Search Documents

By Harvey T. Kennedy, Charles R. Olson

In many investigations of the performance of petroleum reservoirs the assumption is made that the liquid, if below its bubble-point pressure, is at all times in equilibrium with gas. On the other hand, observations by numerous investigators have indicated that gas-liquid systems including hydrocarbon systems, may exhibit supersaturation to the extent of many hundred psi in the laboratory. Up to the present, there has been no reliable data on which ti judge the actual extent of supersaturation under conditions approaching those existing in petroleum reservoirs. The work reported here deals with observations and measurements on mixtures of methane and kerosene in the presence of silica and calcite crystals. Bubbles were observed to form on crystal-hydrocarbon surfaces in preference to the glass-hydrocarbon interface or to the body of the liquid. Statistically, it was found that the number of bubbles formed per second per square centimeter of crystal surface was a function of the supersaturation only. and the function was evaluated graphically. Supersaturations were observed up to 770 psi, under which condition bubbles formed quickly and with considerable violence. With decreasing degrees of supersaturation, the frequency of bubble formation became less, until at 30 psi supersaturation and lower, no bubbles were observed to form, even though the observation at 30 psi was continued for 138 hours. It was found that silica and calcite crystals had identical effects, within experimental error, in accelerating the formation of bubbles, and that small amounts of water and crude oil had no effect on the results. It is shown that the maximum supersaturation that can exist in a reservoir may be calculated from the data presented and from the area of the rock surface. It is also shown that the number of bubbles formed in the reservoir, in order of magni- tude, may be calculated for any rate of pressure decline imposed on the reservoir by production. The bearing of the number and distribution of bubbles on reservoir performance is discussed. INTRODUCTION A liquid system is supersaturated with gas when the amount of gas dissolved exceeds that corresponding to equilibrium at the existing pressure and temperature. The degree of super-saturation may be conveniently expressed as the difference between the bubble-point of the mixture and the prevailing pressure. Thus, if a mixture having a bubble-point of 1,000 psi at a given temperature exists in single liquid phase at 700 psi at the same temperature. it is supersaturated to the extent of 300 psi. There are many examples of high supersaturations, mostly in aqueous solutions, reported in the literature. Thus, Kenrick, Wismer and Wyatt1 showed that water may be saturated with oxygen, nitrogen or carbon dioxide at 100 atmospheres, and the pressure reduced to one atmosphere without producing bubbles immediately. When liquids are in a state of tension, they may be considered as supersaturated at least to the extent of the tension. The tensile strength of water has been reported as 30 atmospheres by Meyer,1 60 atmospheres bv Budgett. 30 to 50 atmospheres by Temperley and Chambers,4,5 200 atmospheres by Dixon6. and 223 atmospheres by Briggs.7 Vincent8,9 determined the tensile strength of a mineral oil as 45 psi. Gardescu1 maintained pressures for short times in a model reservoir at 115 psi below the bubble-point. It should be noted that the high supersaturations observed were obtained on systems carefully purified to remove particles or surfaces which might promote the formation of bubble; These "nuclei" were considered as contaminants which interfered with the determination of a property of the liquid. In

Jan 1, 1952

By George B. Clark

THE " Munroe effect" of shaped explosive charges was discovered by Charles E. Munroe more than 50 years ago (in 1888), but it was not until World War II that it was put to any practical use. Both Allied and Axis armies used the principle effectively in bazooka projectiles, artillery projectiles and in fixed shaped charges. The first two were used primarily to combat tanks and other armor and the latter to assault pillboxes and other fixed concrete emplacements. Many engineers and others who saw the military application of the jet effect of shaped charges believed application would be possible in many industrial fields where blasting is used, such as mining and quarrying. Some work has already been done on the problem of making shaped charges applicable to mining operations. Experimentation conducted at the National Tunnel and Mines' was directed primarily along the lines of use of shaped charges for secondary blasting in connection with long-hole stoping methods. Experimentation initiated earlier and conducted by the author2 at the University of Utah on a more scientific basis was directed at revealing the basic principles of the functioning of shaped charges, as well as the feasibility of using them in mining operations after the principles of their operation had been clearly defined. It was found that: (I) a given design of charge required an optimum standoff to make it most effective, either in penetrating solid rock or steel (see Fig 3); (2) for a given design of charge there exists an optimum ratio of charge diameter to charge height above which the increase in effectiveness of the charge decreases rapidly (see Figs 4 and 5); (3) partial confinement has the effect of making charge performance much more consistent; (4) the higher power and higher velocity explosives tested are much more effective than relatively low-strength explosives; and (5) shaped charges may be adaptable to mining operations in secondary breakage and drilling blasting holes. Fig I is a diagrammatic sketch of the action of a shaped charge for two types of cavities, while Fig 2 shows the approximate manner in which the jets are believed to be formed when an explosive wave encounters the cavity, approaching it from the top. The experimentation already completed has laid the foundation for further research in the study of shaped charges. Standoff effects, effect of the strength of explosives and other features have been fairly well established. Such elements in the design of shaped charges as (I) geometry of cavity liners, (2) relative horizontal dimensions of explosive column, (3) effect of

Jan 1, 1947

New York Meets first Wednesday after first Tuesday of each month. Chairman. PERCY E. BARBOUR, Vice-Chairman. A. D. BEERS, Secretary, 55 Wall St., New York, N. Y. C. A. BOHN,.Treasurer. JOHN V. N. DORR, LEWIS W. FRANCIS. Boston Meets first Monday of each winter month. W.. E. C. EUSTIS. Chairman. R. L. AGASSIZ. Vice-Chairman. E. E. BUGBEE, Secretary-Treasurer, Mass. Inst. of Technology, Cambridge, Mass. ALBERT SAUVEUR, H. L. SMYTH. Columbia Holds four sessions during year. Annual meeting n September or October. W. H. LINNEY, Chairman. OSCAR LACHMUND, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. STANLY A. EASTON. S. SHEDD. Puget Sound Meets second Saturday of each month SIMON H. ASH, Chairman. I. F. LAUCKS, Vice-Chairman. CHARLES SIMENSTAD, Secretary-Treasurer, 425 Lyon Bldg., Seattle, Wash. GLENVILLE A. COLLINS, JOHN N. POTT

Jan 5, 1917

By Magnus Troilius

The heat-calculations of gas-analyses involve cumbrous multiplications, which are apt to lead into errors. The foliowing tables and formulae have been found useful as facilitating such calculations, and therefore I hope that they will be of interest to some of the members. By "heat-unit" will, in the following, be understood the amount of heat required to raise the temperature of 1 kilogram of water l° Cent. All the tables refer to cubic meters at O0 and 760 mm. pressure. The following gas is chosen as an example: C02, - 4.0 vol. per cent. co, = 20.0 " CHI, - 3.5 " H, - 7.0 " N, - 65.5 " " 100.0

Jan 1, 1884

By D. S. Choi, D. L. McCain

A method of estimating the chain pillar size required to support the wide working faces of longwall or shortwall coal mining is presented. The pillar size is determined through the use of coal strength, entry geometry, panel width, and overburden pressure. Design analysis is focused on a three-entry development system in the Pittsburgh Seam but can be used for other development plans and other seams by substitution of the proper geometric and strength data.

Jan 1, 1981

Jan 1, 1930

By George R. Mansfield

INTEREST in the reserves of phosphate rock in the United States and their proper conservation has recently been aroused by hearings held in different parts of the country by the "Joint Committee to investigate the adequacy and use of phosphate resources of the United States." This committee was appointed within a few days after a Presidential message to Congress on the same subject, dated May 20, 1938, and began to function almost immediately. Hearings were held in Washington, D. C., Pocatello, Ida., Wilson Dam, Ala., Knoxville, Tenn., and Lakeland, Fla. The resulting testimony, when published, comprised a volume of 1182 pages.1 At the earlier hearings held in Washington and Idaho the seeming disparity between the great reserves of the West and the smaller reserves in the East led to some suggestions as to the desirability of curtailing or even prohibiting the exportation of phosphate rock so that eastern producers, becoming alarmed, cooperated in making available for the use of the committee information hitherto closely guarded. This information has provided an opportunity for new studies by official agencies, for a restatement of the reserves of Florida and Tennessee, and for some modification of figures for the Western States. The writer, representing the Federal Geological Survey, was given free access to the Florida material and has prepared for publication a report,2 some features of which are summarized in this paper. The Tennessee material was studied by Dr. G. I. Whitlatch,3 of the Tennessee Division of Geology. Prof. J. Stewart Williams,4 of the Utah State Agricultural College at Logan, has published a recent study of the phosphate resources of Utah and the writer has given some further study to reserves of western phosphate from the viewpoint of including material of lower grade than that hitherto considered. Technologic advances in the phosphate industry must be credited with a large share in the expansion of reserves by making available for

Jan 1, 1940

By Clarence Zener

THE internal friction of nonferrous metals vibrating at low stress amplitudes has so far always been successfully interpreted in terms of inhomogeneities of one sort or another. Examples are the fluctuation of stress across a specimen vibrating transversely,1,2,3 the stress inhomogeneities due to the elastic anisotropy and partial random orientation of the individual crystallites,4,5 localized weak regions introduced by cold-working,6,7 grain boundaries and possibly twinning planes.8,9 Perfect single crystals are, by definition, homogeneous. Actual single crystals usually, perhaps always, contains some imperfections. The present investigation. was undertaken to determine whether the internal friction of single crystals may likewise be attributed to inhomogeneities. This study was made possible through the gift of a large single crystal of 70-30 alpha brass by H. L. Burghoff, of the Chase Brass and Copper Co. The specimen, ½ in. in diameter and 10 in. long, was similar to samples previously described by Mr. Burghoff.10 EXPERIMENTAL METHOD The experimental method used has previously been described in Institute papers.5,6,9 The measure of internal friction adopted here, 1/Q, is (1/p) X the logarithmic decrement, a measure used by some writers, and is also (1/2p) X the specific damping capacity, a measure used by other writers. In all measurements the stress level was kept so low that the measurements were independent of stress level. In all measurements in which the temperature was varied, observations were made as the specimen slowly cooled from its highest temperature. The specimen was vibrated transversely. Observations were made at the funda¬mental frequency and at the first overtone, of about 620 and 1710 cycles per second, respectively. No attempt was made to avoid acoustical losses. EXPERIMENTAL RESULTS The specimen was annealed for several hours at 450°C. The temperature dependence of the internal friction was then determined from room temperature to 400°C. As shown in Fig. 1, the internal friction increased by only a factor of 2 from room temperature to 300°C., then by a factor of l00 during the next 100° interval. These measurements are consistent with the view that the observed internal friction is the superposition of two distinct parts. One, dominant at room temperature, is nearly independent of temperature. This part may be accounted for by acoustical losses and by transverse thermal currents. It was not further investigated. The second part, when plotted in the manner of Fig. I, lies upon a straight line. Therefore it has a heat of activation H; i.e., it varies with temperature as Internal friction e~H/RT [I]

Jan 1, 1942

By J. W. R. Rayner

THE conventional method of making water gas involves individual plants for the separate carbonization of coal to coke and the subsequent gasification of coke with steam. The process demands lump coke, preferably made from the best quality of coking coals. The ash in the coke should have a high melting point and the gasification process suffers a loss of efficiency when cokes with law ash-melting points are used. In Britain, these coals are generally the most expensive and they are readily available only in certain localities. The coals not suitable for making lump coke, or yielding only poor quality coke, are much more widely available and are generally cheaper. DEVELOPMENT OF ALTERNATIVE PROCESSES In Germany, processes have been developed and operated commercially for the production of water gas from very low-rank coals such as brown coal and lignites, but much less effort has been spent on processes to use coals of intermediate rank, which are widely available in Britain. The brown-coal processes use coal in the form of either dust or briquettes. The most successful of the dust-gasification methods is the Winkler process, which made a substantial contribution to German oil production during the war. It uses coal in the site range 0 to 8 mm and the fuel bed is blown with a mixture of oxygen and steam at a rate high enough to give it a characteristic boiling motion or, in present-day phraseology, at a rate more than sufficient to fluidize it (Fig. 1). Air cannot be used to provide the heat required for gasification, for various reasons. In the first place, to make the process continuous by mixing air and steam would involve the production of a lean gas-containing much nitrogen. If a separate blow were used, a large amount of potential heat would be lost because the blow gas in such a process would contain a very high percentage of carbon monoxide. Oxygen is necessary therefore and oxygen remains relatively expensive for use in gasification. In the Winkler generator, formation of clinker caused by local overheating does not occur, because of the mobility and high heat transfer of a fluidized bed. These properties of fluidized dusts have been used most successfully

Jan 1, 1953

By C. K. Leith

AT the outset I would like to make it clear that I do not enter this discussion in a controversial spirit, but in an attempt to contribute something helpful to an understanding of a difficult problem. I have too high regard for the sterling quality of the work of the men who have studied this subject in detail to offer anything in the way of essential contradiction to their statements of fact. Difference of opinion arises from differing valuation of the possible alternative hypothesis which these facts suggest. Some degree of recrystallization in limestone contact zones has been recognized by many investigators. Earlier investigators, for the most part, assigned an important, if not the most important, role to recrystallization in development of these zones. With the growing recognition, of introduction of ores and gangue materials into the contact zone from igneous rocks through the medium of primary magmatic solutions, there has been a tendency to ascribe to this process most, if not all, of the chemical and mineralogical characteristics of the contact zone. This has involved a correspondingly diminished emphasis on recrystallization of substances already there as a factor in the process, and in some cases even the complete elimination of this hypothesis. From detailed study of a few contacts, casual observation of others, and a general familiarity with the literature, some of us have been led in recent years to raise the question whether the pendulum has not swung too far away from recrystallization toward direct introduction from igneous sources, and to argue for more recognition of the part played by recrystallization.1 The inevitable sequence has been that those of us who have taken this view have been charged, at least by inference, with emphasizing recrys-tallization to, the total exclusion of the alternative process. Scientists, like other men, like to classify and pigeon-hole views under simple and definite designations, leaving out qualifications which would tend to make the classification more difficult to state. This has made the problem seem more definite and simple, but has tended to obscure the fact that the disagreement is primarily not one relating to essential facts, but one of

Jan 6, 1914

By F. W. Bradley

This chapter on the Alaska Juneau mill is intended to make clear that "choice of methods," or the selection of proper methods, is the first essential step in launching a new enterprise; and to illustrate that when entering into new country where local conditions and physical features are new or strange to an engineer, he should respect the practices already adopted and followed in meeting peculiar conditions in these new countries that may seem strange to a casual visitor. For example, Americans going into Malay Peninsula with their most up-to-date machinery for drilling placer prospect holes found their cost to total about $3 per foot; by adopting native methods, it was found the same work could be done for 50 cents per foot. Also, those not used to frozen road conditions in a country of arctic climate might scrape the snow off such a road and cause unending road troubles into the following spring and summer; while natives understanding local conditions would leave the snow on the road. So in the neighborhood of Juneau, Alaska, where successful gold-milling operations had been going on for

Jan 1, 1932

Reports on process control computer projects at the Kamioka Plant are summarized from the Japanese technical literature (see references). Fluidized Bed Roaster and Sulfuric Acid plant1 A small process control computer (Yokogawa CCS-200 with an OKITAC 5090P 8K central processor) was installed in the Kamioka smelter in the summer of 1964. A year-and-one-half installation project followed, which successfully brought the roaster and acid converters under computer control. The process plant consisted of two 130 RPD fluosolids roasters and two Monsan to acid units. The roasters are charged with lead-zinc concentrates with SO2 from the roaster processed to sulfuric acid. The computer system provides the following functions: 1) log data from the plant--the input is taken from 50 analog signals, 130 high-low digital alarm points, and 50 analog high- low alarm points; 2) set-point control on 18 control loops; 3) direct digital control (DDC) on eight control loops for which conventional controllers were difficult to adapt due to abnormal loop characteristics or delay times; 4) execution of a safe shut-down procedure

Jan 1, 1969

INSTITUTE OF METALS DIVISION Ferrous and Nonferrous Physical Metallurgy (By-laws in Transactions, Vol 156, 1944) Established as a Division April 26, 1918 Walter A Dean, Chairman R. M. Brick, Past-Chairman Morris Cohen, Senior Vice-Chairman J H Scaff, Vice-Chairman Ernest Kirkendall, Secretary-Treasurer

Jan 1, 1952

By Henri S. Swolfs

INTRODUCTION In this paper we present preliminary results of a research program in site characterization methodology. We are interested in under- standing the response of discontinuous rock to mechanical, hydrologic, and thermal loadings. To carry out such a study we selected a field site with simple geology, uniform distribution of lithologies, and easily verifiable boundary conditions on temperature, fluid flow and stresses. The spatial distribution of fractures at the site was established and tests were conducted to determine the temperature field, hydrology, rock-mass properties, and in situ stresses. As part of the study selected borehole instruments were compared to assess their performance and reliability. SITE GEOLOGY The study area is in the eastern part of South Table Mountain, a mesa near Golden, Colo. The exposed cap rock is a single lava flow of uniform thickness (6-7 m) that rests on the clastic sediments of the Denver Formation (Van Horn, 1976). The surface of the cap rock (N. 75º E., 3º S.) is topographically featureless and slopes south- southeast; drainage is predominantly downdip and punctuated by occasional contact springs. The age of the lava flow is 64-65 m.y., or early Paleocene. Paleo- botanic evidence confirms the upper part of the Denver Formation as Paleocene (Van Horn, 1976). "Rapid-rock" analyses of core samples from the lava flow at three depths (0.2, 3.3, and 5.8 m) suggest a uniform chemical composition throughout with an increase in the Fe2O3/ FeO ratio (1.05 to 1.60) with increasing depth, reflecting the existence of a perched water table in the lava flow, To identify the rock

Jan 1, 1984

Flaubert, as we know, laid stress on the selection of the right word, le mot juste, the precise epithet, the word that belongs to the thing. A sentence, or even a paragraph, may be spoiled. by the use of a word that is not proper, that does not fit or is foreign to the meaning intended. An Australian mining expert is reported to have said: You have a property of considerable value, and what I saw warrants s good development of very rich cubicular galena, with gossan intermixed. 'Cubicular' means 'belonging to a small bedroom', a 'cubicle' being a sleeping compartment. He meant 'cubic', of course. This is a malapropism, and reminds me of the lady from Chicago that, on her return from Europe, said how much she had enjoyed the rural parts of France, because, among other things, it was "so delightful to hear the French pheasants singing the mayonnaise to the tune of the Los Angelus". It is impossible to amalgamate coal-tar thoroughly with the pulp in the agitating-tank. In metallurgy, 'amalgamate' refers to the combination of mercury with one or both of the precious metals, forming an amalgam, which is an alloy of mercury with another metal. It differs from other alloys, such as brass or bronze, in being made without the aid of heat, inasmuch as mercury is molten at the ordinary temperature. The word comes to us from the Greek through Old French and means 'something soft'. It is a mistake to use technical terms, having a specific meaning, for purposes that are foreign to that meaning. The writer of the quotation is not discussing any combination of metals; he is dealing with the physical process of mixing and is using 'amal-

Jan 1, 1931

By John E. O’Rourke, Kevin M. O’Connor, Pamela H. Rey

INTRODUCTION The resurgence of coal mining activity in the United States, brought on by the spiraling costs of fossil fw1 energy in the Seventies, has come at a time of intense public concern for the quality of the environment. Notwithstanding pressure on our economy to develop alternate sources of fue1 energy to the import of oil, the legislatures of several states have reacted to public concern over the environment by passing strict regulations aimed at con- trolling the subsidence effect s of underground mining. Agencies of the federal government charged with assistance to the mining industry, including the Department of Energy and the Bureau of Mines, have sponsored a number of instrumentation and field measurement projects aimed at the development of subsidence prediction models that can aid the mine operator's task of subsidence control. There are good empirical models developed in Europe for subsidence prediction, but they were made possible by a large body of mining-induced subsidence data collected there over a long period of time. No com- parable subsidence data base exists in the United States, and consequently empirical modeling of subsidence is not a realistic approach for our near term needs. Moreover, the geologic and topographic diversity of the several coal regions in the United States is expected to necessitate the development of several empirical models, each one expected to be relevant to its own region. Because of the time and costs that are likely to be involved in an empirical modeling approach, it is considered more expedient and cost effective to develop a general, mechanistic model for subsidence prediction purposes. In order to develop such a model, it is necessary to investigate and quantify the mechanics of the subsidence process from the mine level up to the ground surface. The series of projects discussed in this paper are designed to achieve this objective and include the following work: (1) the identification of geotechnical instrumentation that will pro- vide mine level overburden and surface subsidence data. (2) a field demonstration of selected instruments, and (3) documentation of case histories for complete subsidence mechanics, using the demonstrated and preferred instruments. An identification of feasible instrumentation and monitoring techniques was completed by Woodward-Clyde Consultants (WCC) in 1977 (O'Rourke and others). This paper discusses a demonstration of those instruments at a mine in Utah, and at two subsequent projects, currently underway at longwall mines in Colorado and West Virginia. 'he latter two projects when complete will provide documented case histories of subsidence mechanics. The process of optimizing subsidence instrumentation and monitoring techniques to the conditions encountered during installation and monitoring for these underground mines is shown to be an evolving one, and one which has had some notable successes to date. INITIAL DEMONSTRATION The initial design and demonstration of selected monitoring systems was carried out at the SUFCO No. 1 mine, near Salina, Utah. The instrumented panel was approximately 152 m wide. 640 m long. and was 290 m to 320 m deep. The mined height of coal. seam averaged 2.4 m. The mining method was room and pillar using continuous mining machines. This method allowed some monitoring of the supported condition during development, and eventually allowed monitoring of a caved system when both chain pillars and room pillars were extracted on retreat. The two instrument systems shown on Table 1 were selected from the earlier feasibility report for demonstration at SUFCO No. 1. Collectively, the two systems, one for a fully-supported mining method and the other for a fully-caved method, incorporate most of the instrumentation to be found within all five systems listed in the earlier feasibility report. The instrumentation includes surface, subsurface and mine monitoring installations. All of the SUFCO instruments selected to meet the specifications of the general instrument types listed on Table 1 were manually operated. That is, data from the installed system could only be obtained while a person was there to physically observe or operate the system readout. Automatic data recording equipment was available for some installations, but the objectives were to keep the systems as simple as possible for the demonstration project. A complete description of the surface, sub- surface and mine level instruments, and the demonstration project results are given in WCC (1982), and selected features are discussed in this paper.

Jan 1, 1982

JESSE L. JONES,* Pittsburgh, Pa.-I would like to ask Miss Erskine if down-draft has been used in any of the foundries where heavy fumes have to be removed, instead of the overhead draft.? L. -ERSKINE.-The system of overhead draft to remove heavy fumes has been very much more successful. The entire efforts of the New Jersey Department of Labor in regard to stabilizing conditions in the foundry are the result of the physical examination of the foundryman himself on first-hand information as to the prevalence of the minor ailments and the bad timekeeping that naturally accompanies them. These ailments are a factor in not only increasing the labor turnover but in increasing the percentage of bad work as well. The physical exertion of the foundryman himself is of course an important factor. In certain standard shops the amount of energy expended runs from 11 to 13 tons of foot-pounds of energy a day. In certain shops on piece work, I found a record of the energy expended per day to run as high as 22 tons. In one shop, during the war period, the management established a bonus system, and the men increased their output from 60 to 100 molds a day. The result was an increase of some 60 per cent. in output, and an increase of 400 per cent. in defective castings. The question of the physical exertion in the unsanitary foundries, of course, is very much complicated by other factors, for which reason the department has devoted a good deal of attention to estimating what is a reasonable exertion in a sanitary, well ventilated foundry. We have met certain physical difficulties in the brass foundries that the iron foundries did not have. All that information is available through our Bureau of Industrial Information. The question of the physical energy exerted by the molder is found to have a very distinct bearing on the question of contracts, for the possibility of increasing production is balanced by the extra overhead involved. JESSE L. JONES.-I would like to ask if any evidence has been noticed of carbon-monoxid poisoning among the employees of the foundries.

Jan 4, 1919

By P. G. Shewmon, H. E. Collins

We have studied the effect of adsorbed sulfur on the surface self-diffusion of copper using eight diflerent surface orientations and the grain boundary grooving method. The eight orientations studied were the four lying near the low-index surfaces—(loo), (Ill), and two directions in the (110)-plus four higher-index surfaces. Surface-diffusion measurements were made over a range of HZS concentrations (in Hz) from 3 to 1500 ppm between 830°and 1050°C. The results can be divided into two groups—Group 1 contains the two (110) surfaces while Group 2 contains the remaining six surfaces. In Group 1, increasing the temperature increases the effect of Hz S on DS for the Hz S range 5700 ppvn. Qs and Do increase with increasing H2S concentration in this Hz S range. Beyond this range, increasing the temperature decreases this effect on D,; also Q, and Do decrease. In Group 2, increasing the telnperature decreases the effect of H2 S on D, for the H2S range studied, and Qs and Do decrease with increasing Hz S concentration. In any study of surface phenomena, there invariably arises the question of the possible presence of and effect of adsorbed impurities. Such questions are well-founded since the presence of adsorbed atoms can sometimes produce marked changes in the kinetics of surface-energy-driven processes. In the last few years, values of the surface self-diffusion coefficient, D,, have been determined on a variety of metals by studying the decay of scratches or the growth of grain boundary grooves.L~3-L0~L3 Yet there has been relatively little work done in which the concentration of an adsorbed impurity was systematically varied and the effects observed. Work of this sort would provide some basis in fact for the assertions often made about the ro1.e of adsorbed impurities in the differences between the results of different workers in different atmospheres and on different metals. It also is relevant to those cases in which surface monolayers produce profound effects in commercially important processes. The most marked example of such effects is the ability of nickel or palladium to increase the sintering rate of tungsten by many orders of magnitude.' The aim of this work was to study the effect of sulfur partial pressures on the surface self-diffusion of copper. It was felt that this in conjunction with a study of the degree of adsorption and type of active sites involvedL8 would provide a wide range of data for one system and hopefully lead to some insight into the mechanism by which sulfur adsorption influences copper diffusion. The main reasons for choosing the Cu-S system were, first, faceting was reported not to accompany the adsorption of sulfur. This is required if our experimental technique is to work. Second, Oudar has determined a high temperature adsorption isotherm for this system, an event which puts the Cu-S system almost in a class by itself.I4 EXPERIMENTAL PROCEDURE Initially, we considered studying the effect of an adsorbed impurity on surface self-diffusion of copper using isolated (or single) scratch smoothing as the technique and oxygen as the impurity. Copper was chosen as the material because the effects of orientation and anisotropy of the surface self-diffusion coefficient, D,, of copper in a dry hydrogen atmosphere had been studied extensively by Gjostein' and by Shewmon and ~hoi.~,~ The isolated scratch technique was chosen because both the effects of surface orientation and anisotropy of D, in a given surface could be easily studied with this method.~ Oxygen was tried as the impurity because Robertson and Shewmon""~ had studied its adsorption on copper at 1000°C over the range of oxygen partial pressures of 10"22 to 10-l3 atm. After several preliminary runs, it became evident that neither the scratch technique nor the impurity oxygen would be satisfactory for this work. Scratching deforms an annealed surface so that the region near the scratches recrystallizes, thereby disrupting the scratch profiles. One can avoid this by deforming the specimen sufficiently before scratching to give complete recrystallization on subsequent heating.4 However, as a result of Gjostein's success in scratching and annealing undeformed gold single crystals without local recrystallization,13 we attempted something similar with copper single crystals using a 0.7-mil diamond phonograph needle mounted in a Tukon hardness tester. All specimens recrystallized upon being annealed. Also, some copper specimens were sent to Gjostein to be scratched using his technique. The results were the same. As a result, the scratch technique was dropped in favor of the grooving of symmetric grain boundaries. Preliminary work using oxygen showed that faceting began to occur before oxygen adsorption had any measurable effect on D, at 938°C (at Pbo/P, = 0.12). Since heavy faceting would interfere with the measurement, we decided to use a sulfur-containing atmosphere (H2S/H2). Work by Oudar and Benard' and Robertson" showed that sulfur absorbed on copper and that faceting was not observed.

Jan 1, 1967

THE. extraordinary volume of work done in this period, and the multiplicity of subject matter, make a year-by-year historical account undesirable, if the account is not to be an assembly of unrelated fragments. We shall, instead, undertake to narrate the development in this period of each of the branches of the subject separately, hoping that their interrelations will be self-evident. There is a certain arbitrariness in the selection of subject matter in the following sections. The development of important engineering alloys-for example, high-speed steel-is disregarded, for it is the primary purpose of this account to relate the advances in ideas, the growth of the science of metals; other historical accounts relate these parallel advances. Nor are advances in techniques stressed, though occasionally the most important are noted; nor is the progress described in allied fields such as welding, cutting, etc.; for though these developments have very frequently made possible the advances herein related, they are far too numerous to recount in anything short of a ponderous volume. There is a more serious arbitrariness, however; it is not an easy matter to draw the boundaries of physical metallurgy, and some contiguous subjects have been omitted that perhaps should have been included, such as, for example, corrosion, gases in metals, the magnetic behavior of metals and alloys, and certain other fields in the physics of metals. REACTIONS IN ALLOYS--DIFFUSION Many of the reactions occurring in alloys proceed by the operation of the process of diffusion in the solid state: the annealing of mixed powders to form alloys, the homogenization of castings or forgings, the freezing of alloys, the treatment of clad metals, the loss

Jan 1, 1948

By E. K. C. Williams, Nathaniel Arbiter

INTRODUCTION The surface processes involved in preparing ores for flotation and for operations depending on their flocculation/dispersion characteristics * vary widely in agitation dependence. Most of the reagents used for these purposes are added to grinding circuits, pump sumps, launders, or directly to flotation cells with the turbulent flow conditions usually adequate both for mixing reagents and for surface reactions without special conditioners. However, some reagent systems do require specific control of agitation intensities and reaction times, the more important of these being the following: 1. Activation of ZnS with CuSO4. With the usual conditions pH about 10, with collector added with the CuSO4, Cu 2+ is almost completely precipitated as basic compounds and as collector salt. As a result the levels of reagent in solution are extremely low which probably accounts for the need for separate conditioning. The agitation intensities are at about the 0.01 HP/ton level.** 2. Flocculation with natural or synthetic polymers. In this case the agitation problem is two-fold; first, to insure adequate initial mixing of the viscous stock solution of the

Jan 1, 1980