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By H. L. Overton, J. B. Lipson

The concept of sodium single-ion equivalent activity as developed by Gondouin, Tixier and Simard,' was used to determine the filtrate resistivity-activity relationships for 150 laboratory and 49 field drilling muds. With the exception of the native and phosphate high-resistivity muds and the calcium-treated muds, the filtrate resistivity-activity relationships were found to be within 20 per cent of that for pure sodium-chloride solutions. Gondouin, et al,* previously suggested a method of treating the high-resistivity muds in quantitative electrical log analysis. A new treatment is presented which uses the P-alkalinity of the filtrate as a correlating parameter in handling the calcium-treated muds in quantitative electrical log analysis. INTRODUCTION Gondouin, Tixier, and Simard in 1957 introduced new interpretive procedures for analyzing the self-potential curve of electric logging. They re-emphasized the previous work of the Schlumberger brothers, Wyllie and others, and re-defined the activity concept in terms of a number which they termed the effective resistivity. Their procedures are particuarly effective when the connate-water resistivities are less than 0.08 ohm-m or greater than 0.3 ohm-m. For gyp muds where the calcium content is known, a procedure was presented which allows calculation of the connate-water resistivity with improved accuracy. These procedures assume that one of the fluids in the system is a pure sodium-chloride solution, but they are not limited by the assumptions. For the fresh and saline connate waters, for instance, it is assumed that the drilling mud filtrate is a pure sodium-chloride solution. For the gyp mud interpretive procedure, it is assumed that the connate water is a pure sodium-chloride solution. Brown,' on the other hand, has suggested that it would be extremely fortuitous if drilling mud filtrates could all be treated electrochemically as sodium-chloride solutions, and he cites some examples where discrepancies exist. A study has been made of the deviations of sodium single-ion equivalent activities, an of drilling mud filtrates from that of pure sodium-chloride solutions. Drilling fluids in common use on the Texas and Louisiana Gulf Coast and laboratory-controlled muds were investigated. Using a cell patterned after Gondouin, et al, (Fig. I), the equivalent activities were measured. It should be remembered here that the activity measured is merely an index which uses numbers that represent the sodium single-ion equivalent activity a,., of the mud filtrate. The membrane potential developed across the cell was determined with a null-type potentiometer. The resistivities of the solutions were measured by the four-electrode method. The resistivity system was calibrated by using saturated KC1 solution as a standard. Chemical properties of the drilling fluids studied were measured with standard API-approved equipment for the particular property in question. For the activity measurements, two shale discs were chosen to serve as cationic membranes. These two discs were both 1 1/4 in. in diameter and, respectively, 1/4 and 1/8 in. in thickness. The membrane potential, Em, was determined using the shale discs as cationic selective membranes separating two standard sodium-chloride solutions of known mean activity. Then by comparing the constant Km in the following equation, with the theoretical value of — 59 mv at 75OF, the perfection of the membrane was determined. The variation of Km for the two membranes used in this experimental work, as well as one of the many unsuitable membranes, is shown in Fig. 2. The measurement of the activity of mud filtrate involves the balancing of its combined individual activities against a standard solution of known mean activity. At the point where there exists zero potential across the membrane cell, the activity effects may be assumed equal for all practical purposes. The mechanics of making a null reading of this sort requires having a large number of different mean activity solutions. A more practical method involves

By D. Walton

The effect of small solute additions of Cu on the activation energies for creep A1 single crystals were determined over the range from 78° to 850° K. Below 240°K and above 800°K activation energies were unchanged. Between 240°K and 400°K strain aging causes the creep rate to become vanishingly small and the flow stress was independent of the temperature. Between 500° and 50°K the activation energy was increased to 41,000 cal per mole. NUMEROUS investigationsL have shown that solid solution alloying invariably increases the flow stress. A typical example is documented in Fig. 1. Such increases in flow stress can arise from two general effects: Alloying can increase the long-range stress fields through which dislocations must move by causing appropriate clustering; modification of dislocation densities, and so forth. Alloying can also modify the short-range stress fields that determine the activation energies for thermally stimulated migration of dislocations, such as occurs in some solute atom pinning processes, and so forth. Actually both long- and short-range stress-field effects can occur simultaneously. It was the purpose of this investigation to evaluate the effect of alloying on the short-range stress fields by determining the effect of alloying on the activation energies for creep. The resulting observations also shed some light on the effect of long-range stress fields on dislocation processes. EXPERIMENTAL TECHNIQUE Single-crystal bars (6 in. long 3/8 in. wide and l/4 in. thick) of dilute solutions of Cu in A1 were seeded, so as to provide extensive single slip, with the pole of the tensile axis located in the standard stereographic projection as shown in Fig. 2. Each crystal was grown under an argon atmosphere in a graphite mold containing a large reservoir of molten alloy for the purpose of obtaining rather uniform composition of Cu along the length of the bar. The nominal compositions of the alloys which were produced from 99.99 pct Cu and high-purity A1 containing 0.001 pct Fe and 0.001 pct Si, are given in Table I. Strains, measured by linear variable transformers attached by quartz rods to a 3 in. gage section were sensitive to and the stresses were ap- plied by direct loading of the specimen. Temperatures were determined by thermocouples attached to the gage section of the specimens. Below 400°K the apparent activation energies for creep, Q, were determined by the effect of small, rapid changes in temperature of about + 10°K from T1 to T2 on the corresponding creep rates ?1 and ?2 during primary creep according to where R is the gas constant.' Above 400°K, Q was evaluated from Eq. [1] for the secondary creep rate using temperature changes of about ±20K. A typical set of results is shown in Fig. 3. RESULTS AND DISCUSSION The previously obtained effect of temperature on the apparent activation energy for creep of single crystals of high-purity A12 is shown by the broken curve of Fig. 4. The datum points on the same graph illustrate the effect of dilute a solid solution alloying with Cu on the activation energy between 600" and 750°K. Each plotted point is the average of not less than five independent test values between 600° and 750°K and not less than three at other tempera-

Jan 1, 1962

LIMA (PERU) Established May, 1952 James S Young, Honorary Member of Section (Legion of Honor Member) Bernard T Colley, Honorary Member of Section (Legion of Honor Member) Edward H Robie, Honorary Member of Section (Secretary of AIME) Carl W Westphal, Chairman Ernesto A Baertl, 1st Vice-Chairman Pierre L Garrigue, 2nd Vice-Chairman Walter E King, Secretary-Treasurer Avenida Santa Cruz 331 San Isidro, Lima, Peru Daniel M Rodriguez, Assistant Secretary Alberto E Brazzini, Assistant Treasurer Robert P Koenig, Section Delegate Irving L Barker, Special Representative

Jan 1, 1954

YEAR OF ELECTION 1922. FEDERICO GIOLITTI Torino, Italy. 1917. HERBERT HOOVER Washington, D. C. 1941. DANIEL COWAN JACKLING San Francisco, Calif. 1939. HENRY KRUMB New York, N. Y. 1942. Essington Lewis Melbourne Vic., Australia 1921. C. McDERMID London, England. 1942. PAUL DYER MERICA New York, N. Y. 1913. EZEQUIEL ORDONEZ Mexico City, Mexico. 1938. A.M. PORTEVIN Paris France 1937. JOHN V.W. REYNDERS, New York, N. Y. 1937. GEORGE S. RICE Washington, D. C. 1911. ROBERT H. RICHARDS Cambridge, Mass. 1934. T.A. RICKARD Victoria, B.C., Canada

Jan 1, 1943

YEAR OF ELECTION 1913. FRANK DAWSON ADAMS, Montreal, Canada. 1922. FEDERICO GIOLITTI Torino, Italy. 1921. FRANK WILLIAM HARBORD London, England. 1917. HERBERT HOOVER Washington, D. C. 1941. DANIEL COWAN JACKLING San Francisco, Calif. 1939. HENRY KRUMB New York, N. Y. 1921. C. McDERMID London, England. 1913. EZEQUIEL ORDONEZ Mexico City, Mexico. 1935. ROBERT PEELE New York, N. Y. 1938. A.M. PORTEVIN Paris France 1937. JOHN V.W. REYNDERS, New York, N. Y. 1937. GEORGE S. RICE Washington, D. C. 1911. ROBERT H. RICHARDS Cambridge, Mass. 1934. T.A. RICKARD Victoria, B.C., Canada

Jan 1, 1942

By L. A. Walker

DURING the past twelve years the underground shaft of the United States mine at Bingham has been sunk an additional 2000 ft. with stations and pockets cut every 200 ft. without interrupting the mining of 600 tons of ore per day and the advancing of 1500 ft. of development per month. Following is a brief description of the way the joint work is conducted. The vertical underground shaft is a three-compartment shaft with outside dimensions of 6 ft. 4 in. by 15 ft. 6 in., and inside dimensions for each compartment of 4 ft. 2 in. by 4 ft. 8 in. The manway compartment of the main shaft is used as the hoisting compartment in sinking operations; it is partially lined with 2 by 12-in, lagging and a bucket is used without guides or crosshead. Preparatory work includes the placing of a bulkhead in the manway compartment, 60 ft. above the lowest station or level, the installation of a hoist, a head sheave, a fleet sheave, a-signal system, air and water lines, and a trap door for handling waste.

Jan 1, 1937

By W. E. D. Stokes

The application of aviation to mining and petroleum operations, on the basis of economy and attainment, has become a demonstrated fact. According to Dominion Government rccords, 30 Canadian companies engaged in air transportation with northland mining camps, carried 13,000 tons of freight in 1935, and in 1936 carried 16,000 tons. In addition, many mining companies used planes to transport prospectors with canoes, outboard motors, gasoline drums and supplies to remote locations, and one company maintained a plane to take radium-bearing ore from its mine on Great Bear Lake nearly 1000 miles south to the railway at Waterways, Alberta. Heavy pieces of mining machinery weighing 2 tons are being carried by Ford trimotor planes over the Andes, at an altitude of not less than 15,000 feet. At Bulolo, New Guinea, 17,500 tons of disassembled gold-dredging equipment has been flown over inaccessible terrain, while supplies and building materials for a community of 1000 whites have been transported by airplane. A 31/2-ton shaft was carried on one notable trip, while at another time an automobile, 2 tons of rice and a large safe went over the mountains in one plane. Fig. 1 shows an electric generator that was carried by plane to Bulolo. Many large American oil companies operated fleets of planes during 1936, ranging from fast, luxurious air liners for executives to elaborate geological prospecting units, ambulance planes, freight carriers and pipe-line repair crews. According to the U. S. Geological Survey, commercial firms photographed 16,291 square miles during 1935, while the Government compiled from aerial photographs by the Geological Survey in the United States 85,544 square miles. It was found that information could be determined in a fraction of the time required by surface methods. However, sounding a word of caution, a Commonwealth of Australia government report on aerial survey operations had this to say: It is necessary to repeat ad nauseam that aerial photographic survey is in no sense a substitute for geological investigation, though it is a very valuable adjunct thereto, and greatly facilitates and aceeleratcs geological mapping. There are many details

Jan 1, 1937

By C. B. Dudley

IN the spring of 1877, the Pennsylvania Railroad Company became so dissatisfied with the average life and wear of the steel rails it was then able to procure, that it determined to make an investigation into the chemical composition and physical properties of steel rails, with a view, first, to answering the question why one steel rail has to be removed from the track after, perhaps, eight months' service, while another lasts ten years ; and, secondly, if this investigation succeeded in throwing light on this important subject, to use this information in securing better rails in the future. The results

Jan 1, 1879

By Albert F. J. Bordeaux

Discussion of the paper of Albert F. J. Bordeaux (Bi-Monthly Bulletin, No. 23, September, 190S, pp. 629 to 640). A. H. BROMLY, Zihuatanejo, Guerrero, Mexico (communication to the Secretary*) :-The following criticism of what "is offered as a summary which may be found useful by mining engineers," is not dictated by any captious spirit, but in the interest of historical and scientific accuracy. The States of Queretaro and Oaxaca have produced sufficient silver to warrant more extended notice. Referring to Pachuca, State of Hidalgo, the somewhat loose and. inexact statement is made that "the ore-deposit is an andesite, intermixed with quartz-veins, rich from the surface." A better description would be,-the ore-deposits consist of quartz-veins in andesite. It is notable that many of the rich shoots worked in recent days did not come to surface. In consequence, Pachuca, is often quoted by the ill-informed as a camp in which values improve with depth, the truth being that the veins carry shoots, or clavos, some of which were exposed at surface and some not. The name of " electric plow," applied to the mechanical stirrer of recent use, is certainly not to be recommended. The stirrer, or agitator, consists essentially of a traversing gang-plow, operated by power through shafting, drums, and wire-rope. The fact that in certain plants the motive-power used is electricity does not make it an electric plow. Such a name suggests a machine of which the motor is an essential and integral part; which is not so in this case. A lathe in a factory driven by water-power is not called a hydraulic lathe. My experience agrees with Dr. Raymond's note as to azulaque, which in sortie districts is also applied to blue copper carbonate. The El Oro, Esperanza, and Mexico mines should be allocated to the State of Mexico; the Dos Estrellas being in Michoacan, as stated. The El Oro quartz certainly does not appeal to me

May 1, 1909

By H. M. Chance

In almost all coal-fields, the quantity of explosive gases given off by the coal increases as depth is attained, requiring correspondingly enlarged quantities of air to ventilate the workings properly, by diluting and carrying off the gas. Again, with increased depth there is a corresponding increased pressure caused by the weight of the overlying strata. Sandstone or slate, which would form a good roof for a coalbed at a depth of 300 or 400 feet, may be unable to sustain the pressure of 800 or 1000 feet of overlying rock. Hence, in nearly all deep mines, the miner will generally describe the roof as "bad," although the roof-rock may be a firm slate, forming an excellent roof for workings of moderate depth, but unable to stand the pressure resulting from the weight of a great thickness of overlying rock. With increased weight of rock-mass above comes also

Jan 1, 1901

By Thomas W. Yardley

In many years' experience as a maker and purchaser of cast-iron coated pipe, I have never met with any standard form of specifications for such. Each water-works company, employing a hydraulic engineer, has, under his direction, prepared complete specifications for the particular conditions required; but I cannot find that any two are alike; and each foundry, in bidding for the supply of such pipe, makes the price to cover the conditions' required. I, therefore, have the honor of offering to the Institute a form of specifications for cast-iron coated water-pipe, that may be found useful to water-works companies and others requiring pipe of this kind. The conditions are all reasonable, and can be carried out by makers without additional cost, and with advantage to the purchaser. Section 1 gives the kind of pipe, with its general characteristics. Section 2 specifies that neutral pig-iron shall be used, since such iron possesses the strength required, and is uniform in its shrinkage. Section 5, requiring makers to give the brands of pig-iron used

Jan 1, 1890

By K. M. Rolls, J. Wulff, D. A. Colling

Solid-solution alloys of the Ta- Ti system containing up to 70 at. pct Ti were melted and fabricated into wire. Steady magnetic-field measurements of cold-worked wires at 4.2°K indicate that the resistive critical field increases smoothly with increasing titanium, reaching a maximum of 93 kG (J = 1 amp per sq cm) for a composition of about 50 at. pct Ti. The composition dependence of the resistive critical field indicates it is largely paramagnetically limited for alloys containing more than 35 at. pct Ti. For cold-worked wires the value of the critical current density, Jc , was found to be insensitive to composition changes for compositions in excess of 20 at. pct Ti. It was observed that Jc could be increased by final-size heat treatment at 400°C without altering the value of- the resistive critical field. Experimental data are used to calculate the electronic specific-heat coefficient and the "upper critical field" for the alloys studied. THE effect and importance of metallurgical structure on superconducting properties have been summarized by Livingston and Schadler.1 Specific work on solid-solution alloys such as Nb-zr2-7 and Nb-Ti5-7 have shown that critical current density (Jc) and superconducting transition temperature are structure-sensitive. Berlincourt et al.6,8,9 in their studies of transition-metal alloys find that Ta-Ti alloys remain superconducting at fields comparable to Nb-Ti alloys. 6,8 Transverse critical current tests of a Ta-10 at. pct Ti alloy10 and longitudinal critical current tests of a Ta-25 at. pct Ti alloy1' indicate that such alloys are capable of carrying high currents at intermediate fields (-40 kG). The work reported in the present paper was undertaken to explore the superconducting properties of further compositions in the Ta-Ti alloy system as well as the structure sensitivity of the superconducting properties. I) EXPERIMENTAL PROCEDURE Alloys were prepared by melting tantalum (Fansteel Metallurgical Corp., 99.96 pct purity) and iodide, crystal bar titanium (Foote Mineral Co., 99.92 pct purity) mixtures in an arc furnace on a water-cooled copper hearth using a tungsten electrode. Melting was accomplished in a purified, gettered argon atmosphere at pressures from 250 to 400 Torr. Each alloy was turned and remelted fourteen times to assure complete mixing of tantalum and titanium. Ex- cessive coring in the cast samples was, nevertheless, observed. This was somewhat reduced by annealing in vacuo at 1000°C for 13 hr. The ingots were then machined to 0.250 in. diam, jacketed in Type 304 stainless-steel tubing, and swaged to 0.140 in. diam. They were then drawn to 0.010-in.-diam wire. Alloys containing up to 70 at. pct Ti were readily cold-drawn to wire in this manner. Later experiments showed that oxygen additions up to -3000 ppm could also be cold-worked into wire. Test samples for superconductivity measurements in the 2-in, air-core Bitter solenoids of the M.I.T. National Magnet Laboratory were prepared from 10-in. lengths of 0.010-in.-diam wire, cleaned of residual wire-drawing lubricant. Current contacts were made by clamping clean copper tubing over both No. 18 current lead wire and the ultrasonically indium-tinned ends of the specimen wire.12 Potential leads of No. 32 copper wire were connected to the specimen by ultrasonic soldering in an indium bath. The potential lead separation was about 4 cm, corresponding to the circumference of the Bakelite rod to which the wire was affixed with half-mil Teflon tape. The final specimen configuration is shown in Fig. 1. Specimens were lowered into a liquid helium bath (4.2oK) in a double solenoid dewar and positioned so that the maximum magnetic field was oriented transverse to the wire axis of the gage section. Measurements were made by passing a current through the specimen at a preset solenoidal magnetic field. The current was increased until a 1-pv potential difference appeared across the gage section (1/4 µv per cm). At low magnetic fields, however, it was not possible to use this criterion because power-dissipation difficul-

Jan 1, 1967

By A. E. Deruyttere, J. Van der Planken, M. Laurent, Van den Bergen

FahRENHORST and schmid1 observed that zinc single crystals work hardened less rapidly when strained in liquid air (- 185°C)than in a bath at -82°C, whereas at higher temperatures the rate of work hardening decreased with increasing temperature, as would be expected. Cadmium and magnesium showed no such decrease at -185°C. At that time the observed anomaly for zinc at liquid air temperature probably seemed insignificant. However it later was confirmed2 by experiments in liquid nitrogen (-196°C) and in the mixture solid carbon dioxide-acetone (-77"C) and therefore appeared to be real. seeger3 then suggested that the anomaly might be due to the different wetting of the zinc crystals by the cooling media. Recently a new confirmation was obtained,4 however the cooling media again were different: the rate of strain hardening was found to be lower in liquid nitrogen and liquid oxygen than in pentane cooled to various temperatures down to -126°C. Ekperiments will now be reported in which the medium surrounding the specimen at the different temperatures was the same, namely gaseous air. The single crystals were made from "Overcor 99.99" zinc. They were grown in a vertical traveling furnace on seeds of nearly the same orientations. The diameter of the crystals was 5 mm and the length between shoulders 140 mm. The brass shoulders were stuck to the crystals by means of araldite. A thin steel wire was fixed to each shoulder and served to fasten the specimen to a Houns-field tensile testing machine. The crystals with the shoulders and part of the wires were surrounded by two concentric cylindrical containers. The coolant. either liquid air or ground solid carbon dioxide, was poured into the outer container only. During cooling the containers rested on a support which was removed when the straining was started. In order to check the temperature which the crystals would attain inside the inner container, a hollow bar of zinc in which a thermocouple was fitted was first mounted in the apparatus as a substitute for a crystal. It appeared that a constant temperature, respectively - 183° and -72°C, was attained inside the bar, if a soaking time of the order of 1 hr was allowed and if the outer container was constantly kept filled. Accordingly, this procedure was adopted for every tensile test. To take account of the large scatter, fourteen tensile tests were performed with liquid air and seven with solid carbon dioxide. The orientation of the crystals and the results are presented in the table, in which the symbols have the following meaning: 1 : temperature x : initial angle between basal plane and specimen axis : initial angle between slip direction and specimen axis a : shear strain at fracture 0: average rate of strain hardening = —-——- 100 t0 and Te representing respectively the critical shear stress and the shear stress at fracture. Despite the scatter of the a- and 8— values which is of the same order of magnitude as in the work reported by Seeger and Trzuble,4 it is evident that the strain hardening rate is significantly lower at -183°C thanat-72°C. The table also contains the average values calculated from Seeger and Trauble's results at the corresponding temperatures: z.e., four results at -183oC and two at-70°, -71°C. These authors calculated 9 in a slightly different way, but this is unimportant. The agreement between the a-values shows that both sets of experiments are comparable despite the differences in experimental techniques. The rates of strain hardening also agree and it may therefore be concluded that the anomaly is not

Jan 1, 1962

By R. A. Burmeister, G. P. Pighini, P. E. Greene

An open tube vapor phase epitaxial growth system has been used for large area (multiple substrate) growth of GaAs1-xPx on GaAs substrates. The GaCl-GaCl transport reaction is used with either a GaAs or Ga (nonsaturated) source. Selenium and tellurium have been used for donor impurities, and zinc as an acceptor. The useable substrate area in this system is approximately 20 sq cm. The uniformity of thick-ness of the epitaxial layers are typically better than ±5 pct across a given wafer. Electrical and optical measurerments indicute comparable uniformity in electrical and luminescent properties within a wufer. The application of this system to the large scale pro-duction of GaAs1-x Px for display devices, both discrete and arrays, is discussed. Typical electrical and luminescent properties of light emitting diodes fabricated front material produced by this technique are presented. THE most promising materials currently being utilized for visible injection electroluminescence are GaAs1-xPx, Ga1-xAlxAs, and Gap. All have reasonably efficient emissions in the red portion of the visible spectrum at room temperature; Gap also has an efficient green emission.' At present, GaAs1-xPx has a technological advantage over Ga1-xAlxAs and Gap for display applications, since relatively large (several sq cm) areas of GaAs1-xPx suitable for use in electroluminescent devices may be readily grown by vapor phase growth techniques. In contrast, the preparation of Gap and Ga1-xAlxAs for electroluminescent device applications generally employs solution growth techniques which are at present not well suited for the growth of large areas of uniform thickness and doping level. The capability of uniform growth over large substrate areas and the use of multiple substrates is necessary for the practical utilization of electroluminescent devices. This is particularly important when quantity production or monolithic devices are required. Furthermore, in many display applications arrays of light emitting devices are used, the individual elements of which are of a size resolvable by the unaided eye. Thus the overall dimensions of display are substantially larger than those of most semiconductor devices. It is also necessary to achieve a high degree of control over the growth parameters to attain the required degree of reproducibility of materials properties for electroluminescent devices. In the case of GaAs1-xPx it is necessary to accurately and precisely control the phosphorus content of the alloy, both on a macroscopic and microscopic scale, in addition to the parameters generally associated with epitaxial growth such as thickness and doping level. This value is critical, as it has a major effect on the performance of electroluminescent devices. This paper describes the epitaxial growth of GaAsl-xPx suitable for electroluminescent display devices using a system developed specifically for this purpose, and which contains several novel features. The results of studies of selected physical properties of the epitaxial layers are also discussed. Finally, a brief summary is given of the characteristics of display devices fabricated from GaAsl-xPx grown in this system. EXPERIMENTAL A) Reactants. A number of techniques suitable for the vapor phase epitaxial growth of GaAs1-xPx have been reported in the literature.'-' The method selected for this investigation is that in which the Ga is transported by the GaC1-GaCI3 reaction in an open tube process. The results reported here were obtained using either the combination of GaAs, AsC13, and pH3, or Ga, AsH3, pH3, and HC1 as the initial re-actants.* The ASH3 and pH3 were obtained as dilute *Several different sources of supply were used for these reactants, y~elding comparable results._____________________________________________________ mixtures in HZ; the HC1 was obtained from the reduction of AsC13 by Hz at elevated temperatures. Both selenium and tellurium were employed as donor impurities, and zinc as an acceptor impurity. Selenium was introduced in the form of H2Se, tellurium in the form of tellurium-doped GaAs, and zinc in the form of diethy1 zinc. B) Apparatus. The prinicipal difference between the apparatus used in the present study and that of Tietjen and Amick,8 in addition to size and other related design features, is that RE induction heating is utilized in place of resistance heated furnaces. Induction heating was selected for this application because it appears to have several advantages, including: 1) It is possible to keep all fused silica portions of the apparatus at temperatures well below those of the reaction zone, thus minimizing a possible source of contamination. 2) The thermal mass of an induction heated system can be made small, thus reducing the total time required for the growth process. 3) Sharp temperature profiles (desirable for high deposition efficiency) are easily achieved. 4) The volume of the system for a given substrate area can generally be made smaller than a comparable resistance heated unit. This results in shorter time

Jan 1, 1970

By Werner Schwartz, Wolfgang Haase

Lead sulfide concentrates, which may include other lead concentrates, are sintered on an up-draught sintering machine without the addition of any diluting agents or fluxes. Subsequently they are melted in an oil- or gas-fired rotary furnace. The sintering and melting processes are based upon the following roast-reaction: PbS + 2 PbO = 3 Pb + SO, PbS + PbSO, =2 Pb + 2 SO, For obtaining a lead bullion free from sulfur, the sintering process is carried out in such a way that the sinter product contains a small amount of excess oxygen above that to react with the sulfides. At the end of the melting process, when the reactions are finished, the remaining small amount of oxide residues is reduced with coal to which a certain percentage of soda ash (about 1 pct of the lead bullion) is added. For the lead smelting process described neither coke nor fluxes—except soda ash—are required. This process is being utilized by a European smelter successfully and with a high lead recovery. The consumption figures for the smelting of 100 tons per day of lead concentrates are indicated. The lead content of the lead concentrates from modern ore dressing plants ranges from 65 pct to above 80 pct. In most lead smelters of the world these concentrates are smelted in a blast furnace. For blast-furnace smelting the concentrates have to be desulfurized and agglomerated by sintering. A requirement for the perfect operation of a down-draught sintering machine and of a blast furnace is a maximum lead content in the feed of 40 to 45 pct. For this reason, some lead concentrates have to be diluted by adding return slags, limestone, and possibly iron oxide and sand. As an example, 100 tons of lead concentrate with 72 pct Pb would contain 13.5 tons of gangue (including the zinc). To produce a perfect sinter with 42 pct Pb it would be necessary to add 70 tons of flux and return slag, more than five times the original weight of the gangue, to the sinter mix and blast-furnace charge. A correspondingly large amount of coke would be required in order that all of these materials reach the heat of formation and the melting temperatures of the slag (1200" to 1400°C) inside the blast furnace. The roast-reaction process presents a possibility for lead recovery without dilution of the concentrates. In this process the concentrate mixed with coal is placed upon a Newnam-hearth and air is blown through nozzles into the heated mix. AS a result metalllic lead and a relatively great amount of so-called .'Grey Slag" with a lead content of 25 to 35 pct are formed. The slag is sintered to eliminate sulfur and, after addition of the requisite fluxes, treatt:d in a blast furnace. Owing to the poor recovery of lead from the hearths and to the unavoidable heavy hand-work plus the risk of poisoning this process is utilized in very few 112ad smelters today. Since in mxny countries of the world coke is expensive and difficult to obtain, it appeared feasible to use the principle of the roast-reaction by modern sintering and melting methods with recovery of the lead in electric, or oil, gas, or coal-fired furnaces. Two processes are utilized on an industrial scale: A) Lead smelting in the electric furnace of the Bolidens Gruv A/B in Sweden, as described by S. J. Walldcn, N. E. Lindvall, K.G. Gorling, and S. Lundquist. B) The self-fluxing lead smelting of Lurgi Gesell-schaft fiir Chemie und Huttenwesen m.b. H., Frankfurt a M, Germany, which is described in this paper. In the Boliden process referred to above the sinter mix is pelletized by enveloping return fines with layers of flue dust, limestone powder, and dried galena concentrate. The roasting and agglomeration are carried out on a down-draught machine, and a slight excess of sulfur is left in the sinter product. During the smelting in the electric furnance the roast-reactions occur and a slag poor in lead and a sulfur bearing lead are formed. This latter is subsequently oxidized in a converter to obtain lead bullion and dross. The Lurgi-process achieves the maximum possible extent of the roasting reaction on the sintering machine. The wet flotation concentrates are blended with return fines (lead content 70 to 80 pet), any existing flue dusts and lead slimes—but without the

Jan 1, 1962

By S. M. Purdy

Under certain conditions of hot rolling and air cooling from the hot-rolling temperature, bars of a high carbon (0.40 pct C) chrome-nickel austen-itic alloy were found to show magnetism even though no ferrite or martensite could be detected by microscopic or X-yay methods. The appearance of magnetism in such alloys may come from chromium impoverishment of the austenite grains near the precipitated carbide particles. SPORADICALLY, hot-rolled bars of Silchrome 10, an exhaust valve steel, have been found to be magnetic. Because of the analysis of the alloy—0.40 pct C, 18 pct Cr, 8 pct Ni, 3 pct Si —magnetism is unexpected. Preliminary investigation showed neither martensite nor ferrite to be present; only austenite and Cr23C6. Since a literature search was fruitless, a brief study was made of the appearance of magnetism in this alloy. The only basic difference between the two heats is the nitrogen content. Permeability was measured using a Severn magnetic gauge. This instrument consists of a magnet mounted on a counterbalanced arm. A set of calibrated plugs is placed in contact with one pole of the magnet. The specimen is placed close to the other pole of the magnet. If the specimen pulls the magnet away from the plug, it has a permeability greater than that marked on the plug. This technique is swift and reproducible. Previous experience has shown that the permeabilities obtained corresponded to those obtained on a permeater with a field strength of 100 oe. Specimens from both heats were annealed at temperatures between 1700 and 2300°F. One set of specimens was water cooled and another furnace cooled. All the water-quenched specimens were non-magnetic; the furnace cooled ones were magnetic as shown in Table I with no difference being observed between the two heats. Microstructural examination of the specimens showed the expected increase in carbon solubility with increasing temperature. Carbide solution was complete at 2200°F. The specimens heated to 1900°F or below showed some carbide precipitation from the hot-rolled structure. A furnace cooled specimen from a given temperature showed less carbide out of solution than the water-quenched specimen from the next temperature below; e.g., the specimen furnace cooled from 2100°F showed less carbide out of solution than the water-quenched specimen from 2000" F. These studies indicated that the appearance of magnetism was not related to the quantity of carbon in or out of solution and it was related to precipitation at temperatures below 1700" F. A set of samples annealed and water-quenched from 2100° F was aged for 4 hr at temperatures between 1000" and 1600°F; all were non-magnetic. A second set of samples, similarly annealed, was aged 1 to 24 hr at 1200°F with the results shown in Table II. None of the latter set of specimens showed magnetism until they had been aged about 8 hr. Magnetism was quite strong after aging 24 hr. X-ray diffraction studies on several of the magnetic specimens showed that the austenite had a lattice parameter of 3.58A and that the carbide was Cr23C6. Several of these samples were electrolytically digested in 10 pct HCl in ethanol, with a current density of 0.1 amp per sq cm. None of the particles in the residue were magnetic. Accidentally, one cell was run at 1 amp per sq cm; e.g., magnetic particles were found in this residue. After careful separation, the magnetic particles were mounted on a quartz fiber and their diffraction pattern determined using a 5.73-in. Debye-Sherrer camera with CrK radiation. These particles showed a fcc structure with a lattice parameter of 3.57A. Prolonged exposure, up to 16 hr, produced no other lines on the film. The following facts seemed to be established at this time: 1) Austenite was the magnetic phase. 2) Neither ferrite nor martensite could be detected. 3) Magnetization could be produced by aging at 1200°F. One explanation of these data is that the carbide precipitation impoverishes the region immediately around the carbide particle of carbon and chromium and increases the proportion of nickel. All of these serve to increase the Curie temperature of the region around the carbide particle. If the composition change is enough, the Curie temperature will rise above room temperature. If the volume of the affected region is great enough, the magnetism will become detectable. At low aging temperatures, composition changes are great enough but the overall volume of impoverishment is quite small

Jan 1, 1962

The American Steel Treaters Society, which meets at the Seventh Regiment Armory, Chicago, Ill., on Sept. 23-27, has provided an especially interesting program of thirty-five papers. They deal with "Heat Treatment of Steels for Cutting Purposes," "Heat Treatment of Miscellaneous Products," Heat Treatment of Steel for Intermittent Cutting Purposes, "Results of Investigation Pertaining to Heat Treatment," "Heat Treating Equipment," "Solution of Modern `demands on Heat Treating."

Jan 9, 1919

By J. Chipman, N. J. Grant, J. H. Walsh, T. B. King

WITH the development of adequate sampling and analysis techniques, much information has been obtained concerning the behavior of hydrogen in the steel bath during the course of steelmak-ing operations. From studies of this type it has become clear that the slag has an important role to play in determining the hydrogen content found in commercial products. A knowledge of the behavior of hydrogen in slags is necessary to round out our knowledge of hydrogen in steelmaking practice; with this information we are better able to assess practical methods of control. In this paper a method developed for analyzing slags for hydrogen content, studies of the solubility of hydrogen in synthetic slags, and studies of the variation of hydrogen content in slag and steel in industrial heats will be described. Previous Work—While very little has been done in the past to determine the hydrogen content of metallurgical slags, measurements have been made on such slag-like materials as geologic magmas and glasses. Goranson as made extensive studies of the solubility of water in natural and synthetic granites. Many workers have investigated the solubility of gases in synthetic and commercial glasses, but the recent work of Russell" is the most extensive. Russell found that the solubility of water in glass was proportional to the square root of the water vapor pressure in water vapor-oxygen mixtures. It was found that the solubility could either increase or decrease with temperature depending on the glass composition. Wentrup, Fucke, and Rief,' and Piper, Hagedorn, and Backes' have extracted hydrogen by holding a slag at 1300" and 800°C respectively in vacuum. Wentrup et al. reported hydrogen and water vapor as evolved together while Piper et al. passed the evolved gases from the hot extraction treatment over hot ferromanganese to reduce the evolved water vapor to hydrogen and, therefore, reported the analyses in terms of total dissolved hydrogen. Yavoiskii has reported hydrogen and nitrogen analyses on steelmaking slags. Dobrokhotov, Povol-skii, and Khan have studied the hydrogen content of basic open hearth steel under slags of varying viscosity. These authors reported that the hydrogen content of the steel bath increased as the fluidity of the slag was increased by the addition of bauxite. They recommended that a viscous slag be used and the steel tapped without deoxidation in the furnace to ensure a low final hydrogen content. Analysis of Slags for Hydrogen Development of Apparatus—The vacuum fusion analysis equipment described by Shields, Chipman, and Grant" was modified for the analysis of slags." This method depends upon the reduction of water in the slag to hydrogen, which is readily determined by the method used for hydrogen in steel. Preliminary experiments were made with a eu-tectic ferrosilicon melt as the reducing agent. Other experiments included the use of graphite and molybdenum crucibles. The ferrosilicon alloy bath was found to produce a thick coating on the furnace tube which could adsorb hydrogen. Graphite produced CO by the reduction of FeO, MnO, and SiO2 in such quantities that analysis for hydrogen was virtually impossible. Molybdenum, while giving a low blank value, could reduce the slag sufficiently to produce a volatile oxide which again was found to adsorb hydrogen. The arrangement finally adopted is shown in Fig. 1. The molybdenum sheet served as the induction-heated susceptor, and was separated from the escaping gases by alumina guide tubes. An outer jacket of alumina protected the quartz furnace tube, and alumina and quartz stools completed the assembly. The falling sample is shown wrapped in aluminum foil, 0.002 in. thickness, which acted as the reducing agent' This foil was careful'~ washed in acetone and an d and then dried in hot air before wrapping the weighed slag sample for charging into the apparatus. Investigation of the hydrogen content of the aluminum foil itself showed that a small quantity of hydrogen was released in vacuum, but had no relation to the weight of the aluminum charged. This quantity of hydrogen was

Jan 1, 1957

By C. E. Sims, F. W. Boulger, H. A. Saller

Most of the data on equilibrium constant and the deoxidations potentialities of those elements, considered to be stronger deoxidizers for steel than is silicon, have been calculated from thermodynamic data. The reason for this is, primarily, the obvious difficulty of obtaining direct experimental evidence of equivalent accuracy. This is an excellent use of the principles of thermodynamics and has given valuable data not otherwise available. Such results, of course, can be no more accurate than the physical constants used in the calculations, and one can never be sure that the basic data are either complete or accurate. In fact, as in the case with silicon,1 there are not only discrepancies among the calculated theoretical values of the equilibrium constant for deoxidation of steel but also between the theoretical and experimental values. It is highly desirable, therefore, to obtain experimental values for checks on calculated results whenever possible. If they disagree, both cannot be right, but if there is good agreement, their value is enhanced. The present work was done in an effort to obtain experimental evidence in regard to some of the common alloying additions but more particularly the so-called "strong" deoxidizers for steel. The method used was to determine the minimum concentration of the deoxidizer that would effect a certain definite degree of deoxidation in steel. The criterion of deoxidation was the change from the large globular Type I sulphide to the eutectic Type II as described by Sims and Dahle.2 This change is sharp and definite, and inasmuch as it can be produced with equal facility by aluminum, zirconium, and titanium, it is considered a manifestation of a certain degree of deoxidation and not an alloying effect. Ostensibly such a procedure could give only a comparison of deoxidizing powers and no absolute values. Nevertheless, repeated observations have shown that, when increasing increments of aluminum are added to a steel, the residual aluminum content begins to increase simultaneously with the appearance of Type II inclusions. Thus it seems warranted to postulate that the Type II inclusions appear coincident with the virtual elimination of FeO as an active constituent of the steel. Experimental Procedure The data obtained were primarily from the microexamination of polished and unetched specimens and from chemical analysis. Experimental heats weighing 200 to 250 lb were made in a basic-lined high-frequency induction furnace. The base composition was nominally that of a medium-carbon casting steel to which the appropriate additions were made. Specimens were poured into sand-cast ingots 3 in. in diam as shown in Fig 1. Sand-cast ingots were used to prevent chilling and to allow sufficient time in freezing for normal inclusions to form of a size large enough to be studied readily. In the first few heats, the tapered wall ingot was used, but in the majority, the extra large riser was used to prevent piping in heavily deoxidized steels. Specimens for microexamination were taken from the location shown in Fig 1, and drillings for chemical analysis were taken from a similar location. The procedure was to melt the base composition and deoxidize with the usual manganese and silicon additions and then to pour an ingot. The furnace was then tilted back, and the first increment of strong deoxidizer or special alloy was added and allowed to disseminate through the melt, with enough power on to hold the temperature constant, for 45 sec. Then a second ingot was poured. After this, another increment was added, and after the same holding time another ingot was poured. In this way from 9 to 12 ingots were poured from each heat, each successive ingot having progressively larger total additions of alloy. Eighteen heats were made altogether, and the range of alloys used and additions made are outlined in Table 1. The three principal types of sulphide inclusions found are illustrated in Fig 2. The globular Type I sulphides are characteristic of silicon-killed steels, the eutectic Type II are characteristic of steels deoxidized with a small amount of aluminum, while the larger, angular Type III are usually found in steels with a residual aluminum content above about 0.02 pct. In all specimens studied, the transition from Type I to II either did not occur at all or was very abrupt and clear cut. There never was any doubt as to just which increment produced the change, although the individual additions were small, in the order of 0.01 pct. The change from Type II to Type III was considerably less sharp, and, in some cases, both types were found together. Inasmuch as the formation of Type III sulphides is apparently not a deoxidation phenomenon, they will not be discussed here.

Jan 1, 1950

By Robert A. Bauer

This study showed that diametral point-load testing performed parallel to the bedding planes of highly anisotropic sedimentary rocks produced inconsistent results that cannot be used to accurately estimate uniaxial compressive strength. Axial point-load values from tests performed normal to bedding planes and evaluated by the T500 index produce good correlations with the uniaxial compressive strength values obtained for five different rock types. A strong correlation also existed between the moisture content and the uniaxial compressive strength of the tested lithologies. A combination of axial point-load and moisture content indices produces the best correlation with the uniaxial compressive strength test results.

Jan 1, 1984