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By J. A. Fulton, A. B. Foote

Gold was discovered in the Sierra Nevada by J. W. Marshall on Jan. 2, 1848. The town of Grass Valley soon sprang up and contained several stores in 1849; but the population of the town has always reflected the fluctuations in quartz mining. Gold-bearing quartz was found on Gold Hill in September 1850, and in the next two years most of the quartz-bearing veins in the vicinity were located. At first, the quartz was crushed in mortars with spring poles; the IIuff Co. took out $20,000 in this manner during the winter and spring of 1851. The first mill was put up in January, 1851. In 1866, there were in Grass Valley 248 stamps, crushing 71,420 tons of ore with an average yield of $30 to $35; in Nevada City, there were 142 stamps, crushing 14,200 tons, with an average value of $25. Rut in 1918, only two properties in this region, the Empire and the Korth Star, were producing Since then, there has been a revival of mining in the district and the following properties are being opened up: The Golden Center. Grass Valley Gold Mines Co.. Idaho-Maryland Mines Co., while the Su1tana is kept unmatered and work is going on in a half dozen mall propertics Mining Claims At the first meeting of miners in Grass Valley, Jan. 13. 1851, a plot :30 by 40 ft. was allowed for a claim, the boundaries in all cases being perpendicular. In 1852, the quartz miners in Nevada County deeided that "each prospector shall hereafter be entitled to 100 ft. on a quartz ledge or vein and the discoverer shall be allowed 100 ft. additional. Fach claim shall include all the dips, angles, and variations of the vcin." This rule was in force until replaced by the Federal mining laws of 1872; these allowed quartz claims to be 1500 ft along the vein, with all the dips, spurs, and angles, and to have a width of 600 ft. The holdings of the principal companies consist of these early patented mining claims; standard claims, as authorized by the Act of 1872, both patented and unpatented; agricultural tracts, both patented and

Jan 1, 1927

By H. I. Young

Inasmuch as there has been a great deal of activity in this district recently, a paper of this kind should treat of all the various phases of mining, namely, prospecting, developing, and operating. Prospecting .. Where ore is found at a depth of 100 ft. (30 m.) or more, the prospect work is done by churn drilling. Several makes of churn drills are used in this work, both steam- and gasoline-driven machines being used. The drilling is usually started with a 6-in. bit, and the size of the bit is reduced, if necessary, as the hole is advanced. It is general practice to drill from 100- to 400-ft. holes, but this is governed entirely by the location and formation of the ground. In drilling sheet ground, close spacing of drill holes is unnecessary, but in narrow orebodies, the holes are spaced from 15 to 50 ft. (4.6 to 15 m.) apart. Ten years ago, very few assays were kept of the drilling, but during recent years records have been kept very accurately, showing the location, elevation, assays, and also the vertical section of the hole. After the orebody is reached, cuttings are taken every 2 or 3 ft. (0.6 to 0.9 m.) samples being sometimes taken by pouring the water off the cuttings and taking a portion of the coarse material for assay. It has been found, however, that very often the sludge material poured off with the water contains high mineral values. To overcome this, cuttings from each 2 or 3 ft. are put in a container, and, after the water is evaporated, sample for assay is taken by means of Jones samplers. Permanent records of cuttings showing various formations are kept in glass jars or glued on large cards. Drilling at present is costing from $1.25 to $1.50 per foot. In pre-war times, the drilling costs ran from 75c. to $1 per foot. Development After proving property by drilling, shafts are put down to the ore-body. These are usually vertical shafts, either single or double compart-

Jan 1, 1918

By Frank C. Green

Drilling for oil and gas in Missouri in 1935 was mostly confined to proven areas, but was marked by the completion of one of the largest oil wells, 53 bbl., and one of the largest gas wells, 2,000,000 cu. ft., drilled in recent years. A new oil pool, discovered in southern Cass County late in 1934, was further developed; a new pool in southern Platte County is possibly indicated by the completion of a single small well, which flowed naturally; and a deeper sand was developed in the Marota gas pool in Jackson County. Completions dropped to a lower level than in any recent year. A total of 73 wells, which included the deepening of 8 old wells, was drilled. In Bates County, there was one gas well with an open flow of 100,000 cu. ft., and one dry hole. Cass County had six oil wells with about 100 bbl. initial production; one gas well with an open flow of 500,000 cu. ft., and three dry holes. In Jackson County there were seven oil wells with 25 bbl. initial production; 24 gas wells with 7,358,968 cu. ft. open flow, and 27 dry holes. Platte County had one oil well, one small gas well and one dry hole. The oil well flowed naturally about 4 or 5 bbl. per day. It is rather difficult to obtain production figures on either oil or gas leases, but in cases where the figures have been given to the writer in confidence, they disclose conditions comparable with many other regions. One oil lease of 32 acres has produced 125,000 bbl. in four years, or nearly 4000 bbl. per acre. Another lease has made 50,000 bbl., or about 3000 bbl. per acre. It is probable that the total daily production at the end of 1935 was close to 200 hill. per day. A gas pool covering less than one square mile has made 110,111,000 cu. ft. in about 18 months. In this period, the open-flow capacity has been reduced from about 10,500,000 cu. ft. per day to about 3,500,000.

Jan 1, 1936

By T. R. Braithwaite

The brief comments made in this chapter deal mainly with shaft sinking, but don't assume that freezing techniques apply only to shaft sinking. They can be used on tunnel work, on such things as liquid gas storage in sediment, and I think you will probably see other applications for it as we go along. The method was first developed in 1883 and was used to sink shallow shafts through water-bearing overburden in Germany and in England. One of the early shafts was in Germany and was sunk by freezing to 310-ft depth. The project required 17 months for drilling, roughly 5 1/2 months for freezing, and another 7 months for sinking, giving an average progress of 10 ½ fpm. Fortunately there have been numerous improvements and new developments in this technique through the years. With equipment and techniques available today, we can take a 20-ft-diam shaft down through 2000 ft of water-saturated overburden and the time schedule runs roughly 4 months for site preparation, freeze-hole drilling, installing the casings, and setting up the plant; 4 ½ months for freezing; and 6 months for excavating and installing permanent linings. This gives a progress rate of about 140 fpm, on average. I might qualify that a little in that the special linings that are required for some formations can affect the time. If it's straightforward sinking where one can use a heavy concrete lining, up to 630-640 fpm may be achieved in a shaft; but with special cast-iron tubbing or types like that, 5 fpd is pretty good progress, so the lining does affect the time. The freezing method is used mainly for sinking shafts through unstable water-bearing formations which cannot be grouted either effectively or economically and which are too deep to enclose in pile casing. Even with overburden, grouting methods available today can handle roughly 100 lb water pressure; in the range of, say, 100 to 150 ft from the surface, it's very often best to grout 40 or 50 ft. You normally drive a pile casing and go through it. Below that range, freezing is very often the economical

Jan 1, 1970

By Frank C. Green

Drilling for oil and gas in Missouri in 1935 was mostly confined to proven areas, but was marked by the completion of one of the largest oil wells, 53 bbl., and one of the largest gas wells, 2,000,000 cu. ft., drilled in recent years. A new oil pool, discovered in southern Cass County late in 1934, was further developed; a new pool in southern Platte County is possibly indicated by the completion of a single small well, which flowed naturally; and a deeper sand was developed in the Marota gas pool in Jackson County. Completions dropped to a lower level than in any recent year. A total of 73 wells, which included the deepening of 8 old wells, was drilled. In Bates County, there was one gas well with an open flow of 100,000 cu. ft., and one dry hole. Cass County had six oil wells with about 100 bbl. initial production; one gas well with an open flow of 500,000 cu. ft., and three dry holes. In Jackson County there were seven oil wells with 25 bbl. initial production; 24 gas wells with 7,358,968 cu. ft. open flow, and 27 dry holes. Platte County had one oil well, one small gas well and one dry hole. The oil well flowed naturally about 4 or 5 bbl. per day. It is rather difficult to obtain production figures on either oil or gas leases, but in cases where the figures have been given to the writer in confidence, they disclose conditions comparable with many other regions. One oil lease of 32 acres has produced 125,000 bbl. in four years, or nearly 4000 bbl. per acre. Another lease has made 50,000 bbl., or about 3000 bbl. per acre. It is probable that the total daily production at the end of 1935 was close to 200 hill. per day. A gas pool covering less than one square mile has made 110,111,000 cu. ft. in about 18 months. In this period, the open-flow capacity has been reduced from about 10,500,000 cu. ft. per day to about 3,500,000.

Jan 1, 1936

By C. Hertzler

The difference of means of milling characteristics by rock and ore type is tested in a statistical manner in the paper. The null hypothesis being tested is that the sample means of two different populations are equal. It is assumed that the null hypothesis is true when performing the test. Because of this, acceptance of this hypothesis leads to the conclusion that the sample means of the two different populations are equal (or there is no significant difference between the sample means), not that the samples come from the same population, as the author asserts. Rejection of the null hypothesis leads to the conclusion that the sample means of the two different populations are not equal. A P value for this test is reported in Table 2 and is incorrectly identified as the probability that the two samples came from different populations. Actually, what was recorded was 100(1 - p) where p is the usual p-value. The usual p-value measures, on a scale of zero to one, the extent to which the data agree with the null hypothesis. It is the probability of observi" a value of the test statistic (Z score) that is at least as contradictory to the null hypothesis as the one computed from the sample data (McClave and Dietrich 11, 1982). The author makes no mention of the fact that were these tests to be conducted together, the chances of determining that the null hypothesis is not true when it is really true are increased considerably (Snedecor and Cochran, 1980). This is a multiple comparisons problem and should be dealt with accordingly. The usual methods involve adjusting the level of the individual tests. Table 2 reports an incorrect 100(1 - p) value in the comparison of concentrate grades for other rock types with .30 to .69% Cu vs other rock types with .70 + % Cu; 86% should be 98.6%. Although the article can be criticized for poor data presentation and discussion of that data, the point the author makes regarding the use of these statistics in the ore reserve estimation process is well taken. It does not appear that inaccuracies in the statistical interpretations have hindered that usefulness.

Jan 1, 1985

By George H. Ashley

Mining, including quarrying, dates back almost to the dawn of history, beginning almost with the beginning of what we call civilization. State surveys date back about 100 years. Evidently mining flourished for thousands of years before state surveys were thought of. Why should it not continue to flourish without state surveys? First, it may be noted that as mining and civilization were contemporaneous, so state surveys and the science of geology were almost contemporaneous. As recently as 30 years ago the United States mineral laws were interpreted to mean that coal lands in the public domain were only those lands on which workable coal outcropped. The half billion acres of public land underlain by .coal but on which it did not outcrop were treated as homestead lands and open to settlement. Just what did the science of geology do to or for the mining industry? Until geology arose rocks or minerals or ores were where they were found. Their finding might be accidental, or might be the result of deliberate search or prospecting. In open, rocky country, with little or no vegetation, as in parts of the West, prospecting served very well, though at an enormous expenditure of human time and effort, if not money. The old saying that every dollar's worth of gold taken from the earth has cost two dollars may largely be charged to the time value of the usual method of prospecting. Geology changed all that. The science is still young and it still labors under handicaps of immaturity and early errors. Geology, however, has gradually been discovering the relations and conditions under which the several mineral deposits occur. Its elaborate studies of exhausted or nearly exhausted mineral deposits has done for it what human autopsy has done for medicine and surgery. Perhaps in no field is this plainer than in the oil and gas industry. Note might also be made of several important coal fields in England and on the Continent, in which the coal is everywhere deeply buried. Passing over the long period of growth during the past 100 years, geology today is prepared to offer the mining industry: first, a knowledge of the geologic conditions under which most minerals occur and to explore

Jan 1, 1935

By Thomas R. Cunningham, A. B. Kinzel

Silicon, unfortunately, is not in the same category as some other metals with respect to the absolute value of the highest purity material prepared. Tucker, in England, and Becket, in this country have developed procedures for the purification of silicon, and Becket's process has made industrially available silicon of a purity of 99.8 per cent or better. However, even the term "silicon metal" may be a paradox to some people, although not more so than the term "amorphous" as applied to silicon. These terms come from commerce, and "metal" is used to distinguish industrially high-purity silicon from ferrosilicon, silicon-aluminum, and other high-silicon alloys. Alloys of iron and silicon with 95 per cent Si or less are known as ferrosilicon, with a designation of silicon content where necessary, arid the term "silicon metal" is invariably applied to the grades containing 96 per cent Si and higher. The Becket method of purification was referred to in a monograph on the Alloys of Iron and Silicon, and the Tucker procedure was described in some detail in that publication.' In order to get silicon of still higher purity, a sample, prepared by the Becket method, analyzing 99.84 per cent Si, 0.020 Fe, 0.016 Al, 0.005 Ca, 0.025 C, 0.033 per cent 02, 0.006 H2, 0.006 N2, and 0.001 per cent Mn, was crushed to pass a 100-mesh sieve and further purified by a modification of Tucker's procedure. This modification differs from Tucker's method in that after treatment the 100-mesh alloy was centrifuged to remove the last traces of acid. Our directly determined analysis of this purified sample shows: Si, 99.952 per cent; Fe, 0.009; Al, 0.012; Ca, 0.003; C, 0.006; or 99.982 per cent. Silicon by difference equals 99.97 per cent. The variation between silicon by difference and silicon as directly determined is important. Although Tucker mentions the amount of insoluble matter in commercial silicon both before and after his treatment, he does not mention the existence of carbon in the alloy; nevertheless, he reports silicon by difference. Any final figure as to purity obviously results from agreement between direct determination and

Jan 1, 1940

By A. B. Kinzel, Thomas R. Cunningham

Silicon, unfortunately, is not in the same category as some other metals with respect to the absolute value of the highest purity material prepared. Tucker, in England, and Becket, in this country have developed procedures for the purification of silicon, and Becket's process has made industrially available silicon of a purity of 99.8 per cent or better. However, even the term "silicon metal" may be a paradox to some people, although not more so than the term "amorphous" as applied to silicon. These terms come from commerce, and "metal" is used to distinguish industrially high-purity silicon from ferrosilicon, silicon-aluminum, and other high-silicon alloys. Alloys of iron and silicon with 95 per cent Si or less are known as ferrosilicon, with a designation of silicon content where necessary, arid the term "silicon metal" is invariably applied to the grades containing 96 per cent Si and higher. The Becket method of purification was referred to in a monograph on the Alloys of Iron and Silicon, and the Tucker procedure was described in some detail in that publication.' In order to get silicon of still higher purity, a sample, prepared by the Becket method, analyzing 99.84 per cent Si, 0.020 Fe, 0.016 Al, 0.005 Ca, 0.025 C, 0.033 per cent 02, 0.006 H2, 0.006 N2, and 0.001 per cent Mn, was crushed to pass a 100-mesh sieve and further purified by a modification of Tucker's procedure. This modification differs from Tucker's method in that after treatment the 100-mesh alloy was centrifuged to remove the last traces of acid. Our directly determined analysis of this purified sample shows: Si, 99.952 per cent; Fe, 0.009; Al, 0.012; Ca, 0.003; C, 0.006; or 99.982 per cent. Silicon by difference equals 99.97 per cent. The variation between silicon by difference and silicon as directly determined is important. Although Tucker mentions the amount of insoluble matter in commercial silicon both before and after his treatment, he does not mention the existence of carbon in the alloy; nevertheless, he reports silicon by difference. Any final figure as to purity obviously results from agreement between direct determination and

Jan 1, 1940

By George H. Ashley

Mining, including quarrying, dates back almost to the dawn of history, beginning almost with the beginning of what we call civilization. State surveys date back about 100 years. Evidently mining flourished for thousands of years before state surveys were thought of. Why should it not continue to flourish without state surveys? First, it may be noted that as mining and civilization were contemporaneous, so state surveys and the science of geology were almost contemporaneous. As recently as 30 years ago the United States mineral laws were interpreted to mean that coal lands in the public domain were only those lands on which workable coal outcropped. The half billion acres of public land underlain by .coal but on which it did not outcrop were treated as homestead lands and open to settlement. Just what did the science of geology do to or for the mining industry? Until geology arose rocks or minerals or ores were where they were found. Their finding might be accidental, or might be the result of deliberate search or prospecting. In open, rocky country, with little or no vegetation, as in parts of the West, prospecting served very well, though at an enormous expenditure of human time and effort, if not money. The old saying that every dollar's worth of gold taken from the earth has cost two dollars may largely be charged to the time value of the usual method of prospecting. Geology changed all that. The science is still young and it still labors under handicaps of immaturity and early errors. Geology, however, has gradually been discovering the relations and conditions under which the several mineral deposits occur. Its elaborate studies of exhausted or nearly exhausted mineral deposits has done for it what human autopsy has done for medicine and surgery. Perhaps in no field is this plainer than in the oil and gas industry. Note might also be made of several important coal fields in England and on the Continent, in which the coal is everywhere deeply buried. Passing over the long period of growth during the past 100 years, geology today is prepared to offer the mining industry: first, a knowledge of the geologic conditions under which most minerals occur and to explore

Jan 1, 1935

By George Burgess

NOTE BY THE EDITOR.-This resume of a Technologic Paper which is published in full by the U. S. Bureau of Standards, is brought before the membership of the Institute with the object of affording an opportunity for the open discussion of results of an investigation by the authors named above, of some phases of the manufacture of steel rails which are of great importance to manufacturer and consumer alike. This resume will be presented at the Pittsburg Meeting of the Institute. Discussion is invited, by either members or non-members of the Institute. The discussion may be sent in writing to the Editor, in advance of the meeting, or should preferably be presented in person at the meeting. To those who desire to discuss, copy of the full Technologic Paper (No. 38), as published by the Bureau of Stanaards, will be sent upon request addressed either to the Bureau of Standards, Washington, D. C., or to the Editor, American Institute of Mining Engineers, 29 West 39th Street, New York, N. Y. Summary of Researches and Conclusions The main objects of this investigation were to determine, from measurements taken at representative rail mills, the present American practice regarding the temperatures at which rails are rolled; to demonstrate the ease and accuracy with which such temperatures may be measured, without interfering in any way with the manufacture of the product; to find out what the "shrinkage clause" in rail specifications really means; and, finally, to determine some of the physical properties of rail steels, particularly those of interest in manufacture, some of which seem to be insufficiently known as yet. 1. Ingot Temperatures.-Measurements made in four mills show that ingots for rails are rolled at temperatures ranging from 1,075° to 1,150° C. (1,965° to 2,100° F.), and that, in a series of 20 to 40 ingots, the variation in temperature from one ingot to another is only 10° to 20° C. 2. Finishing Temperatures.-Rails are finished at temperatures ranging broadly from 880° to-1,050° C. (1,615 to 1,922° F.), but usually ranging within 50° C. of 935° C., and occasionally above 1,100° C.

Jan 9, 1914

By Brian F. Dyson

The surface tensions at 1550°C of some Fe-S alloys (in the range 0.008 to 0.052 wt pct S), Fe-Sn alloys (0.31 to 48.4 wt pct Sn), Fe-P alloys (0.038 to 2.38 wt pct P), Fe-Cu alloys (2.15 to 22.8 wt pct Cu), and Fe-1 pct C-S alloys (0.005 to 0.076 wt pct S) along with the surface tension of the base iron have been measured by the sessile-drop method. A mean value of 1754 dynes per cm was found for the surface tension of the base iron. Sulfur was found to be highly surface-active, the surface-tension results being in quantitative agreement with existing data. Tin and copper were found to be less surface-active than sulfur while phosphoms was completely nonsurface-active. The surface tensions of Fe-1 pct C-S alloys were found to be lower than those of the Fe-S alloys containing the same sulfur content. This was shown to be a mmzifestation of the increase in the thermodynamic activity of suZfur by carbon. It is only in recent years that attempts have been made to measure the surface tension of liquid iron of known high purity.1-3 Earlier measurements4-7 were made on liquid iron containing variable amounts of what are now known to be surface -active solutes. The exact value of the surface tension of liquid iron is still, however, open to some doubt. Halden and Kingery' reported a value of 1720k 34 dynes per cm at 1570°C, Kozakevitch and Urbain8 gave 1790k 25 dynes per cm at 1550°C, while Van-Tszin-Tan et al. obtained a value of 1865k 37 dynes per cm at 1550°C. The first systematic investigation into the effect of controlled solute additions on the surface tension of iron was made by Halden and Kingery.' They showed that sulfur and oxygen were highly surface-active, whereas nitrogen was only slightly active, and carbon inactive. A subsequent investigation by Kingery indicated that two other group-6B elements, selenium and tellurium, were also surface-active. This highly surface-active nature of sulfur and oxygen has recently been substantiated by Kozakevitch and Urbainla and Van-Tszin-Tan et al. l1 Kozakevitch and Urbainl2 have also conducted an experimental survey of the effects of a number of metals on the surface tension of liquid iron. Their surface-active nature was, in all cases, less than that of the group 6B elements. The present investigation was undertaken to study in more detail the surface tensions of dilute Fe-S alloys and to measure the surface tensions of binary alloys of iron containing phosphorus, copper, and tin. The effect of sulfur additions on the surface tension of Fe-1 pct C alloys was also determined. EXPERIMENTAL PROCEDURE The sessile-drop method was employed in the present investigation. An apparatus was built similar in principle to that described by Humenik and Kingery.lS It consisted of a horizontal silica tube, which could be evacuated to pressures less than 10-5 torr, with its central portion surrounded by a water jacket within which was a high-frequency coil. This generated heat in a tantalum susceptor placed inside the silica tube, which in turn radiated heat to the specimen mounted on a recrystallized alumina plaque. Temperatures were measured by an optical pyrometer and photographs of the molten drop were taken on a fixed-focus plate camera giving a magnification of X2. Surface-tension values were determined from the resultant drop using the method described by Baes and Kellogg.l4 The high vapor pressure of molten iron made it necessary to conduct all the experiments under a 1/4 atm of argon (greater than 99.995 pct purity). The analysis of the base iron used in the investigation is given in Table I. Each sample was approximately 3 g in weight and had a hemispherical base to ensure a uniform advancing contact angle on melting. The iron alloys were prepared individually in the sessile-drop apparatus by drilling a hole in the top of each sample and adding the required amount of solute, the drops being analyzed after the experiment. This method of preparation had the advantage of ensuring a consistent minimal contamination by oxygen due to refractory attack and also allowed surface tension to be measured at the same time. Every precaution was taken to ensure that the specimen was not contaminated by grease when it was introduced into the apparatus, the samples being cleaned in acid, dried in alcohol, and rinsed in petroleum ether. All handling was done with tweezers. Once the specimen had been placed inside the susceptor, the furnace was evacuated and the Sample leveled. The furnace was then degassed at approximately 1000"C before the argon was introduced. In every case the surface tension was determined at 1550" C.

Jan 1, 1963

By S. S. Shen, M. J. Pool, P. J. Spencer

Heats of solution of silver and copper in dilute Ag-Cu-Sn alloys at 720°K have been determined using a liquid metal-solution calorieter. Values of the se2f-interaction coefficient n AgAghave been calculated at constant copper concentrations and n Cu Cuhas been determined at constant silver contents. The reliability of the experimental data is shown by the very good agreement between nCujAg and ij &$; these interaction coefficients have experimental values of -9100 and - 9590 cal per g-atom, respectively. Certain solution models are shown to be inadequate for prediction of solute interaction coefficients in dilute Ag-Cu-Sn alloys. In a previous publication' the results of a thermody-namic study of dilute Ag-Au-Sn alloys were presented. The present work represents the continuation of a program to investigate dilute alloys of the noble metals with tin and in particular is concerned with solute interactions in the Ag-Cu-Sn system. By determination of the magnitude and sign of the various interaction coefficients in dilute alloys it is possible to gain some understanding of the different types of solute-solute and so lute-solvent bonding changes that occur as the solute concentrations are varied. Hence systematic studies of alloys with similar physical characteristics as regards size, structure, electronegativity, and so forth, of their components can contribute a great deal to present theoretical knowledge of solutions. The recent definition of an enthalpy interaction coefficient, 11, by Lupis and Elliott2 is of particular value in calorimetric studies such as the present one: where j and i are solutes and s is the solvent; Si is the relative partial molar enthalpy of component i and x represents the mole fraction of solute or solvent. Values of ?Hi can be obtained directly by solution calorimetry and data for n are thus easily determined, often with a high degree of accuracy. ?Hi is related to the relative partial molar enthalpy at infinite dilution, ?Hi and to the enthalpy interaction coefficients by the expression: ?Hi?Hi + X;nz+ ... [2] The aim of the present work was to determine the self-interaction coefficients n AgAgand 178: in alloys of different compositions and also to establish values for n Agcg| and ncuAg. Since it is a thermodynamic requirement (resulting from the Maxwell-type relationships which can be applied to partial molar properties) that nAgcu and ncuAg should be equal, a further aim of this study was to demonstrate the agreement between experiment and theory. EXPERIMENTAL A description of the liquid metal-solution calorimeter used in this research has already been published,3 and no further details of its construction and operation will therefore be given here. Copper supplied by the American Smelting and Refining Co. was indicated by them as being 99.999 pct pure, and the silver obtained from A. D. Mackay, Inc., was also quoted as being 99.999 pct pure. A solvent bath consisting of between 70 and 80 g of 99.99 pct pure Sn was used for each series of experimental drops. Its weight was accurately determined and the appropriate amounts of copper or silver were added to give alloys of the desired composition. Approximately 0.00125 g-atom additions were used for determinations of the heat of solution of silver in the bath, while, for copper, specimens consisting of approximately 0.0015 g-atom were used. The heat capacity of the bath was determined at regular intervals during a series of drops using tin or tungsten calibration samples. The heats of solution of silver and copper in pure tin were first determined as a function of their concentration in order to establish the self-interaction coefficients 7AgAg and ncucu Alloys containing a constant 0.01, 0.02, 0.03, and 0.04 mole fraction of copper were then used to study 17:: in alloys of different copper content, while alloys of the same mole fractions of silver were used to determine equivalent data for 178: at constant silver concentrations. The composition of the bath was held at the desired copper or silver concentration by making calculated additions of the appropriate solute throughout the experiment. From the limiting values of ?HAg in the constant copper content alloys it was possible to study ?HAg as a function of xCu and hence to determine 42:. A similar analysis of the re, values permitted calculation of nAgcu. Heat content and heat capacity data from Hultgren et al* were used to calculate heat of solution values from the measured heat effects at the experimental temperature of 720°K. RESULTS AND DISCUSSION Determinations of ?HAg. A preliminary investigation of the heat of solution of silver in pure tin at 720°K was first made in order to establish the value of nAgAg before additions of copper were made and also to compare the value of ?HOAg(l) with that obtained in the previous study of Ag-Au-Sn alloys.' Then the heat of solution of silver in Cu-Sn alloys was investigated as a func-

Jan 1, 1970

By John C. Bilello

The brittle fracture behavior of cold-worked sintered tungsten was studied over the temperature range 4.2° to 298°K using a high-sensitivity strain measuring system and electronfractography. Similar observations were made on a swaged electron beam zone-refined monocrystal. In sintered tungsten irreversible plastic deformation was observed during cyclic load-unload tests at stress levels well below the fracture stress for all temperatures, but general microyielding could be detected only down to 202°K. For the zone-refined samples macroyielding occurred at all test temperatures with evidence for twinning below -202°K. The fracture stress of the sintered tmgsten was virtually independent of temperature, while the zone-refined crystal showed a 2.3 times increase over the same temperature range. Electronfractography confirmed the presence of numerous rod-shaped and spherical submicroscopic voids which ranged in diameter from 1400 to 4300A in the sintered tungsten; no voids could be found in the zone-refined tungsten. Contrast effects observed on the replicas in the vicinity of certain voids indicated that plastic deformation could be induced by the local stress concentration. It has been suggested that the presence of these voids may be responsible for the low-temperature brittle failure of sintered tungsten. Based m this suggestim und on the evidence obtained here, a dislocatim model is presented to account for the brittle behavior of sintered tungsten. In this model slip, which is induced by the local high stress concentration in the region at the edge of a favorably oriented void, could cause the void to grow to a microcrack of critical size. STUDIES of brittle fracture in bcc metals have led to the well-known experimental relationships between grain size, yield stress, fracture stress, and temperature which have formed the basis for the various dislocation pile-up1-3 or interaction4'= models for slip-induced microcrack nucleation. While microcracks can be nucleated by deformation twins,6,7 there has been no direct evidence furnished by transmission electron microscopy to support conclusively either the Zener pile-up or Cottrell dislocation reaction models for producing micro-cracks in all "brittle" materials. In addition to the "inverse" grain size relationship for yield and fracture stresses the cottrel14 theory predicts that the fracture stress below the transition temperature should behave in a fashion similar to that of the yield stress above this temperature. Such behavior has been verified for several bcc metals.8-10 With reference to both grain size effects and the tem- perature dependence of the fracture stress below the transition temperature, the behavior of sintered tungsten appears anomalous. Early work by Bechtold and Shewrnon 11 showed no apparent temperature dependence of the fracture stress below the ductile-brittle transition temperature (DBTT). They attributed this result to the intergranular nature of the fractures observed. More recent work by Wronski and Four-deux12'13 on considerably purer material did not show any systematic relationship between the fracture stress and temperature below DBTT. The dependence of flow and fracture stresses on grain size is also not clearly established for sintered tungsten. Koo, for example, has shown that the DBTT for sintered tungsten depended chiefly on the annealing temperature and was relatively insensitive to the actual grain size achieved. Using electrofractography and transmission electron microscopy, Wronski and Fourdeuxl3 showed that numerous spherical and rod-shaped submicroscopic voids could be found in sintered tungsten but not in melted tungsten of nominally the same purity. They suggested that these voids could be responsible for the temperature insensitivity of the fracture stress below the DBTT. In the present work the temperature dependence of the fracture stress for high-purity commercially sintered tungsten has been determined. The presence of submicroscopic voids in sintered materials was confirmed, and these were studied in detail to examine the role they could play in nucleating brittle fracture. A dislocation model is suggested which could cause an inherent spherical void to lengthen into a Griffith crack of critical size. EXPERIMENTAL PROCEDURE Commercially sintered tungsten rod was obtained in the as-swaged condition from Sylvania. A zone-refined crystal was obtained from the same source. This crystal was grown by giving three zone passes (at 25.4 cm per hr) to a sintered rod of high-purity tungsten. The rod axis prior to cold working was -15 deg from the [110] direction. Originally the zone-refined rod was -6 mm in diam; it was reduced to -3 mm by eight swaging passes, at high temperatures, with each step having about the same reduction of area. The final swaging step gave a 7.5 pct reduction of area at 1050°C. All swaging operations were performed in a hydrogen atmosphere. For the sintered rod a similar working schedule was employed. Metal-lographic examination of the sintered material revealed that the cold-worked structure had an apparent grain diameter of -25 u transverse to the swaging direction (obtained by the intercept method). In the longitudinal direction cold-worked grains were approximately 1.5 to 2 times their diameter. No distinct fiber structure could be observed optically for the zone-refined rod. The cold-worked structure in the

Jan 1, 1969

By A. E. Jenkins, O. C. Roberts, D. G. C. Robertson

Using an inverted-cone coil at 450 kHz, it has been possible to levitate iron (FeS), cobalt (CoS), and nickel (NiS) sulfides. Important nontransition metal sulfides such as ZnS, PbS, and Cu2S have proven impossible to levitate although Cu-Fe-S ternary alloys containing 30 wt pct S and up to 10 wt pct Cu, and Cu-Co-S and Cu-Ni-S ternary alloys containing 30 wt pct Cu have been levitated. The levitation technique has been used in preliminary experiments on the vaporization from liquid sulfides and the reaction of liquid metal-sulfur alloys with oxidizing atmospheres. The course of the reactions with pure oxygen were followed using highspeed photography and two-color pyrometry. ELECTROMAGNETIC levitation is now established as a basic laboratory technique in high-temperature research but its application has been restricted mainly to metals and alloys. Applications have included alloy preparation,' metal purification,2'3 determination of liquid metal densities and emissivities,4,5 and studies of metal supercooling,4 alloy thermodynamics,6 and vaporization phenomena.7-9 The application of the technique to compounds has not been considered previously. The successful investigation of the reactions between dilute iron alloys and oxidizing atmospheres10'1 has prompted the current physico-chemical studies involving levitated metal sulfide drops and flowing inert or oxidizing atmospheres. This paper presents the results of such a study and provides a basis for future studies involving a wide range of other compounds of metallurgical interest. The successful levitation of many metal sulfides and mattes provides a method of studying the oxidation reactions fundamental to flash-smelting and similar pyrometallurgi-cal operations under closely controlled laboratory conditions. In addition the system allows the use of a controlled atmosphere (e.g., a gas stream of a certain H2/H2S ratio) with a particular chemical potential to study the relevant thermodynamic equilibria or the mass transfer processes between the atmosphere and the levitated drop under conditions where the hydrodynamics of the system can be closely defined. The optimum frequency for the levitation melting of metals in an inverted-cone coil type inductor is within the radio frequency range 400 to 500 kHz. At frequencies lower than 10 kHz the rate of heat generation is usually insufficient to melt the levitated charge' or where melting is achieved, "dripping" from the charge is encountered.'' At frequencies above 2 mHz the levitation force decreases. Metals, alloys and preheated elemental semiconductors such as germanium and silicon, have been levitated but the levitation of only a few metal compounds has been reported. Jostsons13 and the authors have levitated liquid titanium-oxygen alloys containing 50 at. pct 0 while clark14 has reported the levitation of mixtures of FeS and MnS for short periods. With a "cold crucible" inductor sterling15 has melted ferrites by preheating them by induction in a 4 mHz field and melting at a lower frequency. However this second type of inductor has been designed purely for the melting of materials without contamination; there is only a small gas film between the charge and the inductor and the electromagnetic levitation effect is of secondary importance. For this reason further discussion will be restricted to the use of the coil type inductor. The assessment of the suitability of a particular metal compound for levitation is based upon the following two criteria: i) thermal stability, and ii) physical "levitability". In this paper these two criteria will be considered separately. The thermal stability of a solid or liquid metal compound with respect to a gaseous environment depends upon its chemical reactivity with that environment or, in the case of an inert atmosphere considered here, its volatility. The physical criterion as to whether or not a particular compound can be levitated is based upon a comparison between those physical properties of the compound determining "levitability" which are defined by the fundamental equations of levitation theory as developed by Okress et a1.,16 and the properties of the metals. Since it is not practical to cover the vast field of metal compounds, further discussion will concentrate on the metal sulfides but the treatment would be applicable to any metal compound. THE THERMAL STABILITY OF METAL SULFIDES The temperatures usually encountered during levitation in inert atmospheres cover the range 1400" to 2000°C. The stabilities of the condensed states of the sulfides under these conditions are considered in relation to the periodic classification by reference to Table I. Two general classes of sulfides emerge. The solid sulfides of elements of group IIB and of groups further to the right are volatile while those sulfides of group IB and of groups further to the left are nonvolatile solids. The sulfides described as volatile may be dismissed as unsuitable for levitation. The stabilities of the more favorable nonvolatile sulfides under the anticipated conditions must be studied more closely From Table I it is seen that the alkali metal sulfides exist as liquids in the temperature range of in-

Jan 1, 1970

By H. H. Kellogg

Equations representing the standard free energy of formation as a function of temperature, for thirty metallic chlorides, are presented and plotted on a free-energy vs. temperature diagram. The use of these data for calculations on reduction of metallic chlorides, refining of metals with chlorine, and chlorination of metallic oxides and sulphides is illustrated. CHLORINE metallurgy' has attracted metallur- gists for more than a century because the unusual properties of the metallic chlorides—low melting point, high volatility, and ease of formation from the oxides—make possible many useful extractive processes. Interest in chlorine processes is undergoing a renaissance due to present availability of chlorine at relatively low prices, and to recent advances in technology. During the present century there have accumulated a considerable number of reliable values of the thermodynamic constants for the metals and their chlorides. These data permit the calculation of free-energy equations for many metallurgically important reactions. Consideration of free-energy values makes possible certain predictions of the direction and extent of a given reaction, as well as the effect of temperature, pressure, and composition upon the result. Reaction rate, although not predictable from free-energy data, is usually sufficiently great at elevated temperatures that diffusion of the reactants and products to and from the zone of reaction determines the actual rate. Thus, if the free-energy indication is favorable, the chances are good that a high temperature metallurgical reaction will proceed at a reasonable rate, if adequate provision for rapid diffusion has been made. This paper presents standard free-energy equations for a number of metallic chlorides, based on data which are scattered throughout the literature. The equations are presented in a form that simplifies their use, and typical examples are given of the application of free-energy data to metallurgical processes. Free Energy of Reaction The free-energy change (AG) of a reaction is the true measure of the "driving force" of the reaction under a given set of conditions, and this is related to the standard free-energy change (AGO) of the reaction as follows: For the reaction: bB + cC = dD + eE ?G = ?G°+RTln ADd. AEA / ABb. ACc where A, = activity of constituent (i) T = absolute temperature, OK R = gas constant The criterion of a spontaneous reaction from left to right, at constant temperature and pressure, is a negative value for the free-energy change (?G). The standard free energy of the reaction is equal to the free energy of the reaction when all the reactants and products are at unit activity, since under these conditions the second term on the right-hand side of eq 1 is equal to zero. The concept of activity is treated fully in many textbooks on chemical thermodynamics1 and in a recent article by Chipman.2 Briefly, the activity (A,) of a constituent (i) is a measure of the reactivity of this constituent relative to its reactivity in some arbitrary standard state. For liquids and solids the standard state most often used is the pure liquid or solid constituent. Thus the activity of a pure liquid or solid in a metallurgical reaction is equal to unity. Gases under moderate pressure and at elevated temperatures behave very nearly as 'idea1 gases,' and the standard state is chosen as the gas at 1 atm pressure. The activity of an ideal gas is therefore equal to its partial pressure, and this relation is sufficiently exact for real gases in most metallurgical reactions. For a liquid or solid solution there is in general no simple way to express the activity of a constituent as a function of its concentration, and activity must be determined by experiment. A few solutions follow a so-called 'ideal' behavior, and if the pure constituent is chosen as the standard state, the activity of a constituent in an ideal solution becomes equal to its mol fraction. When a reaction reaches a state of thermodynamic equilibrium at constant temperature and pressure, AG becomes equal to zero and eq 1 reduces to: [ADd . AEe ?G°=RTln Abb ¦ Ac c equilibrium [2] The brackets surrounding the activity term are used to emphasize that each of the activities is an activity under equilibrium conditions—not just any arbitrarily assigned value. The bracketed term is the equilibrium constant (K) of the reaction. Eq 2 makes possible the calculation of equilibrium activities for a given reaction, if AGO is known at the desired temperature. The standard free-energy equations presented in this paper were calculated from the fundamental thermodynamic values of enthalpy of formation at 298°K (AH°,), standard entropy at 298°K (So298), heat capacity as a function of temperature (Cp), and enthalpies of transition, fusion, vaporization, and sublimation for the various constituents. Where possible the data reported in the recent "Selected Values of Chemical Thermodynamic Properties," published by the Bureau of Standards," were used. A large number of data came from the publications

Jan 1, 1951

By N. A. Gokcen, J. Chipman

Aluminum and oxygen dissolved in liquid iron were brought into equilibrium with pure alumina crucibles and atmospheres of known H2O and H2 contents to study the reactions: 1—Al2O3(s) = 2 Al + 3 0; 2—Al2o3(s) + 3H2(g) = 2Al+ 3H2o(g); and 3—H2(9) +O = H2O(g). Aluminum strongly reduces the activity coefficient of oxygen and similarly oxygen reduces that of aluminum. Values of the product [% All" • [% O]3 are much smaller than those found in previous experimental studies and are of the order of magnitude of the calculated values. ALUMINUM is the strongest deoxidizer commonly A used in steelmaking, but the extent to which it removes dissolved oxygen has been debatable. The relationship between aluminum and oxygen has not been determined reliably not only on account of the usual experimental difficulties at high temperatures but also because of uncertainties in the analyses of very small concentrations of oxygen and aluminum. The earliest experimental attempt of Herty and coworkers' was followed by a more systematic study of Wentrup and Hieber.' These authors added aluminum to liquid iron of high oxygen content in an induction furnace and considered that 10 min was sufficient to remove the deoxidation products from the melt. Parts of the melts thus obtained were poured into a copper mold and analyzed for total aluminum and oxygen (soluble plus insoluble forms), assuming that the insoluble parts were in solution at the temperatures from which samples were taken. It is conceivable that the furnace atmosphere in their experiments, consisting of mainly air at 20 mm Hg pressure, was a serious source of continuous oxidation and therefore that their oxygen concentrations were correspondingly high. Scattering of their data was explained to be well within the maximum inaccuracy of 10°C in the temperature measurements and errors of ±0.002 pct each in the oxygen and total aluminum analyses. Maximum and minimum deoxidation values, i.e., values of the product [% All' . [% O] differed by factors of 10 to 15; mean values of 9x10-11 and 7.5x10-9 ere reported at 1600" and 1700°C, respectively. Hilty and Craftsv determined the solubility of oxygen in liquid iron containing aluminum, using a rotating induction furnace. Pure alumina crucibles used in their experiments contained the liquid iron which in turn acted as a container for slags of varying compositions consisting mainly of Al2O3, Fe2O3, and FeO. The furnace was continuously flushed with argon, and additions of aluminum and Fe2O3 were made in the course of each experimental heat. The inner surfaces of their alumina crucibles were covered with a substance other than pure Al2O3, containing both iron oxide and alumina. Although frequent slag additions can change the composition of slag in the liquid iron cup formed by rotation, the inner surface of the crucible must depend upon the transfer of oxygen or aluminum through the liquid iron for any adjustment in composition. It is not clear that their metal was in equilibrium with the crucible wall, but it is clear that it was not in equilibrium with Al2O3. Their deoxidation product, [% A].]" • [% O]3, varied by a factor of more than 50; the average values of 2.8x10- and 1.0x10-7 were selected for temperatures of 1600" and 1700°C, respectively. Aside from the experimental determinations, attempts have been made to calculate the deoxidation constant for aluminum indirectly from thermody-namic data. Schenck4 combined the thermodynamic data for Al2O3 and dissolved oxygen in liquid iron by assuming an ideal solution. His calculated values are 2.0x10-15 and 3.2x10-13 at 1600" and 1700°C, respectively. Later, Chipman5 attempted to correct for the deviation from ideality and derived an expression which led to deoxidation values of 2.0x10-14 and 1.1x10-12 at 1600" and 1700°C, respectively. The errors in these treatments originate mainly from inaccuracies of thermal data and uncertainties regarding the activity coefficients of dissolved oxygen and aluminum. The purpose of this investigation was to study the equilibria represented in the following reactions in the presence of pure alumina: Al2O3(s) = 2Al + 3O K = aAl2.ao3 [1] Al2O3(s) + 3H2(g) = 2Al + 3H2O(g) H2O K2 = aAl2(H2O/H2 ) [2] H2(g) +O = H2O(g) K3 = 1/ao (H2) [3] The experimental method consisted of melting pure electrolytic iron, usually with an initial charge of aluminum, in pure dense alumina crucibles under a controlled atmosphere of H,O and H2 and holding

Jan 1, 1954

By C. S. Harloff, Frank R. Corwin

THE Nichols Copper Co., associated with the Phelps Dodge Corp. and the Calumet & Arizona Mining Co., has constructed at El Paso, Tex., and is now operating a copper refinery with a yearly capacity of 100,000 tons of anodes. Transportation facilities were perhaps the most important of the considerations that led to the selection of this site. The rapid industrial development of the Middle and Far West has increased the consumption of copper there. The advantage of local refining as against shipping the copper to the Atlantic sea- board is apparent. Copper refined in the Southwest is equally competitive for export shipment, either from the Gulf or the Pacific Coast ports. The tonnage of copper produced in the Southwest not only justifies the construction of this plant, but may warrant considerable expansion in years to come.

Jan 1, 1930

By Walter Miller

NOW, after a year's continued impact of war, the task of the petroleum-refining industry stands out clearly and looms up in larger aspect. This time it is not, as it was so largely in the first World War, simply a matter of increased quantity- more and more of the same petroleum products that had substantially been standard for years. In this era the emphasis is largely on newer and improved materials which had been produced, if at all, in comparatively insignificant quantities, and for which manufacturing equipment was not available on a large scale. At the beginning of 1942 four great product needs (besides a number of lesser one-) confronted the industry: 100-octane aviation gasoline, toluene for T.N.T. production, high-quality lubricating oils for aviation and Army equipment service, and petroleum chemicals for synthetic rubber manufacture.

Jan 1, 1943

At Black Lake, Quebec, Lake Asbestos of Quebec Ltd., a wholly-owned subsidiary of American Smelting and Refining Co., has opened a $36-million mining and milling operation which will produce about 100,000 tons of asbestos fiber a year and add 7 pct to the Free World's supply. The orebody once lay beneath Black Lake, and readying the ore deposit for open pit mining meant removing about 37 million cu yd of overburden- 30 million cu yd by dredging and pumping, and 7 million by power shovels and trucks. The enormous amount of material to be dredged, control of drainage during dredging, the need to cope with drainage problems in the area and to provide for flood control to replace the regulating effect of the lake, posed unusual engineering challenges and required tremendous capital investment.

Jan 1, 1959