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By N. L. Ananthanarayanan, J. F. Libsch

A LITERATURE survey1-' of sintering metal pow-A ders and powder compacts indicates that studies have so far been confined primarily to the latter stages of sintering in relatively coarse powders. Presumably this is due to the difficult techniques associated with studies of the early stages of sintering. Recent experimental and theoretical investigationsL-" on the preparation and the magnetic properties of ultrafine ferromagnetic powders suggest the possi- bility of following the sintering process from a very much earlier stage than has previously been considered. It is now well-known that ferromagnetic powder particles which are below a critical size behave as single domains and exhibit permanent magnet qualities characterized by a very high coercive force. When the same particles are fully sintered, the coercive force decreases to very low values corresponding to those of the solid metal. Thus the coercive force appears as a sensitive parameter which may be measured to study the early stages of sintering. To determine the feasibility of this technique, experi-

Jan 1, 1954

By J. R. Kyte, L. A. Rapoport, R. J. Stanclift, S. C. Stephan

Experimental studies covering a wide range of core materials and fluid properties have been conducted to determine the mechanism of oil displacement by water in a partially gas-saturated porous medium. In all instances, the presence of a gas phase was found to have a beneficial effect in reducing residual oil saturations. The practical significance of this benefit is discussed, and a simplified procedure is outlined for evaluating the effects of free gas on water flooding by means of short core tests. INTRODUCTION In addition to oil and water, reservoirs subjected to water flooding frequently contain, also, a gas phase. Common engineering procedures account for the presence of this "free gas" only from the viewpoint of volumetric balance, implying that the only role of the gas consists of providing "fill up" space. It is usually visualized that during the initial stages of the water invasion, the oil, moving ahead of the water, displaces part of the gas and that subsequently the remaining portion of the gas phase is totally compressed and dissolved in the advancing oil bank. Thus, consideration of a two-phase, water-oil flooding mechanism supplies an adequate basis for predictions of oil recovery if the pressure build-up caused by the flood is sufficiently great, so as to reduce the free gas saturation to a negligible value in any portion of the reservoir by the time that portion is reached by the advancing flood water. In many in- stances, however, waterflooding operations are carried out when the reservoir pressure is still relatively high SO that the pressure build-up associated with the water flood may not result in complete dissipation of the gas phase. Under such circumstances it is necessary to ascertain whether or not the presence of free gas has an effect on waterflood behavior and, if so, to account for any such effect in the evaluation of field operations. The difficulties encountered in attempting to arrive at a comprehensive picture of the displacement mechanism of oil by water in the presence of free gas stem from the fact that most of the published data on this subject were obtained under conditions that were either not clearly representative of those existing in a reservoir or not sufficiently controlled to permit evaluation of the effects specifically caused by the gas phase. Some of the most precise data found in the literature were obtained in tests using a "static" gas phase created prior to each water flood by circulating oil through partly gas-saturated cores until a "trapped," residual gas saturation was established throughout the system.' Other investigations were conducted under more representative conditions where the gas phase was free to move during the water flood: but in most cases the results of these tests were obscured by auxiliary phenomena which arise from the compressibility and solubility of the gas and preclude quantitative conclusions.2,3,4 Prior to water flooding, a reservoir usually contains oil and gas, distributed in a manner in which both are free to move. Thus, the principal objective of the present studies was to determine the type of displacement mechanism occurring when water invades a porous medium containing oil and a "mobile" gas phase. Further-

Jan 1, 1957

By M. Muskat, M. O. Taylor

Theoretical calculations have been made on the performance to be expected of gas-drive reservoirs for various characteristics of the oil and gas and the producing rock. Such performante has been expressed graphically as curves for the reservoir pressure and gas-oil ratios of the production as functions of the cumulative oil recovery. The latter has been expressed in terms of percentage of pore space of the reservoir rock. Such curves automatically give values for the ultimate physical recovery, if the latter is interpreted as the recovery obtained when the reservoir pressure has declined to atmospheric, or to any other pressure chosen as defining the state of practical complete depletion. Calculations of these pressure and gas-oil ratio histories have been made for conditions in which the oil viscosity, the gas solubility and shrinkage, the size of an overlying gas cap, if present, the permeability-saturation characteristics of the rock, and the amount of connate water, have been individually varied, The results serve to show the extent to which the ultimate recoveries are sensitive to the important physical parameters characterizing the oil reservoir. As is to be expected, the ultimate recoveries are found to decrease with increasing oil viscosity. Because of the predominant effect of the oil shrinkage associated with the liberation of the gas in solution, the ultimate recovery will decrease with increasing gas solubility. Increasing gas-cap volumes lead to higher recoveries, although the contribution made by the gas-cap gas is small as compared with the oil expulsion by the equivalent amount of solution gas. As a whole, the oil recovery when expressed in percentage of the pore space is not very sensitive to the details of the permeability-saturation relationship. However, if the rocks possess an equilibrium free-gas saturation, the rise in gas-oil ratio will be retarded, and the 'ultimate recovery somewhat increased' The oil shrinkage associated with the liberation of the dissolved gas also leads to the result that as long as the connate water is immobile and the permeability ratio curve for the rock is a function only of the total liquid saturation, the stock-tank oil recovery will be less for a sand containing no connate water than for One with an Original water content as high as 3' per cent. The space voidage in the former case will be somewhat greater, but the effect of oil shrinkage will lead to smaller values for the equivalent stock-tank recovery. These calculations also give data showing how the productivity indexes for the producing wells will vary during the reservoir history. Because of decreasing Permeability to the oil and increasing oil viscosity, the productivity index will fall continuously as Production proceeds, and may finally reach values as low as 10 per cent of the initial productivity index. Introduction In a previous paper1 was developed the basic theory for the prediction of the production histories of gas-drive reservoirs. The data required for the application of this theory included the characteristics of the petroleum fluids, such as the viscosity of the Oil and gas phases, the solubility of the gas in the oil, and the oil shrinkage— all expressed as functions of the reservoir pressure—and the permeability-saturation characteristics of the producing rock, as

Jan 1, 1946

By M. Muskat, M. O. Taylor

Theoretical calculations have been made on the performance to be expected of gas-drive reservoirs for various characteristics of the oil and gas and the producing rock. Such performante has been expressed graphically as curves for the reservoir pressure and gas-oil ratios of the production as functions of the cumulative oil recovery. The latter has been expressed in terms of percentage of pore space of the reservoir rock. Such curves automatically give values for the ultimate physical recovery, if the latter is interpreted as the recovery obtained when the reservoir pressure has declined to atmospheric, or to any other pressure chosen as defining the state of practical complete depletion. Calculations of these pressure and gas-oil ratio histories have been made for conditions in which the oil viscosity, the gas solubility and shrinkage, the size of an overlying gas cap, if present, the permeability-saturation characteristics of the rock, and the amount of connate water, have been individually varied, The results serve to show the extent to which the ultimate recoveries are sensitive to the important physical parameters characterizing the oil reservoir. As is to be expected, the ultimate recoveries are found to decrease with increasing oil viscosity. Because of the predominant effect of the oil shrinkage associated with the liberation of the gas in solution, the ultimate recovery will decrease with increasing gas solubility. Increasing gas-cap volumes lead to higher recoveries, although the contribution made by the gas-cap gas is small as compared with the oil expulsion by the equivalent amount of solution gas. As a whole, the oil recovery when expressed in percentage of the pore space is not very sensitive to the details of the permeability-saturation relationship. However, if the rocks possess an equilibrium free-gas saturation, the rise in gas-oil ratio will be retarded, and the 'ultimate recovery somewhat increased' The oil shrinkage associated with the liberation of the dissolved gas also leads to the result that as long as the connate water is immobile and the permeability ratio curve for the rock is a function only of the total liquid saturation, the stock-tank oil recovery will be less for a sand containing no connate water than for One with an Original water content as high as 3' per cent. The space voidage in the former case will be somewhat greater, but the effect of oil shrinkage will lead to smaller values for the equivalent stock-tank recovery. These calculations also give data showing how the productivity indexes for the producing wells will vary during the reservoir history. Because of decreasing Permeability to the oil and increasing oil viscosity, the productivity index will fall continuously as Production proceeds, and may finally reach values as low as 10 per cent of the initial productivity index. Introduction In a previous paper1 was developed the basic theory for the prediction of the production histories of gas-drive reservoirs. The data required for the application of this theory included the characteristics of the petroleum fluids, such as the viscosity of the Oil and gas phases, the solubility of the gas in the oil, and the oil shrinkage— all expressed as functions of the reservoir pressure—and the permeability-saturation characteristics of the producing rock, as

Jan 1, 1946

By Harry H. Nowlan

A heavy development campaign progressed during the year 1936 in South Texas1, following up important discoveries made in 1935. Oil and gas wells completed during the year were 1473 against 704 in 1935. The drilling program reached its peak of operations in June in consequence of offset requirements made necessary principally in Duval County in the Seven Sisters, Loma Novio, Lopez and Cole fields. There were six new fields discovered during 1936 as follows: Rhode in McMullen County; Peters, El Mesquite and North Kohler in Duval County; Wood in Starr County and Colorado in Jim Hogg County. No discovery of unusual consequence was made during the year. The pools mentioned above are simply in the primary stages of development. The most intensive exploratory work during the year was in Duval, Webb and Zapata Counties. Considerable activity also prevailed in Starr and Brooks Counties. Much significance is attached to the California Company's discovery in the Alta Mesa field in Brooks County, which is considered to be a deep-seated salt dome. The Comitas field, in Zapata County, developed some surprisingly good production in a shallow sand at 900 ft. and is being followed by a heavy wildcat campaign throughout that area in search of like production. In Starr County an active wildcat campaign is in progress in a continued effort to find new fields northwest of the Sam Fordyce field, in Hidalgo County. This play continues in a northerly direction through Starr and Jim Hogg Counties. New Fields Rhode.—The Rhode field, in southeastern McMullen County, was opened in May by the Magnolia Petroleum Co. with a gas well in the Whitsett (Upper Jackson) sand at a depth of 1810 to 1822 ft., this test is located in the southeast corner of sec. 86 on the Rhode ranch. Four gas wells have been completed, proving up a gas area of 1000 acres, more or less. Development will be slow because of lack of market for the gas.

Jan 1, 1937

Q: This is December 1960 and Jafet Lindeberg and myself are sitting around the tape recorder. Jafet, who discovered the gold in Nome, Alaska, in 1898, is going to tell the story of the discovery and of his life up there-a period of some 25 years. Now. Jafet, let's start this off well back of that-start it of1 when you were in Norway and, briefly, tell about when you were born and where you were born, anti so on. Lindeberg: My home in Norway was Varanger in Northern Norway. I was born and raised there and our industry was lumbering, cutting cordwood out of birch, sawing lumber with water power, fishing and dairy work. Q: Did you have anything to do with reindeer? Lindeberg: I never had anything to do with reindeer. But reindeer were raised in the nearby county, called Kautokeino, and they used to come to the coast in the summer, but we had nothing to do with the industry.

Jan 7, 1964

By H. De. Cizancourt

There is no new outstanding fact to be noted concerning the development of petroleum production and research in France and her possessions during 1935. France.—Pechelbronn remains the only important producing field in France. The total output has reached 538,921 bbl., showing a small decrease on last year's figures. Out of this, 302,737 bbl. was extracted by drilling and 236,184 bbl. (44 per cent) was obtained by means of shafts and galleries. Exploration of deeper formations was still in progress, and resulted in the discovery of a new Middle Triassic (Muschel-Kalk) producing horizon. In the vicinity of Hirtzbach (South Alsace) shallow exploration tests (500 ft.) were drilled by the Société de Pechelbronn, oil indications being found in the Tertiary. Two more important wells are now drilling in deeper horizons. The Chantenay well (Niévre) was finished in August, 1935, at a depth of 3544 ft.1 A test is under progress in Savoie. South of Gabian, at Pezenas, the erection of a rig is nearly completed.

Jan 1, 1936

There is no new outstanding fact to be noted concerning the development of petroleum production and research in France and her possessions during 1935. France.—Pechelbronn remains the only important producing field in France. The total output has reached 538,921 bbl., showing a small decrease on last year's figures. Out of this, 302,737 bbl. was extracted by drilling and 236,184 bbl. (44 per cent) was obtained by means of shafts and galleries. Exploration of deeper formations was still in progress, and resulted in the discovery of a new Middle Triassic (Muschel-Kalk) producing horizon. In the vicinity of Hirtzbach (South Alsace) shallow exploration tests (500 ft.) were drilled by the Société de Pechelbronn, oil indications being found in the Tertiary. Two more important wells are now drilling in deeper horizons. The Chantenay well (Niévre) was finished in August, 1935, at a depth of 3544 ft.1 A test is under progress in Savoie. South of Gabian, at Pezenas, the erection of a rig is nearly completed.

Jan 1, 1936

By E. H. Denny

IN the past few years many men, including technically trained engineers, have been asphyxiated in metal mines, coal mines, tunnels and surface wells where a few relatively simple precautions with regard to ventilation and air testing would have saved them. Death from mine gases is analogous in some respects to death from poison and from drowning. The respiratory passages of a victim who has breathed oxides of nitrogen from burning explosives are badly irritated and a few hours or even a day after exposure he may develop a quick and fatal pneumonia; if, however, he enters without respiratory protective apparatus an atmosphere deficient in oxygen (a condition that may occur in unventilated or poorly ventilated parts of all underground mines) he collapses and if not rescued dies more quickly and surely than a lone nonswimmer who falls suddenly into deep water. An example of an atmosphere virtually without oxygen was demonstrated by an air sample taken by a Bureau of Mines engineer wearing oxygen breathing apparatus in a Cripple Creek shaft some years ago, during the recovery of the bodies of two victims of asphyxiation; analysis of the sample by the Pittsburgh laboratory of the Bureau showed the presence of 18.40 per cent of carbon dioxide, 0.27 per cent of oxygen, and 81.33 per cent of nitrogen, although the atmosphere apparently was clear and normal. In a mine one can pass from good, breathable air to an atmosphere that will kill as quickly as one can dive from a board to deep water below. SOME INSTANCES OF ASHYXIATION BY GASES IN METAL MINES The following typical examples of comparatively recent instances of asphyxiation in metal mines were taken chiefly from reports of various kinds of the U. S. Bureau of Mines.

Jan 1, 1938

The Black hills rise like a dark island above the far-flung prairie lands of the Dakotas; to their sombre pine-clad slopes they owe the name, Black mountains, by which they were known to the early explorers. Pahasapa, a Sioux word with the same meaning, was the name given to these hills by the Indians, who avoided them, believing them to be mysterious and dangerous. The aborigines entered the hills rarely, to pick berries, hunt the deer, or to cut lodge-poles, the central supports of their huts. The French explorer Pierre de la Veréndrye reached Dakotan soil in October 1738, coming thither from Montreal by way of Lake Superior and the Lake of the Woods.* Five years later his sons, François and Louis Joseph, reached the Black hills, as is recorded on a plate unearthed at Fort Pierre in 1913. The French-Canadian explorers and trappers of that time, however, appear to have been diverted southeastward to the more promising lands of the Mississippi valley, so that we find no mention of the Black hills in the chronicles of the period until Lewis and Clark, on their way to the Pacific coast, in 1805, met a French trader, named Jean Vallé, on the lower Cheyenne river, and from him they heard of the Black mountains in a casual manner. Next, Wilson P. Hunt, who, at the head of an expedition crossed the Rocky Mountains on his way to the Astor trading-post on the Columbia river, in 1811, had a glimpse of the dark hills to the north, but that was all. Then in 1823 Jedediah S. Smith, one of the earliest discoverers of gold in California, crossed the southern part of the Black hills on his way westward. Two trading-posts were established in

Jan 1, 1932

By E. H. Denny

In the past few years many men, including technically trained engineers, have been asphyxiated in metal mines, coal mines, tunnels and surface wells where a few relatively simple precautions with regard to ventilation and air testing would have saved them. Death from mine gases is analogous in some respects to death from poison and from drowning. The respiratory passages of a victim who has breathed oxides of nitrogen from burning explosives are badly irritated and a few hours or even a day after exposure he may develop a quick and fatal pneumonia; if, however, he enters without respiratory protective apparatus an atmosphere deficient in oxygen (a condition that may occur in unventilated or poorly ventilated parts of all underground mines) he collapses and if not rescued dies more quickly and surely than a lone nonswimmer who falls suddenly into deep water. An example of an atmosphere virtually without oxygen was demonstrated by an air sample taken by a Bureau of Mines engineer wearing oxygen breathing apparatus in a Cripple Creek shaft some years ago, during the recovery of the bodies of two victims of asphyxiation; analysis of the sample by the Pittsburgh laboratory of the Bureau showed the presence of 18.40 per cent of carbon dioxide, 0.27 per cent of oxygen, and 81.33 per cent of nitrogen, although the atmosphere apparently was clear and normal. In a mine one can pass from good, breathable air to an atmosphere that will kill as quickly as one can dive from a board to deep water below. Some Instances of Asphyxiation by Gases in Metal Mines The following typical examples of comparatively recent instances of asphyxiation in metal mines were taken chiefly from reports of various kinds of the U. S. Bureau of Mines.

Jan 1, 1940

By E. H. Denny

In the past few years many men, including technically trained engineers, have been asphyxiated in metal mines, coal mines, tunnels and surface wells where a few relatively simple precautions with regard to ventilation and air testing would have saved them. Death from mine gases is analogous in some respects to death from poison and from drowning. The respiratory passages of a victim who has breathed oxides of nitrogen from burning explosives are badly irritated and a few hours or even a day after exposure he may develop a quick and fatal pneumonia; if, however, he enters without respiratory protective apparatus an atmosphere deficient in oxygen (a condition that may occur in unventilated or poorly ventilated parts of all underground mines) he collapses and if not rescued dies more quickly and surely than a lone nonswimmer who falls suddenly into deep water. An example of an atmosphere virtually without oxygen was demonstrated by an air sample taken by a Bureau of Mines engineer wearing oxygen breathing apparatus in a Cripple Creek shaft some years ago, during the recovery of the bodies of two victims of asphyxiation; analysis of the sample by the Pittsburgh laboratory of the Bureau showed the presence of 18.40 per cent of carbon dioxide, 0.27 per cent of oxygen, and 81.33 per cent of nitrogen, although the atmosphere apparently was clear and normal. In a mine one can pass from good, breathable air to an atmosphere that will kill as quickly as one can dive from a board to deep water below. Some Instances of Asphyxiation by Gases in Metal Mines The following typical examples of comparatively recent instances of asphyxiation in metal mines were taken chiefly from reports of various kinds of the U. S. Bureau of Mines.

Jan 1, 1940

By John D. Sullivan, Chester R. Austin, Edwin J. Rogers

The problem of making a building unit combining the necessary physical and mechanical properties and good thermal insulation has been foremost in the minds of architects and ceramic and construction engineers for many years. This paper presents the results of studies on thermally expanding shales or clays to produce lightweight cellular products suitable for making building units. An expanded clay block suitable for building purposes should be large enough qo that substantial savings may be effected in labor costs in laying the wall. The permeability should be low and it should have sufficiently good "dry-wall" characteristics to permit exposing the exterior surface to the elements, and to permit plastering directly the inside wall surface. The thermal conductivity should be low and the mechanical properties should be adequate. Obviously, a unit possessing satisfactory qualities for constructing an - outside wall would be satisfactory for interior walls and for back-up purposes. The results of studies on bloating various shales or clays† and the properties of the expanded products are reported. In another paper1 basic factors involved in bloating of clays are discussed. Manufacturers of ceramic products, partitularly structural clay, may encounter bloating of the ware during burning, and precautions must be followed to avoid this phenomenon. About 1927 the C. F. Burgess Laboratories, Madison, Wis., while carrying on an investigation for the American Face Brick Research Corporation, conceived the idea of intentionally bloating clay while holding it in a restrained condition, with the hope of producing a unitary cellular mass. Work was carried on until about 1931, when studies were terminated because of business conditions. These studies were continued later by The Western Brick Co., Danville, Ill., which developed a process of "inwardly expansive bloating."² The major purpose of the latter investigation was to produce back-up tile to compete with concrete blocks made from Haydite or cinder aggregate. Haydite is a light-weight aggregate formed by heating certain clays or shales rapidly in a rotary kiln. While the investigations at the C. F. Burgess Laboratories or at Western Brick Co. were not carried far enough to lead to the commercial production of material for the construction of walls, particularly outside walls, they showed that certain clays could be thermally expanded and that it was possible to produce a material of low permeability with a large percentage of the total voids or cells closed. commencing in 1939, the Ozark Chemical Co. sponsored a research program at Battelle Memorial Institute for the Purpose Of determining whether it is technically feasible to make thermally expanded building units, and specifically to get answers to the following questions:

Jan 1, 1942

By John D. Sullivan, Edwin J. Rogers, Chester R. Austin

The problem of making a building unit combining the necessary physical and mechanical properties and good thermal insulation has been foremost in the minds of architects and ceramic and construction engineers for many years. This paper presents the results of studies on thermally expanding shales or clays to produce lightweight cellular products suitable for making building units. An expanded clay block suitable for building purposes should be large enough qo that substantial savings may be effected in labor costs in laying the wall. The permeability should be low and it should have sufficiently good "dry-wall" characteristics to permit exposing the exterior surface to the elements, and to permit plastering directly the inside wall surface. The thermal conductivity should be low and the mechanical properties should be adequate. Obviously, a unit possessing satisfactory qualities for constructing an - outside wall would be satisfactory for interior walls and for back-up purposes. The results of studies on bloating various shales or clays† and the properties of the expanded products are reported. In another paper1 basic factors involved in bloating of clays are discussed. Manufacturers of ceramic products, partitularly structural clay, may encounter bloating of the ware during burning, and precautions must be followed to avoid this phenomenon. About 1927 the C. F. Burgess Laboratories, Madison, Wis., while carrying on an investigation for the American Face Brick Research Corporation, conceived the idea of intentionally bloating clay while holding it in a restrained condition, with the hope of producing a unitary cellular mass. Work was carried on until about 1931, when studies were terminated because of business conditions. These studies were continued later by The Western Brick Co., Danville, Ill., which developed a process of "inwardly expansive bloating."² The major purpose of the latter investigation was to produce back-up tile to compete with concrete blocks made from Haydite or cinder aggregate. Haydite is a light-weight aggregate formed by heating certain clays or shales rapidly in a rotary kiln. While the investigations at the C. F. Burgess Laboratories or at Western Brick Co. were not carried far enough to lead to the commercial production of material for the construction of walls, particularly outside walls, they showed that certain clays could be thermally expanded and that it was possible to produce a material of low permeability with a large percentage of the total voids or cells closed. commencing in 1939, the Ozark Chemical Co. sponsored a research program at Battelle Memorial Institute for the Purpose Of determining whether it is technically feasible to make thermally expanded building units, and specifically to get answers to the following questions:

Jan 1, 1942

By AIME AIME

The following report is published for the information of the members: Meetings. Two meetings for the reading and discussion of papers, etc., have been held during the year 1907-namely, the Ninety-second meeting, held April 16 to 20 in New York, N. Y., and the Ninety-third meeting, held July 23 to 30 in Toronto, Canada. The proceedings of these meetings, including descriptions of the entertainments and excursions connected therewith, have already been published and distributed to the members of the Institute; the New York meeting in Bi-Monthly Bulletin, No. 15, May, 1907, pp. 541 to 559, and the Toronto meeting in Bi-Monthly Bulletin., No. 17, September, 1907, pp. 847 to 875. In addition to these " Proceedings," there were also published in Bi-Monthly Bulletin, No. 15, May, 1907, an illustrated description of the United Engineering Society building (p1 vi. to xxvi.), and a record of the exercises attending its dedication, including the addresses of Andrew Carnegie, Arthur T. Hadley, Samuel Sheldon, Frederick R. Hutton, John Hays Hammond, and T. C. Martin (pp. xxxviii. to lxv.). At the New York meeting, 43 papers and- discussions were presented, and the names of 297 members and guests were registered at the Institute headquarters., this number, however, does not represent all who were present at the sessions and excursions. At the Toronto meeting, 23 papers and discussions were presented. The number of members and guests registered at the Toronto headquarters was 191, which doubtless does not include the names of all who were present at the sessions, or took part in the numerous excursions and visits around Cobalt.

Mar 1, 1908

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

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

Jan 1, 1942

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

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

Jan 1, 1942

By George Sachs

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

Jan 1, 1941

By George Sachs

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

Jan 1, 1941

By H. A. Hoffman

Competition from an all-flotation plant, with demonstrated economies and efficiencies, plus a change in smelting contract and introduction of improved cyclones lead to conversion from gravity-flotation. Detailed descriptions are given of equipment installed and procedures used at St. Joseph Lead's Federal mill. Future plans include further quality control by instrumentation in all aspects of the mill operation. Also planned are improvements in materials handling systems. Competitive conditions will continue to dictate improvements and changes in the mill flowsheet. The advent of all-flotation mills in the Lead Belt was introduced by the Indian Creek mill in late 1953. This modern and efficient plant then became a pattern for the other mills in this area to re-evaluate their circuits in an effort to develop flowsheets that would improve operating conditions and metallurgy. The Indian Creek mill demonstrated that all-flotation would require considerably less operating and maintenance labor than the combination of tabling and flotation that was common in the Lead Belt at that time. Two significant changes occurred in recent years to allow all-flotation to be seriously considered in other Lead Belt mills. One was a change in the smelting contract which did not require gravity concentrate. Another was the development of cyclones which provided classification of the flotation feed in a very small space. Since the Federal mill was the largest concentrating plant in the Lead Belt it was felt that the greatest savings could be made by investigating the all-flotation possibilities at this mill. Interest was stimulated by the milling and ore dressing Depts. to determine if this mill would be converted without undue cost, provided the metallurgy could be improved. Accordingly, laboratory tests were initiated to learn what metallurgical benefit could be derived. Numerous tests were run which indicated that grinding to all-flotation would improve the tailing by as much as 0.02 pct Pb. This was quite significant when multiplied by the tonnage of ore treated. Projecting the added cost of power for extra grinding and flotation, and the additional flotation reagents required, plus additional new equipment that would have to be purchased, it would still add up to a considerable saving. The all-flotation mill would reduce man power by some 30 pct, and make a metallurgical improvement. Operating costs could be reduced bv 2$ per ton. The metallurgical improvement would amount to 4$ per ton, for a total of 6$ per ton of ore milled. An estimate of the cost of the conversion was set at $250,000. With the savings as estimated this could be paid off in about two years. On paper it therefore seemed attractive enough to justify a mill test. MILL TESTING One section of the Federal mill was made available for use as a separate test circuit. Cyclones and density controllers were borrowed from the Viburnum and Indian Creek mills. Denver flotation cells were obtained from the Desloge mill that was then shut down. Two 10-cell groups of Fagergren flotation machines, consisting of eight roughers and two cleaners in each bank, were segregated from the remainder of the plant. The 9x12-ft rod mill was continued as a primary grinding mill. The two 6%x12-ft mills on this section were converted from rods to balls, and the speed increased to 22.0 rpm. Cyclones were installed to close the circuit of these ball mills. The ground pulp from each of the ball mills was fed separately to its own bank of flotation cells so that two completely separated test circuits could be run in parallel. This test circuit operated on a three-shift basis from Dec. 22, 1959 to Mar. 21, 1960. The first few weeks were occupied in developing conditions for proper metallurgy and trouble-free operations. Results were rather erratic but as the ore dressing laboratory and the mill operators became more familiar with conditions they were able to obtain expected results, which could be duplicated day after day. The last five weeks of testing indicated the best results and are tabulated in Table I. During the first two weeks a Denver unit cell was used on No. 1 flotation circuit. Even though it recovered almost one half of

Jan 1, 1962