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By H. O. Hofman

PAGE Part I. Decomposition OF Zinc Sulphate by Heating in Air, . 811 I. Introduction............ 811 II. Zinc Sulphate Used,..814 III. Fumes and Pyrometers,........ 816 IV. Heating Zinc Sulphate—Dehydration,...... 817 V. Heating Zine Sulphate—Decomposition...818 (a.) Beginning of Decomposition..818 (b.) Rapidity of Decomposition,..819 (c.) End of Decomposition..823 (d.) Retardations in Heating.-Curve,..825 (e.) Formation of Basic Salts,..826 Part II. Decomposition OF Zinc Sulphate by Heating with Carbon (Reducing Roast), .830 I. Introduction,........... 830 II. Experiments and Results ,.........832 III. Summay,........... 834 Part 111. Formation of Zinc Sulphate by Roasting,... 834 I. Introduction,........... 834 IT. Description of Blende,......... 836 III. Outline of Operations,.........838 IV. Details of Experiments.......... 839 1. Decrepitation,.......... 839 2. IgnitionPoint,....839 3. Sulphatizing-Roast of Joplin Blende..840 4. Sdphatizing-Roast of Warren Blemde ,..843 5. Sulphatizing-Roast with Addition of Pyrite...848 6. Summary of Sulphutizng-Roasts,....... 854 Part IV. Appendix : Formation of Zinc Ferrate...856 Part I. Decomposition of Zinc Sulphate by Heating in Air. I. Introduction. With the exception of lead sulphate. all common metallic

Jan 1, 1905

By W. Mostowitsh

I. Introductory LEAD sulphate occurs as anglesite, and is formed in every roasting of lead sulphides or sulpho-salts containing lead. In smelting in the blast furnace an ore containing natural or artificial lead sulphate, a large part of the sulphur present goes to the formation of the intermediary product matte which requires further treatment for the recovery of the values it contains. It is therefore of importance to study the behavior of lead sulphate at elevated temperatures, both without and with reducing agents, especially as the information available gives data which are more or less conflicting. II. Decomposition of Lead Sulphate by Heat The dissociation of PbSO4 into PbO and S03 or S02 and 0 has been discussed by many metallurgists. The following data are considered to be representative. Doeltz and Graumann1 found that PbSO4 was not affected by heat at 800° C.; that dissociation began at 900° C., and was rapid at 1,000° when the salt lost in 1 ½ hr. 14.3 per cent. of its weight, the dry salt containing 26.43 per cent. SO3. Hofman and Wanjukow2 summarize their work upon the dissociation of metallic sulphates with the statement that the decomposition of PbSO4 begins at 195° C., but progresses very slowly, with the formation of the basic salt 6PbO.5S03 at 705°; that this salt undergoes a transformation at 847°, begins to be decomposed at 888°, to sinter at 896°, and to fuse at 910°; rapid dissociation begins at 952°, and is accompanied by volatilization of PbO; retardations at 958° and 962° indicate an acceleration of decomposition which, however, is not complete. Proske3 found that PbSO4 gave off at 900° C. in 30 min. only 0.63 per cent. of its SO3, and that the loss increased with

Jan 5, 1916

By W. F. Boericke, T. H. Garnett

The Wisconsin zinc district, or the Upper Mississippi lead and zinc district as it is also termed, lies in the southwestern corner of Wisconsin, and embraces adjacent portions of Illinois and Iowa. It includes Iowa, Grant, and Lafayette counties in Wisconsin, and Jo Davies country in Illinois. In Iowa, Dubuque formerly produced considerable lead, but there has been little mining there in recent years. The map, Fig. 1, shows the entire district, withroads, railways, streams, and the various towns, or "camps," around which the mines are clustered. The hatchwork indicates the areas in which lead and zinc have been mined. The district is about 60 mi. (96 km.) north and south and about 40 mi. (64 km.) east and west. Not all of the territory is mineral bearing, and there are considerable areas that are believed to be barren. The grouping of the mines is patchy and irregular, though certain broad zoncs of mineralization extend almost the full width of the district, as from Mineral Point west through Mifflin and Livingston, and from Shullsburg west through New Diggings and Hazel Green. It is worth noting that the best mines of the district have, to date, been found within 10 mi. ease or west of the fourth principal meridian line, thus lying within a long, narrow, north-and-south belt extending the length of the district. In a field as large as the Wisconsin, which has only within comparatively recent time been worked intensively for zinc, the chances are good for opening new and important orebodies in parts of the district not yet, or insufficiently, prospected. However; the prospecting has been most successful around, or adjacent to, the old lead diggings of nearly a century ago, and the camps that were well known then are still centers of activity. In their order of importance they are: New Diggings, Ben-ton, Mifflin-Livingston, Galena, Linden, Hazel Green, Shullsburg, and Highland. The district is one of the best farming districts in Wisconsin, with deep fertile soil. The farms are large and well improved, and the towns are modern and prosperous. Railroad facilities are good and proximity to Chicago is an asset. Mining is usually done on a leasing system of 10

Jan 1, 1920

By J. W. Spretnak, V. Kandarpa

Stress -induced ordering of carbon atoms is studied in a series of Fe-Mn-C alloys. A prominent peak is found in the vicinity of 280°C at frequencies of the order of 1.0 cps, with an associated activation energy of 37 kcal per mole. The height of the peak is linearly rekzted to the concentration of carbon in solution. The distortion of octahedral holes by manganese atoms appears to be predominant over carbon-carbon pair interactions. RELAXATION by stress-induced ordering of point defects is expected whenever the introduction of these point defects produces distortions which have a lower symmetry than that of the lattice. Under zero stress, the isolated point defects occupy the crystallographic-ally equivalent positions in the lattice, as these represent states of equal energy. However, if the defect sites are asymmetric, application of an uniaxial stress will split the energy states, and a redistribution of the defects among various states will take place. This is the case of the internal friction peak called the Snoek peak,1 resulting from isolated interstitials in bcc metals. The interstitial sites in this case have tetragonal symmetry. In the case of fcc and hcp lattices, such an effect is not expected from isolated point defects because of the symmetrical nature of the interstitial sites. However, internal friction peaks arising from interstitial diffusion have been reported both in hcp2,3 and fcc4-8 lattices. These peaks are often explained on the basis of stress-induced ordering of interstitial solutes, caused by the deviation of interstitial sites from their cubic symmetry through the presence of nearby defects. In the case of fcc lattices, evidence for interactions of both the substitutional-interstitial4,6,13 and interstitial-interstitial types5'798'14 have been presented by various investigators. The purpose of the present investigation was to study the internal friction peak attributed to the diffusion of interstitial carbon atoms in high purity austenitic manganese steels and to account for the peak in the light of the existing models. MATERIALS The Fe-Mn-C alloys used in the present investigation were made in two different ways, designated as Type I and Type 11. Type I alloys were made from high purity Fe-Mn alloys obtained in the form of 0.04- in.-diam wires from Materials Research Corporation, Orangeburg, N.Y. These alloys were carburized to different levels using gas mixtures of H2 and CH4 at 1000°C. Type I1 alloys were made in this laboratory starting with zone refined iron, spectrographically pure manganese, and spectrographically pure carbon. They were melted in an argon arc melting furnace and drawn into 0.04-in.-diam wires. All the wires were annealed at about 900°C for 3 hr prior to the internal friction experiments. After the measurements of internal friction, the phases in the samples were identified by X-ray diffraction and the carbon determined by the combustion method. EXPERIMENTAL PROCEDURE In the present work, a classical Ke-type pendulum was used. The details of the equipment were described previously by D. T. Peters.9 Dry helium at 40 torr was used in all the experiments. The internal friction, measured as the logarithmic decrement of the torsion amplitude of vibration was determined as a function of temperature, from ambient to about 500°C. The background internal friction was assumed to have the form of the exponential of the inverse temperature and was subtracted from the raw data. The height of the peak was measured at the position of the maximum in the plot of the internal friction versus temperature. The activation energies of the peaks were measured by the peak shift method. The internal friction values for an alloy were obtained as a function of temperature at different frequencies of vibration. The position of the peak changes with frequency, the higher the frequency the higher the peak temperature. The activation energy of the process associated with the peak is obtained using the formula

Jan 1, 1970

By Howard Martens, Pol Duwez

XPERIMENTS were performed on a Cr-Fc alloy Econtaining 44.7 pet Cr in order to determine the heat evolved during the transformation of the a solid solution into the s phase, and the change in volume accompanying the transformation. Since previous measurements on the rate of formation of a from s indicated that the reaction was quite fast as soon as the equilibrium temperature of 820°C was exceeded by some 50°, standard thermal analysis experiments were performed on heating specimens of s at the rate of approximately 40°C per sec. A definite thermal arrest was observed at 870"C, Fig. 1. This result indicates that the reverse seaction of into a is exothermic. From the heating curve of Fig. 1, taking 15°C per sec as the heating rate in the neighborhood of the transformation, 2.4 sec as the time for transformation, and assuming that the specific heat of the alloy at 850°C is an average between iron and chromium, namely 9.5 cal per mol per "C, the latent heat of transformation is approximately 342 cal per mol. The order of magnitude of this latent heat was also obtained by comparing the heating curve of Fig. 1 with a similar curve obtained with pure iron under identical experimental conditions. It was found that the length of the thermal arrest for s was about 1.8 times as long as that for iron. Since the latent heat of the a to 7 iron transformation is 203 cal per mol1, 2 the latent heat of it to a would be 365 cal per mol, which is in relatively good agreement with the value determined from the heating curve. For the determination of volume change, thermal expansion curves were recorded using a specimen containing 44.7 pet Cr and completely transformed to cr by previous treatment. The curves were recorded at a rate of heating of about 4°C per min and at approximately 840°C a sharr, increase in length of about 0.08 pet took place. Fig. 2. It is therefore established that the specific volume of a near the transformation temperature is about 0.24 pet smaller than that of a, and consequently, when the s phase forms in an a matrix, it would tend to shrink away from the matrix. Since the s phase is known to be extremely brittle, these results offer an explanation for the microscopic cracks often observed in the a phase under the microscope. The results of this study are in qualitative agreement with previously published data on stainless steel 19-9DLa and on a Cr-Fe alloy containing 45 pet Cr.' The increase in density due to the transformation from n to s given in ref. 4 is 0.90 pet. These measurements, however, were made at room temperature. whereas the presently reported 0.24 pet is the change at the temperature at which the transformation takes place during heating. In the graph of Fig. 2, the percentage change in length that would be observed at room temperature is given by the length X, which is about 0.27 pet. This would correspond to 0.81 pet in volume change. Acknowledgment This work was done at the Jet Propulsion Laboratory, California Institute of Technology, under Contract No. DA-04-495-ORD-18 with the Army Ordnance Corps, Washington, D. C. The authors wish to thank this agency for permission to publish the results of this investigation. References I H. Klinkhardt: Measurements of True Specific Heats at High Temperatures. Annalen der Physik (1927) 84, pp. 167-200. - H. Esser and W. Runghardt: Influence of the Method, of Dctcrmination on the Measured Heat Content of Iron. Archtvo ffur Dct Eisenhiittenwesen 11934) 8, pp. 37-38. J. J. Gilman, P. K. Koh, and 0. Zmeskal. Delta Ferrite Formation and its influence on the Formation of Sigma in a Wrought Heat Resisting Steel. Trans. ASM 1 1949) 11, pp. 1371-1388. 1 J. M. Thomas: Discussion of ref. 3. Trans. ASM (1949) 41, pp. 3 390-1392.

Jan 1, 1957

By Carle Hayward

THIS work was first undertaken in the metallurgical laboratory of the Massachusetts Institute of Technology in 1907 by L. A. Dickinson, E. Phelps, and V. S. Rood, under the author's direction. They attempted to determine the diagram for the system Cu2S-NiS, but several inexplicable results were obtained. The following year, P. H. Mayer with Mr. Dickinson carried, on some experiments with nickel sulphide and found that the molten material slowly lost sulphur until it reached a composition corresponding to the compound Ni3S2, established by Bornemann.1 At this point the composition remained stable. The freezing points of the mixtures gradually fell off with the loss of sulphur. Since the above facts seemed to explain the erratic results obtained in the first experiments, Mr. Mayer with F. Jaeger attempted in 1910 to establish a correct equilibrium diagram for the Cu2S-Ni3S2 series. They prepared pure Cu2S and Ni3S2 and determined the cooling curves for various mixtures. The fusions were made in a platinum resistance furnace and the temperatures were measured with a platinum-iridium thermocouple connected with a Sullivan galvanometer. The curve was established for mixtures containing more than 40 per cent. Cu2S, but they were unable to determine certainly the direction of the curve beyond that point. Nothing further was attempted with this series until the present year, when the work was carried to a successful conclusion with the assistance of A. Butts, Jr., and E. H. Weil. The results of this work are given in the following pages.

Jan 1, 1914

By C. Schlumberger, M. Schlumberger

The object of this paper is to clarify the idea, so important when exploring by potential methods, of the depth of investigation attainable by electrical measurements. After defining, with some precision, .the term "depth of investigation'' in geophysics, the authors show how it is possible to regulate this depth in potential methods and to obtain an 'electrical drilling" from surface observations. They consider also the difficulties encountered in deep measurements and indicate how it is possible to reach greater depths than those having an industrial interest. Depth of Investigation The term, depth of investigation, in its general sense, is easily understood. For instance, a driller who can pull cores from a depth of 2000 m. is capable of working, with accuracy, to that depth. By means of a properly placed drill, he may locate an orebody at a depth of 1999 m., however small this orebody may be. On the contrary, the term as used in geophysics requires precise elaboration. As a matter of fact, no geophysical method, irrespective of the physical property studied (density, magnetic permeability, conductivity), can discover a very small body at a great depth because, in practice, the physical parameter upon which such a geophysical method is based is never regular enough, throughout the ground, to distinguish the feeble anomaly caused by the small, deep-lying body from the numerous anomalies due to irregularities of the encasing terrains. Aside from this question of the ratio between the size of the body being hunted for and its depth of burial, a second factor plays its role in the possible depth of investigation; that is the difference, for the parameter under consideration, between the body and its surrounding material. The greater this difference, and the more homogeneous the encasing terrains, the greater is the possible depth of investigation. This being generally established for all geophysical methods, it is possible to distinguish two main classes of these methods, from this same point of view

Jan 1, 1932

By WALTER S.

(New York Meeting, February, 1912,) THE earliest example of attempting to form finely-divided materials into larger masses for better adaptation to commercial use was probably the briquetting of peat and lignite-waste at Paris by the use of a clay binder. It was from this attempt that our word briquette has arisen (Fr. la brique), the formed masses being shaped similar to ordinary bricks. This term does not, however, lend itself to the many shapes of such formed material as are now being produced, as few of them aside from some of the European brown-coal products bear any resemblance to the shape of that well-known article. The term "agglomeration " has therefore been chosen as more accurately descriptive of the products now being manufactured, this term including the molding as well as the sintering. With the increasing prices of fuel and ores and the greater demand for economy in the operation of industrial plants, more ,attention has been paid in recent years to the utilization of waste products and low-grade ores and fuels. Much of the waste has been occasioned by the inability to utilize finely ,divided ores and fuels in the furnaces because they could not be kept there, or else because they clogged up the furnace-shaft so that gases could not be forced through under ordinary conditions of operation. As a result, all such fines were thrown on the dump. Again, with the exhaustion of the richer deposits of ores, concentration of lower-grade ores becomes a necessity, and most concentrates are produced in a finely-divided condition. Aside from these considerations, there is also the economy in the cost of operating the plant; a furnace running on agglomerated material will have a much greater output than one working on fines. In one instance the charge of an iron blast-furnace was changed from fine concentrates to briquettes and the output was increased four-fold; better results could have been obtained had facilities been at hand for taking care of the increased output.

May 1, 1912

By A. E. Powers

YEARS of experience and research have shown that molybdenum, tungsten, and vanadium are among the most useful and effective elements in augmenting the high-temperature strength of heat-treatable, ferritic steels. Grün, for example, in conducting an early survey of the strengthening effects of various elements in annealed, low-carbon steel at 750° and 930°F (400° and 500°C), found molybdenum and vanadium to be the most effective.' Holtmann comprehensively studied the strengthening effects of molybdenum and vanadium in quenched and tempered steels at 930°F as a function of microstructure and carbon content.' He found creep strength to be related to the saturation of the austenite at the austenitizing temperature, such that strength is increased by alloying until the y loop is reached—the terminus of complete austenitization. Beyond this degree of alloying, the inability to heat treat will result in lower strength, at least for low and moderate creep temperatures. Tungsten, owing to higher cost than molybdenum, has been little used in ferritic high-temperature steels. As a result, very few investigations have been made of its high-temperature strengthening ability, and reliable data on its effectiveness are not available. Grün rated tungsten far less effective than molybdenum at 930°F (500°C) on a weight-percentage basis.' However, Tammann has found that tungsten is as effective as molybdenum in raising the recrystallization temperature of iron. For this reason Smith, in a review of the subject, has advocated a re-examination of the influence of tungsten on the high-temperature strength of steel.' In any study of the effects of alloying additions on high-temperature properties, recognition must be made of the many variables involved, some of which can be controlled but have been ignored in innumerable investigations of the past, and some of which are difficult or even impossible to control. One cannot, for example, assign a definite strengthening index to any one alloying element, for this will be dependent upon the microstructure (heat treatment and mechanical treatment), testing con- ditions (temperature, time, and stress), and the complete composition of the steel (accompanying alloying elements, impurities, etc.). One ever-appear ing variable, hardness or tensile strength at room temperature, may be eliminated by heat treating all of the alloys to a single hardness level. An attempt may be made to control the variable of primary quenched structure by oil or water quenching the test specimen. The control of such variables may not be possible in cases of widely varying compositions, but at least such deviations should be recognized. Material and Procedure The alloys, made as 30-lb ingots in an induction furnace, all had the same base composition of about 0.18 pct C, 0.85 pct Mn, and 0.48 pct Si. They were grouped as follows: Mo Group—Containing up to 5.2 pct Mo. W Group-Containing up to 6.0 pct W. V Group—Containing up to 3.3 pct V. Mo-V Group—Containing up to 2.7 pct Mo and up to 1.4 pct V. Mo-W Group—Containing up to 2.5 pct Mo and up to 2.5 pct W. The steels, listed in Table I, were forged to ¾ in. sq bars and the material for the high-temperature, rupture-test specimens was further swaged to %-in. round bars.

Jan 1, 1957

By Harold Vance

EMPLOYERS of engineers have not always been satisfied with the training that young graduates have received in the conventional four-year course. Specifically, employers of petroleum engineers for a number of years have believed that a four-year course does not allow sufficient time for the student to secure a fundamental engineering background plus the fundamentals of petroleum engineering. A group of California employers went so far as to set up a type of curriculum for a petroleum-engineering course, which was based on four years of undergraduate work and one year of graduate work, with most of the petroleum-engineering courses included in the graduate year.

Jan 1, 1944

By M. C. Dow

Belt conveyors generally are conceded to be the most economical method yet devised for the transportation of large quantities of bulk materials within plants. Belts are coming into greater use for transportation over long distances and are replacing other forms of long-haul conveyance. It is not the intent of the writer to comment on the design of belt conveyors, but to offer some suggestions for improvement in the operation of conveying belts, based on many years experience with belts in several stone-crushing plants. It is the contention of this writer that opportunities for improvement not fully realized by most operators exist in many plants and that a study of the individual conveyors can result in lower unit belt costs. General Reliability It is the fool-proof nature and general reliability of the belt conveyor that is responsible for its neglect. Even when abused, a belt will carry large tonnages and last a long time, often outlasting the personnel responsible for its care. Some operators look upon the purchase of a new belt as an expensive outlay every so many years, rather than a constant and steady cost amounting in belt wear alone to several dollars every operating day. This belt wear for all conveyors in one stone-crushing plant known by the writer costs 1 /12 cents per ton or $12 to $15 per hour, based on the present cost of belt replacements. The fact that these replacement costs are double those of prewar quality emphasizes the necessity of improving the conditions that make belts wear out. Some of those conditions are the responsibility of the conveyor designer, and if a serious original error has been made, this handicap cannot be overcome by the operator. If the belt is too narrow, too steep, or too fast for good loading, the operator finds that he has an inherently expensive belt. The other factors that decrease the life of a belt are more or less under his control. The two factors of most importance are the loading conditions and the alignment. Most of the cover wear and carcass cutting occurs at the loading point and if the alignment is not good under all conditions, edge wear or damage may result, Fig I. Loading the Belt It is difficult to load a belt in an ideal manner; that is, to flow the material on the moving belt at a steady rate, without impact, without turbulence, and with a velocity equal to and in the same direction as the belt. An inclined belt is especially difficult to load and particularly when its speed is over 300 or 350 fpm. Inclined conveyors require longer skirt plates to prevent spillage until the load settles. It does not seem reasonable to expect an inclined the to carry the same load as a horizontal belt of the same width and speed, because of the difficulty in loading

Jan 1, 1948

By M. C. Dow

Belt conveyors generally are conceded to be the most economical method yet devised for the transportation of large quantities of bulk materials within plants. Belts are coming into greater use for transportation over long distances and are replacing other forms of long-haul conveyance. It is not the intent of the writer to comment on the design of belt conveyors, but to offer some suggestions for improvement in the operation of conveying belts, based on many years experience with belts in several stone-crushing plants. It is the contention of this writer that opportunities for improvement not fully realized by most operators exist in many plants and that a study of the individual conveyors can result in lower unit belt costs. General Reliability It is the fool-proof nature and general reliability of the belt conveyor that is responsible for its neglect. Even when abused, a belt will carry large tonnages and last a long time, often outlasting the personnel responsible for its care. Some operators look upon the purchase of a new belt as an expensive outlay every so many years, rather than a constant and steady cost amounting in belt wear alone to several dollars every operating day. This belt wear for all conveyors in one stone-crushing plant known by the writer costs 1 /12 cents per ton or $12 to $15 per hour, based on the present cost of belt replacements. The fact that these replacement costs are double those of prewar quality emphasizes the necessity of improving the conditions that make belts wear out. Some of those conditions are the responsibility of the conveyor designer, and if a serious original error has been made, this handicap cannot be overcome by the operator. If the belt is too narrow, too steep, or too fast for good loading, the operator finds that he has an inherently expensive belt. The other factors that decrease the life of a belt are more or less under his control. The two factors of most importance are the loading conditions and the alignment. Most of the cover wear and carcass cutting occurs at the loading point and if the alignment is not good under all conditions, edge wear or damage may result, Fig I. Loading the Belt It is difficult to load a belt in an ideal manner; that is, to flow the material on the moving belt at a steady rate, without impact, without turbulence, and with a velocity equal to and in the same direction as the belt. An inclined belt is especially difficult to load and particularly when its speed is over 300 or 350 fpm. Inclined conveyors require longer skirt plates to prevent spillage until the load settles. It does not seem reasonable to expect an inclined the to carry the same load as a horizontal belt of the same width and speed, because of the difficulty in loading

Jan 1, 1948

By J. M. Clark

(Wilkes-Barre Meeting, June, 1911.) For some years past, those interested in the development of the increasingly important mining industry of Canada, have urged the adoption by the Dominion Parliament of a federal mining-law, which would have the force and stability of statutory enactment. At present, placer-mining in the Yukon Territory, is governed by the Yukon Placer Mining Act. All other mining under federal jurisdiction is governed by 'Orders in Council and Ministerial Regulations. In the earlier stages of development, it is perhaps a matter of necessity that these important matters should be so dealt with; but it is now felt that the time has come when mining-rights in the extensive regions under federal control should be put on a permanent basis, -and that any changes required from time to time should be made only after full and open discussion in Parliament. A short sketch will suffice to indicate how vast and varied the interests affected really are. When the Dominion of Canada was constituted by the Imperial Statute known as the British North America Act of 1867 (which came into force by proclamation on July 1 of that year), it comprised only the present Provinces of Ontario, Quebec, Nova Scotia, and New Brunswick; but provision was made for the inclusion of Newfoundland, Prince Edward Island, British Columbia, Rupert's Land, and the North West Territories. Subsequently Rupert's Land and the North West Territories were acquired, the 'Crown Colonies of British Columbia and * SECRETARY'S NOTE.-Mr. Clark, an eminent Canadian lawyer, and joint author of the treatise on "The Law of Mines in Canada," has been requested by the Do¬minion Government to prepare a Federal mining-law, and presents this paper, by invitation of the Council, in order to obtain, if possible, useful suggestions from members of the Institute.-R. W. R.

Apr 1, 1911

By A. R. Marder

Fe-C alloys have been investigated at temperatures below the eutectoid transformation to determine whether the superplasticity phenomenon exists for these materials. As a result of void formation at the carbide-ferrite interfaces that led to void coalescence and premature failure, the large elongations characteristic of superplustic matem'als did not develop. It had generally been assumed that the conditions for obtaining superplasticity include: a) T/Tm =0.5, b) a strain rate sensitivity of the flow stress that results in m s 0.3, and c) fine-grain structure. Although superphsticity was not observed in the alloys studied, stress-strain rate measurements indicated that an additional condition for the existence of superplasticitv in Fe-C allovs is that the fine-wain structure be equiaxed in agveement with previous results on Zn-Al al1oys. MANY investigations have been made on the hot deformation of iron-base alloys in order to obtain an understanding of the variables that may affect high-temperature strength and ductility.'-6 However, only a few papers have studied the effect of carbon content on the high-temperature properties of iron-base alloys. Peretayat'ko and Zaikov and Wallquist and carlen4 studied the effect of carbon on strength in the y temperature range, and recently Robbins, Shepard, and sherby6 studied the influence of carbon on the torsional behavior of iron in the a and cu-plus-cemen-tite temperature ranges. In addition to studying hot deformation behavior, current investigations have also been concerned with the phenomenon of superplasticity in nonferrous materials, and, in particular, ferrous alloys. Superplasticity is identified by the increased resistance to necking that results from a high strain rate sensitivity of the flow tress. ackofenr proposed the strain rate hardening coefficient m = d log a/d log e as a measure of strain rate sensitivity and showed that m must be "-0.3 for superplasticity to exist. In addition, a fine-grained microstrcture,- a eutectic or eutectoid ornosition,- and a test temperature in the creep range (TITm > 0.5)" have also been advanced as necessary conditions for superplasticity. Although many workers""23 investigated superplasticity associated with the allotropic transformation in iron and the eutectoid transformation in steel, and recently chadler " and orrison have studied superplasticity in the a - y phase region, no one has measured the superplastic effect in the a + cementite temperature region. Therefore, the purpose of this investiga- tion was to determine the effect of carbon content, microstructure, and test temperature on the strain rate sensitivity of Fe-C alloys at temperatures below the eulectoid transformation. EXPERIMENTAL PROCEDURE Fe-C alloys with carbon contents of 0.2, 0.4, 0.6, 0.8, and 1.0 wt pct were prepared as 100 lb 54 in. ingots by vacuum-induction melting. The compositions are listed in Table I. All the ingots were soaked at 2100°F for 2 hr prior to rolling to 4 in. plate. The minimum finishing temperature for rolling was 1800°F. The plate was sheared in 10-in. lengths and tensile bars were rough-machined prior to heat treatment. The samples were heat-treated according to the schedule in Table I1 in order to obtain a fine-grained microstructure consisting of finely dispersed carbides in a matrix of small ferrite grains. All the tensile specimens were heat-treated prior to finish machining, and tensile testing was accomplished on an Instron machine in conjunction with a clamshell furnace. The buttonhead specimen configuration is shown in Fig. 1. An inert atmosphere, helium, was maintained during testing with a steel tube shroud in a bell jar arrangement. Predried helium was continually purged over the buttonhead specimens and exhausted through ceramic fiber at the bottom of the tube to keep oxidation at a minimum and to prevent

Jan 1, 1970

By J. M. Tobin, L. H. Cadoff, L. M. Adelsberg

The reaction between liquid zirconium and graphite at temperatures above 2000 °C has been investigated. The reaction products were found to be carbon-saturated zirconium metal and ZrC which formed between the graphite and the metal. Parabolic growth behavior was observed for the ZrC Phase at all temperatures of this investigation. The parabolic growth constant at temperatures between 2000° and 2860°C was measured to be 1.83 exp 84,300/RT) sq cm per sec. The reaclion mechanism was proposed to be the rapid carbon saturation of the liquid metal and the formation of ZrC at the metal-carbide interface with diffusion of carbon through the ZrC, the "rate - determining step" of the reaction. The concentration-independent diffusion coefficient of carbon in ZrC, (DZrC), was expressed as 0.95 exp? 78,700/RT) sq cm per sec. This value mas calculated using the temperature-invariant ZrC phase fields proposed in the literature. The [ZrQiq)] — [ZYQiq) + ZrC] phase boundary over the temperature range 2000° to 2800°C was determined and the ZrC + C eutectic temperature was found to be 2890° ± 50°C. ThE Group IV and VB transition-metal refractory carbides are of interest because of their high melting points, high temperature strength properties, and relative inertness in certain corrosive environments. The present-day understanding of these materials, however, is limited by the general unavailability of accurate and reliable physical and chemical property data. This is due primarily to the difficulties associated with the preparation of suitable, high-density, high-purity carbide samples, and the achievement and control of uniform high-temperature environments. Accurate measurement of temperature is also an important factor limiting the reliability of reported data. The Zr-C reaction was selected for investigation because of the high melting point (>34000C) and favorable nuclear properties of the reaction product, ZrC. The direct reaction method afforded an opportunity to obtain kinetic data on the fully dense carbide. In this paper, layer-growth techniques were used to estimate the diffusivity of carbon in ZrC and to investigate the phase equilibria in the Zr-C system at temperatures above 2000°C. EXPERIMENTAL PROCEDURES AND DATA Crystal bar zirconium (99.9 pct Zr), purchased from the Nuclear Materials and Engineering Corp., and ZTA graphite (99.9+ pct) were used in this study. The analyses of the materials are listed in Table I. A schematic of the high-temperature carburization apparatus is shown in Fig. 1. The sample was a zirconium metal charge in a 1/2 -in.-ID graphite crucible which was capped with a tightly fitting graphite stern. The crucible and stem were designed to closely approximate black-body conditions. The graphite crucible was packed in lampblack (outgassed 1 hr at 2100°C) which provided insulation and thermal stability to the system. The inert atmosphere was maintained by a constant flow of high-purity argon or helium gas. The nozzle-diffuser section on the top flange was sufficient to prevent back-diffusion of air into the system. Chemical analysis of the carburized samples revealed oxygen and nitrogen concentrations of less than 44 and 20 ppm, respectively. The sample was heated by induction with a Westing-house 5 kw-450 kc power source. Temperature was measured with a Milletron two-color pyrometer which was sighted into the crucible by reflection from an overhead front surface mirror. Optical losses due to glass absorption and light reflection at air-glass interfaces were minimized by the employment of the dynamic-gas seal. It was found that no correction was required for the front surface reflector. The pyrometer was calibrated periodically against a U.S. Bureau of Standards tungsten ribbon secondary standard. Temperatures inside the crucible were also calibrated against the Zr-ZrC eutectic (1850°C)1 and the Nb-Nb2C eutectic (2335°C)2,3 temperatures and agreed to within ±10°C of these values. The temperature was controlled by manually adjusting the power input; variations of

Jan 1, 1967

By W. C. McClain

In the design of underground excavations, rock mechanics considerations are nearly always based on an elastic behavior of rock. Most rocks do exhibit a certain amount of elasticity, and the application of principles and concepts of elasticity to rock mechanics problems has been largely responsible for progress in the field over the past 10 or 15 years. No doubt the theory of elasticity will remain the most useful analytical tool available for both the design of underground openings and the interpretation of phenomenological data.

Jan 1, 1967

By Elmer A. Jones

Development work in mines of St. Joseph Lead Co., Southeast Missouri, using trackless loading equipment shows definite advantages: Speed of cleaning, ability to work on steep grades and sharp crosscuts, good later tracking conditions, and possibility of wasting rock in old abandoned stopes.

Jan 1, 1950

By F. D. Patchen

Changes in the properties of partland cement upon the addition of fine-ground silica are discussed. Data were collected from formulations cured for periods up to 60 days at temperatures varying from 180" to 350°F. Compressive strengths, permeabilities and thickening times are compared. It is demonstrated that addition of find-ground silica in proper proportion results in a hydrated cement with superior properties above 230°F; i.e., early compressive strengths are higher and increase with additional curing, permeabilities are significantly lnrver and thickening times are increased. X-ray analysis of hydrated cement samples have been used to determine more fully the complex chemistry of these systems. Dicalcium silicate alpha-hydrate was found in all neat cements cured above 260°F. A 10 weight per cent silica addition produced a maximum amount of this phase. Xonotlite and tobermorite have been identified as hydration products at 320°F in systems containing 35 or more weight per cent silica. Formation of these components appears to be primarily responsible for the gain in strength and reduction of permeability observed after the addition of silica. INTRODUCTION For several years it has been recognized that loss of compressive strength occurs when portland cement is cured at a temperature above 250°F. This phenomenon has been called "strength retrogression". More recently it has been recognized that increased permeability usually is associated with decreased compressive strength at these temperatures. At curing temperatures above 300°F, these factors reach serious proportions. A compressive strength loss of 50 per cent between curing times of 24 hours and 14 days has been reported,' and permeabilities as high as 10 md have been measured in neat cements cured at 320°F for seven days.' Earlier investigators,' although unsuccessful in eliminating strength retrogression, stated ". . . .it appears possible that by the proper selection of additives for cement, strength loss with age at high temperatures can be either eliminated or considerably lessened". One solution suggested was the use of a pozzolanic material, hydrated lime, and a retarder. Menze15 in 1934 discovered that portland cement containing finely divided silica possessed high compressive strengths when the curing temperature was 350°F. The use of such a composition is now an established practice in the manufacture of steam-cured cement blocks. It is reasonable to assume that the same beneficial effect can be used advantageously in high-temperature oilwell cementing operations. Ludwig first mentioned the use of sand for this purpose. Later, a portland cement containing moderate additions of silica flour and retarded with CMHEC, a cellulose derivative. was recommended for high-temperature application." These formulations have been successfully employed in the field."'" This paper presents the results of a research program to test the efficacy of finely ground silica in increasing the compressive strength and reducing the permeability of oilwell cement compositions containing portland cement. Included also are X-ray diffraction patterns of powdered samples which have been used to determine some of the important chemical reactions occurring in these systems. LABORATORY PROCEDURES AND MATERIALS All compressive-strength test specimens were prepared and cured from a slurry in accordance with API RP 10B, with two modifications. A final curing pressure of 5,000 psi was maintained for a one- or three-day period; but, for further curing, pressures were reduced to the vapor pressure of water at the curing temperature. Also, the water content was varied in samples containing silica to maintain the slurry viscosity within a range of 5 to 15 poise as measured on a consistometer. Test specimens at 180°T were cured in a water bath at atmospheric pressure. At higher temperatures the specimens were cured in a steam-jacketed high-pressure curing vessel at 5,000 psi for a one- or three-day period. cubes cured for longer periods were removed from the pressure-curing vessel after 24 hours, sealed in small bombs containing water and placed in an aging oven.

By Sherwin F. Kelly

THOUGH the Geophysics Commit- tee limited itself to two sessions this year, both of them marked by a high percentage of absentee authors, even this situation failed to dampen the and or of the ebullient geophysicists, who bandied no small amount of good- humoredlv barbed discussion. Hans Lundherg offered some constructive criticism of last year's report by the Geophysics Education Commit- tee, making a plea for more training in field techniques and less insistence on rigorous theoretical training. Carl Heiland pointed out the necessity of making geophysics and geology courses more attractive in order to draw more students into these fields. Exception was taken to this line of reasoning by Father Macelwane and Sherwin F. Kelly who emphasized the necessity for sound basic training if competent geophysicists were to be turned out. This discussion developed apropos of the report of the Geophysics Education Committee, which had been postponed from the Education Division meetings, but was not read as it was available in mimeographed form. Except for this diversion the morning program fol-

Jan 1, 1944

By E. R. Johnson

The copper concentrator of the Braden Copper Co. is at Sewell, Chile, on the westem flank of the main Cordillera of the Andes, at an air distance of approximately 50 miles southeast of Santiago, the capital of Chile. The region is mountainous and space is at a premium because of the rough terrain and the danger of snowslides. The ore, a porphyry copper, is mined by a block-caving method in the El Teniente mine. It is hauled to the crushing plant, a distance of 2.6 miles, through a tunnel because of the severe climatic conditions. The usual large, coarsely set, primary reduction machines found in many ore-treating plants are not required because of the mining method employed and the limiting 12-in. spacing of the grizzlies at the head of each ore pass in the mine. It is the purpose of this paper to describe the numerous improvements made in the crushing section of this large flotation concentrator during the past I5 years to increase the efficiency of the plant and to raise the daily output from around 20,000 to 30,000 tons. The reader should keep in mind that all changes were made within the existing building because of the limited space and the high cost of the heavy mill construction required to withstand the snow loads. The present plant, as well as the former, operates on a 24-hr, 7 days a week basis. The crushing plant commenced operations at its present site in 1921, the main equipment being No. 7½ gyratories, followed by 48-in. horizontal Symons disk crushers. Fines were removed by I-in. stationary grizzlies ahead of each unit. In 1924 a third stage of crushing was provided by the addition of 55½-in. rolls in open circuit. During 1925, the Symons disks were replaced by 73½-in. rolls. All the rolls were changed to closed circuit, with elevators and screens to give a final product of 9 pct plus 3-mesh. The flowsheet of a typical crushing section of this period is shown in Fig I. The ore was withdrawn from a common bill serving the five crushing sections in the plant by means of any number up to six 36-in. wide-apron feeders, which discharged onto a common conveyor belt. This conveyor was equipped with a magnetic head pulley and the crusher attendant was stationed near the discharge end to pick out pieces of mine timber that might be in the ore. The ore was discharged over a 13/4-in. spaced bar grizzly and the oversize of this grizzly was crushed by a No. 7½ McCully gyratory crusher set at 13/4-in. opening on the closed side. The grizzly undersize joined the gyratory discharge and was conveyed to a set of 73½ by 20-in. Garfield rolls set at I in. These rolls operated in closed circuit with a bucket elevator and two vibrating screens placed in parallel.

Jan 1, 1949