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By John H. Hollomon

IN a recent paper,1 a very early suggestion by Ludwik2 concerning the nature of the mechanical behavior of metals has been reexamined and extended. In essence it was [ ] suggested that there exists, at least under certain conditions, a mechanical equation of state; that the stress required for flow depends upon the instantaneous values of the strain, strain rate, and temperature, and not upon their past values. It is proposed that under these circumstances the stress does not depend upon past history of these variables, but is like the temperature of a gas that depends only upon the I instantaneous values of the pressure and volume. This notion has not been applied to present day studies of metals, though it is especially applicable to the study of creep. It is the purpose of this paper to analyze the significance and possible range [ ] of applicability of this idea and to deter- mine how it influences the accepted ideas concerning creep. STRESS-STRAIN RELATIONS It is well known that the stress-strain curves of metals are influenced by both strain rate and temperature. For a fixed strain rate and temperature there is associated with each metal a stress-strain curve. If either the strain rate or temperature is changed a new stress-strain curve will be characteristic (Fig. I). A much more general relation between the effects of the sevariables is possible, however. Consider the stress-strain curves of Fig. I determined at

Jan 1, 1946

By George W. Maynard

In the course of an examination of some of the California hydraulic mines in November last, I visited the property of the Gold Run Ditch and Mining Company, near Dutch Flat, Placer County. This is one of the most important and extensively worked mines in the district. The gold occurs in the characteristic blue gravel, which averages 175 feet in thickness, the lower 40-60 feet being made rip of cement gravel, which resists the action of water, and can only he loosened by blasting. The specimen which I have the pleasure of laying before the members was presented to me by Mr. I. L. Gould, the intelligent superintendent of the mines, who informs me that he found it in the old river channel, about twelve feet above the bedrock. The flattened water-worn nugget of gold, about the size of a kidney-bean, is imbedded in blue cement gravel, around which quartz has crystallized. When found the projecting portion of the nugget was enveloped in quartz, the core of gravel and gold having only been discovered after breaking the lump of quartz. On the quartz there is a shell of cement. The specimen is a remarkable confirmation of the theory of the deposition of quartz from solution. DISCUSSION. Dr. T. STERRY HUNT, in commenting upon this occurrence, remarked that it is in accordance with what we already know of the recency of some of the quartz of this region, and cited the microscopic

Jan 1, 1880

By George W. Maynard

IN the course of an examination of some of the California hydraulie mines in November last, I visited the property of the Gold Run Ditch and Mining Company, near Dutch Flat, Placer County. This is one of the most important and extensively worked mines in the district. The gold occurs in the characteristic blue gravel, which averages 175 feet in thickness, the lower 40-60 feet being made tip of cement gravel, which resists the action of water, and can only be loosened by blasting. The specimen which I have the pleasure of laying before the members was presented to me by Mr. I. L. Gould, the intelligent superintendent of the mines, who informs me that he found it in the old river channel, about twelve feet above the bedrock. The flattened water-worn nugget of gold, about the size of a kidney-bean, is imbedded in blue cement gravel, around which quartz has crystallized. When found the projecting portion of the nugget was enveloped in quartz, the core of gravel and gold having only been discovered after breaking the lump of quartz. On the quartz there is a shell of cement. The specimen is a remarkable confirmation of the theory of the deposition of quartz from solution. DISCUSSION. DR. T. STERRY HUNT, in commenting upon this occurrence, remarked that it is in accordance with what we already know of the recency of some of the quartz of this region, and cited the microscopic

Jan 1, 1880

By D. P. Morton

SINCE 1023, which closed the speculative era in the bituminous coal fields of the United States, there have been wide annual fluctuations in the national production of bituminous coal. These changes in annual output have been variously attributed to: (I) increased competition from petroleum products, natural gas and hydroelectric power; (2) lower unit consumption of coal; and (3) fluctuations in the general business level. The purpose of this paper is to measure, from a practical standpoint, the net effect upon the annual trend of bituminous coal production, and to give those who are interested a basis for estimating in advance the probable output of bituminous coal. It can readily be shown that changes in the level of general business affect the national production of bituminous coal more than does any other factor. Therefore it is necessary to use some standard measure of the relative business level for purposes of comparison. The Federal Reserve Board Index of Industrial Production offers the basis for such a measure.' This Index, a weighted composite of 81 different series, rests upon the averages of the years 1935 to 1939 as loo, and is presented graphically in Fig. I. Even a cursory examination of the chart will indicate a definite uptrend for industrial production over a period of years. This uptrend is due to at least two factors: (I) an actual increase in national population, and (2) a probable increase in the per capita consumption of goods. This means that there is no such thing as a fixed Normal, rather Normal is a variable, tending to increase from year to year. In order to measure the amount of annual increase in normal, the Index of Industrial Production must be studied in relation to its major components, Durable Goods and Nondurable Goods. Durable Goods are those made from the lasting materials such as iron, steel, other metals, lumber, stone, cement, clay, glass. Nondurable Goods are those for early consumption, such as foods, textiles, tobacco, chemicals, paper, gasoline, and goods made of leather and rubber. The purchase of Durable Goods may be postponed, but Nondurable Goods must be purchased currently unless the standard of living is lowered. The Federal Reserve Indexes of durable and nondurable goods are shown graphically, 1920 to 1939, on Fig. 2 (pp. 764-765 of ref. I). It is apparent that fluctuations in the production of nondurable goods are not nearly so wide as in the production of durable goods, and that the curve of Industrial Production (Fig. I) would fall between the two curves on Fig. 2. It would, however, seem logical that both curves should follow the same long-term trend, or that over a period of two to three decades the relative proportion of durable and nondurable goods, in periods of normal production, should he the same. It is neces-

Jan 1, 1941

By George Sachs

I deeply appreciate the honor of being selected to deliver the twentieth Annual Lecture of the Institute of Metals Division. The subject of my paper is extremely involved and voluminous, therefore I shall discuss only some more recent experimental material and speculate somewhat on the physical and mechanical fundamentals of these changes. The flow and the rupture of a solid material are rather different phenomena. It is therefore surprising that up to a rather advanced stage in metallurgical science these two fundamental phenomena have been simultaneously treated and forced into the general conception of the "failure " of solid material. Only in this century, and particularly during the last 20 years, have the very different physical meanings of flow and rupture been clearly recognized. Several hundred of the more recent publications deal with these subjects.l Law of Similarity The basic values commonly considered responsible for the mechanical behavior of any material are the stresses. From this standpoint both a large and a small article made from the same homogeneous metal and of geometrically similar shapes should behave identically, i.e., they should deform geometrically in a similar manner, if subjected to the same stress values at corresponding points. This "law of similarity" was introduced about 60 years ago simul- taneously by Barba2 and Kick3 and was derived from the classical theory of elasticity. As far as the plastic behavior of a metal is concerned, this rule appears to be valid. The conventional properties of large and small tension or compression test bars, machined from larger sections, are identical; while the force required to deform a section is proportional to its cross-sectional area and the work consumed in deforming geometrically similar articles in a geometrically similar manner is proportional to its volume. The general trend of the stress-strain diagram of a metal is independent of the section size (Fig. I). No exceptions from this rule are known. However, if the deformation of a metal is continued until rupture occurs, and the breaking stress or the work consumed is measured, a test bar of large cross section appears to fail before or at lower stresses than does one having a small cross section. Thus, the specific impact energy has been often found to decrease with increasing size of the test specimen, particularly for materials with a limited ductility.4 Another exception from the rule of similarity is offered by fatigue-strength values, which usually decrease with increasing section size.6'6 The conclusion must be drawn from these experimental facts that the ductility of a homogeneous metal decreases with increasing section size (Fig. I). This effect has been actually confirmed by Docherty,7 who observed that in static notch bending tests large specimens failed earlier and in a more brittle fashion than small specimens ma-

Jan 1, 1941

By George Sachs

I deeply appreciate the honor of being selected to deliver the twentieth Annual Lecture of the Institute of Metals Division. The subject of my paper is extremely involved and voluminous, therefore I shall discuss only some more recent experimental material and speculate somewhat on the physical and mechanical fundamentals of these changes. The flow and the rupture of a solid material are rather different phenomena. It is therefore surprising that up to a rather advanced stage in metallurgical science these two fundamental phenomena have been simultaneously treated and forced into the general conception of the "failure " of solid material. Only in this century, and particularly during the last 20 years, have the very different physical meanings of flow and rupture been clearly recognized. Several hundred of the more recent publications deal with these subjects.l Law of Similarity The basic values commonly considered responsible for the mechanical behavior of any material are the stresses. From this standpoint both a large and a small article made from the same homogeneous metal and of geometrically similar shapes should behave identically, i.e., they should deform geometrically in a similar manner, if subjected to the same stress values at corresponding points. This "law of similarity" was introduced about 60 years ago simul- taneously by Barba2 and Kick3 and was derived from the classical theory of elasticity. As far as the plastic behavior of a metal is concerned, this rule appears to be valid. The conventional properties of large and small tension or compression test bars, machined from larger sections, are identical; while the force required to deform a section is proportional to its cross-sectional area and the work consumed in deforming geometrically similar articles in a geometrically similar manner is proportional to its volume. The general trend of the stress-strain diagram of a metal is independent of the section size (Fig. I). No exceptions from this rule are known. However, if the deformation of a metal is continued until rupture occurs, and the breaking stress or the work consumed is measured, a test bar of large cross section appears to fail before or at lower stresses than does one having a small cross section. Thus, the specific impact energy has been often found to decrease with increasing size of the test specimen, particularly for materials with a limited ductility.4 Another exception from the rule of similarity is offered by fatigue-strength values, which usually decrease with increasing section size.6'6 The conclusion must be drawn from these experimental facts that the ductility of a homogeneous metal decreases with increasing section size (Fig. I). This effect has been actually confirmed by Docherty,7 who observed that in static notch bending tests large specimens failed earlier and in a more brittle fashion than small specimens ma-

Jan 1, 1941

FOR the benefit of those of our members who may be asked what they know about Mr. Hoover's connec-tion with the Kaiping coal mines in China and who will naturally wish to appear thoroughly well informed on the subject, we reprint below an authoritative state-ment, recently made to the Japan Advertiser, by Tang Shao-yi, former premier of China, now retired to his country home at Tang Chia. "Information has reached me at my retreat that persons in America and China insinuate that Herbert Hoover acted dishonorably in dealings involving the Chinese Engineering and Mining Company a quarter of a century ago. I be-lieve myself the only Chinese living who was closely iden-tified with that company during Mr. Hoover's connection. My uncle founded the company and my family always has been a large shareholder and, therefore, I possess direct knowledge of its history. "I am actuated in this statement by a sense of justice and also gratitude for Mr. Hoover's acts in rescuing my family during the Boxer uprising. Mr. Hoover's record in China is clean and honorable, highly creditable and in many ways remarkable. Legal action brought in London in 1905 occurred after Mr. Hoover left the company. There were not any charges against Mr. Hoover and he was not a de-fendant in the lawsuit, but an important witness whose testimony helped the Chinese shareholders to save their property.

Jan 5, 1928

By Frederick Laist

F. N. FLYNN, Clifton, Ariz.-I would like to ask Mr. Mathewson what percentage of his leaching liquor is wasted at this time? It has a bearing on the question in connection with the New Cornelia, and I think it is a very important question. E. P. MATHEWSON, Anaconda, Mont.-I am not sure what the percentage is now, but we don't discard the strong liquors. Something like 25 per cent. of the wash water taken out each day is sent over a special set of scrap iron tanks, and the copper recovered there. We had a little trouble at first. We did not proceed to use the sponge iron for the reason that the plant we originally contemplated was abandoned for flotation. Our original idea was to use a leaching process on all the tailings of the mill, but we found it would take a great deal of time to build a plant; and the cost of operating the plant we estimated to be about the same and the recovery the same. It was a question of time with us, and we decided to adopt flotation. That changed our plans. We now have the leaching plant, treating the tailings of the old dump, and the flotation applied to the current tailings. The sponge iron was figured for the large plant. We can get all the scrap iron necessary for the small plant-plenty from the scrap produced in the main plant of the smelter.

Jan 12, 1916

By Howard Eavenson

SOME time ago, in a conference considering the mechanizing of a group of mines, I was asked if I knew of any data showing the relative frequency of accidents due to the use of 275 or 550-volt current inside mines and having a recollection of seeing some in print, the answer was made that I would find what was available. Subsequent search failed to find any pub-lished records of any kind giving such figures and none of the compensation agencies of whom inquiry was made were able to supply any, excepting the Pennsyl-vania Compensation Rating and Inspection Bureau, which had some data covering a few months for some companies in that State. The inquiry was confined to the three largest producing States, Pennsylvania, West Virginia, and Illinois. The inspection departments of neither of the first two had any such records, and in Illinois, only 275 volts has been allowed inside the mines for many years. A laborious inquiry has resulted in the data, shown in Table 1, which on this account was confined to the years 1921 and 1925, the latter being the latest figures available. In each State, to find the mines using 275 and 550-volt current respectively, it was necessary to list the mines from the Coal Catalog, and then to complete the list by inquiries from the companies directly, from Operators' Associations and from Inspection Depart-ments. As the mines not electrified, and those using

Jan 5, 1928

By Eugene Coste

In a recent paper' I took exception to the opening paragraph of Mr. Hill's paper, in which he says:— " In endeavoring to interpret the geological occurrence of oil, the geologist is confronted by the fact that science has not yet solved the problem of its origin, which lies at the root of the subject.... For the present we must consider oil as a material in the rocks, the origin of which is still unexplained." I take this occasion to repeat my objection to the above statement, as well as to the similar statement of Mr. C. W. Hayes and William Kennedy in their recent bulletin2 on the same oilfields :—" The origin of petroleum is one of the most obscure problems by which geologists are confronted." I do not hesitate to say that these statements, which claim we know so little to-day of the origin of petroleum, are not warranted in the present state of geological science, and that, on the contrary, geology can to-day most clearly prove the origin of oil to be inorganic and the result of solfataric volcanic emanations. It has been so long assumed that oil or bitumen is due to the decomposition of the organic remains of the sedimentary rocks, that the words organic and bituminous are used synonymously and, accordingly, without attempt at explanation, the origin of oil is in every case ascribed to some bituminous-shale horizon, more or less full of organic matter. Such falla

Jan 1, 1905

By J. O. Mack, J. B. Russell

In recent years, solders containing 20 per cent tin with no bismuth or cadmium have been developed by a few companies, and personnel have been properly instructed in their use. In addition, since the tin shortage, a number of solders containing less than 10 per cent Sn, and some with no tin, are being used in special applications; however, a solder of this type has yet to be developed that is satisfactory for general use. Table i.—Composition Ranges Prescribed for a Commercial Substitute Solder Element Per Cent Tin............................ 18.0-20.0 Bismuth (maximum)a............ 0. 80 Silver.......................... O. 10-1. 25 Bismuth plus silver (minimum).... 0. 85 Antimony (maximum)............ o. 50 copper (maximum),,,,,,,,..,,,, 0. I3 Other elements, each (maximum)6 0.03 Lead........................... balance a When silver is present in excess of I per cent, the Bi content shall be 0.50 per cent or over. b Total not to exceed 0.10 per cent. The Purpose of this investigation was to develop an alloy containing a maximum of 15 per cent tin, with no cadmium or bismuth, having solder properties equivalent to or better than those of substitute solders now specified containing 18 to 20 per cent tin (Table I), or even approaching the properties of the standard 40 to 60 tin-lead solder. The wartime restriction of bismuth and cadmium, elements that have beneficial effects on fluidity, solidification range and strength, makes it increasingly difficult to develop a general-purpose solder containing a maximum of 15 per cent tin. In the course of this investigation, 11 elements were used in various combinations with the basic I5-85 tin-lead alloy. These elements were antimony, silver, copper, indium, thallium, lithium, calcium, barium, potassium, sodium and arsenic. In all, 116 low-tin solders were investigated, with the idea of developing a solder that will give satisfactory working properties, specifically in regard to "wetting" of copper, brass and iron, solidification range, capillarity and shear strength of a soldered joint. The relative importance of these various properties plays an important role in the search for substitute solders, since it is almost impossible to retain all of the desired qualities of a high-tin solder and still make drastic changes in the alloy composition. Because of the expected uses of a general-purpose solder, it is necessary that it have properties, especially in regard to wet-tability, that will enable it to be used on the metals in common use. Basic Considerations The maximum liquidus temperature of a solder is determined by the particular application involved and the temperature that can be obtained by the source of heat. If a soldering iron is used, it must not only

Jan 1, 1945

[Appalachian Petroleum Section: James M. Kimbrough, chairman; John H. Adair, first vice-chairman; Walter L. Diddle, second vice-chairman; Byron M. Finch, secretary-treasurer. Balcones Section: Robert V. West, chairman; Frank W. Jessen, first vice-chairman; Zane V. Morgan, second vice-chairman; Brantley G. Myers, secretary-treasurer. Meets 4th Wed., Petroleum Club (San Antonio) or Terrace Dining Room (Austin) Billings Petroleum Section: Charles B. Evans, chairman; L. M. Lyon, first vice-chairman; Gordon E. Lansford, second vice-chairman; Fred. A. Haddenhorst, secretary-treasurer. Meets 3rd Tues., Billings Petroleum Club. California Coastal Section: Robert L. Richardson, chairman; David K. Hayward, first vice-chairman; W. Jackson Bransford, secretary; William N. Harwell, treasurer. Meets 3rd Thurs., Pierport Inn, Ventura. Caracas Petroleum Section: Edwin A. Moo re, chairman;. Jose Cirigliano, vice-chairman; Frank B. Davis, secretary; Robert N. Powers, treasurer. Meets 2nd Tues., Caracas Theater Club.]

Jan 1, 1961

by their overdogmatic picture of geology and their resulting drastic oversimplification and idealization of geologic features. I am in hearty disagreement with the recommendation that geophysics should be done by cooperative work between a geologist and a geophysi-cist. That arrangement would be comparable to doing petrography by having a physicist at the microscope and a geologist sitting by his side. The interpretation of the geological significance of geophysical data can be done efficiently only by a physicist who has become also a good geologist or by a geologist who is also a good geophysicist. Less Well-trained Men The rank and file, composing perhaps two-thirds of the personnel of exploratory geophysics, is not, and should not be, composed of highly trained men. The routine, stereotyped character of the work and the impossibility of promotion of more than a few from these lower ranks even under the best circumstances justify companies in filling the bulk of these rank and file positions with men having only a bachelor's degree at the most. There can be a wide range of training for such positions, although certain lines of study are preferred for certain kinds of work, and different employers have different preferences. For work in gravitational and magnetic prospecting, first preference will be for men having geological training and second for men with civil engineering training. In seismic work, men with geological training are preferred by some employers for computers; physicists, electrical engineers and all whose technical education has covered radio circuits are preferred for the other technical positions. Collegiate training in geophysical prospecting brings no preference and by many employers is given a slightly inferior rating. One large company seldom hires men who have just graduated with a major in geophysical prospecting. This prejudice is based on the reasoning that much of what is learned in college is obsolete or obsolescent, that most of the techniques learned in college will have to be unlearned, because different from those used by the employing company, and that in the long run additional courses in basic physics, mathematics and geology are of more value to a man than the courses on geophysical prospecting. DISCUSSION [This discussion refers to the five papers beginning on page 23 and ending on page 74.1 L. W. Blau,* Houston, Texas.—I have had some rather sad experiences with forecasting. For example, I could not foresee 10 years ago my present occupation, and I do not profess to be able to look ahead 10 years and tell anyone what he will be doing then. Referring to the point raised in the discussion, I do not know, for example, what the price of oil will be 10 years from now. If an appreciable number of

Jan 1, 1940

by their overdogmatic picture of geology and their resulting drastic oversimplification and idealization of geologic features. I am in hearty disagreement with the recommendation that geophysics should be done by cooperative work between a geologist and a geophysi-cist. That arrangement would be comparable to doing petrography by having a physicist at the microscope and a geologist sitting by his side. The interpretation of the geological significance of geophysical data can be done efficiently only by a physicist who has become also a good geologist or by a geologist who is also a good geophysicist. Less Well-trained Men The rank and file, composing perhaps two-thirds of the personnel of exploratory geophysics, is not, and should not be, composed of highly trained men. The routine, stereotyped character of the work and the impossibility of promotion of more than a few from these lower ranks even under the best circumstances justify companies in filling the bulk of these rank and file positions with men having only a bachelor's degree at the most. There can be a wide range of training for such positions, although certain lines of study are preferred for certain kinds of work, and different employers have different preferences. For work in gravitational and magnetic prospecting, first preference will be for men having geological training and second for men with civil engineering training. In seismic work, men with geological training are preferred by some employers for computers; physicists, electrical engineers and all whose technical education has covered radio circuits are preferred for the other technical positions. Collegiate training in geophysical prospecting brings no preference and by many employers is given a slightly inferior rating. One large company seldom hires men who have just graduated with a major in geophysical prospecting. This prejudice is based on the reasoning that much of what is learned in college is obsolete or obsolescent, that most of the techniques learned in college will have to be unlearned, because different from those used by the employing company, and that in the long run additional courses in basic physics, mathematics and geology are of more value to a man than the courses on geophysical prospecting. DISCUSSION [This discussion refers to the five papers beginning on page 23 and ending on page 74.1 L. W. Blau,* Houston, Texas.—I have had some rather sad experiences with forecasting. For example, I could not foresee 10 years ago my present occupation, and I do not profess to be able to look ahead 10 years and tell anyone what he will be doing then. Referring to the point raised in the discussion, I do not know, for example, what the price of oil will be 10 years from now. If an appreciable number of

Jan 1, 1940

By P. E. Fitzgerald

SOME readjustments in the research programs of most of the oil companics and petroleum engineering schools have been made necessary by the war. The most obvious change has been the conversion from production engineering to problems more closely related to the nation's was effort. Many laboratories now devote much of their time to studies on products to be derived from petroleum. such as synthetic rubber, toluene, and substitutes for critical materials. Others are working to improve motor fuels including high-octane gasoline and the special lubricants required by the wide geographical range of the present conflict. Of great importance is the experience of the geophysicists, who are now devoting a great percentage of their time on instrument research and production or special apparatus required by the armed forces.

Jan 1, 1943

By J. B. Bassett, E. S. Rowland

The experimental work reported herein firas inspired by the publication of a paper by Grange and stewart, in which it was suggested that at low chromium contents the effect of this element on the Ma point was greater than at higher chromium contents, It was argued that, if a small increase of chromium in solution in austenite caused a sharp lowering of the M, point, it might lead to an explanation of occasional unsolved stress cracking of SAE 52100 during heat treatment. Commercial hardening is carried out at temperatures of incomplete solution, leaving carbides available to enrich the austenite during any inadvertent increase in temperature, such enrichment of the austenite in chromium content would lower the M, point nearer room temperature where cracking is more likely to occur. According, it was decided to investigate the effect of chromium, in quantities between o and 2 pet, on the M, point of commercial steels. Fig I summarizes the data available on chromium steels. For purposes of comparison, the M, temperature values were corrected by means of the Grange and Stewart formulas to (I) Hypoeutectoid compositions: 0.50 pct carbon and 0.80 pct manganese (z) Hsereutectoid compos-sition': 1." pet carbon and O.35 pct manganese. Only the steels having compositions reasonably close to these corrected values were included, because large adjustments inevitably introduce increased error such as are experienced in using the formula. The straight lines of Fig I were drawn by the authors. These data obviously do not settle the question Of the effect Of chromium On the Md Oint, particularly at low chromium contents. While it is fairly well established that chromium causes the M, to be lowered when present in quantities of I pet Or more, Grange and Stewart1 have suggested that in small amounts (less than 1 pet) it is more effective in lowering the Ma point, while Klier and Troiano2 have suggested that in small amounts it is less effective in lowering the Ma point. Payson and Savage3 concur with Klier and Troiano and further suggest that the effect is not linear at these concentrations. Rose and Fischer4 report that small amounts of chromium actually raise the Ma point of a 0.20 carbon steel. Material Two series of 35 Ib induction heats were melted for this work, the analyses of which are given in Table I. One series was aimed at 0.50 pct carbon and 0.80 pct manganese with chromium additions in 0,25 pet increments from o to 1.5 pct with a single heat at 2.0 pct Cr. This series was considered necessary because the commercial heat treatment of SAE 52100 does not generally introduce more than about 0.60 pct carbon in solution in the austenite. The high

Jan 1, 1949

By D. S. Flett, D. W. West

The solvent extraction of chromium 111 has been studied for the system Cr 111, H,SO., H,O/RNH/RNH., xylene, where the primary amine used was Primene JMT. Rate studies have shown that extremely long equilibrium times are required, ranging from 1 hr at 80°C to 20 days at room temperature. Heating the solution prior to extraction increases the rate of extraction. The variation in the amount of Cr 111 extracted is an inverse function of the acidity of the aqueous phase. Thus, the slow rates of extraction appear to be connected with the hydrolysis of the Cr I11 species. Extraction isotherms for the extraction of Cr 111 have been obtained for two sets of experimental conditions, namely at 60°C and for a heat-treated solution cooled to room temperature. The separation of Fe 111 from Cr 111 and Cr 111 from Cu 11 in sulfate solution by extraction with Primene JMT has been studied and shown to be feasible. A survey of the literature relating to the solvent extraction of chromium showed that, although many systems exist for extraction of Cr VI, only a very few reagents have been found to extract Cr 111. The extraction of Cr III by di-(2-ethyl hexyl) phosphoric acid has been reported by Kimura.' A straight-line dependence of slope —2 was observed between log D,, and the log mineral acid concentration at constant extractant concentration. Since the slope of this plot reflects the charge on the ion extracted, it must be concluded that a hydrolyzed species of Cr III is being extracted. Carboxylic acids generally do not form extractable complexes with Cr III but di-isopropyl salicylic acie does extract Cr 111. Simple acid backwashing of the organic phase, however, failed to remove the chromium. Similar difficulty in backwashing was found by Hellwege and Schweitzer8 in the extraction of Cr I11 with acetyl-acetone in chloroform. The extraction of Cr 111 from chloride solutions by alkyl amines has been reported4-' but the maximum amount of extraction achieved in these studies did not exceed 10%: From sulfate solutions, however, Ishimori" has shown that appreciable amounts of Cr I11 were extracted by amines. The amines used were tri-iso-octyl amine, Amberlite LA-1 (a secondary amine, Rohm & Haas) and Primene JMT (primary amine, Rohm & Haas). The efficiency of extraction with regard to amine type was primary>secondary> tertiary. Appreciable extraction of Cr I11 was recorded for Primene JMT as the aqueous phase acidity tended to zero. The major difficulty with Cr I11 in solvent extraction systems stems from the nonlabile nature of the ion in complex formation. This accounts for the slow rate of extraction generally experienced and the difficulty encountered in backwashing the Cr I11 from the organic phase in the case of liquid cation exchangers. Consequently, the possibility of extraction of Cr I11 as a complex anion is attractive since the backwashing problems should be minimized in this way. From published data, it appeared that the extraction of chromium from sulfate solutions of low acidity by primary amines afforded the best chance of success for a useful solvent extraction system for Cr iii This paper presents the results of a study of the extraction of Cr I11 from sulfate solution by Primene JMT and examines the application of such an extraction procedure for the recovery of chromium from liquors containing iron and copper. Experimental Chromium solutions were prepared from chrome alum in sulfuric acid and sodium sulfate so as to maintain a constant concentration of sulfate ion of 1.5 molar. Solutions of Primene JMT were prepared in xylene and the amine equilibrated with sulfuric acid/sodium sul-fate solutions, of the same acidity as the chromium solution, until there was no change in acidity between the initial and final aqueous phases. The solutions of Primene JMT conditioned in this way were then used for the equilibration experiments. Equilibrations at 25°C were carried out in stoppered conical flasks shaken in a thermostat; equilibrations at all other temperatures were carried out in stirred flasks in a thermostat. After equilibration, the phases were separated and analyzed for chromium. In the tests on the rate of extraction, small samples of equal volume of both phases were withdrawn from time to time and the chromium distribution determined. The chromium analyses were carried out either coloi-imetrically using diphenyl carbazide, or volu-metrically using addition of excess standard ferrous ammonium sulfate and back titration of the excess iron with potassium dichromate. The oxidation of Cr 111 to Cr VI in the case of the raffinate solution was effected by boiling with potassium persulfate in the presence of silver nitrate and, for the backwash solution, by boiling with sodium hydroxide and hydrogen peroxide. Results Preliminary experiments indicated that extraction results were effected by the age of the chromium solution, higher distribution coefficients being obtained with solutions which had been allowed to stand for some time. Consequently a stock solution of chrome alum, 10 m moles per 1 Cr I11 in 1.4 M Na,SO,/O.l M &SO,,

Jan 1, 1971

By S. Mukai, Y. Shah, T. Zshikawa, T. Wakamtsu

In order to recover coal concentrate of low ash and low iron content, the electrostatic separation of coal was studied. It is more successful in the corona discharge field to recover the coal concentrate of low ash and low iron content than in the field without corona discharge. The effect of humidity on the electrostatic separation of coal was then studied. From the experimental results, it was clear that the electrostatic separation was excellent in about 60% relative humidity of atmosphere. Thus, the separation of vitrite from coal is practicable by electrostatic separation. In recent years the demand for high quality coal containing low ash, low iron, and low sulfur has increased. To fulfill this requirement, a higher grade coal concentrate must be produced. Study on the electrostatic separation of coal has been performed for several years in the author's laboratory. From the results of this research, it was considered that the behavior of coal particles in the electrostatic field relates closely to the ash and iron content in coal. In the present paper, the electrostatic separation of coal in corona discharge field was studied in order to recover the high quality coal concentrate and then the effect of humidity on the electrostatic separation was investigated. PREPARATION OF COAL SAMPLES The coals from the Akabira mine, the Kushiro mine, the Miike mine, and the Oshima mine which are famous coal mines in Japan were used in this study. The ash contents of these coals are shown in Table I. From the results of the analysis of the coal samples by the Norelco X-ray diffractometer, it is recognized that the Miike coal includes mainly pyrite, quartz, kaoline, calcite, and epidote; the Kushiro coal: kaoline, quartz, and montmorillonite, and the Oshima coal: siderite, dolomite, and other substances. For the preparation of samples, the coarse pieces of coal were crushed to about 2 mm in diam and then ground in an agator mortar. The ground products were sieved and fractions of 10 — 14 mesh, 14 — 20 mesh, 20-28 mesh, and 28-35 mesh were prepared, respectively. APPARATUS OF ELECTROSTATIC SEPARATION The principal part of the apparatus of the electrostatic separation used in the experiments is shown in Fig. 1. In order to generate the corona discharge field, a needle-shaped electrode combined with a pole electrode is installed as the high tension electrode. In the case of investigating the effects of the humidity on the electrostatic separation of coal, the needle-shaped electrode was combined with a plate electrode instead of the pole electrode as shown in Fig. 2. The pole or the plate electrode was installed to promote the repelling of the charged particles by producing the electrostatic field between this electrode and the grounded roller. It seems to be very useful on the coal separation to install these combined high tension electrodes. SEPARATION OF COAL PARTICLES IN CORONA DISCHARGE FIELD The separation testings on the coal samples in the corona discharge field were performed by the apparatus as shown in Fig. 1. These experiments were carried out under the following conditions: feed size 20 — 28 mesh, room temperature, normal humidity and applied voltage 15-20 KV, and the combined electrodes including the needle-shaped electrode were negatively charged. The results of these testings are

Jan 1, 1968

By G. R. Speich

The interlarnmelm spacing, growth rate, and degree of segregation that accompany cellular precipitation in four Fe-Zn alloys containing 9.7, 15.2, 23.5, and 30.5 at. pct Zn have been determined in the temperature range 400" to 600°C. The chemical free-energy change for the reaction was calculated from the available thermodynamic data and the known compositions of the phases. The fraction of the chemical free-energy change for equilibrium segregation that is converted into interfacial free energy decreases from 0.43 to 0.08 as the magnitude of this free-energy change increases from 35 to 270 cal per mole. At constant temperature the cellular growth rate is proportional to the cube of the dissipated free energy. At 600°C newly 100 pct of the equilibrium segregation is achieved during cellulm precipitation whereas at 400°C only 85 pct of the equilibrium segregation is attained. During cellular growth, mass transport of zinc occurs by grain boundary diffusion; excess zinc remaining in the a! phase after the completion of growth is removed slowly by volume diffusion. A modified Cahn theory of cellular precipitation predicts the observed interlamellar spacing within a factor of two. In cellular precipitation reactions such as pearlite formation or discontinuous precipitation, the basic problem is to predict the variation of growth rate G, interlamellar spacing S, and degree of segregation P with composition and temperature. To accomplish this we need three independent equations relating these quantities. One of these equations comes from the diffusion solution. To obtain two additional independent equations, some assumptions must be made. cahnl has suggested recently that two plausible assumptions are 1) that growth rate is proportional to the dissipated free energy and 2) that the spacing which occurs is that which maximizes the dissipated free energy. According to the first assumption, this spacing also maximizes the growth rate and the rate of decrease of free energy per unit area of cell boundary. The present work was undertaken to test these assumptions. To test the first assumption it is necessary to study a cellular reaction over a wide range of supersatura-tions to establish a relationship between G and the dissipated free energy at constant temperature. This is possible only in discontinuous precipitation reactions since in pearlite reactions constituents other than pearlite form if the composition of the parent phase deviates even slightly from the eutectoid composition. The Fe-Zn system was chosen for study because 1) discontinuous precipitation proceeds to completion over a wide temperature and concentration range, 2) the degree of segregation within the cell can be measured by lattice parameter measurements,2 and 3) the thermodynamics of this system have recently been determined by Wriedt.3 In this system the cells consisting d alternate lamellae of a and r phases form from supercooled iron-rich a phase. The a phase within the cells is bcc as is the original a phase, cia, but has a different orientation and a slightly lower zinc content than the original a phase. The r phase has a zinc content of about 70 at. pct and a crystal structure isomor-phous with T brass. EXPERIMENTAL PROCEDURE Four Fe-Zn alloys with 9.7, 15.2, 23.5, and 30.5 at. pct Zn were prepared from carbonyl-iron powder (400 mesh, 99.8 wt pct Fe) and zinc powder (200 mesh, 99.99 wt pct Zn). The powders were ball-milled together and cold-pressed under 60,000 psi to discs $ in. thick by $ in. diam. The cold-pressed discs of the alloys with 9.7 and 15.2 at. pct Zn were sealed in evacuated silica capsules and heated slowly to 1100°C over a period of 1 week (3 days at 600°C, then 3 days at 80O°C, then 1 day at 1100°C). The alloys with 23.5 and 30.5 at. pct Zn were treated similarly except that the final homogenization temperatures were 1000" and 85O°C, respectively, to prevent melting. The alloys were quenched in iced brine from the final homogenization temperature. Specimens of each alloy were subsequently aged in salt pots at temperatures of 400°, 450°, 500°, 550°, 600°, and 650°C for times that varied from a few minutes to several hundred hours. At a late stage of this work, an alloy containing 11.2 at. pct Zn was prepared by vapor-impregnation of iron foil with zinc vapor at 890°C. This alloy proved useful for electron microscope studies because it was free of porosity. The homogenization and aging conditions were based on the recent Fe-Zn phase diagram of Stadelmaier and Bridgers4 rather than the earlier diagram of ansen.5 They consist of a homogenization heat treatment in the homogeneous a field followed by an aging treatment in the two-phase a + r field. The aged specimens were metallographically polished and etched in 2 pct nital and the radius of the largest cell in the microstructure determined. This radius plotted vs time gave a straight line whose slope is the boundary migration rate or growth rate G of the cell. To determine the interlamellar spacing, specimens were examined by surface-replica and thin-section electron microscope techniques. Because of the irregular nature of the lamellae within the cell, the average interlamellar spacing S .of the cell was measured by the method of Cahn and Hagel,6 where S is defined by:

Jan 1, 1969

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Jan 1, 1917