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By Shabnam Sabah, Geoffrey Brooks

In oxygen steelmaking, splashing and droplet formation play a key role in the kinetics of the process. Though splashing has been studied by previous investigators, there is only limited understanding of how different cavity modes affect splashing. Therefore, a cold model study (at various lance heights and gas flow rates) has been carried out focusing on the issue of cavity modes and how it affects splashing phenomenon. Analysis using Fast Fourier Transform (FFT) was carried out on cavity oscillation that showed that frequency and amplitude of oscillation was highest in penetrating mode. Measurements of splashing over a range of conditions showed splashing greatly reduced when cavities went from splashing to penetrating mode. The results were validated and compared with plant data and previous model investigations.

Jan 1, 2014

By Biswadeep Saha, Meenakshisundaram Ramanathan, Chai Ren, Sivaraman Guruswamy

"Fe-Ga alloys have a large low-field magnetostriction and these alloys are attractive candidates in energy conversion and harvesting applications. Small additions of W also increase the magnetostriction of Fe. In this paper changes in magnetostriction by W substitution for Ga in various Fe-x at.% Ga alloys are presented. Fe-Ga-W single crystals were grown using vertical Bridgman Growth technique. [001]-orientated single crystal samples were prepared with faces within 1 degree off <100> orientation. The samples were annealed at 1150 °C in the alpha-phase region and water quenched. The magnetostriction coefficient (3/2)A-100 measurements were made on these Fe-Ga-W single crystals. The result on the effects of W substitution and annealing on the magnetostrictive behavior of these alloys are discussed.*Support of this work by NSF-DMR under the award DMR-0854166 is gratefully acknowledged.IntroductionMagnetostrictive materials changes their dimension exhibit reversible strains and changes in elastic properties in the presence of an applied magnetic field or the reciprocal effect of changes in the magnetic properties with the application of stress [IJ and are very important in sensor, actuator device, linear motor, magnetomechanical devices, microelectro- mechanical devices, active vibration dampening devices application areas. The discovery of an order of magnitude enhancement in the magnetostriction of Fe with Ga addition coupled with low saturation magnetic fields, and excellent mechanical properties opened up the possibility of obtaining larger magnetostriction values in other low-cost ductile a-Fe phase based alloys with alloying additives that are less expensive than rareearths such as Tb and Dy [2·4l_ The magnetostriction values observed in Fe-Ga single crystals are sensitive to thermal history and composition. The formation of second short range ordering phases and local defects inside crystal structure can also cause a dramatic change to this alloy's magnetostriction behavior [5-9l_"

Jan 1, 2012

By Paul M. Jr. Musgrove, Donald C. Moore

Conventional Smelting Practice Conventional copper smelting practice varies from smelter to smel¬ter, but generally consists of some or all of the following unit processes: roasting, smelting, converting, and fire refining. Roasting. Copper sulfide concentrates can be smelted directly or after an initial roasting step. Roasting is used in some smelters because roasting prior to smelting increases smelting capacity, less energy is required to melt hot roaster calcines than wet sulfide concen¬trates, roaster off gases are high in Sot concentration, 5-15% SO2, and some volatile impurities are removed from the concentrate prior to smelting. However, many smelters do not use roasters, because the problems associated with handling hot dry calcines outweigh the advantages mentioned. Concentrate roasting is performed in multiple hearth or fluid bed roasters. If the moisture is low, roasting can be performed autogenously, usually at 500-600°C. High roasting temperatures are avoided because excess oxidation of the iron compounds may lead to magnetite formation. Magnetite is detrimental to reverb operation because mag¬netite can combine with refractory minerals to form a highly viscous slag. This slag prohibits efficient matte-slag separation and leads to excessive copper losses. Also, magnetite can settle through the matte layer, deposit on the furnace bottom, and consequently reduce furnace capacity. Roasting is carried out only on sulfide concentrates prior to smelt¬ing in reverb or electric furnaces. For smelting processes, such as the flash and continuous that rely on the exothermic heat of oxidation of the sulfur minerals, roasting is not practiced. Reverberatory Smelting. The predominate copper smelting fur¬nace for the past 50 years has been the reverb. These furnaces are typically 100-120 ft long, 30-35 ft wide, and 12-15 ft high. A typical furnace layout is shown in Fig. 2. Refractory brick linings cover all internal surfaces of the furnace. Originally the flame was directed to reverberate or reflect off the furnace ceiling and melt the feed material. Current practice is to direct the flame down the furnace length to melt the concentrate. A method of charging the concentrates or calcines, generally along the side walls to minimize refractory erosion, is incorporated in the furnace design. The copper concentrates, calcines, and fluxes charged into the reverb undergo a series of complicated reactions as the temperature of the mixture increases. The reaction of the iron and copper sulfides with the oxygen in the furnace produces a molten Cu25-FeS mixture called matte. Copper smelting metallurgy is based on the fact that sulfur has a greater affinity for copper than for iron and most other common metals. Therefore, in a system containing copper, the copper will preferentially remain as a sulfide compound until all of the other metals have been oxidized. The oxidized metals combine with silica to form a silicate slag that floats on the matte and is removed from the system. Reverberatory furnace smelting chemistry can be approximated by the following chemical equations: FeS2 + O2 - FeS+ SO2 (1) The formation of FeS ensures that any copper present other than as sulfides will be reduced by the relationship: CuO2 + 2FeS + O2 - CuS + 2FeO+SO2 (2) or 2Cu +FeS - Cu2S + Fe (3) As the molten charge travels down the furnace, continued oxida¬tion of the iron minerals and sulfurization of the copper minerals occurs. When all of the copper has been converted to sulfides, the iron sulfides can then be further oxidized as: FeS + (3)2 O2 FeO + SiO2 (4) The FeO reacts with the silica added as flux in the furnace charge. A simplified equation is: FeO + SiO2 -FeO SiO2 (5) The iron silicate slag formed is skimmed from the surface at the end opposite the burners. The copper content of reverb slag is usually less than 0.6% Cu and is discarded. Matte is removed along the side wall and is taken to the converter for oxidation of the remaining sulfur and iron. The main objectives in reverberatory smelting are to produce a molten Cu2S-FeS matte containing 30-60% Cu and a throwaway slag. Production of matte permits complete conversion of all copper minerals into copper sulfides, which can migrate because of specific gravity differences, through the lighter slag layer. Also, the molten matte droplets collect the noble metals, gold and silver, as the matte settles in the furnace. The large settling area of the furnace provides enough separation time to produce a low grade slag, which can be discarded without further processing. High heat losses are associated with reverberatory smelting be¬cause of the large volume of gases sweeping through the furnace. Therefore, an outside source of heat is required to keep the smelting reaction going. Natural gas, fuel oil, or pulverized coal are used as this heat source.

Jan 1, 1985

By H. C. Brown

SINCE 1934 the steel industry has been utilizing the spectrograph for supplementing wet chemical analysis in the production control of electric and open hearth furnaces. This means of control made great strides during the war years because of the general acceptance of the spectrograph and the increased emphasis that was placed on rapid control methods. However, in the post war era, with the demand still on increased production, it became apparent that a still more rapid and economical means of production control was needed. Since the spectrograph had been used mostly in the analysis of low alloying and residual elements, it also became apparent that equipment was needed to extend the spectrographic technique to the analysis of the high alloying elements in stainless steel. For these reasons, companies manufacturing spectrographic equipment were prompted to start development work on direct reading instruments. In June 1949, the Applied Research Laboratories of Glendale, Calif., announced that a direct method of spectrochemical analysis for stainless type steels had been developed. This paper will describe the use of the Applied Research Laboratories Production Control Quantometer in the quantitative control of stainless, silicon, and plain carbon steels being made at the Butler Pennsylvania Div. of the Armco Steel Corp. The Armco Butler Div. has one 70-ton electric furnace and six 150-ton open hearth furnaces. The electric furnace is employed in the making of all types of stainless steel and the open hearth furnaces are used for the production of silicon, wheel, and plain carbon steels. The ARL quantometer was purchased primarily for the purpose of controlling the steelmaking in the electric furnace, but its use has been extended for the analysis of final tests (ladle tests) on a number of different types of stainless, silicon, and plain carbon steels. Because of this additional work by the quantometer, substantial savings in manpower and time have been realized by the laboratory. In the analysis of a set of preliminary tests from the stainless steel furnace, approximately 40 min in laboratory time are saved due to quantometric analyses. Despite the fact that more specialty grades of stainless steel are being made in the electric furnace, the average tons per hour have been increased since the quantometer was put into operation. Specialty grades require more furnace time than regular commodity grades of stainless steel. The installation of the ARL production control quantometer was completed on March 13, 1952. By May 1, 1952, the instrument was calibrated for nickel, chromium, manganese, silicon, and molybdenum, which are the elements necessary for the production control of the stainless steel furnace. Within the following month, training of personnel on the quantometer was achieved and a study of the accuracy of the instrument showed that the results obtained were sufficiently accurate for control purposes. Therefore, on June 11, 1952, the quantometer was placed on production control for all types of stainless steels. Starting September 11, 1952, the instrument was gradually placed on ladle analysis (final tests) as the analytical curves were refined and additional curves were drawn. The quantometer has been relatively free of breakdowns since placing it on production control. The samples from only one stainless steel heat have had to be analyzed by wet chemistry because of instrument trouble. The previously existing heat-time record was also bettered by 15 min on a commodity grade of 18-8 stainless steel. Scope of Control In general, the quantometer determines all elements necessary for the production control of all types of stainless steel heats and for the ladle analysis of various types of stainless steel heats. It is also used in reporting final results for silicon, manganese, chromium, nickel, molybdenum, tin, copper, and aluminum on all silicon steel grades and manganese, chromium, nickel, molybdenum, tin, and copper on several plain carbon steel grades. Table I shows the elements and the concentration ranges of these elements in the various types of stainless, silicon, and plain carbon steel that are determined on the quantometer. A study of the results obtained on ladle test samples of stainless steel types 410, 430, 430 Ti, 446, 301, 302, 304, 304L, 305, and 17-7 PH will be discussed. Also included in the study are the results obtained on ladle test samples of a number of silicon steels. Apparatus In order to take full advantage of the potentials of the production control quantometer, the unit has been placed in an air-conditioned room with relative humidity control. The temperature is maintained at 73&apos;22°F and the humidity at 45&5 pct. The air conditioning serves as a precaution to minimize the amount of adjustment and calibration needed during operation. It also reduces contaminating fumes and dust and thereby lessens the necessity for maintenance on the equipment. The quantometer is composed of three units: the high precision multisource unit, the 1.5 meter vertical spectrometer, and the console. The source unit supplies excitation conditions varying from spark-like discharges to arc-like discharges. The voltage to the source unit is supplied by a motor-generator

Jan 1, 1955

By George S. Ansell, John B. Hudson, Stephen A. Koffler

The permeability of hydrogen through the a phase of palladium has been measured by a low pressure permeation technique under conditions such that bulk diffusion was the rate-controlling process. The observed permeability is described by the equation: J = 1.80 x 1O-3 P½exp(-3745)/RT) cc(stp)/sec/cm2/en over a range of hydrogen pressure, P, from 2.9 x 10-5 m Hg to 5.0 x 10-3 cm Hg, and over a temperature range, T, from 300" to 709°K. The fact that the permeability shows a square root dependence on pressure and a reciprocal dependence on thickness was taken as evidence that bulk diffusion, rather than surface reactions, was the rate-controlling process. The permeability data were used in conjunction with the solubility data of Salmon et al., to determine the diffusivity of hydrogen through palludium as: D = 4.94 x 10-3 exp(-5745/RT) cm2/sec There was no influence of sub structural defects observed over the temperature range employed. From the permeability data obtained, coupled with grain size measurements, it was concluded that the ratio of grain boundary diffusivity to bulk diffusivity was less than 105 over the range of temperature investigated. THE diffusive mass transport of hydrogen in the a phase of palladium has been studied previously by numerous investigators.&apos; In spite of the large amount of attention this system has received, there is not good agreement between the results obtained in different investigations.&apos; This is due in part to the fact that the mass transport was surface-limited during some of these studies, rather than being diffusion-controlled3-5 The reason for the disagreement in other cases is not clear. These studies made use of such techniques as rate of absorption from solutions6 and gases,&apos; electrochemical potential,8 time lag,&apos; and permeation10,11 to determine the mass transport behavior. Of these, the gas permeability technique is the only method which allows an easy test to determine if diffusion is the rate-controlling mechanism, thus eliminating the uncertainty regarding the limiting transport processes inherent in the other techniques. The two most recent permeability studies are those of Toda10 and Davis." Toda determined the permeability of hydrogen in the a phase of palladium over the temperature range from 170" to 290°C, and over the pressure range from 36 to 630 mm Hg utilizing a steady-state gas-permeability technique. Toda&apos;s result was: J = 1.41 x 10-3 P½ exp(-3220/RT) where J = specific permeability in cc(stp)/sec/cm2/cm, P½ = square root of the inlet pressure in (cm Hg)½, R = Universal gas constant, and T = temperature in deg Kelvin. Davis11 also employed a steady-state gas-permeability technique over the temperature range from 200" to 700°C and over the pressure range from 0.02 to 760 mm Hg. His result for the permeability of hydrogen in the a phase of palladium was: J = 3.15 x 10-3 P½ exp(-A440/RT) In the range of overlapping temperature for these two investigations, the values of the specific permeability calculated from the above two equations differ by a factor of about 1.8. In the present investigation, the permeation of hydrogen in the a phase of palladium was determined over a wide temperature range, 27" to 436oC, and over the pressure range from 2.9 x 10-5 to 5.0 x 10-3 cm Hg. This temperature range overlaps that of the previous investigations of Toda and Davis, but also covers the lower temperature range which has never before been investigated. The lower pressure range used here avoided the interaction between the dissolved hydrogen atoms observed at higher hydrogen concentrations.&apos; MATERIALS The as-received palladium specimens were cold rolled from a casting and were supplied as 5.08 cm discs of 0.508 and 0.762 mm thickness. According to J. Bishop and Company specifications, the composition of the discs was 99.95 pct Pd, the balance being Cu, Ag, Au, and Ir. In order to obtain samples of varying grain size, the as-received discs were then heat treated. Sample 1 was treated for eight minutes in a nitrogen atmosphere at 810°C and then air-cooled. Sample D was heated first to 550°C in helium. The helium atmosphere was then immediately replaced by hydrogen and the temperature was slowly raised to 1220°C and held for 22 hr. The sample was then cooled to 550°C where the hydrogen was replaced by helium and the disc was further furnace-cooled to room temperature. Sample H was given the same heat treatment, only with hydrogen substituted for helium below 550°C. The reason that hydrogen was not used throughout the entire annealing cycle for samples D and H was to prevent the distortion encountered by low-temperature cycling in hydrogen observed by Darling." After these heat treatments were completed, the

Jan 1, 1970

By J. Alfred Berger, O. M. Katz

Selected samples of hydrided Zr-Hf alloys were rapidly quenched to voom temperature and exrtrnined metallographically, by X-ray diffraction, and through micro hardness studies to confirm high-temperutuve data Confirming experiments sllowed that there were five phases in this Lernary system: 1) hextrgonal with lattice parameters similar to that of the initia1 Zr-Hf alloy but slightly enlarged due to dissolved hydrogen; 2) fee with properties of a brittle, intermediate, hydride compound; 3) fct with c/a crvoltnd 1.07 and which appeared as a neetilelike precipitale; 4) hexagonal, designated ?, with c/a ratio of 2.37; and 5) orthorhombic, designated X, with a = 4.67, b = 4.49, and c = 5.093 and whose tnicro-st?ruct~ival nppetrl-nnce depcncled o/i, heat lvecrt~r~ent. The tetragonrrl phase never crppeal-erl witkorct the cubic hydricle. Abpecrrtrnce of 0 and A also tlependet on the hafnium content of the zirconium. A previous paper&apos; on the Zr-Hf-H system described the thermochemical data obtained with a high-vacuum, high-sensitivity mirrogravimetric apparatus. This data presented a fairly complete picture of the phase relationships at elevated temperatures. However, it could not establish the actual crystal structures, lattice parameters, or metallographic disposition of the hydride phases. The present complementary study utilizes X-ray powder patterns along with light and electron microscopy to characterize completely the five hydrided phases found in Zr-Hf-H alloys quenched to room temperature. Crystallographic features of the zr-Hf,2,4 zr-H,5-7 and Hf-H8 systems have been summarized in Table I. Designations of a, ß, and ? were retained in the Zr-Hf-H system for the phase regions through which the pressure-composition isotherms always sloped. However, it was not firmly agreed that these were single-phase regions.&apos; In fact, the region designated y always contained a cubic as well as a tetragonal phase after quenching to -196°C. MATERIALS Preparation of the high-purity Zr-Hf alloys has been described.&apos; The four zirconium alloys which were hydrided contained 37 wt pct Hf (23 at. pct), 51 wt pct Hf (37 at. pct), 73 wt pct Hf (58 at. pct), and 91 wt pct Hf (82 at. pct), respectively. These were designated B-2, B-4, B-6, and B-8. Photomicrographs of the initial alloys showed the material to be quite clean as would be expected from the precautions exercised in producing them. However, there were a number of annealing twins but no other subgrain structure. In addition to the four original alloys, fifteen hydrided samples were observed at room temperature. Hydrogen compositions are given at the top of Tables I1 to V. APPARATUS The phases present at elevated temperatures were studied by quenching hydrided samples to room temperature by two different methods, both under vacuum: 1) fast cooling of the sample tubes of the microgravimetric apparatus1&apos;9 with flowing air and 2) rapid quenching into liquid nitrogen. The cooling rate for 1) was 750° to 250°C in 30 sec. Since the microbalance chamber was not designed to permit very rapid cooling of a hydride sample, all liquid-nitrogen quenching was done in an auxiliary experiment. The auxiliary quenching apparatus consisted of a small-bore, high-temperature furnace, a sealed SiO2 tube containing the sample, and a dewar quenching flask filled with liquid nitrogen. The hydrided sample, previously quenched in the microgravimetric reaction chamber, was placed in a platinum boat in a vacuum-degassed SiO2 tube. A zirconium wire getter and degassed SiO2 rod, to reduce the internal volume, were also in the tube. After sealing the tube under vacuum the zirconium getter was heated to absorb the last traces of gas. Only the sample was heated at the reaction temperature for the desired length of time, and then the tube dropped through the opposite end of the furnace into the dewar. A quenching rate of 200" to 400° C per sec was estimated. Analyses of samples after the auxiliary experiment also showed practically no increase in oxygen or nitrogen content from heating in the SiO2 tube. All of the samples were examined at room temperature by the X-ray powder method. The majority of the powder patterns were obtained with double nickel-filtered CuKa radiation after 8- and 16-hr exposures in an 11.48-cm-diam camera. Cobalt and chromium radiation were also used to spread out the high d value end of the Pattern. Such patterns readily identified the minor phases. NO oxide or nitride lines were found. Where sharp back-reflection lines existed it was possible to reduce the

Jan 1, 1965

By A. J. Lena, M. F. Hawkes

Changes in hardness, tensile properties, microstructure, electrical resistance, and X-ray diffraction effects indicate that lattice strains are necessary for the embrittlement of ferritic stainless steels when heated for relatively short times at 475°C (885°F). It is suggested that 475°C (885°F) embrittlement is due to the accelerated formation of an intermediate stage in the formation of s under the influence of these strains. FERRITIC stainless steels (low carbon alloys of iron with more than 15 pct Cr) are subject to two forms of embrittlement when heated in the temperature range of 375° to 750°C. The embrittlement which occurs after long time heating between 565" and 750°C is well understood; it is caused by the precipitation of the hard, brittle s phase. Sigma is an intermetallic compound of approximate equi-atomic composition with an extended range of formation in Fe-Cr alloys. The maximum temperature at which this form of embrittlement can occur is dependent upon chromium content; and is approximately 620°C for a 17 pct Cr steel and 730°C for a 27 pct Cr steel. The other form of embrittlement occurs after relatively short heating periods in the range of 375" to 565°C; in the higher chromium steels, hours may be sufficient as compared to months for s embrittlement. This phenomenon is not at all well understood and several controversial theories have been proposed. The rate and intensity of embrittlement increase with increasing chromium content but the maximum rate occurs at 475°C re-gardless of chromium content. As a result of this, the phenomenon has been termed 475°C (885°F) embrittlement. The effect of 475°C embrittlement on the properties of ferritic stainless steels has been thoroughly reviewed by Heger.1 The embrittlement causes a pronounced decrease in room temperature impact strength and ductility, a large increase in hardness and tensile strength, and a decrease in electrical resistivity and corrosion resistance. Microstructural changes accompanying embrittlement are minor and difficult to interpret with a general grain darkening, appearance of a lamellar precipitate, grain boundary widening, and precipitation along ferrite veins having been reported at various times. With the exception of reported line broadening, X-ray diffraction studies by conventional Debye analysis of solid samples have been of little value. BY making use of electron diffraction methods, Fisher, Dulis, and Car-roll&apos; have recently shown the existence of a chromi-um-rich, body-centered cubic phase in 27 pct Cr steels which had been aged at 482°C (900°F) for as long as four years. Two types of theories have been advanced to account for the embrittlement. The first of these requires the precipitation of a phase not inherent in the Fe-Cr system with various investigators suggesting a carbide,3 nitride,3 phosphide,4 or oxide." Theories of this type have difficulty accounting for the influence of alloying elements on the embrittlement and for the facts that a minimum chromium content is necessary for embrittlement and the intensity of embrittlement increases with increasing chromium content. The second type of theory that has been proposed relates 475°C embrittlement to s phase formation which is inherent in the Fe-Cr system. An assumption of this kind can adequately explain the influence of alloying elements, for they exert an effect on 475°C embrittlement similar to that on s phase for-mation as can be seen in Table I. The minimum chromium content is essentially the same for both phenomena and it has been shown12,13 that s is a stable phase in the embrittling temperature range. In addition, it has been reported14,15 that pure alloys embrittle to the same extent as commercial type alloys. There are, however, several factors which have prevented complete acceptance of a s phase theory. Foremost of these is that the embrittlement can be removed by reheating for short time periods above 600°C, which in the higher chromium steels is within the stable s region. No s has ever been observed after one of these curing treatments, nor has any s been found as a result of embrittlement at 475°C. In addition, the simple precipitation of s cannot explain the time-temperature relationships for reactions between 350°and 750°C. This behavior is shown schematically in Fig. 1. Newell 16 and Ried-rich and Loib4 have shown that 475°C embrittlement follows a C-type curve as illustrated, while Short-

Jan 1, 1955

By W. J. Maraman, D. R. Harbur, J. W. Anderson

A device for rapidly quenching liquid metals into thin platelets has been developed at the Los Alamos Scientific Laboratory. This rapid quenching equipment is built around the technique of catching a molten drop of metal between a rapidly closing plate and a stationary plate. The design and operation of this unit are described. The closing speed of the smasher plate at impact is 12.6 ft per sec. The quenching rate for this device is controlled by the interface resistance between the plates and the platelet, and is dependent upon the heat content and density of the material being quenched. The initial quenching rate down to the freezing point of the platelet material is lo5º to 106ºC per sec. After an isothermal delay, which is poportional to the heat of fusion of the platelet material, the final cooling rate down to the temperature of the smaslier plates is l04ºto 105cº per sec. RAPID heating of metals by capacitor discharge and other methods has provided the metallurgist with a useful tool for probing into the kinetics of phase changes and the many nonequilibrium phenomena which occur during rapid temperature changes. Equally interesting studies can also be made on metals and alloys which are rapidly cooled from the liquid state.&apos; Studies in this field have been limited, however, because the rates at which metals could be cooled were many orders of magnitude slower than the rates possible for heating. In recent years many new laboratory methods have been developed to rapidly cool metals from the liquid state to ambient temperature and below.2"4 All of these methods involve spreading a liquid drop of metal into a thin foil in a very short time. The methods developed have varied from ejecting a drop of molten metal at the inside surface of a rotating cylinder or stationary curved plate to catching a falling drop of molten metal between rapidly closing plates. The equipment which has been developed at the Los Alamos Scientific Laboratory for rapidly cooling molten materials uses the latter of these two approaches. The basic design, operation, and initial results of this rapid quenching device are given in this report. APPARATUS The drop smasher, which is now being used to obtain rapidly cooled metal foils, is shown in Fig. 1. Basically the device consists of a smasher plate which is driven by a solenoid into a stationary plate. The solenoid is activated by a drop passing through the photoelectric cell and is powered by discharging an adjustable 350-v capacitor bank with a 66-amp peak current into it. This power supply is designed so that the solenoid is powered for 2 m-sec after plate closure to minimize the rebound effect. There is an adjustable time-delay mechanism between the photoelectric cell and the solenoid. Both smasher plates have changeable inserts so that a variety of materials can be used to smash the molten drop. The shaft of the moving plate is guided in an adjustable housing which has ball-bearing walls. The cabinet shown to the left of the drop smasher in Fig. 1 contains the power supply and receiver for the photoelectric cell, the time delay mechanism, and the capacitor bank. The drop smasher can be placed inside a vacuum chamber, for use with radioactive materials, with the upper plate forming the lid, as shown in Fig. 2. On top of the vacuum lid is an induction coil, powered by an Ajax induction generator, which is used to melt drops from the end of the rod extending through the vacuum seal on top the quartz tube. OPERATION The drop smasher shown in Fig. 2 is operated in the following manner. The smasher plates are separated and the unit is lowered into the vacuum chamber using a pressurized cylinder. The induction coil, quartz tube, and lid with sliding vacuum seal are then assembled on top the vacuum chamber. A rod of the material for rapid quenching studies is connected to the rod extending through the sliding vacuum seal. The vacuum chamber is then evacuated and the desired atmosphere established. The photoelectric cell is turned on, and the capacitor bank is charged and armed. Power is supplied to the induction coil, and the rod of material for rapid quenching studies is lowered into the induction field. A molten drop forms on the end of the rod, drops off, falls through the light beam of the photoelectric cell, and is then caught between the smasher plates. .

Jan 1, 1970

By W. F. Chiao

Ultrasonic attenuation, a, measurements in the frequency range of 5 to 55 mc per sec have been studied to determine their quantitative relationship with the following three variables of mixed microstructures in steels: 1) the volume percent, XF, of polygonal fer-rite in mixed structures of martensite and polygonal ferrite in Fe-Mo-B alloys: 2) volume percent, XA, of retained austenite plus martensite aggregates in high-carbon steel; and 3) substructural differences between 100 pct bainitic ferrite structures formed at various temperatures. The quantitative relationship obtained in the first two conditions by plotting a us the known structural parameters can be expressed, respectively, as: where al, a 2 and C1, Cz are constants. In the third condition the nature of the attenuation depends on the state of dislocations generated at the transformation temperatures and also on the alloy composition. From these measured results, the mechanism of ultrasonic attenuation caused by these mixed microstructures can also be studied. MUCH interest has recently been shown in the application of ultrasonic attenuation and wave velocity measurements to the study of the microstructural characteristics of steels. The general aims of most of the investigations in this field can be grouped into two categories: one is to study the mechanisms of ultrasonic losses caused by the characteristic phases in the microstructure of steel,&apos;&apos;&apos; and the other is to develop nondestructive test methods and applications for quality control.~&apos; 4 Apparently no work has been done on the evaluation of ultrasonic attenuation meas -urements as a means of quantitative determination of a given phase in the microstructure of a steel. It is well-established that the decomposition of austenite results in four main microstructural constituents—polygonal ferrite, pearlite, bainite, and martensite—and that each phase has different mechanical properties. Thus, when a steel consists of mixed microstructures, the mechanical properties can often be related to a quantitative measure of the volume percent of each phase present. This study relates ultrasonic attenuation measurements to: 1) the volume percent of polygonal ferrite in mixtures of martensite and polygonal ferrite in Fe-Mo-B alloys; 2) the substructural differences between 100 pct bainitic ferrite structures formed at various temperatures; and 3) the vol- ume percent of austenite in austenite plus martensite aggregates in a high-carbon steel. The choice of the specimen materials was based on the laboratory stocks which were suitable to produce the required mixed microstructures for this study. EXPERIMENTAL PROCEDURES Materials and Heat Treatment. Polygonal Ferrite Plus Martensite Structures. This mixture of phases was produced in a vacuum-melted Fe-Mo-B alloy. The alloy was hammer-forged at 1900" ~ to a -f-in.-sq bar. By isothermally heat treating the alloy at 1300° F for various times and then water quenching, variations in the amount of polygonal (or proeutectoid) ferrite can be controlled in a microstructure in which the balance of the material is martensite. In the present work, four different times of isothermal transformation were adopted; after heat treatment, the four specimens were machined for ultrasonic measurements. The compositions, heat treatments, and dimensions of the four specimens are listed in Table I. 100 pct Bainite Structures Formed at Different Temperatures. It has been well-established by Irvine et al.= that the presence of molybdenum and boron in ferrous alloys can retard the formation of polygonal proeutectoid ferrite and expose the bainitic transformation bay, so that a more acicular or bainitic ferrite can be obtained over a wide range of cooling rates. Their investigation6 also showed that the mechanical properties of fully bainitic steels are usually closely dependent on the substructural characteristics of the steels. For studying the substructural characteristics in completely bainitic structures, six Fe-Ni-Mo alloys, of which five were free from carbon addition and one with 0.055 pct C addition, were selected so that a wide range of hardness values for 100 pct bainitic ferrite structures could be produced by normalizing at 1900" F followed by air cooling. The different bainitic transformation temperatures were recorded during air cooling. All of the alloys were vacuum-melted and then forged at 1900" F to square bars. Data on the six specimens of these structure series are summarized in Table 11. Austenite Plus Martensite Structures. The high-carbon steel used to study austenite plus martensite structures was vacuum-melted and then forged into Q-in.-sq bar. The series of mixed structures of austenite plus martensite was produced by quenching the specimens from the austenitizing temperature to room temperature and then refrigerating them at various temperatures within the range of martensite transformation to produce different amounts of retained austenite. Data on the four specimens of this series are listed in Table 111. Quantitative Analysis of the Microstructures. The microstructures containing martensite plus polygonal ferrite were analyzed by the point-counting technique.

Jan 1, 1969

By Christopher M. St. John, Michael P. Hardy

INTRODUCTION Geotechnical models, particularly those based on the finite element method, have been available to aid in en¬gineering design of underground mining excavations for over ten years. Despite this fact there are remarkably few cases of their use in mine design documented in the literature. It is therefore to be anticipated that many potential users of these models are relatively unaware of their capabilities and limitations and also of the form and detail of geotechnical data needed for their success¬ful application. This subsection attempts to address this problem by discussing the different types of numerical models now available and by noting how some of them have been used to study a variety of problems associated with underground mining. The subsection concludes by discussing the applica¬tion of the displacement discontinuity method to the de¬sign of possible mining systems for the copper-nickel deposits of northeastern Minnesota. The object of the analyses, which were nonsite specific, was to determine the significance of geotechnical parameters, such as ini¬tial stress and rock structure, on the stability of under¬ground excavations and hence to provide guidance for future geotechnical investigation. NUMERICAL MODELS In the geomechanical design of underground mining openings, use is made of numerical models that repre¬sent or simulate the large-scale mechanical behavior of rock. There has been less interest in analysis involving fluid flow and heat transfer, but with increasing interest in such areas as in-situ retorting and solution mining it is likely that there will be a growing need for numerical models embracing and coupling all three physical proc¬esses. However, the emphasis in this subsection will be on mechanical behavior. Models which simulate such behavior will be divided into two groups: continuum models and discontinuum models. These will be dis¬cussed in turn in order that some insight into alternative solution strategies and their merits may be gained. Continuum Models Almost all geomechanical numerical models must be classed as continuum models even though particular computer codes incorporate special provisions for rep¬resenting discontinuities such as faults, bedding planes, or joints. They are continuum models because they pro¬vide solutions for cases where material behavior is governed by the differential equations of continuum mechanics. Two basic solution strategies for such equa¬tions may be identified immediately: the differential ap¬proach and the integral approach. In the differential approach a means of approximating the differential equations over the entire region of interest is sought. In the integral approach use is made of fundamental solutions from continuum mechanics, and these are used to construct a solution to the whole problem, making approximations only on the boundaries of the region of interest. The several differential and integral methods are identified in Table 1. Differential Methods: Problems in continuum me¬chanics involve the solution of three types of partial differential equations. Two of these govern the behavior in so-called initial value problems, in which variables change both in time and in space. Examples of such problems include nonsteady heat transfer and fluid flow, and stress wave propagation. The last type of partial differential equation governs the behavior in boundary value problems. In these, variation is in space but not in time. Solution of initial value problems may be achieved in two significantly different methods: implicit and ex¬plicit. The differences between these two methods will be illustrated by considering a very simple initial value problem, that of one-dimensional heat diffusion. The equation governing this process may be written as: [ ] where T is temperature, K is thermal conductivity, p is density, c is specific heat, t is time, and x is the spacial coordinate. In finite difference form this equation might be written as: [ ] where the superscripts refer to the time and the sub¬scripts to the spacial location. Several solution strategies for this equation have been used. Two important ones may be illustrated very simply by discussing the signifi¬cance of the superscript * on the right-hand side of the equation. If i + 1 is substituted for * then the second derivative of the temperature with respect to distance is evaluated at the end of the next time step (using tem¬peratures not already known). Such an approach leads to a set of equations involving unknown temperatures and a solution procedure which is referred to as being implicit. The important characteristic of the implicit procedure is that it leads to a set of equations that must be solved for each time at which the temperature dis¬tribution is required. If instead of substituting (i + 1) for the superscript *, i is substituted, the following equation is obtained: [ ] {In this case the new temperature is defined in terms of an already known temperature distribution. The solution procedure is now known as explicit and has the impor¬tant characteristic that there are no equations that have to be stored or solved. A practical advantage of this

Jan 1, 1982

By M. J. Spendlove, H. W. St. Clair

The problem frequently arises, particularly in refining metals or smelting scrap metals, of separating metals in the metallie state. Many metals may be separated by taking advantage of their difference in vapor pressure. Such separations can be made at atmospheric pressure, but the separations are much more selective and can be carried out at considerably lower temperatures if the distillation is done at pressures of a few millimeters or less in an evacuated enclosure. Until recently, this has not been considered feasible as a metallurgical operation, but the recent improvemcnts that have been made in vacuum technology have broadened the applicability of vacuum processes and have prompted re-examination of low-pressurc distillation of metals as a practicable process. The distillation of zinc from lead is one separation that has already been reduced to practice.l This paper is the first of a series of studies being made on separation of nonferrous metals by distillation at low pressures. Although these experiments were confined to the separation of zinc from aluminum, the significance of the results is by no means confined to these two metals. The purpose has been to investigate a metallurgical technique rather than merely to devise a means of separating specific metals. The experimental work on distillation of zinc from zine-aluminum alloys at reduced pressure grew out of earlier work on distillation at atmospheric pressure.2 The earlier work indicated that it would not be practicable to decrease the zinc in the alloy much below 10 pct owing to the high temperature required. Therefore attention was turned to distillation ah low pressures, at which lower temperatures are required. After preliminary tests were made in a small, evacuated tube furnace, a larger furnace having a capacity of 100 to 150 Ib of metal per charge was constructed. Distillation tests were first made on pure zinc and then on aluminum-zinc alloys of various composition. Particular attention was given to the limit to which zinc could be reduced in the residual metal. Data were also taken on the rate of evaporation, and heat balances were made for both the crucible and the condenser. Distillation Furnace The vacuum-distillation unit is illustrated schematically in Fig 1. The major components are the induction furnace, the condenser, the vacuum system, and the power-conversion unit. Power is supplied to the induction furnace from a 50-kw 3000-cycle motor-driven alternator. The pressure in the furnace is reduced by a vacuum pump having a nominal pumping speed of 10 liters per sec. When in operation, the metal vapors travel upward from the furnace to the water-cooled condenser where they are collected in amounts of 50 to 100 lb. The condenser is removed with aid of an electric hoist. When the system is under vacuum, the condenser is made self-sealing by a rubber gasket between the smooth-faced, water-cooled flanges at the top of the furnace and the bottom of the condenser. The pressure of the atmosphere is more than sufficient to insure sealing. At the conclusion of an experiment, the residual metal can be removed from the furnace by removing the condenser and tilting the furnace with the electric hoist. The metal was cast into the molds carried on a mold truck. A photograph of the furnace and auxiliary equipment is shown in Fig 2. The details of the vacuum furnace are illustrated in Fig 3. The furnace proper is made vacuum-tight with rubber gaskets placed at each end of a fused quartz cylinder. A clamping plate at the bottom and a ring at the top are made to squeeze the rubber between the metal and the end of the quartz tube. A large graphite crucible placed inside the quartz cylinder is thermally insulated and physically supported by refractory insulating bricks. A thermocouple in a quartz protection tube is located at the bottom of the crucible: the leads pass through a rubber seal in the bottom plate. The supporting structure for the furnace is an angle iron frame with transite board sides. The condenser is made in the form of a water jacketed cylinder with an opening to the vacuum line at the top. The bottom has a projecting skirt inside the machined flange to provide additional cooling for the rubber gasket. Condenser sleeves are made in the form of two semicylindrical pieces of sheet metal that fit snugly inside the cooling jacket. The split sleeve facilitates removal of the condensate. Measurement of Temperatare and Pressure The metal temperature was measured by a platinum-platinilm rhodium thermocouple inserted in a well extending up into the bottom of the graphite crucible. During rapid evaporation there is a wide difference in temperature between the surface and the main body of metal in the crucible because of the large amount of heat that must be conducted to the surface to supply the heat of evaporation. The heat of

Jan 1, 1950

By Yves Fouquet

Recent exploration demonstrates that hydrothermal systems related to upper mantle ultramafic outcrops are common in the modern ocean. Most sites are located on slow spreading ridges with a low magmatic budget. Volcanogenic Massive Sulfide (VMS) deposits, associated with basalt, along the Mid Atlantic Ridge (MAR) are volcanically controlled near the topographic highs at the center of the segments. Three preferential settings are identified for ultramafic sulfide mineralization: 1) Off axis, on rift valley walls, near the amagmatic ends of the segments; 2) Non-transform offsets and 3) Ultramafic dome structures at the ridge transform fault intersection. The upper surface of these domes is often interpreted as a detachment fault. Three processes are considered for driving hydrothermal cells in ultramafic rocks: 1) regional heat flow at the ridge axis 2) Cooling of a deep gabbroic intrusion and 3) exothermic heat produced during serpentinisation. Along the Mid Atlantic Ridge, four types of ultramafic hydrothermal mineralization are observed: 1) High temperature (>350°C) sulfide mineralization related to low pH fluids, (ex. The Logachev field at 14°45? N and the Rainbow field at 36°14 N); 2) Medium temperature carbonate chimneys (<100°C) related to high pH fluids (ex. The Lost City site at 30°N); 3) Low temperature diffuse venting associated with extremely high methane discharge and pervasive alteration and silicification of both volcanic and ultramafic rocks (ex : The Saldanha field at 36°34 N); 4) Stockwork mineralization and quartz veins with sulfides related to gabbroic intrusions within ultramafic rocks (15°N). When compared to mineralization in a basaltic environment, sulfide deposits are enriched in copper, zinc and specific elements related to an ultramafic rock source such as Ni and Co. They are also significantly enriched in gold which, unlike in basaltic environments, has a bimodal occurrence both in low temperature Zn-rich assemblages and in high temperature Cu-rich mineral assemblages. The Cu-Zn-Co-Au deposits along the Mid Atlantic Ridge seem to be more common than on land where few similar VMS deposits are known. We consider that ultramafic VMS deposits on slow spreading ridges constitute a specific marine type of mineralization that is less easily than back arc deposits, incorporated into the continent during obduction processes.

Jan 1, 2004

By Charles E. Lundin

The character of the Er-D system was established by determining pressure-temperature-composition relationships. A Sieuerts&apos; apparatus was employed to make measurements in the temperature range, 473" to 1223"K, the composition range of erbium to ErD3, and the pressure range of 10~s to 760 Torr. The system is characterized by three homogeneous phase regions: the nzetal-rich, the dideuteride, and the trideuteride phases. These phases and their solubility boundaries were deduced from the family of isotherms of the system zchich relate the pressure-temperature-composition variables. The equilibrium plateau decomposition relationships in the two-phase regions were determined from can&apos;t Hoff plots to be: The differential heats of reaction in these two regions are AH = - 53.0 * 0.2 and -20.0 *0.1 kcal per mole of D2, respecticely. The differential entropies of reaction are AS = - 36.3 * 0.2 and - 31.0 * 0.2 cal per mole D2. deg, respectively. Relative partial molal and intepal thermodynamic quantities were calculated from the pure metal to the dideuteride phase. The study of the Er-D system was undertaken as a logical complement to an earlier study of the Er-H system.&apos; The primary interest was to compare the characteristics of the two systems and relate the difference to the isotopic effect. Studies of rare earth-deuterium systems by other investigators have been very limited in number and scope. Furthermore, there is even less information available wherein an investigator has systematically compared a binary rare earth-hydrogen system with the corresponding rare earth-deuterium system. The available information consists primarily of dissociation pressure measurements in the plateau pressure region of a few rare earths. Warf and Korst&apos; determined dissociation pressure relationships for the La- and Ce-D systems in the plateau region and several isotherms for each system in the dideuteride region. They compared these data with those of the corresponding hydrided systems. The study of these systems as a whole was very cursory and did not give sufficient data for a thorough comparison of the effect of the hydrogen vs the deuterium in the respective rare earths. The heat capacities and related thermodynamic functions of the intermediate phases, YH, and YD2, were determined by Flotow, Osborne, and Otto,~ and the investigation was again repeated for YH3 and YD3 by Flotow, Osborne, Otto, and Abraham.4 This investigation studied only these specific phases. Jones, Southall, and Goodhead5 surveyed the hydrides and deu-terides of a series of rare earths for thermal stability including erbium. They experimentally determined isotherms of selected hydrides and plateau dissociation pressures for deuterides. These data allowed comparison of the enthalpy and entropies of formation of the dihydrides and dideuterides. To date, no one rare earth has been selected to thoroughly establish the complete pressure-temperature-composition (PTC) relationships of binary solute additions of hydrogen and deuterium, respectively. The objective in this investigation was to provide the first comparison of a complete family of isotherms of a rare earth-deuterium system with those of a rare earth-hydrogen system. This would allow one to determine what differences exist, if any, in the various phase boundaries and the thermodynamic relationships in various regions of the systems. I) EXPERIMENTAL PROCEDURE A Sieverts&apos; apparatus was employed to conduct the experimental measurements. Briefly, it consisted of a source of pure deuterium, a precision gas-measuring buret, a heated reaction chamber, a mercury manometer, and two McLeod gages (a CVC, GMl00A and a CVC, GM110). Pure deuterium was obtained by passing deuterium through a heated Pd-Ag thimble. A 100-ml precision gas buret graduated to 0.1-ml divisions was used to measure and admit deuterium to the reaction chamber. The reaction unit consisted of a quartz tube surrounded by a nichrome-wound furnace. The furnace temperature was controlled by a recorder-controller to . An independent measurement of the sample temperature in the quartz tube was made by means of a chromel-alumel thermocouple situated outside, but adjacent to, the quartz tube near the specimen. Pressure in the manometer range was measured to k0.5 Torr and in the McLeod range (10~4 to 10 Torr) to *3 pct. The deuterium compositions in erbium were calculated in terms of deuterium-to-erbium atomic ratio. These compositions were estimated to be *0.01 D/Er ratio. The erbium metal was obtained from the Lunex Co. in the form of sponge. The metal was nuclear grade with a purity of 99.9+ pct. The oxygen content was reported to be 340 ppm and the nitrogen not detectable. Metallographically the structure was almost free of second phase (<i vol pct). A quantity of sponge was arc-melted for use as charge material. The solid material was compared with the sponge in the PTC relationships. They were found to be identical. Therefore, sponge material was used henceforth, so that equilibrium could be attained more rapidly. The specimen size was about 0.2 gr for each loading of the reaction chamber. The procedure employed to obtain the PTC data was to develop experimentally a family of isothermal curves of composition vs pressure. First, a specimen

Jan 1, 1969

By A. M. Starfield

Discussion J. de V. Lambrechts (Fellow): The author&apos;s paper is a brilliant follow-up of an earlier paper by Starfield and Dickson.1 I have no quarrel with Dr Starfield&apos;s computerization of a complex problem, but I do not believe that he is getting quite the right answers from his programme. My impression is that his predictions about wet bulb temperature increases in very deep mines are over optimistic; in other words, that it will be hotter than Dr Starfield predicts. This is putting my views in a nutshell. This is not the occasion on which to indulge in lengthy argument about the original paper by Starfield and Dickson, but the present paper is, after all, based directly on that earlier paper and if the one fails, the other cannot succeed. I did level certain criticisms at the first paper and cannot say that the authors&apos; replies were very convincing. I do not think it is a sin to admit that I belong to the old school which believes in thorough field experimentation and practical trials and no amount of mathematical manipulation or physical theorizing, no matter how excellent, can make up for inadequate practical confirmation. This, as I see it, is still the crux of the matter. The original paper by Starfield and Dickson still rests on somewhat scanty practical evidence and I would be much happier if Dr Starfield&apos;s computer programme, based on the Starfield-Dickson model, had been checked against a large mass of observations in the practical mining situation. This is what both Wiles2 and myself3 had tried to do previously. What we lacked in mathematics and/or computer aids, I think the present paper by Dr Starfield lacks in practical substantiation. This is no condemnation of the author&apos;s paper which, taken by itself, is excellent but I think the final stage is still lacking, namely the bringing together of theory and empiricism in a manner acceptable to all. This may be wishful thinking on my part but I hope, within the next year or so, to come up with a modified Starfield-Dickson model in such a way that the computer answers will agree in the majority of cases with the few hundred field observations which are already on record. It might be a case of applying the proverbial &apos;Cook&apos;s Law&apos; to the Starfield-Dickson model! REFERENCES 1. STARFIELD, A. M., and DICKSON,A. J. &apos;A study of heat transfer and moisture pick-up in mine airways.&apos; J. S. Air. Inst. Min. Metall., 68, (5), 1967. 2. WILES, G. G. &apos;Wet bulb temperature gradients in horizontal airways.&apos; J. S. Air. Inst. Min. Metall., 59, (7), 1959, p. 339. 3. LAMBRECHTS, J. DE V. &apos;Prediction of wet bulb temperature gradients in mine airways.&apos; J. S. Air. Inst. Min. Metall., 67, (11), 1967, p. 595. R. Hemp (Visitor): Dr Starfield&apos;s paper has very effectively rounded off one particular aspect of the general problem of heat flow in mines. The ease with which this computer programme can be used to calculate temperature increases in horizontal airways must lead to its wider use in ventilation planning and, in developing this rapid method, Dr Starfield has indeed rendered a valuable service to the mining industry. One could consider further instances of heat flow in airways in which the availability of a rapid computer method would be desirable, e.g. the flow of air down a shaft, where there is an increase in temperature due to adiabatic compression, as well as an increase in virgin rock temperature as the depth increases. However, this particular case would not present any new problems and would merely require an extension of the exisitng work. I should like in this contribution to talk about an aspect of environmental control in mines which, I think, will become more important in the future. It is well known that wet bulb temperatures are subject to fluctuations underground. In some instances, particularly in stopes, the fluctuations, both with time and position, can be considerable. The theoretical work which has been carried out on temperature increases has been aimed at the prediction of mean temperatures, and no account has been taken of fluctuations around this mean. It is questionable whether this approach will, on its own, be sufficient, particularly when temperature increases in stopes are considered. The fluctuations in air temperatures underground arise from two causes. The first of these would be the fluctuations in surface conditions, and here one could list random, diurnal and seasonal fluctuations. The second cause is the multitude of things which vary in a mine and here one could list variations in air flow quantity, sources of evaporation, heat transfer from pump and compressed air columns and, particularly in the stope, variations in air flow patterns. Fluctuations arising from surface temperature variations should be amenable to calculation, and here one envisages figures relating the decay of temperature variation with distance to factors such as air flow quantity. Fluctuations resulting from changes in the mine are perhaps more difficult to tackle theoretically and the best approach could well be to analyse underground observations. In this connection, there is a good case to be made for the increased use of statistical methods in the analysis of underground temperature measurements, and it might be of value to look at current air-conditioning practice. When carrying out cooling load calculations for a particular location it is customary to use design wet bulb

Jan 11, 1969

By B. L. Averbach, M. F. Comerford, M. B. Rough

The volume fraction of ß phase was determined in a Ti-6Al-4V alloy by measurements of integrated diffraction intensities. The (0002), and (100)ß diffraction lines were chosen because this combination minimizes the errors resulting from preferred orientation. The difficulties arising from fluorescence radiation were eliminated by use of a diffracted beam monochromator. A specimen quenched from 1475OF (800°C) contained approximately 5 pct ß, but in specimens quenched from higher temperatures no ß was found. The ß phase formed during aging, and in specimens solution treated at 1570oF (855oC) approximately 10 pct ß was present after aging at 1000°F (540°C) for 24 hr. This ß appears to form by decomposition of martensitic a&apos;. ThE kinetics of the reactions which occur during the heat treatment of titanium alloys are complex &apos; and not completely understood. It has been proposed that hardening occurs in some alloys&apos; on aging by the precipitation of a transition phase w followed by the formation of the stable a and ß phases. It has been proposed for other alloys2 that the a&apos; marten-site decomposes by precipitating finely dispersed a particles. Most investigations have been hampered by the difficulties of determining quantitatively the amounts of the various phases present. This paper is concerned with the measurement of the amount of ß phase by an X-ray method, similar to one developed for the determination of retained austenite. The principal new feature was the use of a mono-chromator in the diffracted beam in order to reduce the fluorescence arising from the sample. EXPERIMENTAL PROCEDURE The experiments were carried out on an alloy of nominal composition Ti-6Al-4V (actual weight percentages: 6.2 Al, 4.1 V, 0.02 Mn, 0.17 Fe, 0.005 H, 0.03 C, and 0.02 N). The material was received as 5/8-in.-diam centerless ground rods in the annealed condition. The heat treatments were carried out in a vacuum of approximately 0.03µHg. The X-ray intensity measurements were made on 3/8-in. thick discs. The surface was prepared by grinding off about 0.060 in. and electropolishing in a solution af 60 ml (70 to 72 pct) perchloric acid in 1000 ml glacial acetic acid with a current density of 0.5 amp per sq cm.q The X-ray determination is based on the proportionality of the diffracted intensity of each line to the volume fraction of the corresponding phase. In calculating the intensities for a powder sample it is assumed that a large number of grains con- tributes to the diffracted intensity and that the grains are oriented at random. The presence of preferred orientation introduces serious errors in the relative intensities. The material used in this investigation exhibited a strong preferred orientation, which could not be removed by heat treatment. Other investigators have also found that preferred orientation may be retained after phase transformations. Glen and pugh5 performed a detailed analysis of the randomness expected after several allotropic transformations, but stated that this is not observed. Burgers,6 and Burgers and Ploos van Amstel,7 found that, in zirconium, the original orientation is retained after two phase transformations. Newkirk and Geisler8 observed similar behavior in titanium. On the basis of this evidence, it appears that, in the absence of plastic deformation, textures present in annealed titanium alloys are retained. Heating an a-ß alloy to the all-ß region and subsequent cooling to room temperature do not make the orientation of the mar-tensite different from that of the original a phase. In the present investigation it was possible to take advantage of the crystallographic relationships involved in the martensitic transformation to minimize the errors associated with preferred orientation. The relative orientation for titaniu-m marten-site9 takes the form (0001), 11 (110)ß; [1120], 11 [lll]ß. The same relationship has been proposed for zirconium&apos; and certain titanium-base alloys.10-12 Additional sets of approximately parallel planes have been determined for titanium-nickel alloys." The influence of preferred orientation can be minimized by comparing intensities from parallel planes in the two related phases. If it is assumed that each family of planes in a given phase is equally well populated, the effect of preferred orientation can be eliminated by using the normal multiplicity for the family of planes since each set of parallel planes is equally preferred for any orientation of the sample relative to the X-ray beam. The most suitable combination of reflections in the Ti-6A1-4V alloy appeared to be (0002), and (110)ß It must be recognized that the ß formed during aging of the Ti-6A1-4V alloy is a precipitate rather

Jan 1, 1960

By P. M. Kelly, E. P. Butler

Four Mn-CLL alloys, containing 60, 70, 80, and 90 pct Mn, respectively, have been examined in the quenched and the quenched and aged conditions using electron microscopy and electron, neutron, and X-ray diffraction. After certain heat treatments the alloys transform from fee to fct and in the tetraom1 condition show a domain structure parallel to {101} planes. Neutron diffraction indicates that the domains are antiferrornagnetically ordered. The domain boundary contrast has been examined using bright- and dark-field microscopy, and the contrast effects observed under favorable conditions have been used to deduce the c axis orientation in each domain. The domains are extremely mobile and can be nucleated at precipitate particles and screw dislocations. The domain mobility is responsible for the high damping capacity. In the aged material a Mn precipitates in the Kurdjumov-Sachs orientation and results of both electron microscopy and neutron diffraction indicate that the matrix separates into two components—one rich in manganese and the other rich in copper. ALLOYS of manganese and copper have the unusual combination of a high damping capacity and good mechanical properties and have been the subject of a number of investigations as part of a general interest in high damping capacity alloys for engineering purposes.&apos;,&apos; SO far, however, there has been no reported electron metallographic study of these alloys. The Mn-Cu system has an extensive range of solid solubility at high temperatures, and the equilibrium phases are expected to be y (fee) and a Mn. The high damping capacity is associated with a metastable tetragonal structure of variable c/a ratio, which forms from the high-temperature y phase. This latter phase becomes more difficult to retain as the manganese content increases, and alloys containing more than 82 wt pct Mn undergo a reversible martensitic fcc — fct transformation on quenching. The X-ray work of Basinski and christian3 showed that the Ms temperature for the transformation was below room temperature for alloys in the range 70 to 82 pct Mn and increased linearly with manganese content. When quenched from the y region, alloys in the range 50 to 82 pct Mn are cubic at room temperature, but become tetragonal if aged at temperatures between 400" and 600°C. The martensite transformation occurs on cooling from the aging temperature. Tetragonal alloys have a banded microstructure and the bands analyze to be traces of (110) planes. Similar microstructures have been observed in In-Tl4 and in other manganese-base systems, such as Mn-Au5 and Mn-Ni.6 The mobility of the bands in Mn-Cu alloys can be demonstrated by optical examination of a polished specimen surface subjected to a cyclic stress.7 The bands appear and disappear as the stress is varied, and X-ray measurements of the (200,020) and (002) peak intensities confirm that a reversible reorientation of the tetragonal structure occurs. Meneghetti and sidhu8 investigated the magnetic structure of Mn-Cu alloys and found antiferromagnetic ordering in furnace-cooled alloys of composition >69 at. pct Mn. Magnetic super lattice reflections occurred at the (110) and (201) positions and the proposed structure was fct with the spins along the c axis. A more complete investigation by Bacon et al.9 confirmed this structure. The magnetic ordering temperature Tn was found to increase linearly with manganese content in the same way as the Ms temperature, and at any composition, Tn > Ms. This relationship suggested that the magnetic ordering was responsible for the cubic — tetragonal transformation in the manganese-rich alloys. The purpose of this investigation was to study the mechanism of high damping and the structural changes that occur on aging. The main technique used was transmission electron microscopy, but X-ray and neutron diffraction experiments were also carried out. EXPERIMENTAL Materials and Heat Treatment. The four alloys, provided by the Admiralty Materials Laboratory. were of nominai composition 60, 70, 80, and 90 Mn and all had low impurity levels, <0.05 pct C, <0.2 pct Fe. This material was cold-rolled to 200-µ strip with intermediate annealing and then given a final heat treatment of 24 hr in the range 800° to 900°C followed by water quenching. An identical heat treatment was given a length of 3/4-in.-diam bar of the 70/30 alloy from which the neutron diffraction specimens were machined. It was suspected that the tetragonal structures would be metastable at room temperature, and so the alloys were not aged until required for experiments. After aging in a salt bath the alloys were water-quenched. Thin Foil Preparation. Initial thinning to 50 to 75 µ was possible in a solution consisting of: 50 ml nitric acid 25 ml acetic acid 25 ml water The surface deposit and grain boundary etching was removed by a final electropolish at around 20 V in an electrolyte consisting of:

Jan 1, 1969

By G. H. Kesler, C. E. Dryden, J. H. Oxley

Rates of heat- and mass-transfer from rods to recirculating air were determined within a one-quarter-scale model of a metals deposition bulb. The dependence of local and averaged rates of transfer upon outlet geometry, number of rods, position upon a rod, and airflow rate was established for flow patterns created by radial and tangential air inlets. The results are given a qualitative interpretation in terms of rates and distribution of metal deposition in a prototype deposition bulb. IT is well known that a number of metals can be prepared from volatile compounds containing them by causing dissociation of their compounds to occur at heated surfaces. Examples of such metals include silicon, titanium, zirconium, and aluminum, which can be prepared from their halides. While the ability to prepare high-purity metals by this technique is of importance in itself, the rate of deposition of metal also is important in considering the commercial potential of such a process. If the over-all process of deposition is broken down into separate steps of transport of materials to and from the heated deposition surface and establishment of chemical equilibrium at the surface, as was described in a recent paper,1 then since surface temperatures are usually high and surface equilibrium is attained very rapidly, the rate-controlling step can be considered as either that of transport of reactants to the surface or of transport of products other than deposited metal away from the surface. These two transport steps are related through the reaction stoichiometry. It can be shown1 that the rate and distribution of metal in such a transport-controlled process are determined by the over-all and local mass-transfer coefficients in conjunction with the equilibrium conversions at the hot surfaces. The rate relationship is: w = [KA(y a-y s)] B.E where the bracketed group is the rate of arrival of the reactant at the surface of area A as determined by the mole fraction driving force (y a - y s) and the convective transport constant K. The factor B is the weight fraction of metal in the reactant, and E is the equilibrium fractional conversion to metal. Numerical values of y, and y, are fixed by the vapor composition and the equilibrium compositim of reactant at the surface; and E can be determined by thermodynamic calculations or by experiment. However, values for the convective coefficient K are available generally only for systems of simple geometry, such as cross-flow past a rod or sphere or parallel flow past a flat plate or through a tube. Often it is necessary to work with systems of more complex geometry and in which the vapor flow may not be uniform or exactly parallel or perpendicular to the surface. It is possible, of course, to establish working correlations for these more complex systems by direct experiment; but the experiments usually are costly in both time and money. To circumvent this objection and to aid in arriving at an understanding of the relationships and interactions of the process variables, it is helpful to construct a model of the flow system in which air, water, or other convenient fluids can be substituted for the process vapors and with which mass-transfer measurements or analogous he at-transfer measurements can be made upon a simulated deposition surface. By this means, a large number of measurements can be made in a reasonable time, and the correlation of these results can be applied to the prototype system. Examples of the application of these techniques are to be found in the literature (e.g., Ref. 2). It is the purpose of this paper to illustrate these techniques by description of a model study which was done at Battelle Memorial Institute. The work to be described was of a preliminary nature; the investigation subsequently was extended to develop quantitative relationships among the significant dimensionless transport, geometric, and flow parameters. This more detailed study will be the subject of a future paper.

Jan 1, 1962

By Julian Wills

The Candrill was developed with Soredem as a one-operator rockdrill for Canadian narrow vein mining. It provides the benefits of increased drilling rates, lower noise and vibration, mass reduction of 20% and system cost saving. The Candrill is to be commercialised at the end of 2001 together with a stoper drill through Parts Headquarters, Novatek&apos;s Canadian agent. The Candrill or pneumatic drills may be further exploited using a simple mechanised drilling system to further reduce operator labour, improve drilling speeds by up to 50% and to enhance drilling accuracy. Novatek&apos;s drilling system for simple mechanisation in gold and platinum mines is integrated with roof supports, can operate in stope widths as low as 800 mm and has resulted in labour savings of 50%, improved advances per blast of 20 to 50% and improved operator safety and ergonomics.

Oct 1, 2001

By John H. Schemel

Large Zircaloy-2 hammer or press forged bars did not exhibit the uniform excellent corrosion resistance to steam normally expected of the alloy in wrought form. Weight gains of coupons cut from forged bars were 40 to 60 mg per sq dm compared to the 28 mg per sq dm obtained on hot rolled sheet and strip. The mechanism of this corrosion and its relation to microstructure is discussed. After these observations, a solution heat treatment followed by rapid cooling was tried on coupons from eight heats of forged bars. The basket-weave structure resulting from the quench did not show agglomeration of intermetallic compounds. These coupons showed uniformly good corrosion resistance with weight gains very close to the 28 mg per sq dm expected of Zircaloy-2 after the 14-day steam test. A large forging was solution heat-treated and tested for structure, mechanical properties, and corrosion resistance. Corrosion resistance was excellent and uniform throughout the section. The normally anisotropic mechanical properties were changed to completely iso-tropic. Strength levels were raised while there was a small loss in ductility at the service temperature. Tempering of the quenched structure below the ß transus did not improve the ductility at the test temperature of 600°F. ZIRCALOY-2 end caps for nuclear fuel elements Zircaloy-2 is an alloy of 1.5 pct Sn, 0.1 pct Fe, 0.1 pct Cr, and 0.05 pct Ni, balance hafnium-free zirconium patented by Westing-house Electric Co. used in pressurized water reactors are machined from large hammer-finished forged bars. The bars forged for this application range from 3 1/2 in. to 7 1/2 in. squares. One of the tests used to evaluate Zircaloy-2 for this service is a 14-day exposure to very high-purity steam at 75oF and 1500 psi pressure. Normally wrought products will exhibit a black lustrous film of zirconium oxide after the test and show a weight gain of approximately 28 mg per sq dm. Coupons representing the forged bars exhibited a wide variety of corrosion results ranging from acceptable black coupons to some covered with white crystals of zirconium oxide that had weight gains of nearly 100 mg per sq dm. One of the most common effects was a white corrosion product that looked like a stain to some observers and the outline of massive metal grains to others. Very careful specimen preparation prior to the corrosion test did not affect the result and metallographic examination did not reveal a structural feature of a size and shape that would correlate with the corrosion product. In addition to the relatively poor corrosion resistance, the forged product was not as ductile as desired. The problem of obtaining uniform and more acceptable properties in these heavy-forged sections seemed to be a function of the microstructure of the metal and, in particular, the distribution of the intermetallic compounds. None of the four alloying elements however are appreciably soluble in a zirconium and are present as compounds which usually appear scattered randomly throughout the structure. Moudryl showed that the distribution of these intermetallic compounds in Zircaloy could be related to a ostringero corrosion failure. Grozier et al. discussed another structural defect that causes a similar corrosion effect. In this case, an elongated gas-void was determined to be the cause. M. L. Picklesimer held in his discussion of the Grozier paper that at least a part of the observed =stringersn were caused by the distribution of the intermetallic compounds. He proposed a

Jan 1, 1962

By Harold M. Smith

Natural gas has been used as a fuel and source of energy almost from its discovery, but its use as a chemical raw material may be said to have begun in 1918, when Brooks and Humphrey3/ showed. presence of alcohols in the diluted acid oil obtained by the sulfuric acid-treatment of cracked petroleum distillates. However, development of the utilization of natural gas for chemical syntheses was slow, partly because erroneous ideas existed regarding the nonreactivity of tine hydrocarbons composing natural gas. Data accumulated by petroleum chemists throughout the world, particularly since about 1930, have shown that these hydrocarbons will react when activated by the effects of heat, pressure, chemical reagents, and light; also that the reactions can be made to proceed of practicable speeds and to provide good yields of useful products with moderate operating conditions, especially if catalysts are employed. As those results became known, the possibility of a synthetic organic chemical industry based upon these reactions became apparent, and today this industry is large and growing rapidly in importance. In this paper the story of the manufacture of chemical products from natural gas is told simply in graphic form. The industry is developing so rapidly that soma products may have been omitted, but every effort has been made to include all that are important or likely to become so. The difficulty of keeping information of this tape up to date is shown by reference to an information circular4/ or, the sore subject published by the Bureau of Mines in 1930, in which the important products are shown on a single chart, where as five charts are employed for the cane purpose at present.

Jan 1, 1940