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By C. E. Birchenall, G. Derge

IN studying the kinetics of slag-metal reactions, it has become increasingly apparent that a complete knowledge of all aspects of interface phenomena will be required to clarify these processes adequately. A part of the data required for all oxidizing slags used in the refining of impure iron to steel is the rate of exchange of iron between the slag and metal phases. The simplest equilibrium of this type is that between liquid iron and iron silicate slag when both phases are equilibrated with the silica crucible containing them. In this study, the exchange of iron between the two liquid phases has been measured by using radioactive Fe as tracer. The observed high exchange rate indicates the ease with which such interfaces may be crossed in refining processes. The experiments required for this study involved relatively minor and normal modifications of well established techniques. Melting was accomplished by induction heating in heavy walled, fused silica, rotating crucibles." Rotation was used to minimize dilution of the slag by crucible erosion. The melting stock was ingot iron. Slags were prefused in iron crucibles using chemically pure grade oxide reagents. The special conditions applying to the active iron additions will be described for individual experiments. Suitable precautions were observed with regard to protection against radiation hazards.' Identification of Activity This particular study was initiated several years ago, but held in abeyance because the radioactive iron available at that time contained a foreign activity which concentrated in the slag so as to mask the iron activity and render the results unin-terpretable. With the benefit of experiences from other studies, radioiron of suitable purity can now be prepared. As received from the Isotope Div. of A.E.C., the unit appears to contain Fe + Fe50 and a high activity cobalt. The cobalt and iron are separated by repeated ether extractions, and the purified iron stored for sufficient time for the Fe'7 44 day half-life) to decay to negligible activity, leaving only Fe as the active isotope. This was confirmed by the absorption curves for slag and metal samples from heat No. 1. In Fig. 1 the experimentally measured points for the absorption curves of slag and metal are fitted by the calculated slope of 5.8 mg per sq cm in aluminum, which corresponds to the Mn K doublet emission resulting from the capture of an orbital electron of Fe" by the nucleus. This shows that the radioactive species are the same in both slag and metal and identifies it as Fe55 Description of Individual Heats For the first heat, the radioactive iron was contained in the prefused slag. The active Fe55 had been precipitated with carrier and was added as Fe2O3 during fusion in the iron crucible. The charge of 500 grams of ingot iron was melted, the protective iron sleeve added, rotation started, and a prefused, inactive slag was added to allow the system to approach equilibrium. After about 5 min at temperature, the wash slag was skimmed and the active slag added. Initial slag and metal samples were taken as soon as the slag was molten. Additional samples were taken at indicated intervals thereafter. Slag samples were dipped with a small iron spoon and metal samples were sucked into 1/4 in. ID silica tubes. The slag and metal samples were pulverized and mounted for radioactive counting. The slag samples were analyzed chemically for FeO. Temperature was read after the last slag sample by immersion of a Pt-Pt-Rh thermocouple protected by a fused silica sheath. Since no significant variation of rate with temperature was observed

Jan 1, 1954

By M. G. Corson

THE iron-silicon alloy series has always been one of the most puzzling among the binary alloys. Examining the well known mechanical properties of the iron-rich alloys only we meet the following situation: The ultimate strength and yield point of alloys worked and annealed under the usual conditions represent nearly a straight line function of the silicon content up to 4.5 per cent. silicon (Fig. 1). Starting at the ultimate strength of 35,000 lb. and at a yield-point of 16,000 lb. for pure electrolytic iron, one reaches a -maximum strength of 93,000 lb. and a maximum yield point of 74,000 lb. at 4.5 per cent. silicon. This corresponds to an increase in ultimate strength by 13,000 lb. per each per cent. of silicon added and nearly the same rate applies to the yield point. The data mentioned are taken from the investigation by T. D. Yensen,1 and while they do not exactly corroborate the results obtained by earlier investigators, they seem to be the most correct. Plastic properties of the alloys are controlled by a much more complicated relationship. Up to 2.5 per cent. Si, the elongation stays close to 50 per cent. (in 2 in.) and the area reduction amounts to 85 per cent., a situation that forms the usual feature of all alloys representing strictly solid solutions. The plasticity of the latter is always nearly equal to that of their base metal. Beyond 2.5 per cent. silicon, the situation becomes much more complicated Yensen observed an enormous drop in elongation and area reduction at about 2.65 per. cent. silicon, where the first hardly reaches 10 per cent. and the second is still lower; he found, however, a considerable recovery in plasticity at about 2.8 per cent. Si and up to. 4.5 per cent. Si it is represented by 20 per cent. for the elongation and 30 per cent. for area reduction.

Jan 1, 1928

By D. W. Lillie

Property changes produced by irradiation of Al-0.4 wt pet Li alloys at 270°C to a burnup of 0.155 pct of all atoms are described. Metallographic evidence of the formation of internal pores and the concentration of gases at grain boundaries is shown. Some conclusions are drawn concerning desirable property characteristics for resistance to radiation swelling. RADIATION induced gases are of great practical significance in nuclear engineering since they affect the behavior of fissionable fuels and control rod materials. In fuels the gases xenon and krypton are the major offenders, producing serious em-brittlement at low irradiation temperatures and gross swelling at high irradiation temperatures. In control rod materials containing boron, the production of helium from the B 10 (n, 0) Li7 reaction produces similar reactions. Since the trend in reactor design is for operation at increasingly high temperatures, the phenomenon of high-temperature swelling by these induced gases has been the subject of considerable recent study. The objectives of such work have been to obtain engineering information and quantitative data on the effects in specific fuels and control rods and to obtain further understanding of the mechanism of gas damage so that more intelligent corrective steps can be made. Analogue systems are often useful for the latter objective and in this case alloys containing Li are suitable in view of the reaction Li6 + n - He4 + He 4. Both products are gases and no serious radiation problem is produced to complicate post irradiation handling. Considerable caution is, of course, necessary in any operations in which tritium release is possible. The present program was initiated to provide a detailed study of the effects of He + H3 generated by irradiation in Li-bearing alloys. The results on Mg-Li solid solution alloys have been reported elsewhere.' This paper presents information on irradiation of an A1-0.4 pct Li alloy in which the lithium was present as highly enriched Li6 in order to maximize the radiation burnup. PROCEDURE The original intent in the selection of the alloy content was to have Li in solid solution at all temperatures. It became apparent, however, that the solubility of Li in A1 was substantially lower than that reported in the original reference consulted.' This was substantiated by the work of Nowak3 who reported solubility of less than 0.01 pct Li at 100°C. The alloy used (0.4 pct Li) was therefore two phase at room temperature. The irradiation temperature was estimated to be about 270° C, and at that temperature all or almost all of the Li would be soluble under equilibrium conditions. The precise state of the alloy under irradiation is not known. Aluminum used was 99.996 pct purity (max. impurities Si 0.002 pct, Mg 0.001 pct, Fe 0.0005 pct, and Cu 0.0005 pct). The lithium was obtained from Oak Ridge National Laboratory; 96.1 + 0.1 pct of the lithium was ~i~, but chemical impurities were 0.25 pct Ca, 0.05 pct Fe, 0.02 pct Na, 0.02 pct Cu, 0.01 pct Sr, and 0.01 pct Ba. The two metals were melted in an alumina crucible in a resistance heated furnace in an atmosphere of helium. A l-in. ingot was cast in an iron mold, machined to %-in. round, hot swaged (350°C) to 0.080-in. round, cold swaged to 0.060-in. round, and finally cold drawn to 0.040-in. round. Four-inch wire lengths were then cut and annealed at 250°C for 4 hr in helium. Irradiations were carried out in a VT hole in the Argonne CP-5 reactor. The wires were held in an aluminum jig, sixteen wires per capsule, and were maintained in a helium atmosphere for maximum heat transfer. Eight wires of pure aluminum and eight of Al-Li alloy were placed in each capsule. Argome Laboratory statements were accepted as establishing flux and exposure levels. These were based on previous experience and flux map-

Jan 1, 1961

By R. E. Carter, C. Wagner, F. D. Richardson

By means of inert markers of radio-platinum, it has been shown that cobalt metal oxidizes by out-ward diffusion of cobalt atoms through the oxide. Oxidation rates have been measured at various temperatures and oxygen pressures and have been found to agree with the rates calculated from the Wagner equation and the authors' values for the diffusion coefficient of cobalt in the oxide. The distribution of radio-cobalt in growing oxide loyers has been accurately measured and found to be different from that predicted from the Wagner oxidation theory. Attempts have been made to measure the change of lattice parameter of the oxide with composition. SEVERAL investigators have shown that cobalt metal oxidizes according to the parabolic law,1-3 but no detailed study has been made of the oxidation mechanism. Cobaltous oxide has a metal-deficient lattice, but the defect concentration which is dependent on the oxygen pressure is only approximately known.' From the similarities in the structures of "CoO" and "FeO" and the rate laws governing the oxidation of cobalt and iron, Gulbransen- as suggested that cobalt, like iron," oxidizes by diffusion of cobaltous ions through the oxide layer. To substantiate this hypothesis, he has attempted to measure the oxidation rate of cobalt as a function of the oxygen pressure but has been able to report only that the rate depends on a "small" power of the pressure. On the other hand, Preece," Valensi,' and Arkharov' all have suggested from indirect evidence that oxygen diffuses through the COO to the metal-oxide interface. The present authors, in a previous paper,' have shown that the rate of diffusion of cobalt in cobaltous oxide is dependent on the oxygen pressure. In that investigation, they also found that cobaltous oxide disks made by complete oxidation of cobalt metal were porous at their centers (Fig. 5L, ref. 4). Both these facts strongly suggest that oxidation of the metal proceeds via outward diffusion of cations. In order to establish the mechanism unequivocally, oxidation experiments were made with inert radioactive platinum markers, and the dependence of oxidation rate on oxygen pressure was measured. In addition, an attempt was made to determine the form of the cation vacancy gradient, which the marker experiment showed must exist across a growing oxide layer. This was done by depositing radioactive Co on the surface of a cobalt disk and then measuring the tracer distribution across the oxide layer produced by partial oxidation of the metal. Finally, an X-ray examination was made in an attempt to find the expected change of lattice parameter of COO with oxygen pressure. Experimental The apparatus and materials used were substantially the same as those previously described by the authors.4 Marker Studies: The use of inert markers to follow oxidation reactions was first attempted by Pfeil" in 1929, and radioactive markers have recently been used by Davies et al.' In the investigation reported here, the markers were applied as an (NH4)2PtCI6 slurry in several thin streaks across both faces of four disks of cobalt metal 1 mm thick and 14 mm in diameter. The disks were then oxidized almost to completion at 1200°C in pure oxygen. After oxidation, they were mounted and sectioned and auto-radiographs were taken to locate the markers. Oxidation Rate: The oxidation rate of cobalt was measured at 1148°C at oxygen pressures ranging from 0.0055 to 1.0 atm and at 1000°, 1148", and 1350°C under 1 atm of oxygen. The rate was deter-

Jan 1, 1956

By C. N. Schuette

The material presented in this paper has been gathered by the writer during a long and varied experience on matters pertaining to the quicksilver industry. During the past 18 years he has visited practically all of the quicksilver mines of the United States and has had occasion to review the literature on quicksilver mining the world over. In a previous publication1 the conclusion was expressed "that the greatest opportunity for increasing the economy in quicksilver production lies in giving more attention to the geology of the deposits ... " The present paper is a contribution toward that end. Due to a lack of correlation of the observed facts, a great deal of confusion exists in the views of various writers concerning the mode of occurrence of quicksilver ores. This paper attempts to show that certain common factors underlie the formation of all quicksilver orebodies. It attempts to present a framework on which to marshall the observed facts and thus make clear the interrelation of various observations which at first sight appear to be contradictory. The material presented is fragmentary in many respects and it is hoped that readers familiar with the deposits mentioned may supply the deficiency. The reader is asked to refer to the publications cited for maps and additional information on the individual orebodies, as this review, in covering so much territory, must necessarily confine itself to a bare outline of the facts concerning each occurrence. The writer hopes that this paper will elicit comment and criticism from the many competent men interested in the quicksilver industry and to all of them he would express his indebtedness for the many courtesies that they have extended to him at various times in the past. Theory op Primary Concentration The mode of occurrence of any given orebody presents an individual problem to the miner engaged in exploiting it. No two orebodies are exactly alike in their geological relationships, therefore an understanding, in detail, of the geology is necessary if the orebody is to be exploited in the most economic manner.

Jan 1, 1931

President and Director JOSEPH L GILLSON, '62 Wilmington, Del Past President and Director HOWARD C PYLE, '61, Los Angeles, Calif President-elect and Director R R McNAUGHTON, '63, Trail, B C, Canada

Jan 1, 1960

By Victor O. Strobel

Fire-brick hot-blast stoves have been the subject of frequent discussions at the meetings of the Institute; and although it is my object to elucidate some of the points in connection with this subject, I will not go into the specific features of all types, but more especially call attention to a new type recently designed by Mr. Fred. W. Gordon. As the economical production of a ton of pig-iron is a more essential feature than a large output, much depends, where fuel cannot be obtained cheaply, upon suitable apparatus whereby high temperatures can be maintained. Where iron-pipe stoves have been employed, the fuel-consumption reached one and a half pounds of fuel, and, when a larger output was desired, often two pounds, to the pound of iron produced. The temperature attained rarely exceeded 900' F., and that at the expense of frequent renewals of the pipes, which was not inconsiderable. The fire-brick hot-blast stoves of the past five or six years have clearly demonstrated their superiority over the old system. Of the accompanying drawings, Fig. 3 illustrates a four-pass regen-

Jan 1, 1886

By H. Foster Bain

(San Francisco Meeting, October, 1911.) [SECRETARY'S NOTE.-This paper, presented in oral abstract, at the San Francisco meeting, was not at first supposed by Mr. Bain to be required for publication in the Transactions; and the excursion to Japan, in which he took part, immediately after the San Francisco meeting, delayed his presentation of the manuscript. After his return to San Francisco, Mr. Bain, in view of the importance of his paper and its discussion, kindly furnished it in full. The delay in its publication (since it was received in April last) has been due, partly to the circumstance that other contributions had meanwhile acquired the "right of way," and partly to the consideration that, the situation contemplated in Mr. Bain's paper having remained practically unchanged, the paper and its discussion would not lose force or timeliness by this lapse of time.-J. S.] No acute observer of public affairs can have failed to observe a growing disposition on the part of the public to change emphasis in government from political equality to social justice. When our own government was founded it was felt to be sufficient to secure to each individual the fullest possible freedom of opportunity, and such a scheme was excellently adapted to the rapid development of a large territory having a small population. As the number of people in a given area increases, there are more points of contact and conflict; each must move in a smaller orbit, and there must be more regulation. Germany is making faster progress in industry than is any other country. The principal reason is the insistence there on team-play. In Germany there are fewer multimillionaires and more socialists (spelled with either a big or little " S ") than in any other of the leading countries; but Germany wins trade and is steadily improving the conditions of life for her citizens. To some, the change from the freest individualism is welcome; to others it is intensely unacceptable. To this fundamental difference in view-point may be imputed much of the vigor with which the controversy regarding coal-lands has been waged. That present conditions in Alaskan coal-fields are extremely unsatisfactory is generally recognized, but there are wide dif-

Aug 1, 1912

By G. B. Gould, F. M. Gibson

IN DECEMBER, 1934, the joint Committee on Fuel Values, of the American Institute of Minim and Metallurgical Engineers and the American Society of Mechanical Engineers, submitted a preliminary report, which briefly stated its conclusion that it was not possible to devise any formula for the valuation of coal, based upon the various physical and chemical properties, that would be generally applicable. That report also listed those chemical and physical properties of coal that are generally recognized to have some effect on its use in steam plants, and those physical characteristics of steam plants which affect, in one way or another the relative importance of the properties of coal used in them. Since then, the Committee has considered and discussed in greater detail the interrelationship of the properties of coal and plant characteristics. The conclusions of the Committee are summarized below, with certain recommendations regarding engineering procedure, which will promote the collection of more easily correlated observations with respect to this subject, and thus advance more rapidly the accumulation of data capable of general application.

Jan 1, 1936

By William H. Bassett, C. J. Snyder

Cable sheaths made from common lead have been used to protect underground cables since the beginning of the power-cable industry. Only within the last few years, however, has a systematic study of the production methods and of the causes of failures in cable sheathing been undertaken. Recent increases in the use and demands for service made upon power cables have emphasized the importance of high-quality cable sheaths. It was customary for the users to attribute the cause for their sheath failures to the lack of purity of the lead, but this contention has not been borne out by field and laboratory inspection of the sheaths. During the past two years the writers have had an opportunity to examine various types of sheaths that were removed from power cables after failure. These samples were obtained from various parts of the country and represent, it is supposed, the production of the principal cable manufacturers. Aside from corrosion, the common field difficulties can be classified either as mechanical or structural, as outlined below, and when structural irregularities are found they can all be attributed to manufacturing causes and in no way reflect the purity of the lead. Clasxification of Cable Sheath Failures Other Than Corrosive Mechanical Irregularities A. Splits caused by excessive internal pressure B. Injuries such as nail holes, cuts, tsars, etc. C. Intercrystalline cracks caused by vibration Structural Irregularities A. Splits C. Voids in wall of sheath a. Caused by imperfect welds a. Blisters 13. Holes through sheath b. Laminations a. Caused by yellow oxide inclu- D. Questionable structures sions in sheath wall a. Prominent flow lines b. Blowouts by entrapped gases b. Large areas filled with suboxide during manufacture c. Scattered yellow oxide or dirt C. Caused by inclusions of dirt and

Jan 1, 1933

BUFFALO C E Moyer, Chairman (Buffalo, N Y ) R M Jordan, Vice-Chairman H A Morlock, Secretary CHICAGO M E Nickel, Chairman (Chicago, Ill) A M Kroner, Vice-Chairman W R McLain, Secretary-Treasurer

Jan 1, 1960

By H. N. Wolcott

AMONG the many cases of replacement of one mineral by another, that of quartz or silicates by pyrite, or even other sulphides, is not uncommon, but the reverse of this process does not appear to have been recorded, even if it has been observed. It, therefore, seemed to the writer that the case described below was worthy of record. FIG. I.-GROUND MASS OF CHALCOPYRITE (C) CONTAINING ROUNDED GRAINS OF PYRITE (P) SHOWING DIFFERENT DEGREES OF REPLACEMENT BY QUARTZ (Q), AND ALSO QUARTZ VEINLETS CUTTING THROUGH THE PYRITE. (PHOTOGRAPHED BY REFLECTED LIGHT.) The specimens described in this paper were obtained by R. B. Morton of Idaho Springs, Colo., from the Old Town Mine, in Russell Gulch, and are in the collection of Cornell University, where the writer studied them. In the rough, the specimens appeared to consist largely of chalcopy- rite, with some grains of tetrahedrite. The polished surface of some of

Jan 6, 1917

THE solid nonmetallic inclusions that are present to some extent in all commercial steels have been variously designated. In early references they were usually called slag inclusions, and. this terminology is still retained to some extent. On the premise that all nonmetallic matter produced in a metallurgical process is slag, this can be justified. We have come to think of slag, however, in a more restricted sense, and calling these particles slag inclusions is further objectionable because it fosters the erroneous concept that they are actually incorporated portions of furnace slag. Rarely is this true. The term sonims (coined from solid nonmetallic impurities) was proposed many years ago but never came into common use. In general the term "nonmetallic inclusions" seems to be satisfactory and adequate. NATURE AND CONSTITUTION OF NONMETALLIC INCLUSIONS From the standpoint of origin, inclusions fall naturally into two classes: (1) those that occur as a result of reactions taking place in the body of the molten or solidifying metal and (2) those that result from the mechanical incorporation of refractories or other materials with which the steel comes in contact. The former are by far the more numerous and have been called indigenous, natural, or native inclusions. The latter are by their very nature sporadic in occurrence and have been called exogenous, accidental, adventitious, or foreign inclusions. They are often referred to as the "slag stringer" type, though here also the material is not likely to be furnace slag. Substances Found in Inclusions. Nonmetallic inclusions are composed principally of oxides and sulphidea but carbides and nitrides sometimes play an important role. In the case of indigenous inclusions the reactions by which these particles are precipitated from the molten or solidifying steel may be caused by (1) oxidation such as may occur during refining or during tapping and teeming, (2) deoxidation by added alloys, (3) change in equilibrium constants as the steel cools to the freezing temperature, (4) decreased solubility with lower

Jan 1, 1944

By V 9. 0 / 300 dpi

ATHOUGH turquoise mining was, so far as we know, the first large, well-organized mining operation,' gem mining, from the Roman con-quest of Egypt until the opening of the South African pipe diamond mines some 50 years ago, was largely carried on' by individuals 01' small companies in a relatively primitive way. Now" however" gem mining does not yield in efficiency or in scale of operations to the mining of other mineral products. In 1926 the diamond mines of the world milled some 9,000,000 cu. yd. and produced 0,43 cu. yd. diamonds, a remarkable example of concentration. The Premier Diamond Mining Co. up to Oct. 31, 1927, had milled 116,455,550 loads (each of 16 cu. ft.) from which 26,-217,144 carats of diamonds" worth £29,897,971 2s, 9d., were recovered. The Burma Ruby Mines, Ltd., operating sever-al alluvial mines in Burma in 1911-12, mined and milled 1,479,845 truckloads of gemmiferous earth for 15c. per load. We of the industry can there-fore, with good grace, disclose some of the myths and also describe some of the primitive mining methods of the, dark ages of our industry. The methods, so far as I know, were not patented, and if they were, the patents have expired, so that engineers in other branches of the art are free to use them if they see fit.

Jan 1, 1928

By A. T. Sweet, C. E. Plummer, H. W. St. Clair, S. F. Ravitz

The ammonium sulphate process for recovering alumina from clays was proposed by Rinman, Buchner, and others many years ago, and more recently various modifications have been investigated both here arid abroad.l-Is The process, as it is being investigated by the Bureau of Mines, involves the following essential steps: (I) sulphating the alumina in the clay by baking with ammonium sulphate at approximately 4m°C., (2) leaching with water to extract aluminum sulphate and ammonium sulphate, (3) crystallization of ammonium alum, (4) conversion of the alum to aluminum hydroxide by the ammonia gases given off during the baking, and (5) calcining the aluminum hydroxide to alumina. The over-all reaction between kaolinite (the most important alumina mineral in most clays) and ammonium sulphate during the baking step may be expressed as follows: Al2O8.2SiO2.2H2O + 4(NH4)2SO4 = (NH4)2SO4.A12(SO4)3 + 6NH3(g) + SH2O(g) + 2SiO2 [i] There is definite evidence. as is shown later. that the aluminum occurs in the baked product as anhydrous ammonium alum rather than as aluminum sulphate, provided the baking temperature is not much above 4o0°C. It is probable that the reaction takes place in the following steps: (NH4)2SO4 = NH3 -(- NH4HSO4 [2] Al2O3.2SiO2.2H2O + ;}NH4HSO4 = A12(SO4)3 + 3NH3 + 5H2O + 2SiO2 [3] A12(SO4)3 + (NH4)2SO4 = (NH4)2SO4.A12(SO4)3 [4] In onc modification of the process, the ammonium sulphate is first decomposed according to Eq. z, and the clay is treated with the resultant ammonium acid sulphate. Reaction I is highly endothermic. On the basis of the best available data, the following values have been estimated for the changes in heat content and free energy in calories per mol: -AH = 331,040 - 34T -AF = 331~040 - 78.3T log T - 671.8T The heat required' at 25OC is 320,900 cal. per mol, or 5650 B.t.u. per pound of alumina. The theoretical equilibcium pressure of NHa, based on the free-energy equation given above, increases very rapidly as the temperature rises above 3o0°C., and reaches one atmosphere at 43s°C. Ammonium alum solutions are almost ideal for crystallization. A saturated solution of ammonium alum contains 126. grams of AlzOa per 1000 grams of water at 90°C. and only 16.5 at 20 C. Hence most of the alum crystallizes out when the

Jan 1, 1944

BUFFALO C E Moyer, Chairman (Buffalo, N Y I R M Jordan, Vice-Chairman H A Morlock, Secretary CHICAGO M E Nickel, Chairman (Chicago, Ill ) A M Kroner, Vice-Chairman W R McLain, Secretary-Treasurer

Jan 1, 1959

By G. R. Speich

The distribution of carbon and the type of substructure in iron-carbon martensites containing 0.02 to 0.57pct C has been studied in the as-quenched condition and after tempering at 25" to 700°C by using electrical resistivity, internal friction, hardness, and light and electron microscope techniques. in marten-sites containing less than 0.2 pct C, almost 90 pct of the carbon segregates to dislocations and to lath boundaries during quenching; in martensites containing greater than 0.20 pct C, appreciable amounts of carbon enter normal interstitial positions located far from defects. Tempering martensites with carbon contents below 0.20 pct at temperatures below 150°C results in additional carbon segregation to dislocations and to lath boundaries but no carbide precipitation whereas -carbide precipitation occurs in martensites with carbon contents exceeding 0.2 pct. Above 150°C, a rod-shaped carbide (either Fe3C or Hagg) is precipitated in all cases. At 400°C, spheroidal Fe3C precipitates at lath boundaries and at former aus-tenite grain boundaries. At 400" to 600"C, recovery of the martensite defect structure occurs. At 600" to 700°C, recrystallization of the martensite and Ost-waW ripening of the Fe3C occur. The effects of the carbon segregation that occurs during quenching and the subsequent substructural changes that occur during tempering on martensite tetragonality, hardness, and precipitation behavior are discussed. A mathematical analysis of carbon segregation during quenching is presented. RECENT studies of the strength of low-carbon martensitel-4 emphasize the importance of carbon segregation to the martensite lath boundaries and to the dislocations contained between them during quenching. Unfortunately, very few studies of the tempering of low-carbon martensites have been conducted, so the exact nature of this segregation is poorly understood. In fact, most early tempering studies5,6 were restricted to carbon contents greater than 0.20 pct. Moreover, these studies did not determine the amount of carbon segregated to the martensite substructure during quenching so that the initial state of the martensite was not established. Aborn7 studied the precipitation of carbide in low-carbon martensite during quenching but did not establish whether carbon segregation occurs prior to carbide precipitation, nor did he study the subsequent tempering sequence in detail. In the present work we have used electrical resistance and internal friction measurements, supplemented by electron transmission microscopy to establish the carbon distribution in as-quenched specimens. Specimens thin enough to avoid carbide precipitation (but not carbon segregation) were employed. The redistribution of carbon on subsequent tempering below 250°C was followed by measurements of elec- trical resistance. Additional studies were made on specimens tempered at 250" to 700°C to elucidate the overall tempering behavior of low-carbon martensites, including the formation of cementite and recrystalli-zation of the martensite. EXPERIMENTAL PROCEDURE Eight iron-carbon alloys with 0.026, 0.057, 0.097, 0.18, 0.20, 0.29, 0.39, and 0.57 wt pct C were prepared as 8-lb ingots by vacuum melting. Typical impurities in wt ppm were 40 Si, 20 Mn, 30 S, 10 P, and 10 N. These alloys were hot rolled to 3 in. plate at 1095°C) (2000°F). The hot-rolled plates were surface ground to remove scale and the decarburized layer, then cold rolled to 0.010 in. sheet. Specimens cut from the sheet were austenitized for 30 min at 1000°C (1830°F) in a vacuum tube furnace in which the pressure did not exceed 2 x 10-3 torr. Chemical analysis of specimens after austenitization indicated no decarburization at this pressure. Immediately before quenching, the furnace was filled with prepurified helium. The specimen was then pushed rapidly through an aluminum foil gasket, which sealed the bottom of the furnace, into an iced-brine bath (10 pct NaC1, 2 pct NaOH). The quenching rate at the M, temperature is about 104'c per sec for 0.010 in thick specimens, as calculated from Newton's law of heat flow2 using a heat transfer coefficient of 25 ft-'. This quenching rate is sufficiently high so that all the alloys transformed completely to martensite throughout the entire 0.010 in thickness and no carbide precipitation occurred in the martensite. All specimens were immediately transferred to liquid nitrogen after quenching and stored there until needed. Tempering below 250°C (480°F) was done in silicone oil baths thermostatically controlled to *;"C. Tempering above 250°C was done in circulating air furnaces or lead pots with the specimens contained in evacuated silica capsules. Electrical resistance was determined by measurement of the potential drop across both a standard resistance and the specimen, connected in series. All resistance measurements were made in liquid nitrogen (77K, -196°C) to minimize thermal scattering of electrons and thus maximize the contribution of impurity scattering to the resistance. Specimen dimensions were 5.10 by 0.19 by 0.025 cm. Although the precision in the electrical resistance measurements was +0.1 pct, the electrical resistivities could only be measured with an accuracy of +5 pct because of uncertainty in the specimen dimensions. Internal friction measurements were performed in an inverted pendulum apparatus at vibration frequencies of either 1.9 or 66 Hz. The specimen dimensions were 5.10 by 0.375 by 0.025 cm. Hardness measurements were made with a Leitz-Wetzlar microhardness machine with loads of 100 g. Specimens were examined by light microscopy after etching in 2 pct Nital and by electron transmission microscopy after preparation of thin sections by electrolytic thinning in a chromic-acetic acid solution.

Jan 1, 1970

By John Mullen

Impingers TWO types of midget impinger apparatus are used at Climax. The Mine Safety Appliances Company's midget impinger (MSA) and the Climax Molybdenum Company's midget impinger (CMC) (Fig. I). The Leiman Brother's No. 25, positive displacement pump is used in the CMC impinger instead of the four-cylinder radial pump that is used in the MSA impinger. With the MSA apparatus it is possible to obtain the proper vacuum by adjusting the needle valve on the vacuum chamber, while with the CMC impinger the proper vacuum is obtained by varying the rate at which the pump is cranked. The Leiman Brother's No. 25 pump is built to displace 0.1 cu. ft. of air per min. when operated at 145 r.p.m. In the CMC impinger this pump is so geared that the required crank speed is approximately 59 r.p.m. Both types of impinger apparatus are equipped with a water gauge mounted on top of the case and they are calibrated and operated in reference to the gauge. The MSA impinger flasks and nozzles are used with both types. Calibrating Impingers A calibrated precision Sargent wet-test meter (Fig. 2) is used in calibrating the impinger apparatus. The apparatus is set up as for taking a sample in the field, except that the hose from the outlet side of the meter is attached to the impinger nozzle. One revolution of the large hand of the meter indicates 0.1 cu. ft. of air displaced. The impinger pump is cranked for one minute, therefore, at a rate that will cause the large hand of the meter to make one revolution. The gauge reading is noted, then the impinger is cranked at this rate for 10 min. and is checked for error. If the meter indicates that more or less than I cu. ft. of air has been displaced, the impinger must be cranked—ither slower or faster according to the error—for another 10 min. and again checked for error. This operation is repeated until the proper gauge reading for a sampling rate of 0.1 cu. ft. per min. has been determined. This gauge reading is used in all sampling operations until the impinger is again calibrated. An impinger is calibrated at least twice each week. MlCROPROJECTOR A Bausch and Lomb model B micro-projector is used (Fig. 3). It consists of a substantial metal base supporting the light source and a microscope. Illumination is provided by a Bausch and Lomb 4.5-amp. arc lamp with mechanical feed. A glass water cell filled with a heat-absorbing and color-filter solution is placed between the arc lamp and the microscope. Two types of solution have been found satisfactory— a 2 per cent solution of copper sulphate or a 2 per cent solution of picric acid and distilled water. This percentage may be varied to give the desired color to the light reflected upon the screen. Any standard microscope may be used. A Bausch and Lomb microscope with

Jan 1, 1946

By T. Saburi, C. M. Wayman

The massive and martensitic transformations in ß Cu-Ga alloys were studied by optical microscopy and by transmission electron microscopy and diffraction. These types of transformation are distinct and do not merge into one another. An internal fine structure due to stacking faults was found in both the massive phase (m) and the martensite, but the origin of the faults is believed to be different in each case. The faults in the martensite are due to the lattice invariant or "second" shear of the phenom-enological theory, while those in the are probably growth faults and deformation faults arising from the transformation volume change. Evidence is presented for ordering in the ß phase prior to transformation into martensite, and the crystal structures of and ß' and ßi martensites are discussed. THE results from some previous investigations1,2 have led to the suggestion that martensitic and massive transformations have certain common characteristics. It presently seems established that massive transformations like martensitic transformations are essentially diffusionless,1,2 but unlike martensitic transformations, when a new phase forms massively there is no shape change or surface relief.= If the massive-type transformation is crystallographically similar to martensitic transformations, one would expect a fine structure as a result of the lattice invariant shear4 which is a part of the transformation mechanism. The existence of such a fine structure (i.e., slip, twinning, or faulting), if any, can be verified by transmission electron microscopy, and thus the present investigation was undertaken to compare the internal structure of massively and martensitically formed phases in Cu-Ga alloys which were derived from a parent of the same composition. The transformation characteristics of ß Cu-Ga alloys were also studied. The bcc ß phase in the Cu-Ga system, Fig. 1, is stable above 616oc.' Depending upon the cooling rate, ß Cu-Ga alloys can undergo three different types of phase transformations. The ß phase of eutectoid composition (23.7 at. pct Ga) decomposes into the ? phase (hcp) and the phase (complex cubic) by means of a eutectoid reaction. When the cooling rate is increased so that the decomposition of 0 into [ and ? is suppressed, the ß phase transforms into a nonequilibrium hcp phase, herein denoted ?m by a process of very rapid growth called a "massive" transformation. At even faster quenching rates the massive transformation can be suppressed and the ß transforms martensitically. Massive transformations, apparently similar to those in the Cu-Ga system, have also been studied in the Cu-Zn2,6-8 and Ag-Cd systems.9 Definitive characteristics if the Massive Transformations in 0 Cu-Ga Alloys1 1) The most remarkable feature of the massive transformation in Cu-Ga is that there is no bulk composition change on transformation. According to Massalski,1 the resulting [, phase is a supersaturated extension of the equilibrium [ phase. The lattice parameters continue the trend exhibited

Jan 1, 1965

By C. D. Hall

This paper may be divided into two main parts: (1) analysis and data to show that Eq. 6 adequately correlates the authors' experimental data, and (2) the assertion that Eq. 20 "should permit scale-up with data taken from one pipe diameter for Newtonian, inelastic non-Newtonian, and viscoelastic fluids, such as dilute polymer fracturing fluids, which produce considerable pressure reductions." The authors might well recommend that this broad grouping of fluid types could be correlated by using Eq. 6 (requiring data from at least two pipe diameters). On the other hand, Eq. 20 is only shown to be adequate for conditions within the range of the present data set. Specifically, predictions by Eq. 20 for diameter scale-up to casing sizes would give larger deviations than implied in Table 2, and scale-up for some other fluids that give large drag reduction could be grossly in error. The description of a class of fluids "which produce a diameter family of straight parallel lines on a log (d?p/4L) vs log (8 v/d) plot. . ." defines a necessary condition for using Eq. 6; i.e., that s shall be constant for each fluid. The proposal that Eq. 20 is applicable to turbulent flow of such fluids is equivalent to saying that the spacing of these parallel lines, with A being constant, will be found to correspond to m = -1.20 for all such fluids. Table 1 shows the values of m derived from data on 16 non-Newtonian fluids. The key statement of this paper is that the diameter exponents "do not vary significantly from . . . -1.20." In statistical terms, this says that the m value for each fluid, which was obtained from all the measurements made on that fluid. has not been shown to be different from the arithmetic mean of the m values for the 16 fluids tested. This implies that the group mean, -1.20, is a more reliable value to use for an individual fluid than is the m value derived from the data on that fluid alone. No statistical test is described to support the key statement that the diameter exponents do not vary significantly from -1.20. Such a test would have to take into account that each individual m value is shown to correlate the pressure gradients for its fluid, with only about 3 percent standard deviation over the diameter range covered. That is, the m value is not the result of a single independent measurement. Thus, it would not be sufficient, or valid, to compare the deviation of one of the m values with the variance of the 16 values of m about their mean. An alternative interpretation of the key statement is that the diameter exponents do not vary appreciably from -1.20; i.e., that using -1.20 does not cause serious inaccuracy. Table 2 seems to be offered in support of such an assertion. However, such a statistical treatment (1) is unnecessary and (2) cannot lead to any valid scale-up generalization. The amount of error introduced by using a 1"wrong" value of diameter exponent — i.e., -1.20 instead of m — is determined by Eq. 6. The ratio of the pressures predicted by Eqs. 6 and 20 for scale-up from ds in small pipe to d, in casing is The pressure for 30-percent calcium carbonate slurry (m = -1.112) in 10-in. ID pipe would be predicted 30 percent higher by Eq. 6 than by Eq. 20, if based on tests in 0.5-in. ID pipe. The data set tested in Table 2 represents only a limited sample of pipe diameters (ratio of about 4:l) out of the population of diameters that would

Jan 1, 1970