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By Joel Watkins

THE terms kaolin, china clay, ball clay, and paper clay are more or less loosely and interchangeably applied to a large class of white-burning clays. These clays are made up chiefly of hydrous amorphous (colloidal) aluminum silicates with variable amounts of free silica and other impurities in small quantities. Occasionally also the term kaolinite is wrongly applied to a white-burning clay, for kaolinite, is a mineral of definite chemical composition and definite crystalline form which occurs but sparingly in nature. It is not the purpose of this paper, however, to define or classify clays, or to enter into a discussion of the chemistry of clays. It is rather a general description of the occurrence and methods of mining of a kindred group of clays, and a discussion of their future economic aspect. In the Southern Appalachian States, the mining of white-burning clays has in recent years become an important industry. Although these clays are of several distinct types, which occur in as many localities under different geologic conditions, they are for the most part. primarily of the same origin. They are essentially the same in elementary constituents, and are largely consumed in the same industrial arts. From the standpoint of a mining engineer, therefore, and for convenience in comparison and correlation, it should be interesting to discuss them under one heading.

Jan 2, 1915

Jan 1, 1902

By Charles F. Ramseyer

The manufacture of iron and steel is one of the largest of our industries; and in point of size of single plant and equipment certainly the biggest of all industries. By the general public it is generally considered a prime example both of the marvelous technical advances achieved by modern science and engineering in the design and operation of equipment and of the efficiency of big business in the coordination of men and materials. Actually the operation of its basic processes has not changed significantly in either theory or fundamental design of equipment in the past 75 years. Though many other process industries have been born and developed, and not seldom completely revolutionized, during this period, the primary processes of making iron and steel are still carried out along the lines laid down, and in the equipment originated so long ago, by Bessemer, Siemens and Martin, and subsequently expanded to practically the modern scale by Carnegie, Schwab and Captain Bill Jones in the eighteen eighties and nineties. The application of the principles underlying the continuous counter-current physical and chemical interaction of solids, liquids and gases, which have been so successfully used in the rapid evolution of our chemical process industries, has been very largely lacking in the steel industry. In the days of the last-named giants, especially Carnegie, the steel industry made great and rapid technical progress. Carnegie's ever driving idea (as later with Ford in the production of automobiles) was the finding of new and better ways of making cheaper steel. Carnegie himself was a steelman, and so long as he dominated the industry its technical progress was rapid; and he, like Ford, was vastly successful financially as well, since his costs were continually being driven lower than those of his competitors by his advances in steelmaking technique.

Jan 1, 1935

By Sunder S. Saluja

Man had to learn to break rocks as early as the Stone Age, when they formed his main source of raw material. He started with chipping and over the years has reached a stage where he can employ atomic blasts and break, with one blast, millions of tons of rock. In between these two extremes there have been several stages of development including firesetting, use of the expansion of water on freezing in chipped cracks in cold climates, the use of low or deflagrating explosive black powder in about the 17th century, the use of high explosives with the discovery of nitroglycerine in 1846 by Sobrero, followed by the monumental discoveries of the great Swedish scientist Alfred Nobel in the latter half of the nineteenth century. The attempts to develop a stronger and still stronger explosive force were accompanied by investigations to understand the mechanism of failure of rock so that the force could be used to the best advantage; the latter, of course, have lagged far behind the former. This is mainly due to the fact that the chemical reactions involving high explosives as well as the processes resulting in the breakage of rock take place at too great a rate to be studied with the equipment that has been only recently available. Moreover, the development of stronger explosive forces was prompted by military necessities in the past and competition, at present, among highly developed nations. With the development, however, of the new techniques such as micro- second photography, microsecond flash radiography, extremely high-speed movies, strain gage assemblies, electronic chronographs and other improved electronic techniques, the investigator has in the last decade or

Jan 1, 1968

By A. E. Outerbridge

I had the honor to present to the American Institute of Mining Engineers at the Pittsburg meeting, February, 1896, a paper having the foregoing title, in which I said : " It has generally been accepted as a fact that cast-iron, under the influence of repeated shocks, becomes brittle, and will finally break under a blow which otherwise it would have withstood. It will probably surprise metallurgists, therefore, to learn that experiment disproves the supposed fact, and establishes exactly its opposite. " The result of about a thousand tests of bars of cast-iron of all grades, from the softest foundry mixtures to the strongest car-wheel metal, enables me to assert with confidence that, within limits, cast-iron is materially strengthened by subjection to repeated shocks or blows." Three tables were appended showing increase of strength

Jan 1, 1905

By Carl Zapffe

A Rise in less than ten years from obscurity into great prominence economically, tersely summarizes the history and status of the Cuyuna manganiferous iron ores. The Cuyuna district produces and ships mostly high-phosphorus iron ore, but the annual production of manganiferous iron ore is increasing rapidly and productions from individual mines are becoming more regular and more dependable as to grades and tonnages. This ore bids fair to become, shortly, the principal product of the district and is responsible for its present economic prominence. The iron ores of the district have been described, by the author and others, in many publications and will not be discussed here. Lately the manganiferous iron ores have been given some attention, but the range and variations of chemical composition of the ores, the principal physical characteristics of the ores and their deposits, the relative importance of the different ores and their possibilities in future developments, and the life of the respective reserves have not been discussed. It is impossible to give all of this information with the positiveness necessary for it to constitute a reliable guide for investment or even for future mine development. Each property and each party presents a special case and deserves critical consideration. We are dealing with special ores and always with a set of new conditions. Sufficient information of a general nature can be given, however, to indicate the reason for and the trend of the presently augmented developments in the district. In a great thickness of a big variety of sedimentary rocks, probably of Upper Huronion age, prevailingly of green, schistose phases of slaty and volcanic material intricately intermixed, lies a thin bed containing lenses of iron-bear ing formation. These lenses occur singly or in groups, thus causing the variation in the thickness of the formation; or they are separated at their ends and give rise to discontinuity or they overlap and display continuity with lateral offsets. Intense folding has added to the complications.

Jan 1, 1925

By Thomas F. Donnelly

The Province of San Cristobal is situated on the south side of the island of Santo Domingo about 25 miles west of Santo Domingo city, the capital of the republic. The copper mineraliza,tion is found about 8 miles north of the town of San Cristobal,. in the section known as Bucaro Hill; in San Francisco Hill; on the Nigua River; and on the Jaina River. The district is reached by automobile from Santo Domingo city over an excellent road for 25 miles to San Cristobal, and then, by horseback 6 or 8 miles up the Nigua River to what is locally known as "Camp

Jan 1, 1916

By W. M. Bertholf

To establish the minimum or break-even efficiency of a preparation plant it is necessary to determine the ratio of production costs per ton of run-of-mine coal to sale price per ton of clean coal. This ratio is then divided by the percentage of plant recovery. Assume, for example, that washability data indicate that 80 pct of the run-of-mine coal may be recovered as clean coal selling for $5.50 per ton. If the same plant incurs $4.00 per ton mining costs and $0.25 per ton preparation costs, the cost to sale price ratio would be 4.25/5.50, or 77.3 pct. Since the plant is capable of recovering 80 pct of the run-of-mine coal the minimum plant efficiency would be 77.3/80, or 96.6 pct. If the plant efficiency were increased to 100 pct the limit on preparation costs would be increased to $0.40. Therefore, the washing operation must be accomplished at a cost of $0.25 to $0.40 per ton and the efficiency must be 96.6 pct or higher. By plotting a curve of efficiency vs preparation costs and taking into consideration the plant cost, feed rate, operating costs, and yields of the various flowsheets it is possible to select a financially sound process. Table I classifies preparation processes according to their nature of separation. It must be remembered that what is thought to be ideal does not always prove practical under actual operation. An outstanding example is the work done on the plunger-type jig. It was determined by the law of equivalence that this unit could treat satisfactorily only sizes differing by no more than a ratio of 2. Yet these same plunger-type jigs are successfully treating sizes considerably greater than this ratio.

Jan 12, 1957

By Charles F. Ramseyer

The manufacture of iron and steel is one of the largest of our industries; and in point of size of single plant and equipment certainly the biggest of all industries. By the general public it is generally considered a prime example both of the marvelous technical advances achieved by modern science and engineering in the design and operation of equipment and of the efficiency of big business in the coordination of men and materials. Actually the operation of its basic processes has not changed significantly in either theory or fundamental design of equipment in the past 75 years. Though many other process industries have been born and developed, and not seldom completely revolutionized, during this period, the primary processes of making iron and steel are still carried out along the lines laid down, and in the equipment originated so long ago, by Bessemer, Siemens and Martin, and subsequently expanded to practically the modern scale by Carnegie, Schwab and Captain Bill Jones in the eighteen eighties and nineties. The application of the principles underlying the continuous counter-current physical and chemical interaction of solids, liquids and gases, which have been so successfully used in the rapid evolution of our chemical process industries, has been very largely lacking in the steel industry. In the days of the last-named giants, especially Carnegie, the steel industry made great and rapid technical progress. Carnegie's ever driving idea (as later with Ford in the production of automobiles) was the finding of new and better ways of making cheaper steel. Carnegie himself was a steelman, and so long as he dominated the industry its technical progress was rapid; and he, like Ford, was vastly successful financially as well, since his costs were continually being driven lower than those of his competitors by his advances in steelmaking technique.

Jan 1, 1935

By Herbert D. Drechsler

Mining Finance-is the interrelated aspects of "determining the total amount of funds to employ in a mining firm; allocating these funds efficiently to various assets; and, obtaining the best mix of financing in relation to the overall valuation of the firm". The first section is an overview of the financing problem through examination and discussion of the Balance Sheet and Income Statement. The next section is a discussion of the nature of the criteria developed in feasibility study. The third section describes type of capital funds, and the final section describes case studies of mining finance.

Jan 1, 1978

An educated man is distinguished neither by his clothes nor by his knowledge; he is remarkable not for the things he says, but for the way he says them. You cannot even stand with him under an archway in the rain without finding him out. He may talk only of the weather. His words and his phrases alike my be simple. What distinguishes him is the arrangement of his words; however desultory his talk, it will be methodical; he has habituated himself to foreseeing the part to be played by each word he uses and the place to be taken by each sentence he utters. On the other hand, the uneducated man, though shrewd and well-informed, will relate facts and events as they recur to him, generally in disorder; in his effort to recollect and in his attempt to rectify forgetfulness he will pause irregularly, filling the intervals with meaningless phrases, such as "and then", "and so", or "said he to me", "said I to him"; and even the continuous parts of his story will be told confusedly-because he has not learned the proper use of words.* My own experience as an editor of technical manuscripts has taught me that the misuse of 'that' and 'which' is a fruitful cause of obscurity and confusion. The relative pronouns have distinct functions, and no writer can express himself clearly until he has learned to discriminate between these functions. For example : The engineers who refused to submit were discharged. The engineers, who refused to submit, were discharged. The engineers that refused to submit were discharged.

Jan 1, 1931

By AIME AIME

NO FEATURE of the annual meeting is considered more important at Institute headquarters than the assembly of delegates from the various local sections and divisions. There the president of the Institute and other officials may learn at first hand what the members are thinking and doing in every part of the country, and the delegates, in turn, may find that head- quarters is not a group of more or less cold-blooded New Yorkers whose primary function is to send out annual bills for $15. This year, the section and division delegates required three sessions to thresh out the matters of common interest: Monday morning and afternoon and Thursday afternoon. They were also guests of the Institute at the Directors' dinner on Tuesday night, and at the Directors' meeting afterward.

Jan 1, 1932

By Charles H. Jacoby, Stanley J. LeFond

Salt, or halite, has a long and most varied history. While we know the Chinese were producing salt as early as 3000 B.C., the first written reference to salt appears in the book of Job recorded about 2250 B.C., which reads: "Can nothing which is unsavory be eaten without salt?" We do not know when man first used or realized that he needed salt. Perhaps one of our early Eolithic ancestors noted a piece of salt shining along the shore of a salt lake or a bay. He may have been attracted by its shining luster and tasted it. He found that it had a tart, zesty, distinctive flavor and perhaps chewing a large piece, became ill. However, by experimentation he soon learned that taken in the proper proportions salt was a very pleasant additive to his food. He may have noticed, too, that it increased his feeling of well-being. Thus, when the curtain of recorded history rises, we find man using salt for his health's sake, seasoning his food with it, feeding it to his animals, and using it in many superstitious and religious ceremonies. These uses, however, are a far cry from the uses for salt today. The first attempts of white man to make salt in continental United States were reported in the year 1614, while the first commercial production was in 1753 from the Kanawha licks. Practically all this salt was for human consumption, preserving food, and curing hides. Prior to the coming of the white man, Indians are known to have made salt from salt springs such as those that existed at Avery Island, LA, Charleston, WV, Saltville, VA, and Onondaga, NY. In 1862 the first rock salt was mined in the US from the Avery Island salt dome. Almost immediately thereafter, rock salt was mined at Saltville, VA and then at Retsof, NY in 1885. Of the more than 39 million tons produced annually in the United States, about 58% or 23 million tons are consumed by the chemical industry in the production of chlorine, caustic soda, hydrochloric acid, sodium metal, and some 30 other basic chemicals. These basic chemicals, in turn, are used in the preparation of approximately 14,000 chemicals which range from soap and detergents, to such chlorinated hydrocarbons as DDT, BHC, carbon tetrachloride, etc. Utilization of cavities created in salt beds and domes has grown rapidly since 1947 until now the waste salt is creating an ecological problem. The uses for both dry- and solution-mined cavities range from the storage of liquid hydrocarbons to containerized storage of toxic wastes, from compressed air for the peak shaving of power to storage of nuclear wastes. Geology Mineralogy Properties: Because of its simple structure, halite, the mineralogical name for salt, was the first structure to be analyzed by X-rays. It has the following properties: Formula: NaCl (Na-39.34%. Cl2-60.66% ) Crystallography: isometric, hexoctahedral, 4/m 32/m Space group: Fm3m A0: 5.627 kX Cell contents: Na4CI4 Habit: usually cubic, rarely octahedral, massive, granular to compact Physical properties: Refractive index: 1.554 Twinning: observed on {111} Cleavage: {001} perfect Fracture: conchoidal, brittle

Jan 1, 1983

By L. R. Woodyatt, H. J. Beattie, C. T. Sims

Theories correlating the formation of u and related intermetallic compounds to the electron-per-atom density of binary and ternary alloys have appeared regularly in recent technical literature. These same principles can be modified and applied to complex precipitation-strengthened alloys such as the iron-, cobalt-, and nickel-base superalloys and the stainless steels. Since these complex alloys contain carbides and other phases that normally precipitate before the U-type phases, the nature and amount of the precipitated phases must be calculated first. The following general formula is then applied to the residual matrix composition of the alloy: element. The magnitude of the resulting number is indicative of whether the alloy will form a a -type phase. When these calculations (which are computerized) are systematically applied to alloys of knoun phase analysis, a breakoff in average electron-vacancy number is noted between U-free and U-prone alloys. Alloys with an average electron-vacancy number higher than the breakoff form a-type phases, while those with lower ones do not form these phases. This method could then be used to eliminate from consideration all experimental compositions that would precipitate undesirable phases. It also is useful in evaluating analyzed heats of alloys where minor heat-to-heat variations determine whether the alloy is o-free or o-prone. THE highly significant development of strong, ductile superalloys to provide reliable construction materials in the 1000" to 2500° F temperature range has been due principally to unremitting application of Edisonian techniques and logic by the dedicated physical metallurgists who have shouldered this responsibility. Tools such as the electron microscope, phase analysis, and computers to accomplish regression analyses have been used heavily, but the effort has been essentially practice of an art, rather than a science. The objective of this paper is to describe and illustrate application of some relatively fundamental principles to certain of these alloy systems in an attempt to remove some of the empiricism from the technology. Specifically, the work presented here deals with the use of periodic-group relationships to predict the formation of intermetallic phases which can occur in primarily austenitic (fcc) structures. Calculations that have been developed might be applied in the design of new alloys and the evaluation of known alloys, and thus have the potential of eliminating vast areas of unnecessary alloy preparation and evaluation. ALLOYING CONCEPTS AND STRUCTURAL FEATURES OF SUPERALLOYS Strength is produced in austenitic superalloys by three principle mechanisms: 1) precipitation of y'; 2) formation of carbides; 3) solid-solution hardening by soluble refractory metals. The first mechanism requires the addition of aluminum and titanium, the second requires carbon and carbide-forming elements, while the third calls for the addition of molybdenum and/or tungsten. A considerable concentration of chromium is usually maintained to resist oxidation/corrosion, but it is also an important carbide-forming element. Fig. 1 shows a sketch and electron micrograph of the structure of a typical wrought nickel-base super-

Jan 1, 1967

By William H. Case

The Bertha zinc-mines of the Bertha Zinc and Mineral Company are in that part of the State of Virginia popularly known as Southwest Virginia, and are included in that division of the " Great Valley " named in recent years the " New River-Cripple Creek Mineral-Region of Virginia." The mines lie wholly in the southeast part of Wythe county, two miles from Pulaski county on the east, and three miles from Carroll county on the south. The only other zinc-mines that are opened in the region are those of Manning & Squier, which adjoin the Bertha zinc-mines on the northeast, and the mines of the Wythe Lend and Zinc Company, at Austinville, eight miles to the southwest. A little farther southwest of Austinville, near Ivanhoe, a new company is preparing to mine zinc-ores. The mining properties named are included within a distance of ten miles along a direct line, bearing north 55' east, on the south side of New river, which here flows northeastward in a tortuous course. The greatest distance of any of the mine-openings from the river is a little less than two miles. It is not the magnitude of the operations in zinc-mining in this particular region, as compared with that of other well-known districts, that merits especial notice. Aside from the exceptional purity of the spelter made directly from the Bertha ores, some peculiar features of the zinc-ore deposih, as shown at the Bertha mines, and

Jan 1, 1894

By Edward P. Chapman

IN the Leadville district toward the close of the "intermediate mesothermal period" of mineralization, there occurred a stage of ore deposition marked by a rather complex mineral association. As bismuth minerals formed in many places during this period, it is here called the "bismuth stage" for convenience of description. The minerals so far identified with this stage, listed roughly in the order of prominence, are: chalcopyrite; several varieties of galena, differing slightly from one another in their small contents of silver, bismuth and tellurium; altaite; hessite; galenobismutite; alaskaite; aikinite; ,gold; tennantite; argentite; and perhaps sphalerite and arsenopyrite. With the exception of gold, the age relations of these minerals are difficult to determine. As shown in their descriptions, they all appear contemporaneous and hypogene. Gold may be in part contemporaneous, but most of it is distinctly later. Where minerals of this stage occur so that they can be mined alone, as at the Tucson mine, they constitute high-grade ore. Elsewhere their presence in small amounts has served to increase greatly the value of what otherwise would be low- grade pyritic or zinc-lead sulphide ore. The distribution of the bismuth ores corresponds closely to the distribution of gold ores, though not so general. It seems probable that most of the gold in the district was deposited during the "bismuth stage." These ores occur relatively near the supposed centers of mineralization in Breece and Printer Boy Hills or deep down along the Tucson-Maid fault, which is one of the well recognized channels of mineralization in the Iron Hill and Graham Park areas. Consideration of the high-grade nature of this mineralization and the fact that it appears to be found relatively close to the source of mineralization suggests that prospecting along some of the known channels, even deeper than they have yet been prospected, may offer hope of commercial success.

Jan 1, 1939

L. D. Ricketts, New York, N. Y.-In recent years the metallurgical field of the copper industry has expanded greatly, the copper ores have become lean and diverse in character, and we are obliged to treat such ores on a very large scale. On the commercial side, the operating and consulting staffs of ,the great mining companies have been enlarged and organized, and no great capital expenditure is decided upon until it has been investigated and recommended by a highly organized force of specialists as a committee. I believe that in the scientific field and in the most valuable proceedings of our various societies the old idea of one-man point of view and one-man treatment of principle and detail together has been. splendidly developed and should continue, but for the advancement of our art we should deliberately discuss subjects among ourselves in order to do away with the idiosyncrasies of the individual and to gain a composite view representing the best thought of many men. In the development of new ideas leading to the introduction of new methods, the societies could enlarge their present great field of usefulness if such discussion be had, and in my opinion further great good could be done if a number of men of different qualifications and experience would join in preparing a joint book, each dealing with his particular problem, but consulting the other men. In this way individualism would be preserved and various processes would be described, and if properly reviewed the paper would be palpably capable of analysis, and the student would have at his command the associated efforts of a group of qualified engineers.

Jan 4, 1915

By W. A. Backofen, D. Lee

Tlze condition of superplasticity or neck-resistanl flow that results front high strain-rate sensitivity has been observed in isothermal tension tests on several titanium alloys and one of zirconium hi general, il was associated with reasonably fine-grain micro-structures being stvained in the transformation range at rates below i - 10 -3 sec-&apos;. The metallographic mean-free path, L, was measured at room temperature after rapid cooling from the temperature of test-ing. The flow stress of Ti-GAL-4V at 950°C was proportional to La at different constanl <; the value of a decreased with increasing. E but at E< 1.5 x 10-4 sec-1 it varied only from 0.9 to 1.25. The findings were interpreted to mean that viscous boundary shear is the rate-controlling process of deformation at high levels of strain rate sensitivity in these materials. Elongation of over 1000 pet could be obtained, but a1 temperatures so high and rates so low that any practical application of the full effect would probably be difficult. As the transformation range was narrowed, by turning from Ti-6AL-4V to Ti-5Al-2.5sn to nomznally pure titanium, the allowable temperature varialion was correspondingly reduced. Superplasticily was not found in Armco iron, presumably because the transformation range was too narrow to allow the developtnenl of a reasonably stable microstructure for isolhermal lesting. THE work represented by this paper grew out of a recent study of texture hardening in a(hcp) titanium and zirconium-alloy sheet,&apos; of which part has now been published.2 It was found that, with heating, the tensile plastic-anisotropy index, R,* was decreased from well above 1 towards 1 as the temperature range for the a(hcp) -ß(bcc) phase change was entered. The clearest example of that trend is illustrated with previously unpublished data in Fig. 1. It might have been thought that such a development resulted simply from introduction of the cubic and therefore plastically less anisotropic phase. However, the accompanying change in the index of tensile strain-rate sensitivity, m = a log a/a log E, was rapidly upwards, to a high of 0.85 in some cases (also illustrated in Fig. 1). At the same time, the total tensile elongation rose to a maximum and the flow strength dropped away as R (and m) approached 1. Taken together, the observations cannot be understood as resulting from the presence of cubic phase, per se. It has been concluded instead that they reflect the largely noncrystallographic deformation which characterizes superplasticity. As demonstrated in other recent work? a necessary condition for super-plasticity is strain-rate sensitivity of flow stress sufficiently high that m is above a lower limit of -0.3. The origin of large m has been traced, in turn, to grain size so small that a substantial amount of viscous deformation is introduced by such processes as Nabarro-Herring diffusional flow4 and/or grain boundary shear.5,6 Because of problems in the processing of titanium and zirconium alloys—problems of high strength, limited ductility, and excessive springback, originating largely in slip resistance-it was natural to wonder if something useful might be done with superplasticity in those materials. Therefore experiments were made for more closely identifying and generally bounding the phenomenon with temperature and strain-rate limits, before attempting to decide about its exploitation. The results are being reported here. EXPERIMENTAL Materials. The two of primary interest were the titanium alloys of nominal composition (in wt pct) 5A1-2.5Sn and 6A1-4V. Others were a 4A1-1/4O2 titanium alloy, titanium of commercial purity (RC-70), Zircaloy-4. and Armco iron. All were received as annealed 3/16 in. thick sheet, except RC-70 which was & in. thick, and tested in that condition. Details of transformation temperature and grain size are given in Table I. The results of dilatometry for the measurement of transformation temperatures were unsatisfactory. Data were finally obtained by metallographic examination of each specimen after test, to determine from the amount of transformed 4 where the specimen had been heated in relation to the critical temperatures. Results were in reasonable agreement with information from the supplier. Strip tensile specimens were of full sheet thickness and taken along the rolling direction, except for those

Jan 1, 1968

By F. E. Pawlek, J. K. Gerlach

The chloridizing roasting of ores is applied when metal sulfides and oxides are to be converted into soluble or volatile compounds. The chlorine required is either obtained from the admixed chlorides of sodium or calcium or added in the gaseous state. In the first part of the investigations the reaction rate of the chlorides of sodium or calcium with gas mixtures of SO,-0, or SO ,-O2 ,-SO , was measured. The rate for reactions with gas mixtures SO2-O2 is ThE chloridizing roasting of ores is applied when metal sulfides and oxides are to be converted into soluble or volatile compounds. At present the process is mainly applied to produce nonferrous metals which occur in pyrite cinders in small concentrations. Thereby the nonferrous metals are converted into water-soluble, acid-soluble, or volatile compounds whereas all the iron remains as insoluble oxide. The chlorine required is either obtained from the admixed chlorides of sodium or calcium or added in the gaseous state. The reactions occurring during the roasting process can be divided into two groups: solid-solid reaction and gas-solid reaction. The reactions between solids proceed by means of solid-state diffusion and are therefore of low velocity. The heterogeneous reactions between solids and gases of the roasting atmosphere5 are high-velocity processes and determine the velocity of the chloridizing roasting. These gas-solid reactions shall be the subject of the paper presented. In order to investigate the still little-known processes which occur during the chloridizing roasting 6-&apos; the complex reaction is split into several partial steps. First the reactions of NaCl and CaCl, with gas mixtures of SO2 and 0, have been investigated at temperatures between 500" and 600°C by measuring the weight increase of the samples. The gas mixtures used in this series of experiments had first variable compositions, then the amount of SO 2 had been increased. Furthermore the influence of Fe 2 O3 admixtures upon these reactions, the behavior of pure Fe 2 O3 with the gaseous reactants, and the chlorination of the sulfides of lead, copper, nickel, and zinc have been investigated. FORMATION OF GASEOUS CHLORINE Pyrite cinders are never completely roasted and therefore contain still a small amount of sulfide sulfur. When heated again in air, this sulfur is converted into SO,. Accordingly the formation of chlorine can first be described by the reactions: dependent on the composition of the gas phase. If more than 1 pct SO 3 is added to the roasting gas, the reaction rate is determined only by the concentrations of the SO,. In the second part the reactions between chlorine and metal sulfides are discussed. The rate of formation of gaseous chlorine is higher by me order of magnitude than is the reaction rate between ZnS and chlorine. The reaction rate of NiS and PbS lies considerably below that of ZnS. The conversion rate of both pure Fe 2 O 3 and Fe 2 O 3 containing NaCl or CaCl2 when reacting with SO2-O2, mixtures with and without SO3 portions was measured at temperatures of 500", 550°, and 600°C. The weight increase of pressings was determined by means of a spiral balanceg and the reaction rate calculated therefrom according to Eqs. [ll to [31 and [5] to [7]. The prepared samples were suspended on a platinum filament in a vertically mounted tube of mullite (ID 4 cm, length 110 cm) which could be heated by a resistance tube furnace. The platinum filament was tied to the lower end of the spiral balance. A supremax glass tube (length 70 cm) was mounted gas-tight on top of the reaction tube. The unit was sealed up at its top by a ground-in stopper which was holding the spiral balance with the sample. The spiral balance therefore hung outside the high-temperature region of the furnace. Fig. 2 shows the experimental arrangement schematically. While lowering the sample into the reaction tube pure nitrogen was flowing through the reaction zone providing a protective atmosphere. After the sample had reached the reaction temperature within approximately 1 min, the protective gas was replaced by the sulfur dioxide-oxygen reaction mixture. It took about 30 sec until the mixture filled the tube homogeneously. A Ni/NiCr thermocouple placed in the center of the furnace where the sample hung during the measure-

Jan 1, 1968

By E. P. Klier, Jane Jellison

The course of the transformations on cooling in a series of Cu-A1 alloys has been followed by means of thermal analysis, X-ray diffraction, and optical metallogrAphy. Specimen size was found to have a pronounced effect on the time of completion of the pearlite transformation due to modification in the unmber of nuclei. The ordeving transformation zvas observed for all cooling rates for all alloys studied, and is considered insuppvessible. At intermediate cooling&apos; rates, a transitional struchire for 011 alloy compositions and based ox the bainite reaction was observed. The alloys of aluminum and copper possess a eu-tectoidal region at from about 9.4 to 16 pct Al. Above the critical temperature, the disordered bcc phase, 0, is stable. At subcritical temperatures, the 0 phase decomposes under equilibrium conditions into the stable phases, a and y,. At the eutectoid composition, these phases develop a lamellar pearlite structure, in appearance much like that found in steels. During rapid quenching from supercritical temperatures, the diffusion processes required for the formation of the equilibrium phases are suppressed, and the 0 transforms to an acicular martensitic phase, designated B or y&apos; depending on the aluminum content, or to a mixture of the two. Early investigators of this system concentrated on determining the equilibrium phase diagram, &apos;&apos;&apos; the structure of the equilibrium phases,3 and later the isothermal decomposition of the 0 phase at subcritical temperatures, or the decomposition of the martensite on tempering. Other work which treated the nonequilibrium transformations concentrated largely on the martensite transformations and the structure of the b and y&apos; phases.15"17 Since the pearlite and martensite transformations in this system resemble those in steels, the one being formed by nucleation and growth of adjacent lamellae of the equilibrium phases, and the other by a diffusionless, shear-type transformation, the present study has been undertaken to investigate the structures formed on continuous cooling, with the objective of constructing cooling transformation diagrams analogous to those derived for alloy steel systems. In particular it was desired to determine whether parallels between the A1-Cu and iron-iron carbide systems on continuous cooling extended to encompass the intermediate phase, namely the bainite structures, which form by a combined martensitic-diffusion mechanism,&apos;&apos; but which are supersaturated with respect to the equilibrium phase upon which their crystal structure is based. To this end the transformations in representative alloys of the Cu-A1 B eutectoid system have been followed, using the methods of thermal analysis, X-ray diffraction, and optical microscopy. EXPERIMENTAL PROCEDURE Materials. The materials tested were those used by Klier and Grmko 5 in their study of the isothermal decomposition of these alloys. The alloys were melted in graphite crucibles and chill-cast into 5 by 2 by 1/4 in. ingots. The ingots were then hot-rolled to sheets 1/8, 1/16, and 1/32 in. thick. The compositions are given in Table I. Specimen Preparation. Specimens for thermal analysis were in the form of small squares approximately 1/4 in. on a side. For the 11.9 and 13.5 Al-Cu alloys, the sheet thickness was 1/16 in. and for the 10.5 A1-Cu alloy the 1/32-in. sheet was used. One lead of a chromel-alumel thermocouple was spot-welded to either face of the square with the specimen itself thus forming the hot junction of the thermocouple. Specimens for X-ray analysis were prepared as filings from martensitic sheet stock and were sealed in glass ampoules under 1/2 atm of argon. Metallographic examination of the powder specimens was carried out on a portion of the heat-treated filings mounted in lucite. All specimens were examined metallographic ally after etching

Jan 1, 1965