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By M. King Hubbert

DURING the past summer the writer was asked by the Illinois State Geological Survey to make a study of some of its economic geological problems with regard to the applicability of geophysical methods of prospecting to their solution. The following four problems were sug-gested for investigation: (1) the fluorspar area of Southern Illinois, (2) oil structures in the south central part of the state, (3) the lead and zinc-bearing area of northwestern Illinois, and (4) the water supply and gravel deposits of the glacial drift. The prime requirements were to find a means of obtaining a maximum of useful information with a fairly modest outlay of expenditure for technical staff and equipment. The method of procedure adopted was that of making a preliminary study of each of the problems named by means of available office data and published reports with supplementary field reconnaissance where necessary.

Jan 1, 1932

Joseph HartshoRnE, Pottstown, Pa.: I have read Professor Akerman's valuable paper with great interest. Few of the present generation of American steel metallurgists are aware of the very important part taken by Swedish engineers in the successful development of the Bessemer proeess, and I am afraid some of the older ones have forgotten it. Certainly, I think, most of us would have said that Terre Noire was the first to introduce the use of metal direct from the blast-furnace. It is very well, therefore, that honor should be given to whom honor is due. I can speak from personal experience upon one part only of Prof. Akerman's paper; namely, the effect of the temperature at which the molten metal is cast upon the quality of the finished steel. In a general way I have, of course, known for a long time that the

Jan 1, 1894

By Joseph Kuti

Longwall mining is the term used for the underground extraction of a wide and deep panel of coal. Such a panel may be blocked out by one or more entries on either side ("head" and "tail") of a longwall face. If all the entries are pre-driven, the panel extraction is termed longwall retreat mining. With one exception, all the longwall faces in the United States are of this type.1 Prior to the general decline in the rates of production with Continuous Miners, the development of the multiple entries generally kept ahead of the longwall extraction rate. This is no longer the case: longwall extraction rates far exceed the rate of development. In addition to this problem, in newly established mines, the development of a haulage and bleeder system based on multiple entries results in a lead-time of three years or more before longwall mining can be applied.

Jan 11, 1979

By Leon Dominian

I. INTRODUCTION APART from local needs in the country's development, the interest attached to Turkish fuels grows chiefly out of the importance of the railway industry in Asiatic Turkey. Geographical conditions make of the tracks in this region the most essential link in a chain of world-girdling lines. By its position Asia Minor can be likened to a bridge in the through routes destined to connect European factories with Asiatic and African markets. An uninterrupted right-of-way from points in central Europe to populous Indian cities must necessarily pass through the valleys A Anatolia. Crossing thence the Taurus Mountains its natural passage is indicated as the Mesopotamian lowland and the shores of the Indian Ocean. Similarly land connection between Europe and Africa can be obtained only by passage through Asia Minor, Syria and Palestine. The occurrence of fuel within an area of such significance from the

Jan 6, 1916

Joseph HartshoRnE, Pottstown, Pa.: I have read Professor Akerman's valuable paper with great interest. Few of the present generation of American steel metallurgists are aware of the very important part taken by Swedish engineers in the successful development of the Bessemer proeess, and I am afraid some of the older ones have forgotten it. Certainly, I think, most of us would have said that Terre Noire was the first to introduce the use of metal direct from the blast-furnace. It is very well, therefore, that honor should be given to whom honor is due. I can speak from personal experience upon one part only of Prof. Akerman's paper; namely, the effect of the temperature at which the molten metal is cast upon the quality of the finished steel. In a general way I have, of course, known for a long time that the

Jan 1, 1894

By G. M. Schwartz

THERE has been considerable controversy regarding the structure and mineral constituents produced when iron ore is sintered. This investigation was undertaken in order to establish the fundamental reactions that take place in the sintering process by determining the nature of the resulting minerals. The writer's immediate interest in the subject arose mainly from the request of E. W. Davis for information based on a microscopic study of sinter submitted by him in May, 1926. In the author's preliminary work, samples of iron-ore sinter were secured from the Minnesota School of Mines Experiment Station and from commercial plants. These were polished by the usual methods for polishing opaque ores. In order to study these surfaces satisfactorily, it is necessary to magnify them rather highly, a range from 100 to 1000 dia. being used. For the higher magnifications oil-immersion lenses and an intense source of light are necessary. After the preliminary study had shown the problems involved, a series of small samples were sintered under carefully controlled conditions and with analyzed materials. Variations in the relative amounts of ore, coal and water were made in order to study the effect of each constituent. The attempt has been to arrive at a clearer understanding of the sintering process and the reactions involved without reference to any preconceived notion as to sinter. It is clear that the study of polished surfaces has yielded results not possible with thin sections alone. The thin sections made in this work were found unsatisfactory at magnification greater than 75, whereas magnifications of 1000 were easily studied with reflected light on carefully polished surfaces. A rather complete statement of observed facts is made so that the reader may form his own conclusions. The writer's interpretations are suggested.

Jan 1, 1929

By Elmer A. Jones

Like the caboose on the end of a long freight train L made up of mineral and metal processing and consuming industries, the mining industry progresses according to the movement of the train to which it is coupled. Sometimes the caboose rolls smoothly; occasionally it bumps along on the ties; almost always it is under criticism from someone for being too small, too large, too expensive, foolishly progressive, or hopelessly out of date. We who ride in the caboose are used to the rough by now, but it is nice now and then to have a bit of the smooth. Last year the train of industrial production rolled ahead swiftly and smoothly, and, except for a hot-box caused by strikes in copper mines, so did the caboose. As is brought out elsewhere in this issue, the outlook for 1956 is for more of the same.

Feb 1, 1956

By Chas. A. Ashburner

The occurrence of oil- and gas-springs in the State of New York has been a fact of historical record since 1627, when the existence of the Cuba oil-spring was first recorded. The utilization of natural gas at Fredonia in 1821 attracted the attention of the public to the possibility of obtaining an illuminating gas by digging and drilling into the rocks. No active search was made, however, for oil or gas by the drilling of wells until after the discovery of commercial oil in Pennsylvania in 1859. In 1862 a well was drilled at Bradford, McKean County, Pennsylvania, but a few miles south of the New York state line, to the depth of 200 feet, in search of the oil-sand which had been found at Titusville, Oil City, and at other points in Western Pennsylvania. Immediately subsequent to this, other wells were drilled in search

Jan 1, 1888

By E. L. Anders

The Mile Six pool is located on the La Brea-Parinas Cullcession of International Petroleum Co., Ltd., in northwestern Peru on the west coast of South America. The reservoir pressure in this pool has been maintained within 200 psi of its initial value throughout its history, and gravity drainage has played an important role in the production behavior. It has now produced 95 per cent of its estimated ultimate recovery. It is estimated that this interesting oil pool will ultimately produce 67 per cent of the initial oil in place and that the resulting residual oil saturation may be as low as 19 per cent of the pore volume (29 per cent of the hydrocarbon pore volume). An evaluation of reservoir rock and fluid characteristics and ultimate oil recovery is presented. INTRODUCTION This study of Mile Six pool was made to evaluate its performance according to latest available information. The production performance of this pool has been discussed in various articles in the past. and the reported behavior has been used as an example for application of computation procedures for gravity drainage depletion' and as an illustration of field behavior under gravity drainage or expanding gas cap drive. There have been wide variations in reported values of initial oil in place, reservoir oil volume factor. connate-water sauration, volume of effective sand, and ultimate recovery because of the paucity of reliable basic data. These various factors have been determined as accurately as practicable with the latest available information, and this evaluation is presented herein. The production history of Mile Six is an excellent example of gravity drainage depleion with effective pressure maintenance by gar injection. GENERAL Mile Six pool was discovered by cable-tool drilling in November. 1927. when well 1996 was completed in the Parinas sand. After slow development with cable tools and sporadic production. the pool was opened to continuous pro(iuction in November. 1933. and develpment was completed with rotary rigs. Pressure maintenance was started in December, 1933. by returning gas to upstructure wells. Most of the development was 'completed by 1937, but some additional wells were drilled in the period 1939-1947. and several old wells were deepened. A total of 46 oil and gas wells and 4 dry holes were drilled on approximately 7-acre spacing. Of the producers. 21 are now flowing. 2 are pumping. 44 are gas input wells. 3 are abandoned. I is a gas well shut in. and 15 are shut in because of non-commercial production or high gas-oil ratio. The locations of all wells are shown on the map of Fig. I. Total oil production on Dec. 31. 1952, was 30,867,373 bbl: cumulative gas production was 22,023,777 Mcf; and 26,410,946 Mcf of gas had been returned to the reservoir. These figures do not include oil and gas lost ill a blowout in January. 1940. GEOLOGICAL DESCRIPTION Mile Six pool is located on the northern end of a structural spur projecting from the La Brea-Negritos uplift.' The spur is probably a reflection of a basement structure. It plunges gently to the north, i broken into a complex series of fault blocks. and contain.; the Verdun Alto. Section Sixteen. and Mile Six pools. The Parinas handstone (lower Eocene!. which is the producing formation in Mile Six. occurs at an average depth of 2,200 ft in the pool and dips north and east at from 15' to 20". The pool covers an area of approximately 350 acres. Mile Six is downfaulted about 600 ft from Section Sixteen pool to the soutb. and a major fault forms its western boundarv. The north and east boundaries are formed by the intersection of the sand top with the water-oil contact which occurs at approximately 2.440 ft subsea. An original gas-oil contact probably existed at about 1.875 ft subsea. Fig. 1 presents the latest structural interpretation of the pool. and Fig. 2 is an isopach map showing thickness of the total Parinas formation above the original water-oil contact. The heavy lints of Fig. 1 are contours on the sand top, and the fine lines are contours on the fault planes. This type of straight-line structural map was developed 1)) International's geologists to reflect structural conditions where the bedding planes dip and have no curvature. 'The La Brea-Parinas Concession is highly faulted by normal fault.. The beds are flat wherever exposed. The Parinas formation is approximately 635 ft thick. and it is etimated that 62 percent II the formation is effective sand. The original oil zone was about 565 ft thick. Fig. 211 presents an electric log showing typical Parinas sand development ill Mile Six pool. The Parinas band in Mile Six i. a well-sorted. medium- to-coal-se-grained. cross-bedded sand with minor lenses of shale and small lenses and pockets of pebble conglomerate. The sand grains are subangular to rounded and consist chiefly of quartz with feldspars. biotite hornblende, and augite as accessory minerals. Because of faulting of the Parinas- formation to the east and north of the pool. there is probably l possibility of a significant, natural water drive in Mile six. The faults within the pool. as indicated in Figs. 1 and 2. are of smaller disI,laceInent and seem to act only , partial barriers to fluid movement within the reservoir. RESERVOIR CHARACTERISTICS Core analysis data are available from five wells. The data were obtained from three wells (Nos. 3401. 3586 and 3719) at the time of their completion and from well 1996 when the original liner was sidetracked and the well was deepened ill 1946. Data from well 2779 were obtained in 1943 from old cores taken when the well was deepened in 1934. From these core analyses. the average porosity was estimated to be 22.6 per cent. and the average permeability to dry ail. was estimated to be 780 and Measured productility indices varied from 3.1 to 71.4 B/D per psi differential. Specific productivity indices varied approximately from 0.1 to 0.3 B./D per psi per ft of sand.

Jan 1, 1953

By K. F. G. Hosking

I read Professor Gaudin&apos;s paper with great interest and pleasure because for some time I have held that the chemical aspect of comminution is a subject of considerable importance to the mineral dresser and deserves to be thoroughly investigated. It does seem appropriate, however, to emphasize the fact that "fresh" edges and corners produced by the grinding of solids display enhanced reactivity has been recognized and utilized in the development of certain mineral identification techniques. Some of these techniques are worth noting, not only because they might facilitate research in the aspect of mineral dressing under discussion, but also because they emphasize the fact that many mineral species commonly regarded as being very inert can display a surprising reactivity when in the freshly ground state. In 1951 Isakov6 published a number of tests for the components of certain mineral species which depend essentially on grinding in a mortar a mixture of the material under investigation with a solid reagent. Thus when stibnite, 4(Sb2S3), is ground with sodium or potassium hydroxide. the antimony is revealed by a momentary development of a yellow color which changes in air to orange-red. Other antimony minerals need a preliminary treatment before the test can be carried out. This consists of grinding with aluminium sulfate, ferric sulfate or potassium bisulfate, and breathing upon the resultant mixture. I have employed a similar technique to determine the approximate magnesia content of certain limestones.&apos; The method depends essentially on the fact that when a sample of limestone is ground under controlled conditions with solutions of sodium hydroxide and Titan yellow the color of the final product is, within limits, a function of the amount of magnesia present. I have also shown that the components of a wide range of minerals can be identified by applying chemicals to their streaks on portions of vitrified, unglazed floor tiles, etc. Under such circumstances the diversity of the reactions which take place in the cold (because of the reactivity of fresh corners and edges) is surprising. Thus, for example, if a garnierite, (Ni,Mg)3Si2O5(OH)1, streak is treated first with a drop of 0.880 ammonia and then with a drop of a 1 pct alcoholic dimethyl-glyoxime it immediately becomes red, indicating the presence of nickel.&apos; Stevens and Carron9 have evolved a simple field test for distinguishing minerals by "abrasion pH." A soft nonabsorbent mineral is scratched in a drop of water on a streak plate until a milky suspension is formed. A piece of pH indicator paper is dipped into the suspension, after which it is removed and the maximum deviation from neutrality noted. When a hard mineral or one which absorbs water is being tested, fragments are first ground for 1 min with a few drops of water in a mortar to make a heavy suspension. The importance of the findings of such tests to mineral dressing may be judged by the abrasion pH values, Table 11, recorded by Stevens and Carron for certain species usually regarded as comparatively inert. The combined results Of the above researches clearly indicate that comminution is capable of altering the pH of a pulp and of causing the chemical nature of the surfaces of some of the components to be profoundly changed&apos; Depending On circumstances such surface alterations may have a beneficial or an adverse effect if these products are subsequently subjected to flotation. The tests also suggest that by grinding "inert" minerals with appropriate solid or liquid reagents "reactive" surfaces may be developed which might facilitate separations by flotation. It is an interesting and instructive problem to determine the reactions that are likely to take place when dry solid substances are subjected to comminution and to the unavoidable heat liberated during the process. To do this it is theoretically necessary to know the free energy values of the reactants and possible resultants, but unfortunately there is a dearth of such data! However, the heats of formation of many substances are known, and generally speaking, if in a reaction of the type AB + CD = AD + CB the sum of the heats of formation of AB and CD is less than that of AD and CB the reaction will probably proceed to the right. Thus, according to a note I have (the author of which I cannot name) if PbS (black) is warmed with CdSO, (white), PbSO., (white) and CdS (yellow) are formed, and that the reaction does, in fact, take place is indicated by the change in color of the mixture. The reaction is expected, as the sum of the heats of formation of PbS and CdSO, is less than that of PbSO, and CdS (as shown below). PbS + CdSO4 = PbSO4 + CdS 22.2 + 218.0 < 216.2 + 33.9 Finally, certain other aspects of the chemistry of comminution, which are neither mentioned by Professor Gaudin nor referred to by me are to be found in a paper by Welsh" and in the printed discussion thereof. A. M. Gaudin (author&apos;s reply)—The observations contributed by Dr. Hosking are indeed welcome, as they add to our experimental knowledge of a topic which is believed to be of the first importance. In connection with the experiments cited it should be kept in mind that oxidation, hydration, and carbonation at various rates should always be deemed to be possibilities when grinding is done in water or in air, even in "industrially dry" air. Special precautions might lead to sufficient minimizing of these reactions and to the assertion, instead, of deliberately-created reactions. The author wishes to thank Dr. Hosking for his contribution.

Jan 1, 1957

By R. D. Lord

The search for the best practical means of storing sulfide bearing tailings, where there is no residual excess of carbonate material is discussed in this paper• Usually the sulfide content decomposes, with the aid of bacterial action, and the resulting sulfuric acid escapes, along with any heavy-metal solutes, through embankments that are usually porous to some degree• The problem is typified in the tailings of the uranium operations of Elliot Lake, Ont., where mining started some 20 years ago• The approach to tailings disposal paralleled the practice for other hydrometallurgical plants treating gold and base-metal ores• Impoundment areas were designed to retain solids, and a clear and neutral overflow was considered satisfactory practice• Now experience has shown that these areas, some of which have been idle for over a dozen years, release acids in seepage and overflows to an unacceptable degree• To protect natural water courses, neutralizing plants are operated wherever required• Lime slurry is fed continuously into the tailings outflows in a quantity sufficient to raise the pH to 8•5 and precipitate heavy metals that may be in solution• The objection to this procedure is that the plants will require servicing indefinitely, unless a better remedy is found• The problem differs only slightly from that common to base-metal concentrators in that here the ore has been leached with sulfuric acid for the recovery of uranium• Any native content of calcareous material has been digested, and only that added for final neutralization is available to maintain a pH unfavorable to bacterial activity• Chemical oxidation slowly lowers the pH and when this reaches a level of 4•5 or less, bacteria become active and greatly accelerate the formation of acid. The bacterial process is probably at least ten times as fast as the chemical oxidation• Location and Processing The operations referred to, uranium and one copper mine, are located at approximately 46°N and 82°W longitude• This is typical Canadian Shield country, a land of lakes, deeply glaciated and rocky, with sparse soil which supports mixed forest cover• Drainage is to Lake Huron, 25 miles to the south• Average temperature is 45°F, ranging from -40° to +95°F• Annual precipitation is 38 in•, about half of which is snow• The ore is Precambrian, quartz-pebble conglomerate, with mineralization in the matrix• From 5 to 10% pyrite is present• All known means of pre-concentration have been tested, but a bulk sulfuric acid leach has proved the most efficient. Tailings have from the outset been neutralized before release• Current practice is to add ground limestone to bring the pH to 4•5, and then lime to raise the value to 10•5• Environmental regulations have recently been increased and the foregoing meets the new standards• Separate measures are taken to precipitate radium• Remedial Measures Since the outstanding environmental problem is the oxidation of pyrite by bacterial action, the solution is to contain the products, or arrest the process• Given the ambient temperature, favorable half of the time, four items are essential to the activity• 1) Pyrite• 2) Moisture pH < 4•5. 3) Oxygen• 4) Bacteria• Removing any one of these out of the range of tolerance will bring the reactions under control• A variety of proposals considered, and a number tested for the arrest of the process, are: (a) render embankments impermeable, (b) provide an impermeable cover, (c) cover with an oxygen absorbing layer, (d) provide a vegetative cover, (e) flood the site, (f) remove pyrite from current tailings, (g) add excess limestone to current tailings, (h) poison the bacteria• Bank Seal-On existing impoundment areas, where the embankments are several thousand yards in length, it is believed that any program of injecting sealants can have small chance of success• However, a moisture barrier is an indicated specification for future construction, and this can be highly expensive• Surface Seal-Depending on the configuration of the deposit, the downward travel of water should be prevented, and oxygen excluded• Burying a plastic membrane just below the surface has been considered, as has the application of a liquid sealant that would penetrate the surface. The objection to these remedies is the excessive cost of dealing with large areas and the expectation of only temporary benefit as a result• Frost penetration is over 4 ft, and frost action breaks up asphalt paving and all but heavy concrete in a few years• Organic Layer-An oxygen-absorbing layer, such as bark fines from paper mills has been proposed as a surface treatment• Cultivated into the tailings such material might be expected to arrest subsurface oxidation for some years• Estimates are 100 tons per acre of bark fines, or 35 tons per acre of sawdust, and these enormous quantities do not so far give assurance of providing a long-term remedy• Vegatative Cover-Several obvious benefits would result from a good growth of grass or other vegetation on abandoned tailings• While restoring the natural green of the tract the growth would prevent wind-blown dust and reduce erosion• Subsurface oxidation should be reduced, as well as the upward movement of ground moisture as occurs in dry weather. To this end, considerable research and field testing has been carried out to arrive at a formula - a prescription which will provide a self-sustaining growth on the tailings surface, or at least one that would survive with reasonable maintenance attention. Many test plots have been run with different combinations of surface treatment and seed mixtures. Generally, by addition and close cultivation of limestone, lime, and fertilizers, technical success has been demonstrated• Plants with a high tolerance for acid soil seem the more hardy, and a pH above 3 is indicated so that nutrients can be absorbed• Recommendations are for 12 to 15 tons of

Jan 1, 1977

By Jacques Steininger, Robert E. England

Single crystals of ZnTe and ZnTe1-,Sex with x up to 0.13 have been grown from the elements by temperature gradient solution zoning using excess tellurium as a solvent. Best results have been obtained with charges with the compositions 45/55 at. pct Zn, Te, for ZnTe and increasing amounts of selenium for ZnTe1-xSex. The temperature in the molten zone was maintained at about 1070°C with a gradient of about 10°C per cm. Chemical analyses of quenched ZnTe ingots show tellurium concentrations in the molten zone as high as 70 pct with concentration differences across the zone of 1 to 2 at. pct Dark dots which are observed by transmitted light microscopy in as-grown crystals can be removed by annealing in zinc vapor at 900 C. INTEREST in wide band gap semiconductors has led to a new study of ZnTe and ZnTel-xSex crystal growth. ZnTe is the only II-VI compound with a wide band gap (2.3 ev) that can be made p type with low resistivity. Attempts to make it n type with low enough resistivity to be useful for p-n junctions have so far been unsuccessful.1 ZnSe has a band gap of 2.65 ev but can be made n type only. However, ZnTel-xSex solid solutions with x as low as 0.36 have been made both highly n and p type2 with a minimum band gap around 2.12 ev3 at room temperature and appear to hold the best promise for efficient injection electroluminescence in the visible. ZnTe has the lowest melting point of the zinc chal-cogenides (1295°C) and consequently attempts have been made to grow crystals from both the liquid and the vapor phase.4 Complicated apparatus is required for growth from stoichiometric melts because of the high vapor pressures of the elements at the melting point of ZnTe and because of the problem of quartz devitrification. Small crystals have thus been grown in high-pressure equipment by Fischer5 and by Narita et a1.6 with pressures of the order of 50 atm of argon to prevent excessive evaporation from the melt. Large crystals of ZnTe can be obtained by growth from the vapor phase4 but they often present numerous dislocations and inclusions. An improvement in the quality of vapor- grown ZnTe crystals was reported by Albers and Aten7 by equilibration of mixtures of small crystals with compositions lying on either side of the solid single-phase field at fixed temperature. The same technique was later applied by Aten8 to the growth of ZnTe1-xSex crystals with less than 1 pct inhomo-geneity. Because of the higher liquidus temperatures of the solid solutions and the high vapor pressure of selenium, previous attempts to grow ZnTel-xSex from the melt have been limited and unsuccessful.9 The phase diagram of the Zn- Te system is reproduced in Fig. 1, based on data from Kobayashi10 and Kulwicki.11 Carides and Fishher12 have reported lower liquidus temperatures on the tellurium-rich side, but their data would require confirmation. The liquidus temperature on the tellurium-rich side decreases rapidly with increasing tellurium concentration and the Te2 vapor pressure over the liquidus also decreases accordingly.&apos;3 The decrease in liquidus temperature and vapor pressure therefore makes it possible to use conventional apparatus if there is a sufficient excess of tellurium in the melt. Single crystals of ZnTe have thus been grown by Kucza,14 in a modified Bridgman technique, from solutions containing up to 60 at. pct of Te by lowering unsupported quartz ampoules through a temperature gradient at about 1200°C. Under these conditions, the phase diagram indicates that the entire charge is initially molten. Crystal growth can therefore proceed by normal freezing and rejection of excess tellurium into the melt. The modified Bridgman technique has several major limitations. Because of the rejection of excess tellurium into the melt during freezing, the melt composition and the temperature at the growth interface vary continuously. They tend to follow the liquidus until the eutectic which is very close to pure tellurium (447°C, >99 pct Te). Since the solidus composition also varies with temperature,15 crystals grown by this method are inhomogeneous. They present small variations from stoichiometry which may affect their structure and physical properties. The simultaneous increase in tellurium content and decrease in melt temperature also combine to reduce the rate of diffusion of tellurium away from the growth interface, thereby causing constitutional supercooling and possibly dendritic growth. To minimize these effects, the initial melt composition is in practice kept relatively close to stoichiometry (less than 60 pct Te). This however limits the possibilities of operating at low temperatures and pressures. This paper describes a modified method of crystal growth by temperature gradient solution zoning (TGSZ) which is an adaptation of the temperature gradient zone-melting technique developed by pfann16 and of the traveling solvent method of Mlavsky and weinstein.I7 The TGSZ method now applied to the growth of ZnTe and ZnTel-xSex crystals is characterized by its very simple experimental arrangement and sample preparation technique. Unlike the modified Bridgman technique, there is no increase in the tellurium concentration in the melt and therefore it is possible to operate at lower temperatures and pressures. This method is also suitable for maintaining a constant temperature at the growth interface.

Jan 1, 1969

By Ravindra M. Nadkarni, Milton E. Wadsworth

The kinetics of cetnentation of copper with iron were observed to follow first-order kinetics and increase with speed of agitation to a limiting value. Maximum rates agree closely with theoretical values based upon a model of aqueous solution diffusion through a litniting boundary film. Back reaction kinetics are shown both theoretically and experimentally to be independent of ferrous iron concentration in solution. The inlportance of attnospheres of air, oxygen, nitrogen, and hydrogen was studied and the results have been correlated with several impovtant oxidation processes involving metallic iron and copper. The kinetics of the reaction of ferric ion with metallic iron were found to be slow in the absence of metallic copper and essentially proportional to the surface area of metallic copper present in the system. THE precipitation of copper on iron is classic as an example of a relatively ancient art applied successfully for centuries with little fundamental understanding of the important parameters involved. There is some indication that the process has been a commercial means to produce copper since the sixteenth century.&apos; The amount of fundamental work on the cementation of copper with iron is not great. Wartman and Roberson2 carried out a series of detailed copper cementation experiments using natural and synthetic mine water. The following were presented as the three principal reactions: Reaction [I] is the desired cementation reaction and accordingly 0.88 lb of iron would produce 1 lb of copper. In actual practice iron consumption would more normally fall in the range of 1.5 to 2.5 lb per lb of copper. Wartman and Roberson attributed the excess consumption of iron to Reactions [2] and [3]. They found that Reactions [I] and [2] proceeded at approximately the same velocity while Reaction [3] was much slower and would be diminished by controlling the contact time. It was also pointed out that increased agitation is beneficial in removing hydrogen bubbles and barren layers of solution at the iron surface as well as removing contaminants resulting from the hydrolysis of iron. Episkoposyan3 and Episkoposyan and Kakovskii4 studied copper and silver cementation on rotating iron disks in chloride solutions. The kinetics based upon a diffusion model were first order and varied linearly with surface area and with angular velocity raised to the one-half power according to the Levich equation. The experimental activation energy for both copper and silver was approximately 3 kcal per per mole. Excess iron consumption was found to increase with temperature. The rate of cementation first increased with increasing acidity and then diminished at high acid concentrations. sutolov5 has presented an excellent review of the Leach-Precipitation-Flotation (LPF) process including a discussion of copper cementation from an electrochemical point of view although few experimental results were presented. From voltage considerations he predicted that cementation should not be influenced by the concentration of ferrous iron in solution. He considered several secondary reactions including Reactions [2] and [3] and pointed out the importance of oxidation of ferrous iron to ferric with oxygen. In addition it was suggested that Reaction [2] was enhanced by the dissolution of metallic copper by ferric iron which in turn consumed excess iron by the cementation reaction, Eq.[1]. Cementation of copper on metals other than iron has been studied by several investigators but, as in the case of iron, the amount of fundamental work is not extensive. Bashkova and kovalenko6 and Bashkova7 studied the cementation of copper on indium from copper and indium sulfate solutions. The rate was found to be first order and to increase with acidity. This was associated with a decrease in potential (EIn — ECu) and the simultaneous reduction of hydrogen ions at low pH. The rate of cementation also decreased with increasing indium concentrations which was postulated to be due to the decrease in the rate of diffusion of the ions in solution. Below 97°C the experimental activation energy was found to have the unusually low value of 2 kcal per mole and was attributed to diffusional control. Above 97°C the rate increased suddenly and was explained as a change in the rate-controlling step to a chemical reaction. In Part I of this study Nadkarni et a1 .1 have reported on preliminary results obtained in a laboratory study of the kinetics of the cementation process. The rate was found to be first order, proportional to the surface area of the iron, and to increase with speed of stirring until a maximum rate was observed. At low stirring speeds the deposit was spongy and adherent. At medium speeds the copper peeled off in bright strips and at high speeds finely divided copper was produced and continually removed from the surface. The amount of excess iron consumed increased with speed of stirring and with temperature. The average experimental activation energy combining results from several types of iron was 5.8 + 1.6 kcal per mole suggesting diffusional control through a limiting boundary film. Traditionally copper cementation has been carried out over the centuries in gravity-fed launders of various design containing scrap iron. More recently rotating drum precipitators and activated launders8&apos;10 have been used. In the latter, copper-bearing solutions are

Jan 1, 1968

By Hugh H. Waesche

Of all the military services, the Signal Corps is the most concerned with piezoelectric minerals because of its function as a supply service to the strategic and tactical military forces. Consequently this paper is written from the point of view of one associated with that organization. The Signal Corps is responsible for the research, development, and supply of communications, radar, and components to the using services of the Department of the Army and to some extent the Other branches of the National Defense Department. Their work therefore includes the study of the sources* characteristics, and application of quartz and other piezoelectric materials. These materials have become a vital consideration in strategic planning and are essential for efficient tactical operation by all the Armed Forces. The Signal Corps at the beginning of world War 11 Was respon-sible for both Army Ground and Air Force electronic equipment. Since that time this Army service organization has probably done more in the development of frequency control devices using piezoelectric materials than any other group. The U.S. Department of the Interior, Bureau of Mines, Minerals yearbook of 1945, shows that during the four war years, 1942 through 1945, 9,598,-410 Ib of quartz crystal were imported for all uses and of this total, 5,168,000 lb were consumed to produce 78,320,-000 crystal units for electronic application. Other government records confirm these data which conclusively show that approximately 53 pct of the crystalline quartz imported was consumed in the production of electronically applied quartz crystal units. It may be assumed that some effort was made to maintain a stockpile over demands for all purposes. and this would mean that the actual percentage of quartz used electronically was considerably over the 53 pct figure. These data only emphasize that electronic application of crystalline quartz was the greatest requirement, and per- haps the actual value in this application to national defense is many times greater in importance than is apparent on first inspection. Current electronic research and development programs of the Armed Forces are planned around the fundamental use of piezoelectric minerals for frequency control and this at present, at least, means quartz. Definition and Early Development The word piezoelectricity is formed from combination of the Greek word "piezein". meaning "to press," and "electricity." It is that property shown by numerous crystalline substances whereby electrical charges of equal and opposite value are produced on certain surfaces when the crystal is subjected to mechanical stress. It appears to be intimately associated with the better known property, pyro-electricity and in fact, the two may be manifestations of the same phenomeuon. This property was discovered by Pierre and Jacques Curie in quartz, tourmaline, and other minerals in 1880 while studying the symmetry of crystals. The converse effect, that is, mechanical strain in the crystal when placed in an electrical field, was predicted by the French physicist, G. Lippman, in 1881, and verified by the Curies almost immediately. As has been the case with many discoveries of similar character in the basic sciences, not much attention was paid to this property for man)- years except as an entertaining curiosity. Between 1890 and 1892 a series of papers was published by W. voigt in which the theoretical physical properties were put into mathematical form. The first practical application of piezoelectricity occurred during World War I when professor P. Langevin of France used quartz mosaics to produce underwater sound waves. The same mosaics were used to pick up the sound reflections from submerged objects which were in turn, amplified by electronic means and used to determine the distances to such objects. This device was intended for use as a submarine detector but development was not completed in time for war service although it was used later for determining ocean depths. About the same time, A. M. Nicholson, of Bell Telephone Laboratories, developed microphones and phonograph pickups using Rochelle salt crystals. A major step in the application of piezoelectric quartz came in 1921, when professor W. G. Cady, of wesleyan university, showed that a radio oscillator could be controlled by a quartz crystal; from that date, this use of quartz has increased steadily, reaching its peak in world war 11 as is shown by the figures previously given. Essentially all American electronic equipment for communication, navigation, and radar, utilized quartz crystals for the exacting frequency control required. Crystalline Minerals with piezoelectric Properties QUARTZ Hundreds of piezoelectric crystalline materials are known, most of which are water soluble. Of these, quartz appears to be without a peer for electronic frequency control. Unfortunately, the quartz must be of superior quality. It must be free of mechanical flaws, essen-tially optically clear, free of both Brazil and Dauphiné twinning and must be, for average uses, over 100 g in weight. Because of these stringent requirements, raw quartz of the quality desired is of rare occurrence. In addition to quartz, several other naturally occurring crystalline materials are known to have the piezoelectric property and could perhaps be substituted for quartz in some applications. These

Jan 1, 1950

By J. J. Tietien, R. O. Clough

A technique previously used to prepare alloys of InAs1-xPx and GaAsl-x Px, miry: the gaseous hydrides arsine and phosphine, has been extended to grow single -crystalline GaAs 1-x Sb x by replacing the phos-phine with stibine. Procedures were developed for handling and storing stibine which now make this chemical useful for vapor phase growth. This represents the first time that this series of alloys has been grown from the vapor phase. Layers of P -type GaSb and GaSb-rich alloys have been grown with the carrier concentrations comparable to the lowest ever reported. In addition, a p-type alloy containing 4 pct GaSb exhibited a mobility of 400 sq cm per v-sec which is equivalent to the highest reported for GaAs. RECENTLY, interest has been shown in the preparation and properties of GaAs1-xSbx alloys, since it was predicted1 that for compositions in the range of 0.1 < x < 0.5, they might provide improved Gunn devices. However, preparation of these alloys presents fundamental difficulties. In the case of liquid phase growth, the large concentration difference between the liquidus and solidus in the phase diagram, at any given temperature, introduces constitutional supercooling problems. It is likely that, for this reason, virtually no description of the preparation of GaAs1-xSbx by this technique has been reported. In the case of vapor phase growth, problems are presented by the low vapor pressure of antimony, and the low melting point of GaSb and many of these alloys. In previous attempts1 at the vapor phase growth of these materials, using antimony pentachloride as the source of antimony vapor, alloy compositions were limited to those containing less than about 2 pct GaSb. This was in part due to the difficulty of avoiding condensation of antimony on introducing it to the growth zone. A growth technique has recently been described2 for the preparation of III-V compounds in which the hydrides of arsenic and phosphorous (AsH3 and pH3) are used as the source of the group V element. With this method, GaAs1-xPx and InAs1-xPx have been prepared2&apos;3 across both alloy series with very good electrical properties. Since the use of stibine (SbH3) affords the potential for effective introduction of antimony to the growth apparatus, in analogy with the other group V hydrides, this growth method has been explored for the preparation of GaAs1-xSbx alloys. In addition to GaSb, these alloys have now been prepared with values of x as high as 0.8. In the case of GaSb, undoped p-type layers were grown with carrier concentrations equivalent to the lowest reported in the literature. Thus it has been demonstrated that, with this growth technique, all of the alloys in this series can be prepared. EXPERIMENTAL PROCEDURE A) Growth Technique. The growth apparatus, shown schematically in Fig. 1, and procedure are virtually identical to that described2 for the growth of GaAs1-xPx alloys, with the exception that phosphine is replaced by stibine.* HCl is introduced over the gallium boat to *Purchased from Matheson Co., E. Rutherford,N+J. transport the gallium predominantly via its subchlo-ride to the reaction zone, where it reacts with arsenic and antimony on the substrate surface to form an alloy layer. The fundamental limiting factors to the growth of GaAs1-xSbx alloys from the vapor phase, especially GaSb-rich alloys, are the low melting point of GaSb (712°C) and the low vapor pressure of antimony at this temperature (<l mm). Thus, relatively low antimony pressures must be employed, which, however, imply low growth rates. To provide low antimony pressures, very dilute concentrations of arsine and stibine in a hydrogen carrier gas were used. Typical flow rates (referred to stp) were about 4 cm3 per min of HC1 (0.06 mole pct)+ from 0.1 to 1 cm3 per min of ASH, (0.002 to 0.02 mole pct), and from 1 to 10 cn13 per min of SbH3 (0.02 to 0.2 mole pct), with a total hydrogen carrier gas flow rate of about 6000 cm3 per min. Although no precise data on decomposition. kinetics exist, it is known4 that stibine decomposes extremely rapidly at elevated temperatures. However, the high linear velocities attendent with the high total flow rate (about 2000 cm per sec) delays cracking of the stibine until it reaches the reaction zone and prevents condensation of antimony in the system. To improve the growth rates of the GaSb-rich alloys, growth temperatures just below the alloy solidus are main-

Jan 1, 1970

By V. S. Gupt, W. H. Somerton

Rock may undergo great changes in physical properties when heated to high temperatures and then cooled, The temperature and intensity of reactions causing rock alterntiorl.s can he controlled by introducing certain chemicals during heat treament. Three typical outcrop sandsone samples were saturuted with common salt solutions, then heated to several maximum temperatures. After cooling, it was found that per-rrreuhilities had increased much more for salt-saturated samples than for samples not saturated with salt but heated to the same temperatures. This was only true, however. for samples heated above the melting points of the particrrlar salts. Potassium chloritle was particularly effective with Bandera sandstone. Samples saturated with potassium chlorirlr. solution and heated to 900C showed an 11-fold increa.se in perrrieahility. Samples without potasrirdrn chloritle but heated to the .same temperature. showed only a 2.7-jold incresre in permecahility. In application, it seems possible that injecting chemicalc into the formations from a wellbore followed by applying intensive borehole heating might promote reactions which would greatly improve permeability of the formalions. INTRODUCTION Great changes in the physical properties of rocks which have been heated to temperatures in the range of 600 to 800C have been reported earlier. Permeability increases of 50 per cent, and equivalent decreases in sonic velocity and breaking strength have been observed. Although there might be some suppression of certain reactions responsiblc for these changes when rock samples are heated under simulated reservoir pressure conditions. recent work has shown that these are more than offset by the increased importance of other reactions at high pressures. The reactions considered responsible for alteration of rock properties by heating include differential thermal expansion. dehydration, phase changes and dissociation of mineral constituents. Ceramists have long known that temperatures at which reactions occur can be raised or lowered by the presence of certain impurities in the sys. tcnl. Thus the possibility exists that by saturating rocks with appropriate solutions. desired reactions might be accelerated and unwanted reactions might be suppressec! when the rock is heated. Purpose of the present work was to investigate the effects of several common salts on the thermal alteration of sandstones. Types of reactions which might occur are reviewed and the findings of a number of thernlochemical alteration tests are presented. THEKMOCHEMICAL ALTERATION OF SANDSTONE MINERALS The most abundant constituent of most sandstones is quartz. Quartz can exist in at least eight different forms, but in the temperature range of immediate interest (to 900C) only two forms are of importance—alpha quartz below 573C and beta quartz above this temperature. Although the alpha-beta inversion of quartz is very important in thermal alteration of rocks. it is not particularly important here because the inversion temperature cannot be changed significantly by the presence of impurities or by the application of pressure. The transition temperature of quartz to tridynlite is 867C. but the transition is very sluggish. Tridymite is considered to be a metastable transition phase between two stable phases: quartz?cristobalite. However. the transition temperature for tridymite to cristobalite is 1,470C.4 The quartz-tridymite-cristobalite transition can be accelerated substantially by the presence of fluxing agents. Finely divided calcium, magnesium and titanium oxides accelerate the conversion while A12O may retard it. A Mixture of NaCl and CsCl reduces the temperature for cristobalite formation by as much as 420°C. Feldspars constitute the second most important mineral in sandstones. The melting points of feldspars range between 1,000 and 1,700°C depending upon the variety. No information available indicated any important role of fluxing agents in the thermal alteration of this group of minerals. Carbonate minerals are subject to dissociation at temperatures within the range of the present investigation. The dissociation of magnesite can start at a temperature of 373°C, but the reaction is sluggish and might not occur untll a temperature of 500°C or ,higher is reached. Dolomite dissociates in two stages at 500°C and 890°C, whereas calcite dissociation temperature is about 885C. Because CO2 is released in the dissociation of carbonates, ail such reactions are somewhat dependent upon CO2 partial pressure. In the absence of CO: in the surrounding atmosphere, the dissociation of calcite starts at 500°C.However. when 1 atm of CO surrounds the sample, the dissociation does not start until 900C. The other carbonates are apparently much less sensitive to a change in partial pressure of CO2. The aragonite calcite transformation can occur an!. where within the temperature range of 357 to 488°C. depending upon the presence of impurities such as barium. strontium. lead and perhaps zinc. The differential thermal analysis (DTA) curves of both magnesitc and dolomite vary with the presence of &apos;impuritics. The presence of iron in particular seems to affect the magnesitc DTA curve

Jan 1, 1966

By G. W. P. Rengstorff

In an effort to find an oxidation-resistant alloy of molybdenum, binary and ternary alloys containing aluminum, chromium, cobalt, iron, nickel, silicon, titanium, tungsten, vanadium, and zirconium were screened. Fourteen other alloying additions were also tested. Many of the alloys were more oxidation-resistant than molybdenum, but none were entirely satisfactory. MOLYBDENUM oxidizes extremely rapidly above 1450°F in air. At 1800°F, a loss of metal at the rate of 0.1 in. in 4 hr is typical. The high speed of this oxidation may be judged by comparison with the oxidation rate of 0.1 in. per year (0.00005 in. in 4 hr), sometimes taken as the maximum permissible oxidation rate at 1800°F for a satisfactory Fe-Cr-Ni alloy. Great strides have been made in the development of coatings and cladding to protect molybdenum from oxidizing atmospheres. These developments in surface protection will undoubtedly make it possible to take advantage of the excellent hot strength of molybdellum and its alloys in many new applications. Still, even the best coating can protect molybdenum only as long as the surface layer is unbroken. Research was undertaken to determine whether an alloy of molybdenum could be found which would resist oxidation. Such an alloy would not deteriorate suddenly when the protective surface layer was destroyed in a small area. In seeking an alloy of molybdenum to resist oxidation, the physical properties of molybdenum could not be sacrificed entirely. The development of an alloy with the desired resistance to oxidation was not achieved. The information obtained on the effect of a large number of elements on the oxidation of molybdenum is, however, of value in the development of coatings. Indeed, many of the alloys tested for oxidation resistance were already known to have poor mechanical properties but were tested to aid in the development of coatings. Oxidation of Molybdenum The rapid oxidation of molybdenum is usually attributed to the volatility of Moo,,. Gulbransen and Wysong have shown that molybdenum oxidizes very slowly up to 850°F, the temperature at which the oxide film begins to evaporate. Melting as well as evaporation of molybdenum oxides promotes the oxidation of molybdenum. MoO melts at 1465°F. MOO, the oxide which is believed to form at the metal-oxide interface, combines with MoO, to form a eutectic having a melting point of 1432°F.&apos; The liquid oxide, even if nonvolatile, could cause poor resistance to oxidation by allowing easy transport of molybdenum and oxygen ions through the oxide. Actually, a sudden increase in the rate of oxidation of molybdenum at 1460°F has been observed to coincide with the appearance of a liquid phase. The formation of a volatile oxide is not unique with molybdenum. The problem is also encountered with vanadium, tungsten, and some of the Pt-Pd group of metals. Vanadium not only forms the volatile V2O3 but, like molybdenum, forms a liquid oxide coating. Few attempts have been made, however, to prevent the rapid oxidation of these metals by alloying. Oxidation of Molybdenum Alloys At the beginning of this work, very little was known of the oxidation resistance of molybdenum alloys. It was known that molybdenum disilicide (with 37 pct Si) has extremely good oxidation resistance,&apos; but this compound is so brittle that it has few uses. It is an effective protective coating for molybdenum when allowance can be made for its brittleness. Chromium was known to retard the oxidation of molybdenum,&apos; but at least 50 pct Cr was necessary to have an appreciable effect. Other, unpublished, reports show that a few other alloys have been given preliminary tests, but the results have not been promising." Choice of Alloys to be Investigated An alloying element might be expected to protect molybdenum in either of two ways: Its oxide might combine with molybdenum oxide to form a stable, nonvolatile complex oxide (a molybdate); or the oxide of the alloying element might form in preference to molybdenum oxide, developing an impervious layer which would prevent the formation of a volatile molybdenum oxide. The knowledge available about the formation of molybdates was meager. Therefore, the initial study was made on alloys of molybdenum with elements having especially stable oxides. On this basis, binary and ternary alloys containing the following six elements were investigated: aluminum, chromium, titanium, zirconium, silicon, and vanadium. Nickel was also added as an alloying element. Although it does not form a more stable oxide than molybdenum, it does impart some oxidation resistance to copper and iron. Its inclusion in the study was fortunate because its alloys proved to be the most promising of those first tested. Apparently nickel formed a stable molybdate. Because nickel was effective in reducing the oxidation rate of molybdenum, the elements iron, cobalt, and tungsten were added to the list. The ten alloying elements mentioned form ten binary and 45 ternary alloying systems with molybdenum. A series of alloys was tested in each of these systems. In addition, at least one test was made on the effect of each of the following alloying elements:

Jan 1, 1957

By H. J. Ramey

The wellbore acts as a storage tank during drawdown and build-up testing and causes the sand-face flow rate to approach the constant surface flow rate as a function of time. This effect is compounded if non-Darcy flow (turbulent flow) exists near a gas wellbore. Non-Darcy flow can be interpreted as a flow-rate dependent skin effect. A method for determining the non-Darcy flow constant using this concept and the usual skin effect equation is described. Field tests of this method have identified several cases where non-Darcy flow was severe enough that gas wells in a fractured region appeared to be moderately damaged. The combination of wellbore storage and non-Darcy flow can result in erroneous estimates of formation flow capacity for short-time gas well tests. Fortunately, the presence of the wellbore storage eflect permits a new analysis which can provide a reasonable estimate of formation flow capacity and the non-Darcy flow constant from a single short-time test. The basis of the Gladfelter, Tracy and Wilsey correction for wellbore storage in pressure build-up was investigated. Results led to extension of the method to drawdown testing. If non-Darcy flow is not important, the method can be used to correct short-time gas well drawdown or build-up data. A method for estimation of the duration of wellbore storage effects was developed. INTRODUCTION In 1953, van Everdingen and Hurst generalized results published in their previous paper3 concerning wellbore storage effects to include a "skin effect", or a region of altered permeability adjacent to the wellbore. Later, Gladfelter. Tracy and Wilsey4 presented a method for correcting observed oilwell pressure build-up data for wellbore storage in the presence of a skin effect. The method depended upon measuring the change in the fluid storage in the wellbore by measuring the rise in liquid level. To the author&apos;s knowledge, application of the Gladfelter, Tracy and Wilsey storage correction to gas-well build-up has not been discussed in the literature. It is, however, a rather obvious application. Gas storage in the wellbore is a conlpressibility effect and can be estimated easily from the measured wellbore pressure as a function of time. Several approaches to the wellbore storage problem have been suggested. As summarized by Matthews, it is possible to minimize annulus storage volume by using a packer, and to obtain a near sand-face shut-in by use of down-hole tubing plug devices. Matthews and Perrine have suggested criteiia for determining the time when storage effects become negligible. In 1962, Swift and Kiel&apos; presented a method for determination of the effect of non-Darcy flow (often called turbulent flow) upon gas-well behavior. This paper provided a theoretical basis for peculiar gas-well behavior described previously by Smith. Recently, Carter, Miller and Riley observed disagreement among flow capacity k,,h data determined from gas-well drawdown tests conducted at different flow rates for short periods of time (less than six hours flowing time). In the original preprint of their paper, Carter et al. proposed that the discrepancy in flow capacity was possibly a result of wellbore storage effects. Results of an analytical study of unloading of the wellbore and non-Darcy flow were recorded by carter.14 In the final text of their paper, Carter et al.!&apos; stated that they no longer believed wellbore storage was the reason for discrepancy in their kgh estimates. In view of the preceding, this study was performed to establish the importance of non-Darcy flow and well-bore storage for gas-well testing. In the course of the study. a reinspection of the previous work by van Everdingen&apos; and Hurst&apos; was made, and the basis for the Gladfelter, Tracy and Wilsey&apos; wellbore storage correction was investigated and extended to flow testing. WELLBORE STORAGE THEORY As has been shown by Aronofsky and Jenkins,11-12 Matthews," and others, flow of gas can often be approximated by an equivalent liquid flow system. The following developnlent will use liquid flow nomenclature to simplify the presentation. Application to gas-well cases will be illustrated later. First, we will use the van Everdingen-HursP treatment of wellbore storage in transient flow to establish (1) the duration of wellbore storage effects, and (2) a method to correct flow data for wellbore storage. DURATION OF WELLHORE STORAGE EFFECTS When an oil well is opened to flow. the bottom-hole pressure drops and causes a resulting drop in the liquid level in the annulus. If V. represents the annular volume in cu ft/ft of depth, and p represents the average density of the fluid in the wellbore, the volume of fluid at reservoir conditions produced from the annulus per unit bottom-hole pressure drop is approximately: res bbl-- (V, cu ft/ft) (144 sqin./sq ft) psi -(5.615 cu ft/bbl)(pIb/cuft) ........(I)

Jan 1, 1966

By G. H. Turner, R. C. Bell, E. Peters

Zinc oxide activities in a typical lead blast furnace slag have been calculated from plant operating data. These activities were used to assess the probable effect of fuel composition, oxygen enrichment, and air preheating on the efficiency and capacity of the slag-fuming operation. THE physical chemistry of zinc fuming has been examined with three objectives in mind: 1—to predict conditions favorable to increasing furnace capacity, 2—to predict the changes required to fume zinc more economically, and 3—to explain reported differences in the efficiencies of various slag-fuming plants. This study, made at ail in the plants and laboratories of The Consolidated Mining and Smelting Co. of Canada Ltd., developed from a program undertaken some three years ago on behalf of the AIME Extractive Metallurgy Div. subcommittee on slag fuming. Lead metallurgists first became interested in the recovery of zinc from lead blast furnace slags in 1905 and 1906. An excellent review of the early experimental work has been made by Courtney,&apos; who described blast furnace, reverberatory furnace, and converter methods of fuming zinc from slag. Some of the investigators did not appreciate the importance of reducing the zinc oxide content of the slag to metal in order to fume it, since they tried compressed air blast without fuel in their earliest attempts. However, by 1908, the importance of reducing the zinc was established.&apos; In 1925, the Waelz process for the recovery of zinc oxide from oxidized zinc ores was developed in Germany.&apos; This process was not readily adaptable to lead blast furnace slags because of the difficulty in handling fusible charges in a kiln. What appears to have been the first slag-fuming operation as it is known was commenced by the Anaconda Copper Mining Co. at East Helena, Mont. in 1927." The first Trail furnace was completed in 1930, and this was followed by the construction of several other slag-fuming plants. During the period in which slag fuming has been extensively employed, little development of the chemistry of this process as a whole has taken place. Several good papers on the petrography of lead blast furnace slags have been published,""= but these studies could do little more than establish the forms in which lead and zinc occur in the initial charge and final products of the slag-fuming operation. In recent years, zinc-smelting problems have been ap- proached from a thermodynamic point of view. Maier has published an excellent thermodynamic treatment of zinc smelting." The important thermodynamic properties of zinc and its compounds have been determined and checked by other investigators.&apos; However, to the best of the authors&apos; knowledge, no thermodynamic treatment of the fuming of zinc from slag has been published. A thermodynamic study of any process requires that the essential chemistry of that process be known. In slag fuming there appear to be some differences of opinion as to whether the active reducing agent is elemental carbon or carbon monoxide. Furthermore, some observers have noted that high volatile coals appear to be more efficient than low volatile coals, indicating that hydrogen is also an important factor in the reducing efficiency of a fuel. That both hydrogen and carbon monoxide are effective reducing agents for the zinc oxide content of lead blast furnace slags can be demonstrated readily by introducing these gases into a slag bath held in a neutral vessel at 2100°F (1150°C). Elemental carbon also will reduce zinc oxide, but it is improbable that much free carbon is available for reduction of zinc, as the reaction between the finely powdered coal and air should be largely completed before the solid coal particles reach the slag. Some large-scale fuming experiments using gaseous hydrocarbons have been carried out by other investigators, but, as far as is known, these have not been developed yet into operating processes. The thermodynamic treatment in this paper is based on the following reactions: 1—to supply the thermal requirements C+V2O2- CO [1] C + 0,-CO, [2] H2+ ~z0,-H,O 131 and 2—to reduce ZnO ZnO + CO + Zn + CO, c41 ZnO + H, e Zn + H,O. [51 The furnace-gas composition also is controlled by the equilibrium constant of the familiar water-gas reaction H,O + CO + CO, + H2. C6l In order for the thermodynamic calculations to be quantitatively applicable, it is necessary that the chemical reactions to which they are being applied

Jan 1, 1956

By W. M. Baldwin, J. T. Brown

The effect of hydrogen on the ductility, c, of SAE 1020 steel at strain rates, i, from 0.05 in. per in. per rnin to 19,000 in. per in. per rnin and at temperature, T, from +150° to —320°F was determined. The ductility surface of the embrittled steel reveals two domains: one in which and the other in which The usual "explanations" of hydrogen embrittlement are in accord with the first of these domains only. THE purpose of this investigation was a fuller A characterization of this of the investigation effects of varying temperature and strain rate on the fracture strain of hydrogen-charged steel. To be sure, it is known that low and high temperatures remove the embrittlement that hydrogen confers upon steels at room temperature,1 * see Fig. la and b, and that high strain rates have a similar effect,&apos;-&apos; see Fig. 2a, b, and c. However, the general effect of these two testing conditions on the fracture ductility of hydrogen-charged steels is not known, i.e., the three-dimensional graphical representation of fracture ductility as a function of temperature and strain rate is not known—only two traverses of the graph are available. The need for such a graph is not pedantic. To demonstrate this point, Fig. 3a, b, and c shows three of many three-dimensional graphs, all possible on the basis of the two traverses at hand. The important point (as will be developed in the Discussion) is that each of them would indicate a different basic mechanism for hydrogen embrittlement. It will be noted that the four types of ductility surfaces in Fig. 3a, b, and c may be characterized as follows: Material and Procedure Tensile tests were made at various temperatures and strain rates on a commercial grade of % in. round SAE 1020 steel in both a virgin state and as charged with hydrogen. The steel was spheroidized at 1250°F for 168 hr to give the unembrittled steel the lowest possible transition temperature. The steel was charged cathodically with hydrogen as follows: The specimen was attached to a 6 in. steel wire, degreased for 5 min in trichlorethylene, rinsed with water, and fixed in a plastic top in the center of a cylindrical platinum mesh anode. The assembly was placed in a 1000 milliliter beaker containing an electrolyte of 900 milliliters of 4 pct sulphuric acid and 10 milliliters of poison (2 grams of yellow phosphorous dissolved in 40 milliliters of carbon disulphide). A current density of 1 amp per sq in. was used which developed a 4 v drop across the two electrodes. All electrolysis was carried on at room temperature. Temperatures for tensile tests were obtained by immersing the specimens in baths of water (+70° to + 150°F), mixtures of liquid nitrogen and isopen-tane (+70° to —24O°F), and boiling nitrogen (-240" to-320°F). Specimens were tested in tension at strain rates of 0.05, 10, 100, 5000, and 19,000 in. per in. per min. The 0.05 and 10 in. per in. per rnin strain rates were obtained on a 10,000 lb Riehle tensile testing machine, the 100 in. per in. per rnin rate on a hydraulic-type draw bench with a special fixture, and the 500 and 19,000 in. per in. per rnin rates on a drop hammer. The fracture ductility of hydrogen-charged steel at room temperature and normal testing strain rates (-0.05 in. per in. per min) is a function of electro-lyzing time, dropping to a value that remains constant after a critical time.&apos;* Under the conditions of • The hydrogen content of the steel continues to increase with charging time even after the ductility has leveled off to its saturated value.&apos; this research the saturated loss in ductility occurred at approximately 30 min, see Fig. 4, and a 60 min charging time was taken as standard for all subsequent tests. After charging the steel with hydrogen, the surface was covered with blisters. These have been described by Seabrook, Grant, and Carney.&apos; The original diameter of the specimen was not reduced by acid attack, even after 91 hr. Results The ductility of both uncharged and charged specimens is given as a function of strain rate in Fig. 5, and as a function of temperature at four different strain rates in Fig. 6. These results are assembled into a three-dimensional graph in Fig. 7. It is seen that the locus of the minima in the ductility curves of the charged steels divides the ductility surface into two domains. At temperatures below the minima,

Jan 1, 1955