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Jan 1, 1940

By D. L. Feucht, R. L. Longini

The semiconductor heterojunction is considered in terms of simple models which may lead to an understanding of move complex heterojunctions. Metallurgical and electrical properties of hetero-junctions aye discussed including the interface structure, energy -band diagram, and carrier transbovt across the interface. It is found that in a heterojunction all mechanisms such as injection, tunneling, and junction recombination found in simple junctions play modified voles. INTERFACES between materials (grain boundaries, the electrical junction between two differently doped materials in a single crystal, the oxide-metal interface, or metal-metal junctions) are of considerable importance in many situations. These various interfaces all have one very fundamental thing in common. Quantum mechanically speaking, the wave functions of the electrons in one material may penetrate the other material but, in general, only to the extent of angstroms. From an electrical point of view the conduction mechanism changes as a current passes through such junctions. In some cases the change is tremendous, in others almost negligible. The interface, then, is the locus of a change of conduction mechanisms. Some of these, particularly in semiconductors, are well-understood. The ordinary p-n junction in a single crystal can be the locus of an injection mechanism or a tunneling process, depending on conditions. The mechanisms are probably best understood in semiconductors because of the possible simplified view of particlelike conduction. The bands are either nearly filled or nearly empty and band overlap is seldom involved. The same fundamentals are probably important in other situations too but they are very difficult to look at naively. Although the simple look at the semiconductor case only gives us a relatively rough picture which must then be refined, the other systems, which involve a more complex situation, immediately are in many ways too difficult. There are too many initial choices of complex systems and therefore it is not possible to be even reasonably certain of any one model. Because of the relative simplicity of semiconductors, their good and controllable structure, and because of the ability to make many measurements on them not normally available to either metals or insulators! they are probably the best understood materials. It is therefore desirable to use them as a tool to further the understanding of interfaces in general. Semiconductor-heterojunction concepts were first proposed by kroemer1 in 1957. This was followed several years later by reports on the fabrication and experimental characteristics of heterojunction structures by Anderson2 and Diedrich and jotten.3 I) THE HETEROJUNCTION STRUCTURE To get down to hardware, when we refer to a semiconductor heterojunction we imply that there exists an intimate contact between different semiconductor materials. We could put two pieces of material together, complete with oxide layers, we could remove the oxides, or we could even melt the interface and hopefully get wetting and a good "bond" on solidifying. In fact we could by some means grow a crystal of one material using the other as a seed. Essentially we are interested only in the last two because they are the simplest to look at analytically. The degree of perfection of fit varies greatly and is reflected somewhat in the arc welder's joint strength. The lattice match of the two materials, their orientation, and so forth. is obviously necessary for a good bond but so is the continuity of any polar bonds which are involved such as in the III-V semiconductors. The mechanical misfit between two similar lattices can be described in terms of edge dislocations. The edge-type dislocations must be very close together for the usual misfit and there must be dislocations for each of several different Burger's vectors in order to produce a lattice match. The .'dangling bonds'' resulting will be involved in producing interface charge. Order of magnitude estimates of the charge density extrapolated from low densities of dislocations in homogeneous materials give 5 x 1013 cm-2 Ge-Si and 1 X 1012 cm-2 Ge-GaAs electronic charges. Edge dislocations also act as very active recombination centers between holes and electrons. One lattice "matching" difficulty usually exists even if two structures have essentially the same lattice constants as they will have different coefficients of therma1 expansion. Thus, on cooling from the usually high temperature of fabrication to room temperature, dislocations are produced, a good fit not existing at both temperatures. In brittle materials this shrinkage may even result in cracking. For the Ge-Si interface the mismatch is about 2 x 10 -6 per degree whereas it is less than 10"7 per degree between germanium and GaAs. The exact effect of the misfit is dependent on the thickness of the materials involved. For a very

Jan 1, 1965

By V. Niemitz

Approximately 30 miles east of Chicago on the southern shores of Lake Michigan stands Bethlehem Steels newest fully integrated steelmaking facility-the billion dollar Burns Harbor plant. The first phase of what will ultimately be the most completely integrated and flexible materials handling system for a steel mill in the western hemisphere is now complete.

Jan 1, 1970

By GUY C. RIDDELL

ZINC, manganese, and aluminum received attention at the two nonferrous metallurgy sessions at the Annual Meeting. L.P. Davidson, general superintendent of the rebuilt Monsanto zinc plant, described its operation, which reflects Polish practice and is really a combination of electrolytic, Waelz, and retort procedure. Briefly, it embraces leaching of roasted concentrate with sulphuric acid, electrolysis of sulphate solution using Tainton lead-silver anodes with ?goulac? added to the electrolyte, treatment of tailing in Waelz kilns, and retorting of the recovered zinc oxide, casting furnace dross and residues. Recovery is good, equipment and maintenance costs low. Ferrate zinc that might be lost in the electrolytic process appears to be recovered as oxide in the Waelz treatment.

Jan 1, 1942

Jan 1, 1940

By N. Jaffe, J. E. Dorn

This investigation is concerned with the possibility that the creep resistance of metals might be reduced as a result of recovery at the creep temperature when the applied stress is reduced. For this purpose the effect of stress on the recovery of the creep behavior of pure polycrys talline aluminum was investigated in the cross-slip temperature range where the activation energy for creep is 28.000 cal per mole. Before recovery all specimens were given the same substructure by creeping them under a stress of 7800psi to a strain of 0.218. Recovery was then accomplished by holding the specimens at the creep temperatures of 327" and 337°K under a series of reduced stresses for various periods of time. When the original stress was reapplied the specimens crept more rapidly than when the original stress was first removed, illustrating that recovery did take place. The extent of recovery could be indexed in terms of the UNDER certain conditions of test, the creep rate decreases over the primary stage of creep often by as much as a factor of 10~B. Since the external variables of stress and temperature are held constant, such pronounced and significant changes in the creep rate must be attributed to various substructural modifications that are introduced as a result of creep itself. At the secondary stage of creep, over which the creep rate remains constant and the substructure no longer changes, a balance must be achieved between the rate of increase in creep resistance due to creep straining and the rate of recovery of the substructural modifications. The general validity of these concepts on substructural changes has already been shown,' including the corollary that a more creep-resistant substructure is introduced under a more rapid creep rate arising from a higher applied stress.' In spite of these well-documented facts, very little progress has been additional strain undertaken by the recovered specimen to achieve the same strain rate as the unrecovered specimen. It is significant that the higher recovery stresses gave the most rapid rates of recovery. Over the high range of reduced stresses, where some creq took place during recovery, the activation energy for recovery equaled that for creep, namely 28,000 cal per mole. But for stresses during recovery below 0.80 of the original creep stress, no creep was detected during recovery and an activation energy for recovery of about 72,000 cal per mole was obtained. Whereas the activation energy of 28,000 cal per mole suggests that cross-slip of dislocations is responsible for this recovery, the mechanism for the 72,000 cal per mole process is not known. This activation energy, however, is about twice that for self-difhsion. made in determining, in satisfactory detail, precisely what substructural changes so effectively modify the creep rate.' Up to the present, electron microscopy has failed to uncover, in a satisfactory quantitative manner, the mechanistic processes involved. Since, however, creep, at least at moderate and high temperatures, arises from one or more types of dynamic recovery processes, it should be possible to shed additional light on the total problem by investigating the recovery of creep resistance. The importance of such an investigation becomes apparent when the fact is recognized that there has yet been no direct experimental proof that the rate of softening due to substructural changes as a result of recovery equals the rate of hardening due to creep-induced substructural strengthening over the secondary stages of creep. Furthermore the problem of what happens to the creep-strain induced strengthening when the material recovers either at zero or some reduced operating stress has significant engineering consequences. It was for these reasons that the present investigation on the recovery of creep behavior was initiated. Inasmuch as a substantial background has now developed on the creep of high-purity aluminum, this material was again selected for the current investigation. Furthermore extensive evidence is now

Jan 1, 1963

By W. M. Small

Austria.—Austria produced some 430 cisterns of 10,000 kg. each of crude oil of a 0.9428 sp. gr. during 1934. Gosting II well near Zis-tersdorf was placed on the pump in August and at the end of the year was still producing about three cisterns daily. This well is owned by the Erdöl-Produktionsgesellschaft while Gösting I is owned by Raky-Danubia. Only five wells were completed in the republic during the year. These accounted for 1783.5 meters of the 2225 meters drilled. The only producer completed was Gosting 11. At the close of the year, four rigs were in operation and one rigging up. At least 8 or 10 new wells are planned in Lower Austria for 1935. The European Gas & Electric Co. put its 6-km. gas line into operation in May and has sold 12,301,550 cu. m. of gas to the Vienna City Electric Works. A 2-km. pipe line was built from Gösting II to the railway loading rack near Zistersdorf. Hungary.—No oil or gas was produced except a small amount of gas trapped from flowing artesian wells. The Government completed and abandoned a 1500-m. hole at Tisztaberek in northeastern Hungary and is drilling at 967 m. near Bogáes, 120 km. northeast of Budapest. It is unofficially reported it plans to drill two new wells in 1935. The European Gas & Electric Co. has a rig up for a test at Mihalyi in Transdanubia. Czechoslovakia.—In Gbely (Egbell) there were produced 1283 cisterns of 10,000 kg. of 0.935 sp. gr. oil and a small amount of gas used for fuel. This field is operated by the Government; 17 shallow producing wells and three dry holes were drilled, with a total of 3351 m. of hole completed. In Hodonin (Goding) there were produced approximately 1300 cisterns of 10,000 kg. each of 0.91 sp. gr. oil and a small amount of gas used for fuel. The field is operated by the Apollo, which drilled four producing wells averaging 460 m. in depth, one small gas well of 550 m., one small gas well 260, and one dry hole 230 m. Two wells were deepened a total of 80 meters. The Government is drilling below 800 m. in a wildcat test in eastern Czechoslovakia near the Rumanian frontier.

Jan 1, 1935

THE total crude production from the Dutch East Indies, and the British Protectorates of Sarawak and Brunei for 1932 is given in the following table: BARRELS BARRELS (42 GAL.) (42 GAL.) North Sumatra 4,226,935 Ceram 326,207 South Sumatra 13,956,157 Sarawak 2,739,650 Java 3,845,568 Brunei 1,322,725 Dutch Borneo (main island) . 9,406,733 Dutch Borneo (Island of Tara- kan) 6,579,184 Total 42,403,159 Production, which had shown a rapid increase from 1921 to 1929, has since been reduced. Exploitation drilling in the majority of the larger fields was suspended and existing production kept within predetermined limits by beaning. Most of the smaller fields were shut down entirely. The depth of producing levels varies widely in the different fields. Shallow fields with drilling depths to 500 meters (1650 ft.) are still numer-ous as well as those with depths between 500 and 1000 m. (3300 ft.). A few of the newer fields reach greater drilling depths. up to 1600 m. (5250 ft.). The deepest exploration well drilled to date (Djambi field, South Sumatra) reached a depth of 2332 m. (7650 ft.) before abandon-ment in March, 1930. The specific gravities of the various crude oils produced range between 0.65 (86.2° A.P.I.) and 0.95 (17.5° A.P.I.). The lighter crudes have a high gasoline content and fuel oils are derived from the heavier crudes, which usually are rich in paraffin.

Jan 1, 1933

By W. R. Crane

The support of roof in mines is dependent largely on the character of the top rock and its occurrence. The formations overlying the orebed in the Birmingham district are sandstone and slate. The sandstone occurs in beds of sufficient thickness to constitute important elements in the system of support; the slate is relatively strong but is thinly stratified. The alternating beds of sandstone and slate furnish an excellent combination in that the former are strong and the latter are impervious; however, their continuity is broken by jointing or slip planes. The thickness, and consequent weight of the overlying formations, is important in so far as the size and arrangement of pillars are concerned but may be relatively unimportant, temporarily at least, as a factor in the support of the roof. The position of the respective beds of sandstone and slate, their relative thickness, and their inherent weakness because of the occurrence of faults and folds, may exert a predominating influence on their support in place, which is affected only in part by the weight of the cover. The only mine in this district that operates under a cover of approximately 2000 ft. (1900 ft.) is the Shannon so-called "twin slope," situated 14,000 ft. southeast of the portal of the No. 7 mine of the Tennessee Coal, Iron, & Railroad Co. The conditions in this mine indicate what may be expected in other mines when the same depth is attained; in fact, the effect of pressure is shown in several mines that have not reached two-thirds of that depth. It is evident, then, that conditions affecting the support of roof will not improve but rather will become more difficult with the extension of the mines into the valley under a constantly increasing weight of cover. Further, the difficulties will probably be augmented by the occurrence of faults and other disturbed ground, the presence and position of which at present are largely unknown.

Jan 1, 1925

By John Nelson

AN OUTLINE survey of the economic outlook for the United States export trade in petroleum products resolves itself broadly into two general divisions; first, a consideration of our present position in this trade, and second, a discussion of the visible factors which promise to affect appreciable changes in the immediate future in that trade. The UNITED STATES PETROLEUM EXPORTS OF MAJOR PETROLEUM PRODUCTS 1925, 1926 and 1927 Gasoline, Naphtha, and Other Light Products 1925 1926 1927* Quantity (gal.) 1,286,787,796 1,784,154,802 1,851,494,190 Value $197,491,588 $263,199,938 $214,721,652 'Illuminating Oil, Kerosene 1925 1926 1927* Quantity (gal.) 885;136,041 924,680,979 827,162,280 Value $84,699,724 $100,352,877 $80,358,082 Gas and Fuel Oil 1925 1926 I 1927 Quantity (gal.) 1,365,358,988 1,449,688,394 1,815,130,464 Value.... ? $49,040,024 $45,354,108. .. $50,343,031 Lubricating. Oil 1925... ....1926 .. 1927 Quantity .(gal.) 402,572,584 388,767,055 403,369,512 Value $90,596,671 $86,414,621 $88,926,815

Jan 1, 1928

By Hamilton Wingate

In his paper on the hydraulic mining of a low-grade gravel in California,* Mr. W. H. Radford expresses the hope that other members of the Institute will contribute, for the benefit of all, their experience in similar lines. In these notes 1 shall describe the conditions and results of the operation of the Gold Bug Mining Co., of Cleveland, O., at Georgetown, Eldorado county, Cal.

Jan 1, 1903

By Thomas Lane Carter

The history of mining in South Africa differs somewhat from that of other countries in the part taken by the aborigines in the development of the mineral deposits. The Spaniards in America, and the fortune-seekers of Australia and New Zealand, found large numbers of natives in these new countries, but the inhabitants did not become willing or efficient workers in the mines which the white men started. The Kaffirs of South Africa have not shown the same antipathy to labor, nor do they show any signs of dying out in the presence of the white man's civilization. They are a virile race, and so far the vices of civilization have not killed them. While it is true that the brain and skill necessary for the exploitation of the mineral resources of this sub-continent have been supplied by the white race, it is also a fact that most of the rough labor in the development of the mining industry of South Africa has been done by the Kaffirs. The Kaffir tribes differ greatly in their mental and physical capabilities. Compare, for instance, a Zulu of Natal with a Bechuana, or a Xosa of Cape Colony with some of the degenerate tribes of Central or East Africa, and you will find that they have little in common, save that their skin is black and that they do not believe in clothes. As a general rule, the tribes in the milder, healthier climates are far superior, both in mind and body, to the Kaffirs brought up in the hot malarial sections of Central Africa; and it naturally follows that the black men from the temperate zones of the country are much finer workmen than the degenerates from less favorable sections. It is universal in South Africa to speak of the Kaffirs as " boys." No matter if he is 90 years old, the Kaffir is always a a boy," and in this paper the word " boy " is synonymous with Kaffir.

Jan 1, 1909

By AIME AIME

MESSRS. BURT and Shockley and others have been for three years urging upon the Institute the matter of simplified spelling. The Institute endeavors to be progressive in the matter of spelling and. is in cooperation with the national body which has this in hand and which has its principal office in New York. Our spellings are changed as fast as-good usage will permit (so it seems to the Board of Directors) and the national body, which is the real representative of the simplified spelling interests, deems that the Institute is making real progress, although not quite as fast as extremists would wish. In January, 1919, Mr. Shockley sent out letter ballots which created a misconception in the minds of many members, who received the impression that the communications came from the Institute instead of from a small group of members. As a result of this propaganda 163 proposal-ballots were sent in to the Institute divided as follows: Yes ?114 No ?20 Negative letters ?9 Split ballots ?20 Total ?163 The total membership at this time was about 7200. The disgusted members would not vote.

Jan 1, 1920

By Henry Louis

Henry Louis, Newcastle-upon-Tyne, England (communication to the Secretary*).—In this paper Mr. Simons derives the various forms of revolving slime tables, of which the Harz and the Linkenbach tables are typical examples, from the old rectangular or box buddle. This I believe to be an error, at any rate if Mr. Simons attaches the same meaning as I do to the ((evolution" of a dressing appliance. By the '(evolution" of such an appliance I understand the progressive development and improvement of an appliance acting on a definite principle, such improvements having usually for their object the economy of labor in working the same, or the increase of its capacity; when an entirely new principle is introduced, I no longer look upon this as evolution from the old type, but as the origination of an independent type of appliance. The box buddle was no doubt the predecessor of the old Cornish round buddle, which was evolved from it with the object of saving the labor required to work the box buddle; both machines are horizontal-current separators, in which the separation of sands of different densities is effected by their differential rates of fall in a horizontal current of water of considerable depth. These appliances, though well suited to sands, are for obvious reasons not adapted to the treatment of slimes. The revolving tables of the Harz and similar types, on the other hand, act on the principle which I have called separation in thin films of water, and which Mr. Simons calls the film sizing principle, in which the resistance of the surface over which the pulp flows plays an essential part in determining the separation of the particles, and which is well suited to the treatment of slimes. Unlike the last principle, it will not work in deep bodies of water and cannot be used where considerable depth of material accumulates in the appliance, as in the box buddle and round buddle. As I have shown in my book, The Dressing of Minerals, p. 326, these revolving tables are a development of the appliance known variously as the flat buddle, flat table, or frame, the last name, which is the old Cornish one, being the one that I personally prefer. These primitive appliances, as well as the continuous-acting round tables described by Mr. Simons (his Figs. 10 et seq.) all work on the principle of separation in thin films, and are all adapted for the treatment of slimes; his buddles and round tables (Figs. 1 to 9) do not work upon this principle, and should therefore be sharply differentiated from the former. The evolution in each case of the continuous acting, more or less automatic, circular appliance from the primitive, intermittent, hand-worked, rectangular appliance has proceeded upon strictly parallel lines. The question of the evolution of the respective types involves a point of some importance as regards the principles of ore dressing.

Jan 1, 1915

By A. M. Nicholas

WheN attempting to lift mill pulp containing a considerable percentage of wolframite, in an ordinary bucket elevator, difficulty was encountered from the tendency of the tungsten minerals to settle, on account of their high specific gravity. Lifts not exceeding 20 ft. (6 m.) could be accomplished without particular difficulty, because there was insufficient time for consolidation of the heavy minerals in the bottom of the bucket; but with higher lifts, the heavy tungsten minerals would settle so solidly that when the bucket turned over at the top of the elevator the contents could be only partially dumped. In this case it was necessary to lift the material a distance of 34 ft. (10m.); hence some means had to be adopted to prevent settling, at least to such an extent that the material could be dumped from the buckets. To reduce the carrying time to a sufficient extent would have required a belt speed of 475 ft. (144.7 m.) per minute, which was not feasible. It was decided to try, by vibrating the belt about midway of its span, to keep the material sufficiently agitated during elevation to prevent settling. Underneath the rising side of the belt was placed a 12-in. (30.48-cm.) idler pulley, 18 ft. (5.5 m.) up in the total lift of 34 ft. The idler pulley was set eccentric by % in. (19 mm.) and it was hoped that the vibration thus imparted to the belt, running at a speed of 280 ft. (85 m.) per minute, would prevent settling in the buckets. It was found that the pressure of the belt on the idler, due to the small inclination of the elevator, was not sufficient to overcome sliding on the idler, and the agitation was insufficient to accomplish the desired purpose. The idler was then connected to the drive shaft of the elevator through an intermediate pulley, gearing down to a speed of 20 r.p.m., so that a positive vibration was imparted to the belt; this imparted enough motion to the belt to prevent settling and the contents of buckets dumped satisfactorily. Protecting Elevator Belts When elevating, from the crusher, a rock which was very sharp and abrasive, considerable difficulty arose from cutting of the belt under-

Jan 1, 1918

By A. S. Hewitt

After an interval of fourteen years, saddened for all of us by the death of David Thomas, the father of the anthracite iron-trade, first president of the Institute, and by the untimely loss of his successor, Alexander L. Holley, whose memory we are about to honor by loving services, the members of the American Institute of Mining Engineers have conferred upon me for the second time the office of president, under circumstances similar to those which led to the choice in 1876. Then the whole world was represented at the great exposition of industry which was held in Philadelphia to celebrate the one hundredth anniversary of our declaration of political independence. In 1890 it is our privilege to receive as guests the members of the British Iron and Steel Institute, who, with singular and graceful felicity, have appointed a meeting in the United States in the year when we pass from the second to the first place in the international column of the production of iron, and thus celebrate our industrial independence. For the honor of being chosen to extend to our distinguished guests the right hand of fellowship and a hearty welcome I return to my associates the grateful acknowledgment of one whose chief claim to your favor is to be found in his love for the professional occupation in which we are all engaged, and in his efforts, public and private, to promote its advancement into new fields of usefulness. In order to indicate the full significance of the visit of our foreign guests at this time, it will be proper to explain briefly the origin, aims and work of the Iron and Steel Institute. It unquestionably owes its birth to the International Expositions held in London in 1851 and 1862, and in Paris in 1867. These expositions served to break down the jealousies of nationality and to diffuse a better knowledge of industrial processes. Trade-secrets, which had been carefully guarded, became common property; manufacturers who had previously regarded themselves as rivals formed bonds of union and ties of friendship, as the results of an intercourse which

Jan 1, 1891

By S. C. Sun, John A. L. Campbell

The surface properties exhibited by bituminous coal and bituminous coal lithotypes were ascertained by using streaming potential techniques. The electro kinetic prop-erties wereascertainederties of bituminous coal were found to be similar to those of anthracite. The principle electrokinetic properties of the coal and lithotypes, zero-points-of-charge (ZPC), and potential determining ions, were established. The effects of indifferent electrolytes, hydronium and hydroxyl ion sources, and polyvalent ions (cationic and anionic) were also evaluated. Location of the ZPC's with respect to pH is discussed in terms of chemical and mineralogical composition of the respective surfaces. To account for the observed electrokinetic phenomena, a generalized surface model and adsorption mechanism are proposed. Surface-dependent processes, such as froth flotation and flocculation, are important or potentially important techniques for combating some of the current major problems in coal preparation. In order to correctly apply or improve a surface-dependent process, it is of paramount importance to understand the interfacial phenomenon, especially the double layer properties, exhibited by the solid. The specific objective of this research was to determine the properties of the bituminous coal/liquid interface by an electrokinetic method, streaming potential, and to relate the findings, wherever possible, to the existing unit operations of froth flotation and floccula-tion tion. The electrokinetic properties of both the whole coal and its lithotypes were investigated. As part of the total investigation, the role played in the double layer by the reagents commonly employed in the surface dependent process was also established.' These data will be presented at a later date. Experimental Procedures The coal samples used in this research and their designations are listed in Table 1. The classical description of humic coal lithotypes as developed by Stopes" was used for the delineation of the lithotype samples. The samples were taken from the working face of a producing deep mine of the Pittsburgh seam in the area of Ellsworth, Pa. To avoid oxidation, only freshly exposed areas were sampled. The normal precautions against contamination were also exercised. Two types of samples were taken, specimens rich in a particular lithotype and a representative channel sample. The latter sample was prepared for analyses by grinding it to —35 mesh. It was screened repeatedly during the grinding to provide the largest amount of 35 x 48-mesh (standard Tyler sieves) material possible. The screened fraction was passed over a magnet and then washed several times with distilled water and finally with conductivity water. The resulting sample now termed "whole coal" was stored under conductivity water in a glass bottle. Pure lithotypes were obtained from the lithotype concentrates by hand picking, and were processed in the same manner as the representative sample. Maceral analyses, employing standard petrographic procedures," were performed on the lithotype samples to determine the purity of the samples. The results are presented in Table 2. Reflectance measurements of the vitrinites and fusinites are also reported in this table. Proximate and ultimate analyses of the samples are given in Tables 3 and 4. The electrokinetic properties of the coal samples were determined by streaming potential methods.'-' All of the chemicals used in the investigation were reagent grade (Baker analyzed). The conductivity water was prepared by doubly distilling the water in a pyrex Yoe-type still and passing the distillate through a mixed bed ion exchange column. Results In general, the electrokinetic properties of the investigated bituminous coal were found to be similar to the results of a previous study of anthracite by Camp-bell bell5 and are in accord with the suppositions of Brown." The zeta potentials of the coal and all the lithotypes were found to be negative in conductivity water. Jowett? in a study of slime coatings on coal also found bituminous coal to exhibit a negative surface. Fig. 1 shows that the negative charges, at neutral pH's, for both fusain and the gangue are very small, almost zero, while at the same pH, vitrain has the largest negative charge, almost 30 mv. Durain has a negative charge of 17.5 mv. The determination of the affect of pH on the charge of the coal surfaces revealed that hydronium and hydroxyl ions apparently behave as potential determining ions; however, they do not appear to be potential determining for the gangue. These results are illustrated in Fig. 1. As the pH of the solution was decreased, hydronium ions were adsorbed, causing the surface of the coal to reverse polarity and become

Jan 1, 1971

By W. E. Bergman, P. G. Carpenter, H. B. Fisher

The conditions under which barium carbonate can be used to remove sulfates from drilling muds are limited The amount of sulfate remaining in solution in the system after treatment with barium carbonate is shown to be a function of the concentration of the carbonate and barium ions and the concentration of other electrolytes. Barium hydroxide may advantageously replace barium carbonate when the contamination is not entirely due to anhydrite (calcium in the system is then stoichiometrically less than sulfate) or when the carbonate concentration is high. The effect of substances such as quebracho, phosphates, and chromates, which form complexes or precipitates with barium, is discussed. INTRODUCTION As the complexity of the operations in drilling for oil has increased, more attention has of necessity been directed to the problems pertaining to the maintenance of good drilling mud properties. As a result, chemical treatment of muds has become an important factor in recent years. Some of these treatments have been designed to eliminate the deleterious effects of contaminants in aqueous mud systems by precipitation or other means. The most common of substances encountered during drilling include sodium chloride, cement, and calcium sulfate while various other contaminants: usually in small amounts, may be introduced from the water, clays, and other materials used in preparation of the mud. In certain cases, for example where continued salt-water flow is encountered or massive anhydrite is drilled, special muds may be used so that the physical properties of the mud will remain satisfactory for drilling. In other cases, it is desirable to remove the contaminants so that soluble electrolytes in the system are maintained at low values. For sulfate contamination, the conlmon practice in the field is to add barium carbonate to precipitate the sulfate as barium sulfate Ordinarily such a procedure gives satisfactory results. There have been important instances, however, where addition of barium carbonate was not effective in removal of soluble sulfates from drilling muds. and it is to these cases that the present paper is directed. While it is generally known that barium carbonate is not always effective in removing soluble sulfates from drilling muds, certain inconsistencies appear in the literature as to the limitations of its use, and little explanation for the limitations are given. Varnell and Kimbrel state that "the treatment (with barium carbonate for removal of sulfate) is simple and consists in maintaining a pH of 9 with caustic soda and quebracho." They caution that concentrations of quebracho greater than 1 lb./bbl. may inhibit the reaction. In another publication', a pH of 10.5 is considered "the maximum desirable," and the indication is that as much as 2.5 lb. quebracho per barrel may be present in the particular mud under discussion. Lancaster and Mitchell5 state that appreciable amounts of phosphates in the mud will inhibit the reaction with barium carbonate and that the phosphate treatment should be discontinued at least 24 hours before addition of the carbonate. Experimental work was initiated to ascertain the factors involved in using barium carbonate for the removal of sulfate contamination in drilling muds. While the experimental data herein reported are limited, they focus attention on the pertinent factors which must be considered for successful treatment. These factors are discussed from a practical and a theoretical view, the latter being supported by equilibrium data found in the literature. Further, it will be appreciated that the factors involved in this specific study will be closely analogous to those in certain of the other chemical treatments which involve a precipitation of the soluble contaminant. A thorough comprehension of these factors should result in a more fruitful application of this type of chemical reaction to the treatment of drilling muds. EXPERIMENTAL A. Reagents Two muds were used during this investigation. For one series of tests, bentonite suspensions were prepared by dilution of a stock suspension containing 8 per cent by weight of bentonite (Aquagel). For another series, a 6.4 per cent ben-tonitic mud weighted to 9.7 lb./gal. with barium sulfate (Mag-cobar) was used. Distilled water was used in all preparations. The quebracho (72% tannin extract) was obtained from the Thompson-Hayward Co. of Tulsa and contained 11.4 per cent moisture (105 C.). All other materials were reagent grade, and concentrations were corrected for water of crystallization, if any. All concentrations are expressed in pounds per barrel (42 gallons). B. Technique The systems — either mud or water — were contaminated with either sodium or calcium sulfate after treatment with the desired amounts of sodium hydroxide and quebracbo. For treatments with barium carbonate an approximately 3-fold excess (5 lb./bbl.) was used over that computed to be required to precipitate all the sulfate as barium sulfate. Barium hydroxide was used in concentrations of 2 lb./bbl. — about

Jan 1, 1949

By P. G. Carpenter, H. B. Fisher, W. E. Bergman

The conditions under which barium carbonate can be used to remove sulfates from drilling muds are limited The amount of sulfate remaining in solution in the system after treatment with barium carbonate is shown to be a function of the concentration of the carbonate and barium ions and the concentration of other electrolytes. Barium hydroxide may advantageously replace barium carbonate when the contamination is not entirely due to anhydrite (calcium in the system is then stoichiometrically less than sulfate) or when the carbonate concentration is high. The effect of substances such as quebracho, phosphates, and chromates, which form complexes or precipitates with barium, is discussed. INTRODUCTION As the complexity of the operations in drilling for oil has increased, more attention has of necessity been directed to the problems pertaining to the maintenance of good drilling mud properties. As a result, chemical treatment of muds has become an important factor in recent years. Some of these treatments have been designed to eliminate the deleterious effects of contaminants in aqueous mud systems by precipitation or other means. The most common of substances encountered during drilling include sodium chloride, cement, and calcium sulfate while various other contaminants: usually in small amounts, may be introduced from the water, clays, and other materials used in preparation of the mud. In certain cases, for example where continued salt-water flow is encountered or massive anhydrite is drilled, special muds may be used so that the physical properties of the mud will remain satisfactory for drilling. In other cases, it is desirable to remove the contaminants so that soluble electrolytes in the system are maintained at low values. For sulfate contamination, the conlmon practice in the field is to add barium carbonate to precipitate the sulfate as barium sulfate Ordinarily such a procedure gives satisfactory results. There have been important instances, however, where addition of barium carbonate was not effective in removal of soluble sulfates from drilling muds. and it is to these cases that the present paper is directed. While it is generally known that barium carbonate is not always effective in removing soluble sulfates from drilling muds, certain inconsistencies appear in the literature as to the limitations of its use, and little explanation for the limitations are given. Varnell and Kimbrel state that "the treatment (with barium carbonate for removal of sulfate) is simple and consists in maintaining a pH of 9 with caustic soda and quebracho." They caution that concentrations of quebracho greater than 1 lb./bbl. may inhibit the reaction. In another publication', a pH of 10.5 is considered "the maximum desirable," and the indication is that as much as 2.5 lb. quebracho per barrel may be present in the particular mud under discussion. Lancaster and Mitchell5 state that appreciable amounts of phosphates in the mud will inhibit the reaction with barium carbonate and that the phosphate treatment should be discontinued at least 24 hours before addition of the carbonate. Experimental work was initiated to ascertain the factors involved in using barium carbonate for the removal of sulfate contamination in drilling muds. While the experimental data herein reported are limited, they focus attention on the pertinent factors which must be considered for successful treatment. These factors are discussed from a practical and a theoretical view, the latter being supported by equilibrium data found in the literature. Further, it will be appreciated that the factors involved in this specific study will be closely analogous to those in certain of the other chemical treatments which involve a precipitation of the soluble contaminant. A thorough comprehension of these factors should result in a more fruitful application of this type of chemical reaction to the treatment of drilling muds. EXPERIMENTAL A. Reagents Two muds were used during this investigation. For one series of tests, bentonite suspensions were prepared by dilution of a stock suspension containing 8 per cent by weight of bentonite (Aquagel). For another series, a 6.4 per cent ben-tonitic mud weighted to 9.7 lb./gal. with barium sulfate (Mag-cobar) was used. Distilled water was used in all preparations. The quebracho (72% tannin extract) was obtained from the Thompson-Hayward Co. of Tulsa and contained 11.4 per cent moisture (105 C.). All other materials were reagent grade, and concentrations were corrected for water of crystallization, if any. All concentrations are expressed in pounds per barrel (42 gallons). B. Technique The systems — either mud or water — were contaminated with either sodium or calcium sulfate after treatment with the desired amounts of sodium hydroxide and quebracbo. For treatments with barium carbonate an approximately 3-fold excess (5 lb./bbl.) was used over that computed to be required to precipitate all the sulfate as barium sulfate. Barium hydroxide was used in concentrations of 2 lb./bbl. — about

Jan 1, 1949

By C. W. Goodale

THE motives behind the organization of the Bureau of Safety were twofold. First, there was the policy of the company toward its employees, which was one of fairness and consideration for their welfare and which entails the prevention of injuries; second, in order to prevent injuries, a study of their causes was essential, and this study could be made only by a thorough systematic classification of accidents, which required a special department to form and carry out the plans. The Bureau of Safety was organized to begin operation Jan. 1, 1914, but practically all of the first year was spent in collecting data, making plans, etc. This department is semi-independent of others and reports directly to the president and general manager. It consists of the president of the company and the managers of the following departments: Mines, Washoe Reduction Works, Great Falls Reduction Works, Coal Department, Lumber Department, B. A. & P. railway, and the chairman of the Bureau of Safety. Working under this group is the General Safety Committee consisting of the manager of mines, as chairman, the general superintendent, two assistant general superintendents, and the heads of the following departments: mechanical, geological, purchasing, sampling works, and framing plant, as well as the safety engineer. Operating under the General Safety Committee are the group safety committees, consisting of the Anaconda group of mines, Boston & Montana group of mines, zinc group of mines,.Washoe reduction works at Anaconda, B. & M. reduction works at Great Falls, coal department, lumber department and the B. A. & P. railway. Each of these group safety committees was in charge of the superintendent or manager of the group represented and the committee consisted of the foremen of the mines or works that the committee served, as well as the safety engineer.

Jan 2, 1922