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By J. D. Sullivan, Chester R. Austin, J. L. Nunes

IT is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investigators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from 1100° to 1706°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxidation of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous days burned to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,5 the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery6 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the day, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid; i.e., the sulphur was in combination with the silica. Orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By A. V. Deforest, C. W. Macgregor, A. R. Anderson

One of the important problems in the design of structures and machine parts subjected to rapidly applied loads is the determination of the strength and ductility of the material itself under such conditions. Realizing the need for such information, many investigations have been carried out in the past. Most of these experiments have been made using notched bars in bending either with the Charpy or Izod impact machine. While yielding valuable data on the effect of notches in the energy absorption of the material and on the condition of heat-treatment, this form of test does not lend itself readily to a determination of fundamental stress-strain relations. For this and other reasons, more attention has been paid recently to the tension impact test. An extensive literature already exists on the subject and only those investigations somewhat closely related to the present paper will be mentioned. For a more comprehensive list, the reader is referred to the Symposium on Impact Testing or the A.S.T.M., 1938. The work of Mann.' Clark and Dätwyler,2 Nádai and Manjoine,3 Winlock and Leiter,4 Deutler,5 and Brinkmann,6 however, deserves especial mention. In most of the previous investigations on the subject, when stress-strain relations were obtained under high rates of loading, it was the common procedure to determine stresses based on the original area and strains based on the original length. Stress-strain curves were then constructed by P ALo plotting So = 1/A0 as a function of eo = ALr,o where A0 and Lo refer to the original area and gauge length, respectively. At present there exists a paucity of true stress-strain data in the impact problem. The advantages of constructing so-called true stress-strain curves in order to reveal the fundamental physical properties of the material for the tension test were discussed recently by one of the authors.7'8 It was shown that the true physical behavior of the material in the tension test could best be represented P by plotting the average true stress, S = 2P as a function of 6 = q' = log —r = log ~9L where P, A, L, S, E, and q' refer to the load, the cross-sectioned area while the load P is applied, the actual gauge length, the average true stress, the true strain and true reduction in area, respectively. Besides giving a better physical representation, the method has certain additional advantages in that the stress-strain curve so plotted becomes a straight line from the maximin load point to fracture. The construction of such curves, however, while comparatively simple for the slow rates of loading customarily used in the tension test, presents certain dificulties for tensile impact in that both loads and diameters are required throughout the test. The continuous measurement of test-piece diameters to fracture under impact conditions offers considerable experimental difficulty. In order to make it feasible to

Jan 1, 1942

By A. V. Deforest, A. R. Anderson, C. W. MacGregor

One of the important problems in the design of structures and machine parts subjected to rapidly applied loads is the determination of the strength and ductility of the material itself under such conditions. Realizing the need for such information, many investigations have been carried out in the past. Most of these experiments have been made using notched bars in bending either with the Charpy or Izod impact machine. While yielding valuable data on the effect of notches in the energy absorption of the material and on the condition of heat-treatment, this form of test does not lend itself readily to a determination of fundamental stress-strain relations. For this and other reasons, more attention has been paid recently to the tension impact test. An extensive literature already exists on the subject and only those investigations somewhat closely related to the present paper will be mentioned. For a more comprehensive list, the reader is referred to the Symposium on Impact Testing or the A.S.T.M., 1938. The work of Mann.' Clark and Dätwyler,2 Nádai and Manjoine,3 Winlock and Leiter,4 Deutler,5 and Brinkmann,6 however, deserves especial mention. In most of the previous investigations on the subject, when stress-strain relations were obtained under high rates of loading, it was the common procedure to determine stresses based on the original area and strains based on the original length. Stress-strain curves were then constructed by P ALo plotting So = 1/A0 as a function of eo = ALr,o where A0 and Lo refer to the original area and gauge length, respectively. At present there exists a paucity of true stress-strain data in the impact problem. The advantages of constructing so-called true stress-strain curves in order to reveal the fundamental physical properties of the material for the tension test were discussed recently by one of the authors.7'8 It was shown that the true physical behavior of the material in the tension test could best be represented P by plotting the average true stress, S = 2P as a function of 6 = q' = log —r = log ~9L where P, A, L, S, E, and q' refer to the load, the cross-sectioned area while the load P is applied, the actual gauge length, the average true stress, the true strain and true reduction in area, respectively. Besides giving a better physical representation, the method has certain additional advantages in that the stress-strain curve so plotted becomes a straight line from the maximin load point to fracture. The construction of such curves, however, while comparatively simple for the slow rates of loading customarily used in the tension test, presents certain dificulties for tensile impact in that both loads and diameters are required throughout the test. The continuous measurement of test-piece diameters to fracture under impact conditions offers considerable experimental difficulty. In order to make it feasible to

Jan 1, 1942

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

IT is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investigators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from 1100° to I700°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxidation of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous clays burned to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,5 the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery6 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the clay, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid,i.e., the sulphur was in combination with the silica. Orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By James F. Watson, Jack L. Christian

The austenite to martensite solid state phase transformation in the 300 series austenitic stainless steels was studied over the temperature range of 788° to -423°F. The primary variables controlling this transformation are temperature, plastic strain, and chernical composition. Consequently, temperature effects were studied by measurements at 78", -100°, -320°, ad -423°F; plastic strain was controlled by cold-rolling the alloys varying amounts between 40 and 80 pet; and chemical compositions were varied by using 301, 302, 304 ELC, and 310 stainless steel alloys which exhibit varying degrees of austenite stability. The martensite contents of various alloys were correlated with several mechanical properties including yield and ultimate tensile strength, elongation, and notched tensile strength (Kt = 6.3). The yield and tensite strengths generally increased with increasing martensite content, but ) no correlation was observed between elongation and martensite content. The notched/un-notched ratio (Kt = 6.3) at -423°F exhibited a maximun at about 65 pct martensite. Attempts to correlate austenite stability (as measured by the Ms temperature) with both martensite content, and incremental increases in martensite content resulting from tensile testing were generally unsuccessful because the variable of cold Work could not be separated. As a result, only a general correlation of these variables was obtained. A (111) pole figure of austenite in a cold-rolled 301 stainless steel mas prepared an attempt to further investigate directionality as exhibited by mechan- ical properties. Yield strength was correlated with this pole figure, but ultimate and notched tensile strengths were not. 1 HE literature contains a wide variety of references pertaining to the austenite to martensite solid state phase transformation in austenitic stainless steel, see references 1 through 18. Discussions of the crystallography and kinetics of this transformation are given in references 2, 7, 8, 'and 11, while further discussions of austenite stability and hardening mechanisms are given in references 1, 3, and 10. Two important processing variables involved in this reaction are the degree of cold work and the temperature at which cold work is performed, and the nature of these effects are outlined in references 4 and 12, and 15 and 16 respectively. The latter two references deal primarily with cold rolling conducted at subzero temperatures. The effect of chemical composition on the austenite to martensite reaction was treated in detail by Eichelman and Hull, and they determined an equation for the M, temperature of this type of steel which included the effects of nickel, chromium, carbon, nitrogen, silicon, and manganese.5 Previous studies have shown that austenitic stainless steels of AISI types 301, 302, 304ELC, 310, and 301-N exhibit mechanical properties between 78" and -423"~ that are microstructure dependent, and the dependence of this microstructure on chemistry, temperature, tensile stress, and prior deformation is in general accord with previous investigations which have measured the effects of each of these variables on structure, or more specifically, the austenite-to-martensite transformation.lg The behavior of fully stable alloys, such as ATST type 310, at cryogenic temperatures is

Jan 1, 1962

By David J. Mack

THE structures and properties of the copper-aluminum alloys have been the subject of much study since the classic investigation of Carpenter and Edwards1 focused attention on the engineering utility of these alloys. It was recognized at an early date that the metallographic structures developed in the aluminum bronzes were similar to those developed in steels, both in the annealed and the rapidly cooled state. Most investigators have been concerned with the acicular, martensitic-like structure formed from the ß solid solution upon rapid quenching; the transformation of the ß under equilibrium cooling to a lamellar eutectoid having been relatively neglected. With the introduction in 1930 by Davenport and Bain2 of the isothermal transformation technique for studying eutectoidal decompositions, a new field was opened. Although an enormous amount of work has since been done on the isothermal transformation of steel, study of structurally analogous systems has been almost totally overlooked. The outstanding exception was the prize-winning paper† of Smith and Lindlief3 who investigated the decomposition of the ß phase in copper-aluminum alloys by isothermal methods. This was followed in 1934 by Wasserman's reviews of available information on analogous transformations in eutectoid alloys. Since that time no comprehensive study of isothermally transformed eutectoids analogous to steel has appeared, although many valuable contributions have been made to an understanding of the structures developed in such systems. Important papers have been published by Kurdjumow, Gridnew and co-workers, 5-17 Obinata,18,19 Greninger,20,21 and others .22.28 The work to be described in this paper was an out-growth of preliminary studies on the isothermal transformation of a eutectoid aluminum bronze, after it became apparent that the alloy under study was reacting somewhat differently than the similar alloy used by Smith and Lindlief. PRELIMINARY EXPERIMENTS The material used in this study was a high purity aluminum bronze especially prepared by Ampco Metal, Inc. It analyzed: Copper-88.o7 pct, Aluminum-11.89 Oct, Iron-0.02 pct, Manganese-0.01 pct, Others-Balance. Although some disagreement exists on the exact composition of the eutectoid, this alloy was believed to be of essentially eutectoid composition even though some pro-eutectoid* delta particles existed in the microstructure of furnace cooled specimens. Specimens transformed isothermally at temperatures slightly below the eutectoid showed relatively large amounts of pre-eutectoid delta, but as will be shown later, this results

Jan 1, 1947

By L. E. Young

THE progress of mineral industry education will be limited to the period prior to World War II and will be considered as primarily a division of engineering education. Its relation to progress in the mineral industry and to the activities of the American Institute of Mining and Metallurgical Engineers will be emphasized. The history of mineral industry education has been recorded most completely and authoritatively by Dr. T. T. Read in his recent volume in the Seeley W. Mudd Series of American Institute of Mining and Metallurgical Engineers publications, entitled, The Development of Mineral Industry Education in the United States. Therefore, most of the historical details will be omitted from the discussion and an effort will be made to point out significant developments and to analyze trends. INTRODUCTORY STATEMENT AND SIGNIFICANT POINTS IN PROGRESS Among the significant points in the development of mineral industry education in the United States since 1871, the following deserve particular mention: I. The number of institutions offering undergraduate instruction has increased, particularly during the years 1890 to 1925; the number of students enrolled in undergraduate study has increased greatly, largely on account of the development of courses in petroleum engineering and increasing interest in metallurgy. 2. The selection of students to be admitted to undergraduate courses has been improved through the advisement, counseling, and guidance programs sponsored by the Engineers' Council for Professional Development. 3. Improved instruction methods and the training of the teaching staff have been promoted by the educational institutions themselves, but with the most effective stimulus and guidance of the American Society for Engineering Education and the Engineers' Council for Professional Development. 4. The accrediting of undergraduate curricula through the Engineers' Council for Professional Development, considering both qualitative and quantitative criteria, has done much to improve standards of instruction in engineering education for the mineral industry. 5. Undergraduate curricula and courses are revised currently to meet the needs of the American mineral industry. New curricula are developed currently to permit specialization in technical fields, particularly in the fourth year of undergraduate work. 6. There has been a strengthening of the fundamental courses in mathematics, physics, mechanics, and chemistry, and at the same time these courses are being adapted to the most recent developments in the industry, including metallurgy, geophysics, petroleum engineering, petroleum technology, ceramics and so forth. 7. There has been continuing improvement in plant and laboratory facilities of the educational institutions.

Jan 1, 1947

By Ronald C. Koo

SMALL additions of potassium, aluminum, and silicon as oxides (referred to as dope) to tungsten have been known for several decades to have a very large effect in raising the recrystallization temperature and altering the recrystallized grain morphology of heavily drawn wire. Previous investigations of this doping effect1 6 have led to various speculations but all failed to deduce unequivocally the physical state or the mechanistic influence of the dopant. Recently, walter7 has observed, by transmission electron microscopy, strings of "fine particles" in heavily rolled and annealed doped tungsten sheet and concluded that they were particles of mullite (Al6Si2013). His conclusion was inferred from the electron diffraction patterns of large particles ex-trated by carbon replication of fractured surfaces of slabs rolled from sintered ingots. That the strings of "fine particles" in heavily rolled and annealed sheet were also mullite was an assumption for which no evidence was presented. A similar investigation has been carried out in this laboratory over the past 2 years on a variety of tungsten wire: doped tungsten, and undoped tungsten, as well as 218 doped tungsten purchased from the Lamp Metals and Components Department of the G.E. Lamp Division. Although the electron microscope observations are similar to those reported by Walter, the writer has reached a different conclusion concerning the physical state of the dopant in annealed tungsten. The purpose of this communication is to present evidence that the strings of "fine particles" observed in transmission specimens are not mullite, but are voids. In the present investigation, tungsten wire, 0.88 mm in diam, was rolled into ribbon 0.2 mm by 125 µ thick. The ribbons were annealed in vacuo at a pressure of -1 x 10-5 Torr and then thinned electrolytically in a 2 pct KOH solution. Fig. 1 shows a typical transmissicjn electron micrograph of a sample annealed at 1700°C for 30 min which reveals rows of closely spaced voids having a light contrast (referred to as "fine particles" by Walter) aligned parallel to the working direction. Stereo micrographs (by D. Moon, Westinghouse Research and Development Center) have shown that these voids do not exist on the surfaces of the specimens as a result of thinning but are within the thin-foil specimens. The following experiments have been performed to verify that these are indeed voids. I) Effect of Annealing. Voids are absent in unannealed specimens and appear only after annealing. This behavior cannot be explained if they were solid particles such as mullite. Precipitation (in an unquenched specimen) upon annealing requires solute elements having decreasing solubilities with increasing temperature. Although the solubility of aluminum in tungsten does decrease with increasing temperature, precipitation requires a concentration in excess of 1.4 wt pct,8 which is at least two orders of magnitude higher than the aluminum content in doped tungsten. It is also unreasonable to assume that particles aligned in rows initially present in unannealed specimens were too

Jan 1, 1968

Reserves of Lake Superior Manganiferous Iron Ores Appendix-to paper by CARL ZAPFFE, presented at the Cleveland Meeting and issued, as Pamphlet No. 1664-C, with MINING AND METALLURGY, May, 1927. The author has made several test calculations on the basis of manganese units that are and may be involved. These are summarized here, as follows: On the basis of ore produced since 1902, the average annual requirement of manganese units would be 91,000 tons; on the basis of the production of the past 4 or 5 years, the requirement would be 145,000 tons; on the basis of the year 1925 only, the requirement would be 155,000 tons. Applying the percentage of increase for the next 20 years, as determined by the plat shown as Fig. 3, the total requirement for 20 years would be 3,254,000 to 3,572,000 tons, if one used either 145,000 tons or 155,000 tons as a starting point. We have the following interesting facts: (1) The Michigan ores contain only about one-half the manganese that the Cuyuna ore does; (2) the Cuyuna district now produces one-half the ore required; (3) the known tonnage of Cuyuna reserves is greater than the speculative reserve offered for Michigan; (4) at the present rate of production considered by tons, Michigan ores ought to be exhausted in 20 years or less while Cuyuna ores would last up to 44 years. We should now reduce the estimated reserves to a basis of manganese, units. Using the tonnages listed in Combinations 2, 3, 4 and 5, the reserves total 3,118,225 tons, 3,781,995 tons, 5,041,995 tons and 5,560,342 tons, respectively. Therefore, needing at the most 3,572,000 tons, as shown above, either Combination 3, 4 or 5 will not only suffice but will leave an excess-enough for 1 or 2 years for Combination 3, 9 or 10 years for Combination 4, and 12' to 13 years for Combination 5. This means that for Combination 5, without using tonnages obtained from beneficiating or from mixing poor ores, the reserves are ample for about 33 years.

Jan 5, 1927

By George H. Ashley

At the beginning of the war, about 13 years ago, a conference was called in Washington to lay plans for pooling the coals of the United States. A careful review of the various systems of classification then extant showed none well adapted to the needs of coal pooling. The system of Tidewater pools then adopted, using numbers to distinguish one pool from another, was based on typical coals of different localities. At that time, the writer undertook the preparation of such a practical classification. Aside from drawing on his experience of over 20 years in the coal fields of the United States, reaching from the Pacific Coast and the Rio Grande to Rhode Island, he first examined and carded all of the large collection of coals in glass jars made by and for M. R. Campbell. Next, he carded all of the descriptions of coals he could find in the U. S. Geological Survey bulletins and elsewhere, as well as practical tests of coals by the Navy and other organizations and then took account of every published coal analysis of the U. S. Geological Survey and U. S. Bureau of Mines. A study of this information, involving thousands of recomputations, led to the presentation of a paper on "A Use Classification of Coal" before this Institute at the Chicago meeting, September, 1919. That classification was unique (1) in a classification based on "standard coal" which included moisture, but used standardized ash, sulfur and nitrogen, (2) in using physical properties to distinguish the major classes or orders, (3) in recognizing British thermal unit values in the minor subdivision, (4) in the large number of classes recognized (thirty-six), (5) in proposing mineral names for all classes, (6) in proposing a letter code for the several classes for practical use, (7) in proposing a code for expressing what has commonly been called "grade" of the coal, the grade code to be combined with the rank code to designate and describe a coal. The writer still thinks that the principles then offered, though not necessarily the exact proposals, are valid and desirable in any practical classification. The actual classification of coal by rank was based on the ratio of fixed carbon to volatile matter for the high-rank coals—the well-known

Jan 1, 1930

I. PRESIDING OFFICER. At all business meetings of the Institute the President, or, in his absence, the First Vice-President, or, in the absence of both of them, any other Vice-President or Director, chosen by the meeting, shall preside. At all other meetings of the Institute the President, or, in his absence, one of the Vice-Presidents, shall preside. If none of these be present the meeting shall elect a Chairman. II. ORDER OF BUSINESS. At each business meeting of the Institute the order of business shall be as - follows : 1. Reading of minutes-of preceding meeting. 2. Report of the President. 3. Report of the Treasurer. 4. Report of the. Secretary. 5. Election of Directors. 6. Reports of Standing Committees. 7. Reports of Special Committees. 8. Special Orders. 9. Miscellaneous business. This order of business may be changed at any meeting, by a vote of a majority of the Members and Associates present. At all sessions of the Institute, other than business meetings, the order of pro¬ceedings and the time of adjournment shall rest in the discretion of the presiding officer. III. SECRETARY OF THE INSTITUTE. The Secretary shall keep a record of the proceedings of all meetings of the Institute. He shall be custodian of the corporate seal, of the minute books, and of all legal documents belonging to the Institute. He shall have charge, on behalf of the Institute, of all correspondence except such as pertains directly to the office of the Treasurer. He shall notify all Officers and Directors and all members of committees of their election and appointment; shall issue notices of all meetings of the Board, and of the annual and other business meetings of the Institute; and shall; in calling, special meetings of the Directors, specify the objects of such meetings. He shall act as clerk at all the meetings of the Board of Directors and at all meetings of the Institute. The Secretary shall be custodian of all technical or scientific papers submitted to the Institute for its consideration, shall have general charge and supervision of the editing and proof-reading of all material published by the Institute, and of the distribution thereof, and be ex officer Chairman of the Committee on Publications. On the first day of May following the year in which each volume of Transac-

Jan 1, 1925

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-' 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 G. Derge, Lo Ching Chang

The chemical and physical propertties of slag systems are of special interest to metallurgists, for nearly all metals are in contact with molten slags during the primary reduction from their ores and then during the subsequent refining and alloying processes that determine their ultimate use. These processes are carried out at high temperatures and involve such complex chemical systems that funda-mental scientific knowledge of the Properties and behavior of these slags is inadequate. Various hypotheses have been Proposed to explain known slag characteristics. The commonest of these regard the molten slag as constituted of compounds that are dissociated in varying degrees into their constituent oxides, as illustrated by Schenckl and the recent Papers of Chipman and co-authors. Another proposal is that these compounds dissociate by com-plete6 or partial ionization, the evidence for which has been reviewed by Martin and Derge.? whatever hypothesis is favored, the exact formulation of these compounds is incomplete. It is based on three principal types of information: 1. Studies of solidified 51% samples by X ray diffraction, petrography, and similar methods that can be used at room temperature. The correlation of this information with the high-temperature properties of the molten slag is uncertain. 2. Studies of slag-metal equilibria, which have the advantage of providing observations on the molten slag at high temperature. However, even these data present problems of interpretation because they require a complete knowledge of the metal phase. 3. Direct measurements of properties of molten slag at the temperature of greatest metallurgical interest. Viscosity, electrical conductivity, specific heats, and similar properties have been measured, but the data of this type are widely scattered and frequently difficult to interpret. Additional direct measurements of properties of molten slag that can be interpreted in terms of chemical behavior are required, and this paper shows that the standard physical-chemical measurement of reversible electrode potentials, which measure the activity of specific constituents, is a fruitful source of such information. The purpose of this investigation, therefore, was to find an electrode combination that would yield reversible electromotive force measurements when dipped into the molten slag to be studied. Slags of the systems cao-sio2 and cao-120,-SiO2 were chosen for study because graphite containers could be used and the data could be correlated with those for viscosity, conductivity, and other proper-

Jan 1, 1948

By G. Derge

The chemical and physical propertties of slag systems are of special interest to metallurgists, for nearly all metals are in contact with molten slags during the primary reduction from their ores and then during the subsequent refining and alloying processes that determine their ultimate use. These processes are carried out at high temperatures and involve such complex chemical systems that funda-mental scientific knowledge of the Properties and behavior of these slags is inadequate. Various hypotheses have been Proposed to explain known slag characteristics. The commonest of these regard the molten slag as constituted of compounds that are dissociated in varying degrees into their constituent oxides, as illustrated by Schenckl and the recent Papers of Chipman and co-authors. Another proposal is that these compounds dissociate by com-plete6 or partial ionization, the evidence for which has been reviewed by Martin and Derge.? whatever hypothesis is favored, the exact formulation of these compounds is incomplete. It is based on three principal types of information: 1. Studies of solidified 51% samples by X ray diffraction, petrography, and similar methods that can be used at room temperature. The correlation of this information with the high-temperature properties of the molten slag is uncertain. 2. Studies of slag-metal equilibria, which have the advantage of providing observations on the molten slag at high temperature. However, even these data present problems of interpretation because they require a complete knowledge of the metal phase. 3. Direct measurements of properties of molten slag at the temperature of greatest metallurgical interest. Viscosity, electrical conductivity, specific heats, and similar properties have been measured, but the data of this type are widely scattered and frequently difficult to interpret. Additional direct measurements of properties of molten slag that can be interpreted in terms of chemical behavior are required, and this paper shows that the standard physical-chemical measurement of reversible electrode potentials, which measure the activity of specific constituents, is a fruitful source of such information. The purpose of this investigation, therefore, was to find an electrode combination that would yield reversible electromotive force measurements when dipped into the molten slag to be studied. Slags of the systems cao-sio2 and cao-120,-SiO2 were chosen for study because graphite containers could be used and the data could be correlated with those for viscosity, conductivity, and other proper-

Jan 1, 1948

By L. R. van Wert

CAREFUL research into the nature of the metallic state has yet to discover, with any certainty, its essential quality. We do riot yet know, for sure, what it is that makes the metallic elements different from, if not actually unique among, all created things. We do know, of course, that metals have certain more or less characteristic properties-they are hard, strong, and tough, and good conductors of heat and electricity, and these so-called metallic properties provide a definition of a sort. How- ever, it is the structure rather than the behavior of the metals which gives the really fundamental information necessary to the understanding of metallicity. But this information is not easily obtained. Nature has a way of keeping secrets. But happily we do possess some knowledge of how a metal is built up, and it is this matter, rather than the presentation of a formal definition, that will be discussed here.

Jan 1, 1937

By Clyde E. Williams

DESPITE the confusion resulting from the depression and the beginnings of recovery, important progress in all branches of iron and steel metallurgy has been accomplished during the year 1933. Research work has been intensive and highly technical, with increasing attention paid to fundamentals. Plant application of research developments has been rapid. Highly specialized laboratory methods were used for the study of iron-ore concentration methods. More attention has been given by the blast-furnace operator to the sizing of ore and the elimination of fines from the charge by the use of sinter. Combustion in the open-hearth has been placed under better control and the insulation of open-hearth furnaces has spread rapidly, with resultant higher fuel efficiency and better control of the melting and refining operations. Control of iron oxide content in the slag and the determination of iron oxide and other inclusions in steel received great attention during the year.

Jan 1, 1934

By E. J. Roberts

Prior to 1916, thickening was an art, and any accurate decision as to what size of machine to install to handle a given tonnage of a specific ore must have been one of those intuitive conclusions, based on both intimate and extensive acquaintance with thickners and ore pulps. Then in 1916 "knowledge of acquaintance," became "knowledge about" with the publication of the Coe and Clevenger paper.' The unit operation of thickening had graduated to the status of an engineering science. The fundamental similitude relationships for the two major phases of the operation were defined so clearly that batch tests on models as small as liter cylinders could serve to specify protypes as large as 325 ft in diameter.

Jan 1, 1949

By J. H. Reynolds

The possibility of using a semiconductor, metal, semiconductor structure as a light detector is discussed. A brief theoretical argument is presented which predicts that this structure should have pho-toresponse characteristics similur to those of a metal-semiconductor diode, but with the magnitude of the current increased by a transistor gain factor. Measurements made at low frequencies on a particulur S-M-S device agree u~th this prediction aizd shoul that significant gain factors are attainable. The current gain is substantially higher than that predicted for the metal base transistor. It is proposed that the operation of these units is more closely approxinzated by the metal-gate model which predicts higher current gains. A qualitative discussion of its high-frequency performance indicates that detection of light modulated at microwave frequencies by a S-M-S deuice is possible. ADVANCES in the technology of chemical vapor deposition'-4 have made it possible to form a S-M-S structure consisting of a thin metallic layer sandwiched between layers of single-crystal semiconductor. It has been proposed5-7 that, if the metal layer is made sufficiently thin, this structure could be used in an amplifier having several advantages over presently available transistors including higher-frequency performance. Calculations8 predict that the maximum gain-bandwidth product is nearly an order of magnitude higher than that of a bipolar transistor having the same geometry. Maximum oscillating frequencies in the microwave range are predicted. Electrical measurements made on S-M-S devices have shown that, although the theoretical frequency characteristics are not presently attainable, current and power gain is obtained. Another possible application of the S-M-S structure is its use in a light detector. This structure is a three-layer relative of the metal-semiconductor diode. Light detection using M-S diodes is the subject of considerable present interest. They are known to have a short response time and the ability to detect light having a photon energy below the semiconductor bandgap. In this paper, the mechanism by which S-M-S photocurrent is generated is discussed. An expression is derived which shows that the response characteristics are similar to those of a M-S diode, but that the magnitude of the current is increased due to the transistorlike behavior of the device. The results of low-frequency response measurements on a particular S-M-S structure are presented. These agree with the theoretical predictions and show that significant gain factors are attainable. A qualitative discussion of the high-frequency characteristics is presented which predicts that detection of light at microwave frequencies by a S-M-S device is possible. THEORY In this discussion, the photocurrent, iT, measured across terminals attached to the semiconductor emitter and collector layers is related to the current pho-toemitted from the metal base layer. The latter will be referred to as the primary photocurrent. The behavior of the primary photocurrent is determined by the characteristics of the two metal-semiconductor diodes. The diode photoemission is illustrated in Fig. 1, which shows the emitter and collector potential barriers. The metal thickness has been greatly exaggerated. As will be discussed later, the actual barrier shape can be much more complex, but this diagram illustrates the essential features of the photoemission process. An absorbed photon having an energy greater than the barrier height can emit an electron into the emitter or collector. Since this process is discussed

Jan 1, 1968

By Walter Rose

In a recent technical note, Owen Thornton&apos; suggests that wetting liquid relative permeability may be derived from the relationship: where Pd/Pc is the ratio of displacement pressure to capillary pressure at the wetting liquid satdration Sw, and I is the resistivity index at this saturation. Thornton shows that this expression gives values for relative permeability in good agreement with those experimentally determined by Leverett. We have recently developed another expression for krw which seems preferable to Equation 1 since it requires fewer experimental data for its verification. This equation may be derived in the following manner. Making use of the analogy between mass transfer of fluid in a porous medium and electrical conductivity through the fluid in the same medium, we can postulate a hydraulic formation resistivity factor analogous to an electrical formation resistivity factor. From Poiseuille&apos;s Law the resistivity to flow in a tube of radius R is of the form 8u/R², where is the viscosity of the fluid. Similarly7 the resistivity to flow in a porous medium of the same dimensions as the tube is given by D&apos;Arcy&apos;s Law as where k is the permeability of the medium. The hydraulic formation resistivity factor, Ff, is thus the quotient of these two resistivities, or: But permeability is defined by the KO-zeny equation as: where: r is the average pore radius of the porous medium, L. is the average tortuous length of the average pore, + is the porosity, and L is the bed length. This gives Fr as a function of the (La/L) .-.-.tortuosity ratio and porosity, or in explicit form: where: T = (La/L)&apos;, and N is the number of pores of radius, r, which will be found in any cross sectional area, x R&apos;. That is, N = R²/r². It will be clear from the foregoing considerations that the hydraulic formation fat. tor should be dependent on the value of R which in every case must be arbitrarily selected. By analogy, the hydrauiic formation factor, Fcf, characterizing the porous medium at Sw<1,will be given by: R² NT. where ke is the effective wetting liquid permeability obtaining at Sw<l, and Te is the square of the (Las/L) ratio defined by Thornton. Therefore, the hydraulic resistivity index, If, is: However, Thrnton gives I as: and it follows that: Equation 2, when checked against the data of wyckoff and Botset² and some of the Morse et al data³, gives comparisons as shown at the bottom of this page. Computations based on Leverett&apos;s data, quoted by Thorntaon, gives computed krw values somewhat lower than the experimental values. Moreover, other instances can be cited where we find that neither Equation 1 nor Equa tion 2 is checked by experimental data. The work of Botset&apos; on the Nichols Buff sandstone and Morse et a1 on oil wetted Bradford sandstone are such instances. A reason for these discrepancies may lie in the fact that if both Equations 1 and 2 are presumed always to give accurate values for krw, it follows that PC = Pd/Sw". Such an expression, it is well known, is too simple to describe accurately the capillary pressure behavior of all porous media. However, it is believed that a particular advantage resides on the use of Equation 2, since it is not dependent for its utility on a knowledge of the capillary pressures obtaining in dynamic flow svsterns. No practical technique for measuring the capillary pressures characterizing the fluid distributions in dynamic flow systems has yet been proposed. Acknowledgment is given to Dr. Paul D. Foote, executive vice-president of the Gulf Research and Development Company, for permission to publish this note. 1. Owen F. Thornton, "A Note on the Valuation of Relative Permeability," J. Pet. Tech., 1:7, Section 1, July, 1949. 2. R. D. Wyckoff arid H. G. Botset, "The Flow of Gas-Liquid Mixtures through Porous Media," Physics, 7:325-345, 1936. 3. R. A. Morse, P: L. Terwilliger, .and S. T. Yuster, "Relative Permeability Measurements of Small Core Samples," Oil and Gas J., 46:109-125, Aug. 23, 1947. 4. H. G. Botset, "Flow of Gas-Liquid Mixtures Through Consolidated Sand," Trans. AIME, 136:91, 1940.

Jan 1, 1949

By Walter Rose

In a recent technical note, Owen Thornton&apos; suggests that wetting liquid relative permeability may be derived from the relationship: where Pd/Pc is the ratio of displacement pressure to capillary pressure at the wetting liquid satdration Sw, and I is the resistivity index at this saturation. Thornton shows that this expression gives values for relative permeability in good agreement with those experimentally determined by Leverett. We have recently developed another expression for krw which seems preferable to Equation 1 since it requires fewer experimental data for its verification. This equation may be derived in the following manner. Making use of the analogy between mass transfer of fluid in a porous medium and electrical conductivity through the fluid in the same medium, we can postulate a hydraulic formation resistivity factor analogous to an electrical formation resistivity factor. From Poiseuille&apos;s Law the resistivity to flow in a tube of radius R is of the form 8u/R², where is the viscosity of the fluid. Similarly7 the resistivity to flow in a porous medium of the same dimensions as the tube is given by D&apos;Arcy&apos;s Law as where k is the permeability of the medium. The hydraulic formation resistivity factor, Ff, is thus the quotient of these two resistivities, or: But permeability is defined by the KO-zeny equation as: where: r is the average pore radius of the porous medium, L. is the average tortuous length of the average pore, + is the porosity, and L is the bed length. This gives Fr as a function of the (La/L) .-.-.tortuosity ratio and porosity, or in explicit form: where: T = (La/L)&apos;, and N is the number of pores of radius, r, which will be found in any cross sectional area, x R&apos;. That is, N = R²/r². It will be clear from the foregoing considerations that the hydraulic formation fat. tor should be dependent on the value of R which in every case must be arbitrarily selected. By analogy, the hydrauiic formation factor, Fcf, characterizing the porous medium at Sw<1,will be given by: R² NT. where ke is the effective wetting liquid permeability obtaining at Sw<l, and Te is the square of the (Las/L) ratio defined by Thornton. Therefore, the hydraulic resistivity index, If, is: However, Thrnton gives I as: and it follows that: Equation 2, when checked against the data of wyckoff and Botset² and some of the Morse et al data³, gives comparisons as shown at the bottom of this page. Computations based on Leverett&apos;s data, quoted by Thorntaon, gives computed krw values somewhat lower than the experimental values. Moreover, other instances can be cited where we find that neither Equation 1 nor Equa tion 2 is checked by experimental data. The work of Botset&apos; on the Nichols Buff sandstone and Morse et a1 on oil wetted Bradford sandstone are such instances. A reason for these discrepancies may lie in the fact that if both Equations 1 and 2 are presumed always to give accurate values for krw, it follows that PC = Pd/Sw". Such an expression, it is well known, is too simple to describe accurately the capillary pressure behavior of all porous media. However, it is believed that a particular advantage resides on the use of Equation 2, since it is not dependent for its utility on a knowledge of the capillary pressures obtaining in dynamic flow svsterns. No practical technique for measuring the capillary pressures characterizing the fluid distributions in dynamic flow systems has yet been proposed. Acknowledgment is given to Dr. Paul D. Foote, executive vice-president of the Gulf Research and Development Company, for permission to publish this note. 1. Owen F. Thornton, "A Note on the Valuation of Relative Permeability," J. Pet. Tech., 1:7, Section 1, July, 1949. 2. R. D. Wyckoff arid H. G. Botset, "The Flow of Gas-Liquid Mixtures through Porous Media," Physics, 7:325-345, 1936. 3. R. A. Morse, P: L. Terwilliger, .and S. T. Yuster, "Relative Permeability Measurements of Small Core Samples," Oil and Gas J., 46:109-125, Aug. 23, 1947. 4. H. G. Botset, "Flow of Gas-Liquid Mixtures Through Consolidated Sand," Trans. AIME, 136:91, 1940.

Jan 1, 1949