time equivalent to that required to produce, for example, a fine ground finish on 1/2 sq. in., the sample must be held in a furnace or oxygen stream above 600°C. By using longer heating times, it is possible to achieve measurable oxide films on samples , whose surface temperatures exceed only about 250°C. Experimental Procedure The apparatus, material, and technique described in the previous paper1 were employed in this investigation. Samples of 18-8, I by I cm. by 4 mm., were carefully annealed in the austenitic range to produce a coarse-grained structure. They were then quenched and pickled to remove scale, On a lapping machine of the Graton2 type, both sides of each sample were polished to a a of 1/6 a wave length of sodium D light. Thereafter they were electrolytically etched to remove at least 1 X 10-3 cm. of the surface, a depth that is well below that of any defermations induced by surface preparation. samples of this material, carefully mounted in steel holders, were then sent to various industrial organizations known for special finishing techniques. In the instrue ment shops at the Massachusetts Institute of Technology check samples were finished by the same methods, as far as they were available. Abbot profilometer3 readings Were made on all the samples, which were then carefully degreased in double distilled benzine and alcohol, dried in a hot-filtered air blast, and kept in a desiccator. SUC-

Jan 1, 1941

By Walter R. Hibbard, Cyril Stanley Smith

IN 1929 one of the authors1 determined the constitution of copper-silicon-manganese alloys contailling over go per cent copper. Through a combination of circumstances the presence of the copper-silicon kappa phase was overlooked in both binary and ternary systems. In the binary system the omission has already been rectified.2,3 To establish the limits of this phase in the ternary system, the samples that had been heat-treated at the time of the original research have now been re-examined, using more careful technique. Full details of the compositions used and the temperatures and times of heat-treatment are to be found in the earlier paper.2 The etching reagent now used to distinguish the kappa phase had the following composition: hydrogen peroxide (30 vol.), 2o c.c.; water, 25 c.c.; 20 per cent potassium hydroxide solution, 5 c.c.; ammonium hydroxide (0.90 sp. gr.), 50 c.c. 'I'able I lists the newly observed structures. In virtually every case the constituents are the same as those previously recorded, except where kappa is now shown to be present as a result of the improved etching technique. X few other changes will be noted (No. 138 at 450°C., No. 147 at 550°C., Nos. 153 and 149 at 75o°C.). The change from liquid to beta in equilibrium with kappa in No. 137 at 800°C. is based upon newly heat-treated samples. The alloy is very near the solidus at 800°C. and probably there was a slight error in the old heat-treatment temperature. The isothermal phase diagrams shown in Figs. I to 6 were reconstructed on the basis of the new studies. The presence of manganese does not greatly change the composition limits of the kappa phase or cause the K-a + Y change to occur at a markedly different temperature. There is some uncertainty regarding the range of existence of beta, for alloys were not spaced very closely in composition. The proposed diagrams, however, are in accordance with the available experimental data and with the dictates of the phase rule. Theoretically necessary fields with no experimental points are delineated by dotted lines. The alpha boundaries at all temperatures are shown together in Fig. 7. This includes also some additional points on the alpha boundary at 300' and 350°C., which were obtained as a result of electrical-conductivity measurements. Two series of seven alloys with increasing manganese content but with silicon constant at 1.90 + 0.03 per cent or 2.42 ±. 0.05 per cent were cast in ingots of 3-in: diameter. These were hot-rolled, homogenized and drawn to wire, finished at 0.08-in. diameter with a 61 per cent reduction of area following annealing at 700°C. Conductivity determinations were made before and after annealing for 30 days at 300°C. or 21 days at 350°C. Figs. 8 and 9 show the change of conductivity produced by this annealing, plotted against manganese

Jan 1, 1942

By Walter R. Hibbard, Cyril Stanley Smith

IN 1929 one of the authors' determined the constitution of copper-silicon-manganese alloys containing over 90 per cent copper. Through a combination of circumstances the presence of the copper-silicon kappa phase was overlooked in both binary and ternary systems. In the binary system the omission has already been rectified.2,3 To establish the limits of this phase in the ternary system, the samples that had been heat-treated at the time of the original research have now been re-examined, using more careful technique. Full details of the compositions used and the temperatures and times of heat-treatment are to be found in the earlier paper .2 The etching reagent now used to distinguish the kappa phase had the following composition: hydrogen peroxide (30 vol.), 20 c.c.; water, 25 c.c.; 20 per cent potassium hydroxide solution, 5 c.c.; ammonium hydroxide (0.90 sp. gr.), 50 c.c. Table I lists the newly observed structures. In virtually every case the constituents are the same as those previously recorded, except where kappa is now shown to be present as a result of the improved etching technique. A few other changes will be noted (No. 138 at 450°C., No. 149 at 550°C., Nos. 153 and 149 at 750°C.). The change from liquid to beta in equilibrium with kappa in No. 139 at 800°C. is based upon newly heat-treated samples. The alloy is very near the solidus at 800°C. and probably there was a slight error in the old heat-treatment temperature. The isothermal phase diagrams shown in Figs. 1 to 6 were reconstructed on the basis of the new studies. The presence of manganese does not greatly change the composition limits of the kappa phase or cause the [K = a + ?] change to occur at a markedly different temperature. There is some uncertainty regarding the range of existence of beta, for alloys were not spaced very closely in composition. The proposed diagrams, however, are in accordance with the available experimental data and with the dictates of the phase rule. Theoretically necessary fields with no experimental points are delineated by dotted lines. The alpha boundaries at all temperatures are shown together in Fig. 7. This includes also some additional points on the alpha boundary at 300° and 350°C., which were obtained as a result of electrical-conductivity measurements. Two series of seven alloys with increasing manganese content but with silicon constant at 1.90 ± 0.03 per cent or 2.42 ± 0.05 per cent were cast in ingots of 3-in, diameter. These were hot-rolled, homogenized and drawn to wire, finished at 0.08-in. diameter with a 61 per cent reduction of area following annealing at 900°C. Conductivity determinations were made before and after annealing for 30 days at 300°C. or 21 days at 350°C. Figs. 8 and 9 show the change of conductivity produced by this annealing, plotted against manganese

Jan 1, 1942

By John Wulff

In a previous paper Burwell and Wulff1 have shown by electron diffraction studies that allotropic transformations can be induced in 18-8 stainless steel by polishing to a depth of about 5 X 10-5 cm. The development of a successful etching technique, which removes accountable amounts of metal from the surface without pitting and without changing the root-mean-square profile as measured with an Abbot pro-filometer, led to the application of the whole technique and material to an investigation of various mechanical methods of surface preparation, such as grinding, lapping, superfinishing and cold-rolling. Ideally suited to such a study is 18-8 of low carbon and nitrogen content. The material can be heat-treated to produce a coarse-grained single-phase structure. On cold deformation there occurs not only a reduction in grain size but, at regions of maximum stress, a change of face-centered material to body-centered material, provided the metal is worked below about 200°C. When worked between 200"about and 415°C., diffraction studies evidence a reduction in grain size without the appearance of any new body-centered ferrite. Ferrite, which can be referred also to strains induced by carbide precipitation, is evident when the material is worked at temperatures between 4150 and 800°C. Stainless steel is advantageous because the usual surface-finishing operations do not readily oxidize it to any appreciable depth. In order to produce detectable oxide films on the surface of austenitic 18-8 in a time equivalent to that required to produce, for example, a fine ground finish on 1/2 sq. in., the sample must be held in a furnace or oxygen stream above 600°C. By using longer heating times, it is possible to achieve measurable oxide films on samples , whose surface temperatures exceed only about 250°C. Experimental Procedure The apparatus, material, and technique described in the previous paper1 were employed in this investigation. Samples of 18-8, I by I cm. by 4 mm., were carefully annealed in the austenitic range to produce a coarse-grained structure. They were then quenched and pickled to remove scale, On a lapping machine of the Graton2 type, both sides of each sample were polished to a a of 1/6 a wave length of sodium D light. Thereafter they were electrolytically etched to remove at least 1 X 10-3 cm. of the surface, a depth that is well below that of any defermations induced by surface preparation. samples of this material, carefully mounted in steel holders, were then sent to various industrial organizations known for special finishing techniques. In the instrue ment shops at the Massachusetts Institute of Technology check samples were finished by the same methods, as far as they were available. Abbot profilometer3 readings Were made on all the samples, which were then carefully degreased in double distilled benzine and alcohol, dried in a hot-filtered air blast, and kept in a desiccator. SUC-

Jan 1, 1941

By John Wulff

IN a previous paper Burwell and Wulff1 have shown by electron diffraction studies that allotropic transformations can be induced in 18-8 stainless steel by polishing to a depth of about 5 X 10-5 cm. The development of a successful etching technique, which removes accountable amounts of metal from the surface without pitting and without changing the root-mean-square profile as measured with an Abbot profilometer, led to the application of the whole technique and material to an investigation of various mechanical methods of surface preparation, such as grinding, lapping, superfinishing and cold-rolling. Ideally suited to such a study is 18-8 of low carbon and nitrogen content. The material can be heat-treated to produce a coarse-grained single-phase structure. On cold deformation there occurs not only a reduction in grain size but, at regions of maximum stress, a change of face-centered material to body-centered material, provided the metal is worked below about 200°C. When worked between 200° and 415°C., diffraction studies evidence a reduction in grain size without the appearance of any new body-centered ferrite. Ferrite, which can be referred also to strains induced by carbide precipitation, is evident when the material is worked at temperatures between 415° and 800°C. Stainless steel is advantageous because the usual surface-finishing operations do not readily oxidize it to any appreciable depth. In order to produce detectable oxide films on the surface of austenitic 18-8 in a time equivalent to that required to produce, for example, a fine ground finish on ½ sq. in., the sample must be held in a furnace or oxygen stream above 600°C. By using longer heating times, it is possible to achieve measurable oxide films on samples whose surface temperatures exceed only about 250°C. EXPERIMENTAL PROCEDURE The apparatus, material, and technique described in the previous paper1 were employed in this investigation. Samples of 18-8, 1 by 1 cm. by 4 mm., were carefully annealed in the austenitic range to produce a coarse-grained structure. They were then quenched and pickled to remove scale. On a lapping machine of the Graton2 type, both sides of each sample were polished to a flatness of 1/6 a wave length of sodium D light. Thereafter they were electrolytically etched to remove at least 1 X 10-3 cm. of the surface, a depth that is well below that of any deformations induced by surface preparation. Samples of this material, carefully mounted in steel holders, were then sent to various industrial organizations known for special finishing techniques. In the instrument shops at the Massachusetts Institute of Technology check samples were finished by the same methods, as far as they were available. Abbot profilometer3 readings were made on all the samples, which were then carefully degreased in double distilled benzine and alcohol, dried in a hot-filtered air blast, and kept in a desiccator. Suc-

Jan 1, 1941

By C. E. McCarthy, A. George Stern, Stanley J. Green

The national interest prompts consideration of any new source of mineral wealth even though the immediate need may be of minor importance. A critical shortage of potash in the United States during the World War of 1914-18 stimulated broad development, which established an American potash industry on a basis so sound that this commodity is not even listed as urgent in the present war program. However, this should not minimize its importance, and the need remains, not only for adequate supplies of the usual potash salts (the chloride and the sulphate) but of all potash chemicals. Potassium carbonate (known commercially as pearl ash) has been a high-cost commodity; in consequence, the quantity used by industry has been relatively small. By a combination of fortuitous geographical circumstances, there is opportunity to produce a low-cost potassium carbonate with the possibility that this might become an important source of chemical potash. The following paper considers a recently developed process1 taking advantage of these conditions. Wyomingite Deposit For many years it has been known that a deposit of potash-bearing igneous rock known as wyomingite occurs in the south- western part of Wyoming at Zirkel Mesa, which is 44 miles northeast of the town of Green River (Fig. I). The western escarpment of this deposit is about 3 miles east of the Superior Branch of the Union Pacific Railroad. This mesa alone covers approximately 3300 acres, and the average thickness of the wyomingite flow is 75 ft. It has been estimated2 that about one billion tons of wyomingite occur in this one deposit, all of which can be mined by open quarrying without overburden. In addition, there are several smaller deposits within 10 miles, so that the aggregate wyomingite in the area approaches two billion tons. This is one of the world's largest sources of leucite, and the only known deposit of its kind in the United States. The wyomingite (which is in the form of a lava flow and numerous small craters), with the mineral leucite as its most important component, has a mineral composition3 of: leucite, 50 per cent; phlogopite, 15; diopside, 12; kataphorite, 15; glass and apatite, 8. The phlogopite is present in visible phenocrysts 1/8 to 1/2 in. in diameter, but the leucite usually is almost microcrystalline and not capable of liberation by grinding. Chemically, the Wyomingite has a potash Content averaging slightly higher than eleven per cent K2O. The potash is mainly in the leucite, but part of it is in the phlogopite and a small amount is in the feldspars that are occasionally seen as undigested occlusions of the granite country rock, through which the leucite-bearing lava intruded, and as sanidine feldspar both in the crystalline and glassy phases of the rock. A typical analysis of the wyomingite from Zirkel Mesa is as follows:

Jan 1, 1948

By A. George Stern, Stanley J. Green, C. E. McCarthy

The national interest prompts consideration of any new source of mineral wealth even though the immediate need may be of minor importance. A critical shortage of potash in the United States during the World War of 1914-18 stimulated broad development, which established an American potash industry on a basis so sound that this commodity is not even listed as urgent in the present war program. However, this should not minimize its importance, and the need remains, not only for adequate supplies of the usual potash salts (the chloride and the sulphate) but of all potash chemicals. Potassium carbonate (known commercially as pearl ash) has been a high-cost commodity; in consequence, the quantity used by industry has been relatively small. By a combination of fortuitous geographical circumstances, there is opportunity to produce a low-cost potassium carbonate with the possibility that this might become an important source of chemical potash. The following paper considers a recently developed process1 taking advantage of these conditions. Wyomingite Deposit For many years it has been known that a deposit of potash-bearing igneous rock known as wyomingite occurs in the south- western part of Wyoming at Zirkel Mesa, which is 44 miles northeast of the town of Green River (Fig. I). The western escarpment of this deposit is about 3 miles east of the Superior Branch of the Union Pacific Railroad. This mesa alone covers approximately 3300 acres, and the average thickness of the wyomingite flow is 75 ft. It has been estimated2 that about one billion tons of wyomingite occur in this one deposit, all of which can be mined by open quarrying without overburden. In addition, there are several smaller deposits within 10 miles, so that the aggregate wyomingite in the area approaches two billion tons. This is one of the world's largest sources of leucite, and the only known deposit of its kind in the United States. The wyomingite (which is in the form of a lava flow and numerous small craters), with the mineral leucite as its most important component, has a mineral composition3 of: leucite, 50 per cent; phlogopite, 15; diopside, 12; kataphorite, 15; glass and apatite, 8. The phlogopite is present in visible phenocrysts 1/8 to 1/2 in. in diameter, but the leucite usually is almost microcrystalline and not capable of liberation by grinding. Chemically, the Wyomingite has a potash Content averaging slightly higher than eleven per cent K2O. The potash is mainly in the leucite, but part of it is in the phlogopite and a small amount is in the feldspars that are occasionally seen as undigested occlusions of the granite country rock, through which the leucite-bearing lava intruded, and as sanidine feldspar both in the crystalline and glassy phases of the rock. A typical analysis of the wyomingite from Zirkel Mesa is as follows:

Jan 1, 1948

By J. H Lightfoot, Stuart E. Buckley

Deep drilling has led to the development of numerous pools which yield products consisting predominantly of natural gas accompanied by high-gravity water-white or slightly straw-colored liquid. Yields of this "condensate" or "distillate," as it is commonly called, vary from traces to over a hundred barrels per million cubic feet of gas. The fact that this liquid exists in the reservoir as an integral part of the gas phase and is formed by condensation attending simultaneous reduction of pressure and temperature after its entry into the well was apparently first recognized about 1932.l The nature of the physical phenomena involved in this condensation was clarified for the petroleum industry in 1933 by a report by Sage, Schaafsma, and Lacey2 of the results of an experimental investigation of the behavior of mixtures of methane and propane. Search of the literature has revealed that the condensation of liquid from gaseous mixtures by isothermal pressure reduction is not a new discovery. Kuenen was led by theoretical considerations to expect such a phenomenon, and in 1892 reported3 the results of experimental verification of his deductions. This was followed by a considerable amount of work on the phase relations of mixtures by Kuenen 4,5,6 and by 0thers,7,8 mostly in European universities. Since 1930 investigators in this country have reported experimental data on the properties and behavior of a number of hydrocarbon systems."' It is now generally known that in the presence of natural gas the solubility in the gas phase of the heavier and normally liquid hydrocarbons increases rapidly with increasing pressure above 500 to 1000 Ib. per sq. in. Thus, at pressures of 2500 Ib. per sq. in. or higher a gas may contain appreciable quantities of hydrocarbons with normal boiling points as high as 6o0°F., which in turn may be condensed from the gas phase by the reduction of their solubility therein attending pressure reduc-tion. The combined effects of pressure and temperature on condensation and vaporiza-tioi of mixtures are most readily visualized by the study of phase diagrams. Since the construction, application, and interpreta-tion of such diagrams have been described fully in readily available literature, 18-20 this paper will not review the theoretical aspects of this subject. While the behavior of gas-distillate sys tems is now clearly understood, at least in a qualitative way, most of the published work deals with the results of laboratory studies of binary systems or of synthetic mixtures of hydrocarbons, and although several systematic investigations of the effects of separator pressure and temperature on the yields of liquid product from gas-distillate wells have been made21,12z it appears that in all cases the limitations have precluded the construction of even approximately complete phase diagrams for naturally occurring systems. There has 2

Jan 1, 1941

By Charles Hart

The art of electric smelting came with the turn of the present century and owes its existence to the introduction of alternating current, which found its first wide use in the establishment of the great power plants at Niagara Falls, N. Y. Prior to that time current was largely direct. The furnaces were electrolytic in nature and found their first metallurgical use in the production of aluminum, and this process still prevails. The normal production of pig iron up to that time was carried on in blast furnaces in which charcoal, coke and anthracite were used as the fuel. This new electric process called for sufficient carbonaceous material to reduce the oxides and impregnate the pig iron with sufficient carbon, but the remainder of the energy was to be supplied by electric power. The chemical reactions are essentially the same in electric smelting as obtains in the older blast furnace. All of these data are so well known in both methods as to need no discussion at this time, for they can be found in scientific : publications and books written during the first two decades of this century. Types of Furnaces The 40 years devoted to the practice of electric smelting may be divided into two . periods of 20 years each. The first was devoted to experimentation with furnace types and with many publications on theories and processes. The second half of this term was devoted to perfecting the types of furnaces and their active commercial operation. The arc furnace may be found in three types: (1) the direct-heating arc furnace with the positive electrode included in the bottom and the other electrode suspended above; (2) the independent arc furnace with its electrodes entirely above the charge, which of necessity depends upon heat reflected from the roof; (3) the direct-heating series arc furnace equipped with two or more electrodes suspended from the roof. Of these three types, only the last is used in electric smelting of iron ore at the present time. The elimination of the other types automatically removed many of the early designs, to the end that there are now only two general types in operation: (I) the " Electrometalls" or high-shaft furnace of Sweden, and (2) the low-shaft or pit-type furnace as offered by Tysland-Hole and Siemens-Halske. The "Electrometalls" furnace takes its name from the corporation formed by the engineers that had undertaken its perfection. After trying several designs they brought forward the furnace shown in Fig. I, which by the way is the highest development of this type of furnace as of today.l Note the trend in the lines, which have kept pace with modern blast-furnace design. The high-shaft furnace lends itself to skip filling and is fitted with tuyeres immediately under the crucible roof, whereby the gases are recycled and the roof preserved. The failure of the Electrometalls furnace in Norway, because of its inability to meet

Jan 1, 1941

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 Charles Hart

The art of electric smelting came with the turn of the present century and owes its existence to the introduction of alternating current, which found its first wide use in the establishment of the great power plants at Niagara Falls, N. Y. Prior to that time current was largely direct. The furnaces were electrolytic in nature and found their first metallurgical use in the production of aluminum, and this process still prevails. The normal production of pig iron up to that time was carried on in blast furnaces in which charcoal, coke and anthracite were used as the fuel. This new electric process called for sufficient carbonaceous material to reduce the oxides and impregnate the pig iron with sufficient carbon, but the remainder of the energy was to be supplied by electric power. The chemical reactions are essentially the same in electric smelting as obtains in the older blast furnace. All of these data are so well known in both methods as to need no discussion at this time, for they can be found in scientific : publications and books written during the first two decades of this century. Types of Furnaces The 40 years devoted to the practice of electric smelting may be divided into two . periods of 20 years each. The first was devoted to experimentation with furnace types and with many publications on theories and processes. The second half of this term was devoted to perfecting the types of furnaces and their active commercial operation. The arc furnace may be found in three types: (1) the direct-heating arc furnace with the positive electrode included in the bottom and the other electrode suspended above; (2) the independent arc furnace with its electrodes entirely above the charge, which of necessity depends upon heat reflected from the roof; (3) the direct-heating series arc furnace equipped with two or more electrodes suspended from the roof. Of these three types, only the last is used in electric smelting of iron ore at the present time. The elimination of the other types automatically removed many of the early designs, to the end that there are now only two general types in operation: (I) the " Electrometalls" or high-shaft furnace of Sweden, and (2) the low-shaft or pit-type furnace as offered by Tysland-Hole and Siemens-Halske. The "Electrometalls" furnace takes its name from the corporation formed by the engineers that had undertaken its perfection. After trying several designs they brought forward the furnace shown in Fig. I, which by the way is the highest development of this type of furnace as of today.l Note the trend in the lines, which have kept pace with modern blast-furnace design. The high-shaft furnace lends itself to skip filling and is fitted with tuyeres immediately under the crucible roof, whereby the gases are recycled and the roof preserved. The failure of the Electrometalls furnace in Norway, because of its inability to meet

Jan 1, 1941

By John Wulff, Robert Kamm, M. A. Steinberg

IN a previous paper1 from this laboratory, the development of a lead grid method for exploring the distribution of strain and density within metal powder compacts was described, In that work thin lead foil with rectangular holes cut at regular intervals was inserted with the powder fill, the arrangement pressed and then radiographed to permit measurement of the deformation of the lead grid. Densities at each grid element obtained in this manner were plotted as a function of the die dimensions. From such plots it was, found that the densest part of a compact pressed from one side (the top) is at the top outer region and the least dense at the bottom outer region -of the specimen. The axial density maximum occurs more often nearer the bottom than at the top. As a result of such exploratory measurements, it appeared reasonable to conclude that variations in density could be attributed in the main to die wall friction. Thus compacts of large diameter appeared relatively uniform in density except where the die fill had been uneven. Finally it was found that lubrication of the finely finished die cavity contributed more to magnitude and uniformity of density within the compact than interparticle lubrication. Since publication of the above results, it was found that circular-hole grids could be more accurately made and, when deformed within the powder, more readily measured and analyzed. Much of the former work was repeated and new results which include the effect of lubrication, compact height, pressure, speed of pressing and vacuum pressing are reported in the present paper. CIRCULAR-HOLE GRIDS AND ANALYSES OF RADIOGRAPHS Commercial lead sheet 0.008 in. in thickness was used in all the work reported. The 0.0938-in. diam holes were punched in the sheet on 1/8-in, centers to an accuracy of 0.001 in. The finished grid used contained eight or more holes in a row and from I to 24 rows. The lead sheet was clamped between two pairs of brass strips bolted to a small milling machine table which was itself bolted to a bench in correct position near a vise which held the punch. Travel of the lead grid in two dimensions was controlled by two steel lead screws calibrated in 0.001-in. divisions. A stripper plate was used on the punch to avoid distortion of the lead foil. A high carbon-high chromium (chrocar) one-piece steel die was used throughout the work. The die cavity was 1,125 in. in diam and the clearance between plungers and die wall was 0.001 in, The die was also used for pressing from both ends with two long plungers. Finally, lapping of die and plungers gave a surface whose rms value on an Abbot profilometer was 5 micro-in. The die walls and plungers were, except where otherwise noted, lubricated with a stearic acid suspension in benzene. This was put on in multiple layers and allowed to dry before filling the die.

Jan 1, 1948

By J. H. Lightfoot, Stuart E. Buckley

Deep drilling has led to the development of numerous pools which yield products consisting predominantly of natural gas accompanied by high-gravity water-white or slightly straw-colored liquid. Yields of this "condensate" or "distillate," as it is commonly called, vary from traces to over a hundred barrels per million cubic feet of gas. The fact that this liquid exists in the reservoir as an integral part of the gas phase and is formed by condensation attending simultaneous reduction of pressure and temperature after its entry into the well was apparently first recognized about 1932.l The nature of the physical phenomena involved in this condensation was clarified for the petroleum industry in 1933 by a report by Sage, Schaafsma, and Lacey2 of the results of an experimental investigation of the behavior of mixtures of methane and propane. Search of the literature has revealed that the condensation of liquid from gaseous mixtures by isothermal pressure reduction is not a new discovery. Kuenen was led by theoretical considerations to expect such a phenomenon, and in 1892 reported3 the results of experimental verification of his deductions. This was followed by a considerable amount of work on the phase relations of mixtures by Kuenen 4,5,6 and by 0thers,7,8 mostly in European universities. Since 1930 investigators in this country have reported experimental data on the properties and behavior of a number of hydrocarbon systems."' It is now generally known that in the presence of natural gas the solubility in the gas phase of the heavier and normally liquid hydrocarbons increases rapidly with increasing pressure above 500 to 1000 Ib. per sq. in. Thus, at pressures of 2500 Ib. per sq. in. or higher a gas may contain appreciable quantities of hydrocarbons with normal boiling points as high as 6o0°F., which in turn may be condensed from the gas phase by the reduction of their solubility therein attending pressure reduc-tion. The combined effects of pressure and temperature on condensation and vaporiza-tioi of mixtures are most readily visualized by the study of phase diagrams. Since the construction, application, and interpreta-tion of such diagrams have been described fully in readily available literature, 18-20 this paper will not review the theoretical aspects of this subject. While the behavior of gas-distillate sys tems is now clearly understood, at least in a qualitative way, most of the published work deals with the results of laboratory studies of binary systems or of synthetic mixtures of hydrocarbons, and although several systematic investigations of the effects of separator pressure and temperature on the yields of liquid product from gas-distillate wells have been made21,12z it appears that in all cases the limitations have precluded the construction of even approximately complete phase diagrams for naturally occurring systems. There has 2

Jan 1, 1941

By W. F. Kieschnick, and W. J. McGuire&apos, Eugene Harrison

This paper concerns the induction and extension of fractures into rock formations as involved in drilling, completing, and production stimulating operations on wells. Conclusions concerning formation breakdown are derived from (I) a review and extension of published analyses relating to mechanical theories of rock stress and the state of stress in the earth's crust and (2) a correlation of field data from fracturing operations. Conclusions concerning the mechanics of fracture extension, which indicate the relationship between fracture dimensions and rock properties, depth, and volume of injected fluid, are tentative and largely establish limits of relationships. These conclusions are derived from stress calculations, limited field data, and laboratory experimental studies. The experimental work involves the study of the stresses at the fracture boundaries and the geometry of pressurized fractures by means of photo-elastic modeling methods. Results of this investigation indicate that a large majority of pressure induced wellbore fractures are vertical, particularly in deeper wells; and variations in the pressures necessary to create and extend fractures can be explained largely on a basis of established rock properties. It is also shown that variations due to tectonic forces should usually be expected to be slight. Other results indicate that during that extension of fractures rather large fracture volumes are temporarily created by the parting of the formation. The purpose of this paper is to present the results of calculations and laboratory experiments concerning the mechanics of fracture induction and extension with a view to broadening existing knowledge relating to these phenomena. It is believed that continued progress in developing knowledge of this type is important to the further development of techniques for drilling and completing wells. When a wellbore is subjected to sufficiently high pressure, fracturing of the formation surrounding the well occurs. This phenomenon is a common cause of lost circulation during drilling operations, is a deliberately planned factor in most squeeze cementing operations, and is the controlling factor in many productivity stimulation operations. The exploitation of formation fracturing in recent years has been particularly impressive in sand-viscous fluid well stimulation treatments which were first introduced to the industry by the Stanolind research group1,2,3 several years ago. The borehole fracturing phenomenon has been analyzed mathematically by application of the principles defining the elastic and inelastic behavior of thick-walled cylinders of homogeneous, isotropic, and impermeable material.1,5,6 This basic argument is re-presented in this paper along with new considerations which strengthen it. In addition to these arguments relating to fracture induction some calculations and experimental results relating to the mechanics of fracture extension are presented. Since the nature of the pressure induced fracture at distances from the well is of great importance in considerations of well stimulation procedures there appears to be a need for an integrated approach which deals with the mechanics of fracture extension as well as with wellbore rupture.

Jan 1, 1955

By N. H. Fisher

GEOGRAPHICAL DISTRIBUTION THE most important known deposits in Australia of what are commonly referred to as the beach-sand minerals are along the most easterly part of the Australian coast, between Southport, 17 miles north of the Queensland-New South Wales border, and Ballina, 50 miles south of the border, and most of the production has come from this area (Fig 1). Smaller deposits are known to occur farther to the south at intervals for several hundred miles, and beaches have been worked at Yamba, 96 miles south and Woolgoolga, 150 miles south of the border and at Swansea, 60 miles north of Sydney. Important deposits have been shown to exist on north Stradbroke Island and others have been located farther to the north, as far as Tin Can Bay at the south end of Frazer Island. (Fig 2). Table I gives the list of operators with the location of their deposits and workings, their approximate maximum monthly capacity expressed in tons of heavy mineral produced by their concentrating plants before separation into individual mineral concentrates, their methods of mining and concentrating the minerals, and the products obtained. This table applies as of June 1948, but all the operators are remodeling or improving their plants and plant practices will be modified accordingly. In addition, active boring campaigns have been carried out by Alluvial Gold, Ltd., of Sydney, in the Cudgen-Cudgera area, and by Zinc Corporation. Ltd., of Melbourne, on Stradbroke Island, and in other places. PHYSIOGRAPHY Submergence of the order of 100 to 200 ft at the close of the Pleistocene period left the pre-existing hills as promontories and the valleys as deep inlets. Wave action has built bay-bars and sandspits in a northerly direction from the headlands, and lakes and marshes have formed between these bars and the initial post-submergence coast line. These lakes and swamps have been or are being filled in by river-borne sediments or wind-blown sand. Beasley1 has presented evidence that suggests a recent emergence of the coast line of about 10 ft. The evidence for this belief is the presence of a black sand seam 1/3 mile inland and 17 ft above sea level (Fig 3), and although it is not entirely certain that this seam is of beach formation and owes nothing to windblown concentration, other evidence supports the suggestion of recent emergence. Such emergence would undoubtedly aid the formation of bars and sandspits and the easterly progress of the beach front, leaving a series of parallel dunes (Fig 4). This belt of north-south coastal dunes ranges up to 1/2 mile in width and as many as 15 lines of dune have been counted (Fig 3). The foredune is generally the highest, up to 25 ft high, and there is in many places a flat platform in front of the dune known as the berm. The dunes behind the foredune are lower and less well defined

Jan 1, 1947

By N. H. Fisher

Geographical Distribution 'he most important known deposits in Australia of what are commonly referred to as the beach-sand minerals are along the most easterly part of the Australian coast, between Southport, 17 miles north of the Queensland-New South Wales border, and Ballina, 50 miles south of the border, and most of the production has come from this area (Fig I). Smaller deposits are known to occur farther to the south at intervals for several hundred miles, and beaches have been worked at Yamba, 96 miles south and Woolgoolga, 150 miles south of the border and at Swansea, 60 miles north of Sydney. Important deposits have been shown to exist on north Stradbroke Island and others have been located farther to the north, as far as Tin Can Bay at the south end of Frazer Island. (Fig 2). Table I gives the list of operators with the location of their deposits and workings, their approximate maximum monthly capacity expressed in tons of heavy mineral produced by their concentrating plants before separation into individual mineral concentrates, their methods of mining and concentrating the minerals, and the products obtained. This table applies as of June 1948, but all the operators are remodeling or improving their plants and plant practices will be modified accordingly. In addition, active boring campaigns have been carried out by Alluvial Gold, Ltd., of Sydney, in the Cudgen-Cudgera area, and by Zinc Corporation Ltd., of Melbourne, on Stradbroke Island, and in other places. Physiography Submergence of the order of 100 to 200 ft at the close of the Pleistocene period left the pre-existing hills as promontories and the valleys as deep inlets. Wave action has built bay-bars and sandspits in a northerly direction from the headlands, and lakes and marshes have formed between these bars and the initial post-submergence coast line. These lakes and swamps have been or are being filled in by river-borne sediments or wind-blown sand. Beasley1 has presented evidence that suggests a recent emergence of the coast line of about 10 ft. The evidence for this belief is the presence of a black sand seam 1/3 mile inland and 17 ft above sea level (Fig 3), and although it is not entirely certain that this seam is of beach formation and owes nothing to windblown concentration, other evidence supports the suggestion of recent emergence. Such emergence would undoubtedly aid the formation of bars and sandspits and the easterly progress of the beach front, leaving a series of parallel dunes (Fig 4). This belt of north-south coastal dunes ranges up to 56 mile in width and as many as 15 lines of dune have been counted (Fig 3). The foredune is generally the highest, upto 25 ft high, and there is in many places a flat platform in front of the dune known as the berm. The dunes behind the foredune are lower and less well defined

Jan 1, 1949

By Harry M. Bendler, W. A. Wood

Electron metallography has been applied to the study of the torsional fatigue of polycrystalline OFHC* copper. The development of slip bands, fis- sures, and microcracks has been followed as a function of strain amplitude and number of cycles. Those factors that have been found to be relevant to a geometrical theory of the fatigue process are described. From the point of view of this theory it is important to distinguish between the effects of cycling at large amplitudes and at small amplitudes (true fatigue deformation). EARLY investigations showed metal fatigue cracking is caused by continued reversal of a small plastic strain. Fundamental study of fatigue, therefore, has been largely concerned with the cumulative effects of these plastic reversals on the metal structure. In particular, recent work has shown that the plastic reversals produce slip movements that are finer than the slip movements produced by unidirectional increments of plastic strain; individual slip movements in fatigue, for instance, are too fine to see by optical microscopy.2 It has also been shown that the fine slip movements of fatigue tend to concentrate in bands and that in this way they can build up, after enough cycles, a progressive surface disturbance. It is this disturbance which, in effect, makes the slip movement visible. It is also in this disturbance that the first cracks appear to form. From this point of view, therefore, the problem of fatigue becomes one of finding why the fine slip movements should concentrate in bands and why the. bands should finally open into cracks. Thus far, study of the slip bands has been limited to the changes they produce at the surface only. These studies have given interesting results. Ewing and Humfrey3 many years ago showed that the bands in iron could extrude debris. Forsyth found that bands in aluminum alloys could extrude thin tongues of material. Thompson showed that, after lightly dissolving away the surface of copper specimens, some bands persisted as superficial cracks might, and that the life of a specimen under fatigue deformation might be prolonged by dissolving away the surface at intervals. Thus these and related results have suggested that the metal structure in fatigue bands may disintegrate and that this may happen long before obvious cracking. These surface studies, however, have not shown definitely how cracking may begin, for they do not show sufficiently what is happening in depth. However, some advance in this direction has been made recently by a new approach, summarized later, which reveals slip bands and their surface disturbances in section. In the work done thus far, the sections have been studied by optical microscopy only. In the present work they have also been studied by electron microscopy with extended results. This paper also describes some observations on the surface disturbances prior to sectioning. These observations are relevant to a suggested theory of fatigue cracking. REVERSED SLIP MOVEMENTS Slip movements in fatigue deformation must reverse direction in each cycle. The question arises: DO the "backward" and "forward" movements take

Jan 1, 1962

By Donald D. Carr, Lawrence F. Rooney

Perhaps no other mineral commodity in this volume has as many uses as limestone and dolomite. These carbonate rocks are the basic building blocks of the construction industry, the material from which aggregate, cement, lime, and building stone are made. Carbonate rocks, and their derived products, are used as fluxes, glass raw material, refractories, fillers, abrasives, soil conditioners, ingredients in a host of chemical processes, and much more. Although the use of limestone and dolomite goes back before recorded history, new uses and products are continually being found. Carbonate rocks form about 15% of the earth's sedimentary crust and are widely available for exploitation. Found extensively on all continents, they are quarried and mined from formations that range in age from Precambrian to Recent. Reserves of carbonate rock are large and will last indefinitely, although high-purity deposits may be absent or have limited availability in certain areas. Limestone and dolomite are so useful and so abundant that in 1981 about 644 million tons were produced in the United States. In fact, about 75% of all stone quarried or mined in the United States was carbonate rock. Sand and gravel was the only mineral commodity produced in greater quantity. In this chapter we have sought to provide the general reader an overview of carbonate rocks, their composition, distribution, production, and uses, with emphasis on developments since 1960. In doing so we borrowed extensively from our report on the applied geology of limestone and dolomite (Rooney and Carr, 1971). The literature on the limestone and dolomite resources of the United States and Canada is so vast and diverse that one can easily become mired down in print. We tried to list those references that are easily accessible and that provide the economic geologist with a starting point for more intensive study. The table listing selected references on limestone and dolomite resources in Canada and the United States reflects our attempt to be selective rather than exhaustive and to direct the reader to the best sources of detailed information. Geology Mineralogy The principal carbonate rocks used by industry are limestone and dolomite. Limestones are sedimentary rocks composed mostly of the mineral calcite (CaCO3) and dolomites are sedimentary rocks composed mostly of the mineral dolomite (CaCO3 • MgCO3). Aragonite (CaCO3), which has the same chemical composition as calcite but a different crystal structure, is economically important only in modern deposits, such as oyster shells and oolites. Aragonite is metastable and alters to calcite in time. Some other carbonate minerals, notably siderite (FeCO3), ankerite (Ca2MgFe (CO3)4), and magnesite (MgCO3), are commonly found associated with limestones and dolomites but generally in minor amounts. Because of their similar physical properties, the carbonate minerals are not easily distinguished one from the other. Specific gravity,

Jan 1, 1983

By W. D. Ludemann, J. E. Dor, L. A. Shepard

Recovery of the creep resistance of 99.99 pct pure Al was studied at temperatures 540°, 573°, 600°, and 611°K. Poly-crystalline specimens crept under a stress of 950 psi to a strain of 5.5 pct were allowed to recover for periods of from 1 min to 16 days under a residual stress of 4.4 psi. Increased creep rates upon reapplication of the 950 psi stress evidenced softening of the material. The activation energy for the recovery process was found to be 64,000 cal-per mol. THREE major observations have clearly revealed that the creep of polycrystalline aluminum above about 510°K is controlled by the rate of climb of jogged edge components of dislocations past the barriers impeding their motion: 1) Extensive polygonization, characteristic of climb, takes place during creep.'9' 2) The activation energy for creep equals the estimated activation for self-diffusion. 3) The stress law for creep coincides with theoretical predictions based on the climb mechanism.4,5 The decreasing rate during the primary stage of creep must be ascribed to the introduction of additional barriers to the glide of dislocations. During secondary creep the density of barriers must remain constant, the rate at which new barriers are formed being equal to the rate at which they recover. For this reason the nature of the barriers, and their rates of formation and recovery, are significant to a complete understanding of creep. It is proposed here to study the kinetics of the recovery of barriers to creep of high-purity polycrystalline aluminum in the climb range. The technique will consist of creeping a series of tensile specimens under a prescribed stress to given state following which the specimens will be recovered for various times and temperatures under approximately zero stress. The amount of recovery will be determined by comparing creep curves following the recovery. EXPERIMENTAL PROCEDURE The material used for this investigation was a 99.99 pct pure Al supplied by the Aluminum Co. of America in sheets of 0.001-in. thickness having an H-18 temper. The spectroscopic analysis of impurities gave Cu-0.004 wt pct, Fe-0.002 pct, Si-0.001 pct, others-0.000 pct. Creep specimens were machined with their tensile axes in the rolling direction of the sheets. Annealing in a molten potassium nitrate-potassium nitrite bath for 1 hr at 686K, followed by air-cooling, resulted in a grain diameter of from 0.22 to 0.27 mm. Creep machines were equipped with constant stress lever arms of the type suggested by Fullman, Carreker, and Fishher,' which maintained the applied stress to within 0.04 pct of the reported value of 950 psi. Creep strains were calculated from extensions over a 6-in. gage section to the nearest 3 X 10"5. The temperatures of testing, 540°, 573", 600°, and 611°K, were obtained by immersing the specimen and extensometer assembly in a molten KNO2-KNO3 bath. Temperatures during the periods of creeping could be maintained constant to within better than ± 1°K. Correlation of creep data at different temperatures of testing demanded the use of an appropriate temperature-compensated time 8. Previous investigations have shown that the creep of pure metals at temperatures above about 0.55 of their melting temperatures can be correlated by the functional relationship3" e=f(0), s= const. [1] where e = total plastic strain during creep f = a function that depends on stress a = stress 6 = te-Q/RT = a temperature-compensated time t = time under test Q = 35,500 cal per mol = activation energy for creep R = gas constant, and T = absolute temperature In the present series of tests all of the creep was conducted under the same stress of 950 psi. To provide identical initial conditions for the recovery all specimens were first crept to a temperature-compensated time of = 47 X 10-14 min which resulted in a creep strain of 0.055 + 0.005 regardless of the creep temperature. During recovery, a small stress (4.4 psi) was permitted to remain upon the specimens to maintain tautness in the pulling assembly and to prevent mechanical damage to the soft specimen. After each recovery period, the full stress was reapplied and

Jan 1, 1961