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By Charles W. Merrill

IF we follow the threads of the mining problems, upon which I have touched, we find them all leading to one great fundamental desideratum. The people of this State, of this Nation, and of this world must be brought to a better understanding of the basic nature of our industry-must be made more mineral-minded. It is my belief 'that there is not a man present among this earnest gathering of those interested in the mining industry, who has not a deep-seated and heartfelt desire that the existing unprecedented welfare and prosperity of the whole mass of American people be maintained not merely through our own generation but through the generations of our children and their children. In the decades to come there can be no question of the keenness of the foreign competition which we are doomed to meet, and in this great international contest that Nation which has the best balanced program of development and that broadness of vision in its governmental direction, which recognizes the necessity of a sympathetic attitude toward the upbuilding of such a broad pro- gram will be the Nation which will maintain and pre- serve that welfare of all of its people.

Jan 1, 1929

By F. D. Rosi, C. H. Mathews

THE plastic properties of face-centered cubic metals below room temperature present a field of investigation which has not been extensively ex-plored. The work by Schmid and Boas1 has demonstrated the importance of temperature upon such properties as strain hardening and critical resolved shear stress. The work by Yamaguchi2 upon the shear stress as related to the number of slip bands accentuates the necessity for further experiments of a similar nature. The approach to a mechanical equation of state from the standpoint of thermal fluctuations and activation energies by Becker3 and more recently by Kauzmann4 further emphasizes the need for a quantitative and more comprehensive analysis of the dependence of fundamental plastic properties on temperature. The purpose of the present work was to investigate specifically: (1) The gross shape of the stress-strain curves at several temperatures, (2) the change in the critical shear stress as a function of temperature, and (3) the number and appearance of slip bands as a function of strain and temperature. Preparation of Specimens Single-crystal specimens of 99.996+ pct alumi-num, 1/2 in. in diam and 5 to 6 in. in length, were made by the Bridgman method of gradual solidification from the liquid state. The crystallographic orientation of the single crystals was determined from back-reflection, Laue X-ray photograms ac-cording to the method described by Greninger.6 In most specimens the Laue photograms showed double diffraction spots indicative of the lineage structure type of imperfection, discussed in great detail by Buerger.7 The angular spread of these spots was never observed to exceed 2". Most of the crystals were radiographed to insure against microporosity. In preparing the metal surface for optical microscopy, the following sequence of operations gave good results: The as-cast crystals were turned down in a lathe, 0.001 in. per cut, to obtain a 2.5 in. gauge length. The cold-worked layer resulting from this operation was removed chemically by etching with Tucker's reagent. Then the specimen was polished mechanically through 2/0 metallographic emery paper, after which it was etched again to remove the cold-worked layer resulting from the mechanical treatment. A 48-hr anneal at 580°C ±10°C followed so as to insure an essentially stress-free single crystal. After the annealing treatment, the specimen was electrolytically polished in a 2:l solution of methyl alcohol and concentrated nitric acid. With a current density of 10 amp per sq dm (decimeter) the time required to obtain a satisfactory surface varied from 10 to 12 min. The polish-ing was carried out for short periods of 2 min to avoid rapid deterioration of the solution as well as to enable the rotation of the specimen 180" for uniformity of polish. It was necessary to place the solution in a bath of dry ice in view of its explosive nature at room temperature. Etching of the electrolytically polished surface was accomplished by using the fuming etch-pit method recommended by Lacombe and Beaujard8 for high-purity aluminum. Method for Tensile Testing A modification of the loading equipment devised by Miller9 was used. In this apparatus, the specimen was suspended from a chain and gimbal arrangement (for axial loading) in a heavy steel framework connected at the bottom to a balanced 6:1 lever and bucket system. Loading of the specimen was accomplished by allowing sand to flow from a reservoir into the bucket suspended from the longer end of the lever-arm at a rate of approximately 3 lb per min. Strain measurements were made using the Baldwin SR-4, bonded, resistance-wire, strain gauge and an SR-4 portable strain indicator (type K), which permits a reading accuracy of 2 microinches per inch. For low-temperature study, the gauge was calibrated by measuring the elastic modulus of an annealed stainless steel rod, which is known to be independent of temperature."

Jan 1, 1951

By Douglas J. Harvey

The surface tension of lead-tellurium alloys (in the range 0 to 6.70 at. pct Te) ad lead-arsenic alloys (in the range 0 to 10.53 at. pct As) has been examined by the maximum bubble pressure method. The surface tension of high purity lead can be expressed over a range of temperatures (M.P. to 750°C) by the relationship = 512 — 0.133t. Arsenic and lellurium were both found to be surface active in lead. The surface excess concentration at 700°C was .found to be constant at 0.74 x 10-10 moles per sq cm for tellurium. The surface excess of arsenic at 700°C varied between 0.26 x 10-10 moles per sq cm at 0.16 at. pct to 1.5 x 10-10 moles per sq cm at 8.3 at. pet. The surface tension of lead has been investigated sporadically over the last 90 years. The first recorded study was made by Quincke1 who used a rather crude application of the drop-weight method. Hogness2 obtained the first reliable value for the surface tension of lead by measuring the pressure necessary to force the liquid metal from the end of a small capillary of known radius. Hogness gives the empirical formula: ?(surface tension)= 444 - 0.077 (l-327) which describes the relationship between surface tension and temperature ("C); This work was followed by that of Bircumshaw3 who applied the two-capillar maximum bubble pressure method of Sugden.4 The values published by Bircumshaw are in good agreement with those found by Hogness. Matuyama5 examined the surface tension of lead by the drop weight method. However, the values found are somewhat higher than those previously reported. More recent investigations by Greenaway6 and by Melford and oar' have resulted in data which are not in close agreement, but which are well within the expected range at most temperature levels. The study of the surface tension of lead alloys began with Drath and sauerwald8 who examined the lead-bismuth system. They found that the surface tension values of the alloys in this system deviated only slightly from the ideal mixture rule. Matuyarna5 examined the lead-antimony system. Bircumshaw the lead-tin, and the lead-indium system was studied by Hoar and Me1ford.10 The results of these investi- gations are summarized in Fig. 1. It may be seen that the data vary only slightly from the ideal mixture rule. As none of the metals studied and reported in the literature has a very interesting effect on the surface tension of lead,*the next logical step might be to examine the effect of metals of low solubility or nonmetals having some liquid solubility. Baes, and Kellogg11 have pointed out that the elements most likely to be surface active in liquid metals are ones of limited solubility in the liquid state and possessing weak intermolecular bonding forces in the solid state. Therefore, Group V, VI and VII nonmetals are most likely to be surface active. It was decided to examine the effect of a borderline metal, arsenic, and a nonmetal tellurium. Arsenic forms a eutectic with lead having a melting point of 290°C and a composition of 6.9 at. pct As.13 Pure arsenic sublimes when heated above 610°C. Even though alloying with lead lowers the vapor pressure, fumes containing arsenic are evolved at a very noticeable rate when lead-arsenic alloys are heated above 650°C. Tellurium raises the liquidus temperature of lead sharply to 904°C,14 the melting point of PbTe (lead-telluride). The solid solubility of tellurium in lead was determined by Greenwood and worner15 to be 0.0007 at. pct at room temperature. EXPERIMENTAL METHOD Surface Tension Measurement—The two capillary maximum bubble pressure method for measuring surface tension developed by Sugden,4 and used later

Jan 1, 1962

By E. R. Macgregor, J. Halpern

The kinetics of the reduction of cupric salts in aqueous solution by molecular hydrogen to metallic copper are described. The rate of reduction appears to be homogeneously determined and shows a marked inverse dependence on the hydrogen-ion concentration. Precipitation of copper is more rapid and complete in sulfate than in per-chlorate solution. A mechanism is proposed which accounts for this behavior. IN recent years a number of important hydro-metallurgical processes have been developed in which metallic salts in aqueous solution are reduced by gaseous hydrogen, usually at elevated temperatures and pressures, and thereby precipitated either in metallic form (e.g. Ni, Co, Cu) or as an oxide or salt of lower valence (e.g. VO, and VA).1 ; In connection with applications such as these, most of which involve heterogeneously catalyzed reactions, recent demonstrations"-" that salts of certain metals, e.g., Cu", Ag' , Hg" , and Hg,+ can activate molecular hydrogen homogeneously and thus catalyze hydrogenation reactions in aqueous solution, are of considerable interest. For example, cupric salts catalyze the otherwise slow homogeneous reduction of dichromate and ceric salts by hydrogen, i.e. Cr,O; + 3HL. + 8H1 ? 2Cr'- -- 7H,O [1] 2Ce ' ! H.. ? 2Ce" | 2H . [2] In perchloric-acid solution, where Cu" is not appreciably complexed, the kinetics have been found" " to be of the form -d [H,] _- k,[HJ [CU"]' dt -LCu+' l+ (k ,/k,) [H] [3] where, K = 1x10"' exp [—26,600/RT] 1, mole-' min-' ... [4] and (k ,/k,) - 0.25 at 110°C. This kinetic behavior suggests that the reaction proceeds by a mechanism involving the following sequence of steps kt Cu" +H1CuH' 4-HA [51 k., CUH + CU" ? + 2Cu f H' [GI 6Cu'+ Cr,07 + 14H'+ 2Cr- (¦ 7H,O + 6Cu" ['i] fast The catalytic activities of the undissociated cupric-sulphate and cupric-acetate complexes are somewhat greater (by factors of 6.5 and 120, respectively) than that of the simple hydrated Cu" ion.'" These considerations suggest that, in contrast to the other hydrometallurgical hydrogenation reactions, referred to previously, reduction of cupric salts in aqueous solutions by molecular hydrogen, should proceed homogeneously, and in the absence of an extraneous catalyst. This has already been demonstrated" for acetate-buffered solutions where the product of the reaction is a precipitate of cuprous oxide (Cu,O). In the present paper, an investigation of the reduction of cupric salts in perchloric-acid and sulphuric-acid solutions, leading to the precipitation of metallic copper, is described. Some results for the sulphate system, which is of considerable hydrometallurgical interest, have been reported previously by Ipatieff",' " and by Schaufel-berger' but these do not give a quantitative account, of the kinetics and mechanism of the reaction. Experimental The reduction experiments were conducted in the 1-gal, titanium-lined autoclave described in connection with earlier related investigations," " and using a similar procedure. The solutions were made up by dissolving known amounts of CP grade Cu(ClO,), and HC10, (or CuSO, and HISO,) in dis-tilled water. While in the autoclave, the solution was stirred and maintained at a constant temperature (±loc) and under a constant partial pressure of hydrogen gas. It was ascertained that the agitation (provided by two 3-in., four-bladed stirrers, rotating at 900 rpm) was adequate so that at no time was the rate of reaction limited by solution of hydrogen. During each experiment, samples of the solution were withdrawn periodically, allowed to cool, and the concentration of copper remaining in solution was then determined electrolytically. Some Cu' is formed during the reaction, but undergoes disproportionation when the solution is cooled to room temperature. For purposes of kinetic calcula-

Jan 1, 1959

BOSTON LOCAL SECTION Executive Committee HENRY L. SMYTH, Chairman ALFRED C. LANE, Vice-Chairman AUGUSTUS H. EUSTIS, Secretary-Treasurer, 131 State St., Boston, Mass. ROBERT H. RICHARDS ALBERT SAUVEUR Meets on the first Monday evening of each winter month Twenty-first Meeting The Twenty-first meeting of the Boston. Local Section of the Institute was held at the Engineers' Club, 2 Comonwealth Avenue, Boston, Monday evening, Oct. 5, 1914. Twenty members and two guests were present. The Chairman, Henry L. Smyth, presided at the dinner, at the close of which he introduced, as the speaker of the evening, John M. Longyear, who gave a most interesting talk about his work in exploring for coal on the islands of Spitzbergen, 400 miles north of the North Cape of Norway. The talk was illustrated with many photographs, which showed clearly the nature of the work and the extraordinary difficulties of the location. AUGUSTUS H. EUSTIS, Secretary.

Jan 12, 1914

By I. N. Knapp

Foreword I HEREWITH present some notes on the use of Portland cement to cement in the casing, and for plugging, to exclude water from oil and gas wells, and the methods employed. I have used my best efforts to make each step of the operation of cementing wells perfectly clear. The information is the result of actual experience and observation. The illustrations are from original drawings made especially for this paper. Portland Cement It is not necessary to discuss here the manufacture of cement. Any established brand of the slower setting Portland cements may be purchased with the confidence that it will harden, if properly used, and exclude water from and plug wells efficiently. Setting.-By the setting of cement is meant its initial change from a soft or plastic mortar to a friable solid. After the cement has become thoroughly set it is still very weak and can be readily pulverized in the fingers. Setting is thought to be effected by the crystallizing out of the silicate and the aluminate of lime, which are soluble in water in their anhydrous form. After dissolving in the water they pass to the hydrated state, in which they are insoluble, and hence are precipitated in a crystalline form.

Jan 3, 1914

By R. P. Smith

Iron-carbon alloys containing a single-phase austenite region and a two-phase azcstenite + cementite region at the desired temperature were prepared by partial carburization of iron or partial decarburization of carburized iron. Each sample was held at a fixed temperature until equilibrium was achieved. Analysis of the austenite for carbon then gave the solubility of cementite in austenite. Solubility measzcrements were made for the temperature range 734° to 1012°C. These values together with other data give 7560 cal for the mean heat of solution of cementite in austenite, and 0.765 pct C for the eutectoid composition of austenite. They also indicate that graphite is the stable phase at all temperatures between the eutectoid and eutectic temperature. Measurements of the solubility of cementite in austenite at 927oand 1011 "C, using a method based on the equilibration of iron with boro-cementites, are reported. The solubility of cementite in austenite (?-iron) has been computed by Darken and Gurry1 from the observed solubility of graphite in austenite, and the thermodynamic properties of pure iron and of iron-carbon alloys. They have shown that the solubility of cementite is greater than that of graphite in the temperature range between the eutectoid and eutectic, and thus that cementite is metastable with respect to graphite and austenite saturated therewith. Since their computation is not in accord with the earlier experimental work of Mehl and wells,' the present direct determination of the solubility of cementite in austenite was undertaken. EXPERIMENTAL PROCEDURE Each iron rod about 1/2 in. O.D. by 4 in. was first carburized at a temperature and with a H2-CH4 gas mixture such that the carbon content would be greater than that corresponding to the solubility of cementite in austenite at the desired (lower) temperature; sufficient carburizing time was allowed that the carbon content became substantially uniform, as illustrated by Curve A, Fig. 1. The sample was then partially decarburized with a hydrogen-water vapor mixture, giving a carbon distribution as schematically illustrated by Curve B. The sample was then held in a helium atmosphere at the temperature at which the solubility was to be determined until the decarburized portion of the sample came to equilibrium with that containing cementite. Curve C of Fig. 1 represents schematically the final carbon distribution; the horizontal portion corresponds to the carbon content of austenite saturated with cementite. To bring the sample to room temperature without change in the carbon distribution and in machinable condition, it was first quenched in a salt pot at 480°C, then in water at room temperature. Successive layers were machined from the center 2 in. of the sample and analyzed for carbon by the usual

Jan 1, 1960

ARTHUR KNAPP, Ardmore, Pa. (communication to the Secretary*). -The author has failed to consider the point which in my mind is the most convincing in advocating some sort of a bureau for the collection of well logs. I venture to say that 90 per cent. of the logs as taken today are absolutely worthless to any one but the one who has taken the log. This is largely due to the careless use of nomenclature. The author says on page 289, "He must ascertain which of the many factors might account for the dry hole in question and often only careful examination of well logs will convey this information." I believe that even a most careful examination of the average log reveals nothing. I have at hand a book on petroleum, by a well-known author. This book has a number of logs from fields all over the world, from which I shall illustrate. In a well log from Kansas I find "Soft gray shale" and in one from Humble I find "Hard blue shale." As a matter of fact the shale from Humble is softer than the shale from the Kansas well. The difference is that the drillers in Kansas, being used to limestone and

Jan 5, 1917

By C. F. Tolman

Discussion of the paper of C. F. TOLMAN, JR., presented at the New York meeting, February, 1916, and printed in Bulletin No. 110, February, 1916, pp. 401 to 433. Louis C. GRATON, Cambridge, Mass.-Of particular interest at this time is any paper that deals with chalcocite, the characteristic product of secondary enrichment and the copper mineral of greatest commercial importance, and that seeks to aid in the distinction between primary and secondary chalcocite-a distinction of much scientific and practical importance but one which thus far it has proved difficult to draw. The present paper on this subject by Professor Tolman, like the ,many preceding it which he and his colleagues at Stanford have published in the last couple of years, contains much of interest and suggestiveness. Without endeavoring at this time to review or comment upon Professor Tolman's conclusions in detail, I may say that many of them are in accord with the findings that my associates and I have been accumulating in the course of studying secondary enrichment in many of the copper deposits of the country. On the other hand, it goes without saying that in this comparatively new field of research or, at least, a field in which

Jan 5, 1916

By Frederick Sharpless

THE term "segregation," as here used, means the separation of certain natural resources into groups, consisting of one or more members, with the idea that when thus segregated, each group may be more easily and effectively administrated. We may, for example, consider surface rights as distinct from underground rights, and stop there; or we may go further, and deal separately with timber, water, and agricultural rights, or, going underground, we might deal separately with such groups as precious and base metals, clay, oil, gas, etc. The present paper contemplates only the separation so far as practicable, for administrative purposes, of surface from mineral rights. "Classification," in this paper, has reference to the groups into which the government has divided, is dividing, or will hereafter divide its natural resources; first, into the broad classes of mineral and agricultural lands; and, second, into coal, oil, phosphate, brine lands, etc., the central idea being the separation into natural groups for the purpose of simplifying administration and for the purpose of encouraging maximum development and minimum waste. The two subjects are in some respects quite distinct, but as my argument develops, I think it will be obvious why they are discussed in the same paper.

Jan 4, 1914

By W. L. Dudley

It is my desire to call attention to a new industry which was started about four years ago, through the discovery by Mr. John Holland, a resident of this city, of the methods employed in working the metal iridium. This metal has been known since the year 1803, having been discovered by Smithson Tennant while investigating the metallic residue which remained when platinum ores were dissolved in aqua regia. The metal is classed among the rare metals, as it is not found in large quantities, although it is quite widely distributed geographically. It is found in California, Oregon, Russia, East India, Borneo, South America, Canada, Australia, and in certain parts of France, Germany, and Spain. The principal sources of supply of the metal are Russia and California; it is nearly always found with either platinum or gold, is extracted from those ores as a by-product, and is always found in small grains or fine powder, the largest pieces being about the size of a grain of rice. In nature it is generally alloyed with other metals, and the two metals with which it is most commonly alloyed are platinum and osmium; the platinum alloy is called platin-iridium, and the osmium alloy osmiridium, or iridosmine. The grains of platin-iridium are

Jan 1, 1884

By W. B. Mather

R. G. Wuerker (University of Illinois, Urbana)—Mr. Mather is to be congratulated for stressing the most urgent need for a program of testing the physical properties of rocks, as they are encountered by the petroleum engineers on their drilling jobs and by the miners on their excavating, roof control and mineral preparation tasks. Another valuable source of information is the Handbook of Physical Constants.22 It stresses the physicist's approach rather than the engineer's procedure. The study of hardness, and rock hardness in particular, is beset with many difficulties. There is no satisfactory definition of hardness yet, and the term hardness is used to describe a number of quite dif- ferent properties. Hardness tests are grouped into static and dynamic determinations. They should be expressed with reference to the mechanical action of the applied force, like indentation hardness, scratch hardness, abrasion hardness, rebound hardness. A discussion of all these various hardness tests and of the special difficulties encountered in hardness testing of such heterogeneous material as rocks is given in the U. S. Bureau of Mines' standard proposal. The more critical student may be referred to the book by D. Landau: Hardness, which is in my opinion the best existing treatise on this subject.

Jan 1, 1952

By Richard Moldenke

In crowding the recent mass of work on the physics of cast-iron into the compass of a short review, I cannot do better than to follow the lines of Mr. W. R. Webster's suggestion, made at the Florida meeting of the Institute, March, 1895.' The classification of the properties of the metal, and the influences to which it is subjected during the various processes it undergoes, is quite complete; and as Mr. Webster gives it again in full in another paper at the present meeting, a simple reference to it now will be sufficient. I. Correspondence Between Chemical Composition, and Melting-Point, Fluidity, Shrinkage, Fracture,Chill, Micro-Structure, and Other Physical Properties. Melting-Point.—The melting-point of cast-iron had long been a subject of controversy among foundrymen. They knew that a hard iron melted faster than a soft one, but this effect was occasionally disputed, and the reasons given were unsatisfactory; but could not be well controverted. It was my good fortune to take the actual melting-temperatures of some 70 pig-irons and castings; the Le Chatelier pyrometer, suitably protected, being introduced into the interior, and the iron melted off in a specially-constructed cupola. The irons had been previously analyzed by taking the borings at the point of the intro-

Jan 1, 1905

By S. P. Sharples

Under the act providing for the taking of the Tenth Census, the superintendent was authorized to appoint experts to inquire into special industries; accordingly Professor Charles S. Sargent was appointed to gather statistics in relation to the forest industries. As chief of the Department of Forestry of the Tenth Census he has been busily engaged in this work since the fall of 1879. Soon after his appointment he became convinced that it would be desirable to make an examination of the fuel-value of the various woods of the United States, and this work was placed in my hands. At the same time I made the suggestion that while we had the opportunity, it would be well to test also the strength of these woods. The suggestion was adopted and Professor Sargent at once set his agents to work in various parts of the country to collect specimens of all the trees growing in their localities, employing as a rule botanists who were familiar with the flora of the region in which they were at work. The result of this work was the collection of over thirteen hundred specimens of wood, comprising over four hundred species and varieties, nearly one hundred of which had not before been described as trees existing in the United States.

Jan 1, 1883

By Ashbel Welch

Ashbel Welch, Lambertville, N. J.: Dr. Dudley has given the wear of steel rails under four different conditions. He arrives at the conclusion that the softer rails, or those that from their composition ought to be softer, wear better than the harder. But there is another condition which has an important bearing on the subject, and should not be overlooked,—the weight on a wheel. With the lighter weights of the past, the softer rails may have worn best; with the heavier weights of the future, the harder may wear best. Weights will probably be increased up to the capacity of steel to bear; then doubtless the harder steel will wear best. A leaden rail with ten pounds on a wheel might carry millions of tons, but with one hundred pounds on a wheel, it would be destfoyed by a few thousand tons. So in the days of iron rails, my experience was that the softer rails under light machinery stood better than some of the harder; but under heavy machinery the softer were much the most rapidly destroyed. It is doubtless the same with steel. The pounding motion of the wheels loosens or spreads the particles of a thin film of steel; the pull lengthwise on the rail de-

Jan 1, 1881

By W. A. Backofen, R. L. Fleischer

AN effect of orientation on the creep behavior of aluminum at 4.2 OK has been observed. Stress relaxation was measured in a hard-type tensile device after stopping the drive. From the spring constant of the device the load-time record could be converted to strain as a function of time. The strain sensitivity was 2-10-=, and the usual creep time of 1 min normally allowed a stress drop of about 25 g per sq mm. Further details of the apparatus and sample preparation appear elsewhere.' It should be noted that neither stress nor strain were constant, so that quantitative comparison with current creep theories will not be made. Shear strain (y) as a function of time (t) was consistent with logarithmic behavior: y = A In t, where A is a constant. In some cases t was made as large as lo3 sec. In the results the quantity A divided by t (the resolved shear stress, which is the driving force for creep) is plotted as a function of strain prior to creep. The quantity A/t is thought to indicate qualitatively the ease with which dislocations can move during creep. In Fig. 1 are drawn tensile stress-strain curves and A/T-strain measurements for single crystals of three orientations: l(a) and l(b) for the maximum resolved shear-stress orientation, l(c) for an orientation 2 deg from [211], and l(d) for a [111] stress axis. The following observations were made: 1) At low strains the A/t values are nearly the same for the three orientations. 2) As strains increase, A/t drops most rapidly for [Ill.] and less rapidly for [211], while for the maximum shear-stress orientation it is constant during easy glide and drops abruptly at the termination of easy glide. 3) In stage 11, A/t values are again approximately the same for the three orientations. These observations are regarded as evidence that 1) the initiation of slip produces obstacles of essentially the same effectiveness for all of these orientations, while 2) the rate at which slip obstacles are produced before stage I1 is fully developed is strongly controlled by the amount of slip on more than one system. This second statement is consis-

Jan 1, 1961

By Riki Kobayashi, D. L. Katz

The conditions at which methane and water form solid hydrates have been extended from 4,000 to 11,200 pounds per sq. in. The curve at high pressure had been in doubt because of Villard's report of a critical decomposition temperature. The paper explains the nature of the hydrate curve at high pressure and its dependence on fluid phase behavior. Extropolation of the methane hydrate curve indicates a pressure of 40,000 pounds per sq. in. will cause hydrates to form at a temperature of 100" F. INTRODUCTION The conditions under which natural gases form hydrates when liquid water is present have been studied by several investigators up to pressures of about 4,000 pounds per sq. in. The early work by Villard on hydrates of methane and ethylene13, ethane'', and propane14 included references to critical decomposition temperatures of the hydrates. Villard's work raised the question as to whether the pressure-temperature curve for methane-water hydrate continued above a temperature of 70.7°F. or whether this was the maximum temperature at which hydrates would form. This paper extends the experimental data on methane hydrate to 11,200 pounds per sq. in. A discussion of phase relations in the hydrate region for the hydrocarbons and of the methane-water system at high pressures is included. PREVIOUS WORK Villard suspected that methane hydrates could not be formed at temperatures above 21.5°C. (70.7°F.)la irrespective of the pressure of the liquid-vapor system. However, he was limited in his studies by his apparatus in 1888 to pressures not greater than 300 atmospheres (4,410 pounds per sq. in.) so that there has remained some doubt as to the existence of such a maximum temperature in this region. For the case of ethylene hydrates, however, Villard does specifically state the occurrence of what he terms a "critical temperature for the decomposition of the hydrates"13. Fig. lB shows a pressure-temperature projection of the three-phase locus, hydrate-ethylene rich liquid-vapor (H-L2-V) terminating at the critical locus in which L² and V assume similar properties. Throughout this paper the following phase designations will be used: H for hydrate, Ll for the water rich liquid. L2 for the

Jan 1, 1949

By Riki Kobayashi, D. L. Katz

The conditions at which methane and water form solid hydrates have been extended from 4,000 to 11,200 pounds per sq. in. The curve at high pressure had been in doubt because of Villard's report of a critical decomposition temperature. The paper explains the nature of the hydrate curve at high pressure and its dependence on fluid phase behavior. Extropolation of the methane hydrate curve indicates a pressure of 40,000 pounds per sq. in. will cause hydrates to form at a temperature of 100" F. INTRODUCTION The conditions under which natural gases form hydrates when liquid water is present have been studied by several investigators up to pressures of about 4,000 pounds per sq. in. The early work by Villard on hydrates of methane and ethylene13, ethane'', and propane14 included references to critical decomposition temperatures of the hydrates. Villard's work raised the question as to whether the pressure-temperature curve for methane-water hydrate continued above a temperature of 70.7°F. or whether this was the maximum temperature at which hydrates would form. This paper extends the experimental data on methane hydrate to 11,200 pounds per sq. in. A discussion of phase relations in the hydrate region for the hydrocarbons and of the methane-water system at high pressures is included. PREVIOUS WORK Villard suspected that methane hydrates could not be formed at temperatures above 21.5°C. (70.7°F.)la irrespective of the pressure of the liquid-vapor system. However, he was limited in his studies by his apparatus in 1888 to pressures not greater than 300 atmospheres (4,410 pounds per sq. in.) so that there has remained some doubt as to the existence of such a maximum temperature in this region. For the case of ethylene hydrates, however, Villard does specifically state the occurrence of what he terms a "critical temperature for the decomposition of the hydrates"13. Fig. lB shows a pressure-temperature projection of the three-phase locus, hydrate-ethylene rich liquid-vapor (H-L2-V) terminating at the critical locus in which L² and V assume similar properties. Throughout this paper the following phase designations will be used: H for hydrate, Ll for the water rich liquid. L2 for the

Jan 1, 1949

By D. J. MacKinnon, J. M. Brannen

Smooth, compact, dendrite free 24-h zinc deposits have been electrowon from zinc chloride electrolyte using a diaphragm cell. The cell consisted of sealed anode compartments containing DSA anodes separated from an open cathode compartment by Dynel cloth membranes. Fresh electrolyte was fed to the cathode compartment where zinc deposition onto an aluminum cathode was aided by air sparging. The catholyte passed through the diaphragms into the anode compartments from which chlorine gas and spent anolyte were withdrawn. Standard electrolysis conditions were: 15 g/L Zn, 0.12 M HCI, I5 mg/L tetrabutylammonium chloride (TBACI) as the addition agent, 35°C, and 323 A/m2 (30 ASF) current density. The effect of variations in these conditions on the morpohology orientation, current efficiency, and energy requirement for 24-h zinc deposits was determined. The effect of total chloride ion concentration on the zinc deposit was studied by adding various amounts of NaCl to the electrolyte.

Jan 1, 1983

By P. F. MINISTER

AT Lime Spur, Mont., the East Butte Copper Mining Co. has been quarrying limestone for twenty years. The quarry is beside the Northern Pacific R. R. in the Jefferson River canyon, 4 ½ miles east of Cardwell, at Lime Spur, Montana. HISTORY This quarry was opened early in 1900 by Dan Morrison of Whitehall, the discoverer of the Morrison cave, to supply a demand for smelter flux. Limestone was sold to the Pittsmont smelter of The East Butte Copper Mining Co. and to the Butte Reduction Works. As no particular effort was made at the quarry to select the rock that delivered to the smelters was unduly high in magnesia and impurities. The East Butte com¬pany, therefore. Bought the quarry. in 1909 and confined operations to the high-grade beds in order to supply rock of the desired purity for its own smelter and the Butte Reduction Works until the latter shut down. It also developed a market for some of its rock with the sugar factories. The latter market increased until in later years all rock, larger than 4 in. in size over a bar grizzly, was being shipped to the sugar factories, and the rock smaller than 4 in. was being used as a flux in the blast furnaces at the Pittsmont smelter. In 1924, the East Butte concluded a contract with the Anaconda company for the treatment of its ores, and the Pittsmont -smelter -was shut down: which made the minus 4-in. rock a useless by-product. Since there was not enough revenue in the sugar rock alone and also because of limited waste room it became necessary, if Lime Spur was to continue to operate, to increase- the proportion of plus 4-in. rock and to develop a market for the minus 4-in.

Jan 1, 1930