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By Ronald K. Linde

Metastable Ag-Cu solid solutions at two compositions beyond the maximum limits of solubility obtainable by quenching from the solid state were obtained by rapid quenching from the liquid state. The process of transformation of the metastable solid solutions into the equilibrium phases was studied by means of X-ray diffraction intensity measurements and electrical-resistance measurements; metallographic examination was also performed. Results are compared with those for an alloy quenched from the solid state at a composition which exists as a solid solution at elevated temperatures. Activation energies for the trans-formation were computed to be 33,600 * 2500 and 33,100 * 2000 cal per g mole for the 60.1 and 75.0 at. pct Ag;Cu compositions, respectively THE kinetics of precipitation in supersaturated solid solutions obtained by quenching from high temperature has been thoroughly studied in many alloys, and detailed investigations of the early stages of nucleation and subsequent growth of the equilibrium phases have been carried out. All of these studies have been made on alloys quenched from the solid state, however, and it is the purpose of this paper to present some of the results on the kinetics of transformation of metastable solid solutions in Ag-Cu binary alloys whose compositions lie outside of the solid-state limits of solubility. Limits of solubility in the solid state can be increased by rapid quenching from the liquid state. This was first demonstrated by Falkenhagen and Hofmann, who obtained appreciable increases in solubility limits of the elements of the first transition series in aluminum by rapid cooling of liquid alloys through contact with a copper mold maintained at liquid nitrogen temperature.' The same basic idea of cooling a liquid alloy by conduction onto a substrate rather than by convection of a gas or liquid (conventional quenching) has been recently revived and extended to very high rates of cooling by Duwez and his collaborators. The new technique was first applied to Ag-Cu alloys because the existence of a eutectic in this system is not predicted by the Hume-Rothery rules of alloy phase formation. Rapid quenching from the liquid state resulted in metastable solid solutions at all concentrations. The kinetics of decomposition of these metastable solid solutions containing 60.1 at. pct Ag;Cu (eutectic composition) and 75.0 at. pct Ag;Cu is the subject of the present paper. EXPERIMENTAL TECHNIQUES Alloys were made in 10- to 20-g heats using silver of purity 99.99 pet and copper of purity >99.999 pct. Components were weighed accurately to 0.1 mg and melted by induction heating in an alumina crucible under an atmosphere of hydrogen. Weight losses amounted to less than 0.02 ~ct in all cases. Rapid cooling from the liquid state was achieved in an apparatus of the type described by Pietrokowsky. 3 In this technique a freely falling drop of molten alloy is caught between a stationary anvil and a fast moving piston, both anvil and piston being lined with copper. The resulting foils were approximately circular (about 2 cm in diam) and from about 50 to 150 u in thickness, depending on the pressure driving the piston. Metallographic samples were prepared for polishing by edge-mounting foils in Quickmount. The mostef-fective etching procedure was found to be: 10 parts NH4OH (concentrated), 1 part H2O2 (30 pct), 5 parts H2O, swab for 5 to 10 sec. The transformation of the metastable alloys to equilibrium was followed by X-ray diffraction and electrical-resistivity measurements. The peak intensity and the integrated intensity of suitable Bragg reflections of the metastable and stable solid solutions were studied with a Norelco dif-fractometer, using nickel-filtered copper KO radiation. The peaks were step-scanned at intervals of 0.05 deg. Using either a Kelvin bridge or a null circuit with a Leeds and Northrup K-2 potentiometer, the changes in electrical resistance due to phase transformation were measured for specimens cut into strips about 20 mm long and 4 mm wide. All resistivity measurements were carried out at liquid-nitrogen temperature. The isothermal heat treatment was accomplished by sealing the samples in argon-filled aluminum containers with stainless-steel O-rings. Containers were then suspended in wax baths with temperatures in the

Jan 1, 1967

By J. H. Waxweiler, L. C. Ikenberry, R. J. Bendure

Carbon which is present as insoluble carbides in austenitic stainless steels can be measured quantitatively by dissolving the steel in iodine-methanol and analyzing the residue for carbon. Severe sen-sitization was observed in Type 302 due to precipitation of only 0.003 pet carbon. Both cold work and the presence of delta ferrite caused a marked acceleration in rate of carbide precipitation. Carbide precipitation rates in 17-7 PH were stzulied for the austenite conditioning and also the aging heat treatment. CARBON and its compounds exercise a major influence on the properties of stainless steels and their response to thermal treatment. Sensitization in 18-8 type stainless steels has been the subject of numerous investigations throughout the years. Bain, Aborn, and utherford," and Binder, Brown, Frankss all studied the effects of heating austenitic stainless steels in the temperature range of 1000° to 1500°F. The primary purpose of most of these studies was the investigation of susceptibility to in-tergranular attack in acids due to these sensitizing heat treatments. Intergranular precipitation of carbides was always associated with intergranular attack but it was recognized2 that severe attack could occur with but minute quantities of precipitated carbide. Mahla and ielsen utilized the electron microscope to make a significant contribution in illustrating the appearance and method of growth of chromium carbides during sensitizing heat treatments. However, as they stated, their studies of residues could not be used to obtain a quantitative measurement of the amount of carbon which was actually precipitated. The aim of the present investigation was to devise a relatively fast, simple method for the quantitative measurement of carbides in stainless steel. EXPERIMENTAL WORK The initial investigations were made to determine the best means of separating carbides from the matrix. A number of dissolving media were tried using both chemical and electrolytic attack. Qualitative examination of the extracted residues by X-ray diffraction indicated that solution in iodine-methanol would furnish a good means of separation. Consequently, further work was pursued along this line. The method is quite simple. The sample in the form of millings or nibblings is dissolved in iodine-methanol solution at room temperature (6-g iodine, 25-ml methanol per g of sample). The insoluble residue containing the carbides is separated by suction filtration through an ultra-fine glass filter disc. This is a very fine filter medium that will retain particles as small as 0.1 to 0.2 p in diameter. After washing with methanol and drying, the filter disc and residue are placed in a conventional combustion carbon-tube furnace and the carbon determined gravimetrically. Using this technique it was found that reproducible insoluble carbon values were obtained. However, since such small amounts of insoluble carbon were obtained on Type 302 after sensitizatipn at 1250°F and 1500°F, the values were confirmed by a second method. In the second method the sample was dissolved with copper potassium chloride and filtered through a millipore paper. This treatment dissolves the matrix but leaves undissolved practically all of the carbon irrespective of how it is present in the steel. The amount of insoluble carbon present as chromium carbide is determined by calculation from the analysis of the residue for chromium and iron. The derivation of the formula used for this calculation is discussed later. The values obtained by the indirect copper-potassium-chloride method were in agreement with those obtained by the iodine-methano1 method. See Table I. It should be pointed out that the sensitivity of the direct combustion method is not too high when the amount of carbide present is small. This is due primarily to inherent blanks and to analytical errors such as weighing. For this reason it cannot be stated with any degree of certainty that there is a significant difference between values of 0.002 and 0.005 pct. Having confirmed that the iodine-methanol extraction gave a quantitative measurement of the precipitated carbides in Type 302, exploratory tests were conducted on Armco 17-7 PH stainless steel. Samples from commercial Heat 54807 were solution annealed at 2000°F, water quenched and heated at 1250" and 1500°F, and water quenched. The analysis of Heat 54808 is as follows:

Jan 1, 1962

By Morris E. Fine, Richard A. Kloske

The stress-strain beha1,ior in tension of Au-Ag alloy single crystals containing nominally 1,3, 5, 95, 97, and 9.9 at. pct Ag was studied uS strain role and lektlperalure down lo 4.2K. A slrain aging yield hob lc,rrs observed on aging under stress in the temperature range 30° lo 75°C. The species diffusing to the dislocation is thought to be a divacancy-solute complex wilh /he. solute then pinning the dislocation by short-Range ovdering and possibly Suzuki locking. At room tempevullcve the critical reso1ved shear stress .follo~c.s an empirical equation of the form tc = A +Bc' where A and B are 90 and 420 ,g per sy mm tor gold base alloys and 60 and 510 g p~r sq )11ttz .tor si1ver base alloys. This strengthening was attributed to a long-range size ejtect. The alloy slrenglliening at i.2'K is greafer than at room temperature. The additional atrloutzf was altribuled lo a uwak skovl-range i?~levacIion between the solute and dislocallon cove. The activation energy .tor deformation a/ 4.Z0h7 decreases on alloying. 11 increases irr other fee systetns. hi the 5 at. pcl Air-Ag- alloy in pmvlicular there is very extensive easy glide and lavge overshooting- of the synmetry line at 4.Z°K. There is also u sharp decrease in the vale of. strain hardenitlg near the widdle of stage II with the new rate bezng abold the sarne as tlzal In easy glide. This uws attributed to a sudden reduction of activity on the pvitrrarg sgstertr. In Au-Ag alloys the critical resolved shear stress Tc. at room temperature is essentially a parabolic function of atomic concentration:' the 50 at. pct Ag-50 at. pct Au alloy is about 10 times stronger than the pure metals. This strengthening occurs in spite of the similarity in valence and atomic size. Solid-solution strengthening in fcc metals is characteristically greater at low temperatures than at room temperature. In Ag-10 at. pct Au and Au-10 at. pet Ag; r, (20.4K)/Tc (300°K) is 2.3 and 2.5. respectively.- compared to 1.2 in pure silver.3 Suzuki' and Flinn5 explained the alloy strengthening at room temperature as a combination of Suzuki locking and short-range order hardening. The agreement between the computed and measured strengthening was very good: however, in Ag base-A1 alloys Hendrickson and Fine6 concluded that Suzuki locking resulted mainly in a yield drop effect. Recent reviews of the solid-solution strengthening in fcc metals by Fleischer2 and Haasen8, 9attributed the strengthening at room tenl-perature to the combined effect of atom nlisfit and change in shear modulus 011 the long-range stress field surrounding a dislocation. The parameter used by Fleischer was The shear tnoduli of Ag-0 to 6 at. pct Au alloys were measured by Pur-wins. Labusch. and Haasen.In While addition of 4 at. pct Au caused an appreciable increase in the C,, elastic constant. there was a decrease on increasing the solute to 6 at. pct Au: C,, and C :: were not measured in the 6 at. pct alloy. The greater solution hardening at low temperatures implies the presence of short-range interactions between the solute atoms and dislocations These include size and electronegativity effects. Whether the extra alloy strengthening at low temperatures is due to locking or friction hardening is still a controversy."".' In the present research the stress-strain behavior of Au-Ag single crystals containing 1 to 5 at. pct Ag and 1 to 5 at. pct Au was measured vs strain rate and temperature down to 4.2' K. Particular attention was paid to yield drop effects. These have not been previously reported. PROCEDURES The alloys were supplied by the Engelhard Industries. Inc.. as strips 0.050 by 0.250 by 12 in. The compositions are given in Table I. Single crystals were grown under static vacuum using a traveling molten zone technique. Crucibles shaped to the size of the strips were made of high-purity graphite prebaked for 24 hr at 1100°C in vacuum. The crucible and its charge were placed in

Jan 1, 1970

By D. J. Rose, W. M. Armstrong, A. C. D. Chaklader

The wetiability of single crystals of MgO by specimens of vacuum-cast iron was studied using the sessile drop technique in vacuo at 1550ºC. Formation of FeO at the liquid-vapor interface caused the contact angle (6) to decrease from 117 to 65 deg during the first minute. After cooling, all specimens possessed a peculiar annular interfacial deposit of Fe,O,. Within the annulus the interface showed no sign of chemical attack. Chemical reaction occurred where the iron was alloyed with Ti, V, Cr, Nb(Cb), Ta, cmd Zr. Vnriation of 6 with alloy concentration was studied. Although vanadium md chromium improved the wettability of MgO by iron, the effect of Zr, Ti, Nb, and Ta was indeterminable because the 8 derived from sessile drop considerations was that of the metal against a restrictive peripheral volume of liquid oxide wetting the substrate. INTEREST in the nature of metal-ceramic interactions has been stimulated by progressive development of metal-ceramic combinations. One of the more valuable methods used for bond investigation is the sessile drop technique. Recent attempts to improve wettability through solute additions to the drop have revealed that the solute may a) react with the oxide creating new compounds at the solid-liquid interface, b) adsorb at the interface in a monolayer formation, or c) distribute throughout the drop uniformly causing no wettability variation. This work, part m in a series1,2 of investigations of interface reactions between metals and ceramics, embraces a study of the Fe-MgO system. MgO possesses a large negative free energy of formation (-173 kcal per g mole 0, at 1550ºC) compared to FeO at this temperature (-73 kcal per g mole 02). Hence the electronegativity difference between the drop and substrate allows selection from an extensive group of metal solutes with intermediate electronegativity differences that would, in the absence of chemical reactions, be expected to adsorb pre- ferentially at the solid-liquid interface. However, the high oxygen pressure of MgO in vacuo creates an oxidation environment which influences the solute behavior. Recent studies of the Fe-MgO systemJ74 have been restricted by chemical reactions that obscured observations. In view of the current interest in liquid-phase sintering of metal-ceramic combinations under partial oxidizing conditions,5 a more comprehensive study of the Fe-MgO system seemed beneficial. EXPERIMENTAL PROCEDURE 1) Specimen Preparation. Optical-grade MgO single crystals and Ferrovac vacuum-cast iron were used in all experiments. A spectrographic analysis of the iron indicated 0.008 C, 0.05 V, 0.005 Mo, 0.01 Ti, 0.002 S, 0.01 Cr, 0.001 Mg, 0.01 Si, 0.003 A1 (wt pct). The MgO crystals were cleaved along (100) planes into plates approximately 20 by 20 by 1 mm. Following annealing in vactto at 1100°C for 3 hr, surface irregularities were removed by a chemical etch in phosphoric acid at 100°C. The iron rod was machined into small cylinders approximately 0.250 in. in diam and length and these were carefully cleaned in organic and acidic solutions to remove surface impurities. All specimens were weighed to the nearest 0.1 mg. 2) Apparatus. The apparatus described in detail by previous authors1,2 was modified for this work. A Polaroid Land Camera was incorporated into the optical system so that drop measurements at ten-second intervals after melting were possible with ultra-high-speed self-develop ing film. 3) Procedure. The iron cylinders were placed upright on the MgO plates and positioned in the molybdenum susceptor. After furnace assembly the system was pumped down to a vacuum of 1 µ and flushed with H2 at 800°C. The system was again evacuated to 5 x 10-5 mm of mercury and the temperature raised to 1550°C within 2 min. The molten drops were photographed at appropriate time intervals. TWO min after melting the iron vapor pressure caused gas discharge, or corona, within the tube. The specimens were then slowly cooled to room temperature, sectioned and examined metallographi-cally. X-ray identification of interfacial reaction products was attempted by the powder diffraction technique. Alloying elements (Ti, V, Cr, Zr, Ta, Nb) were added to the iron in various concentrations up

Jan 1, 1963

By G. S. Tint, M. Herman, V. V. Damiano

Dislocation arrays and substructures were studied in cadmium doped zinc crystals using a newly devised etching technique. Cadmium precipitates delineating the dislocations were revealed by etching a surface closely parallel to the (0001) slip plane. Cinephotomicrography of the continuous etching process revealed the three-dimensional aspects of dislocations in the bulk crystal. Dislocation etch patterns were studied in both deformed and annealed crystals after suitable aging at room temperature. The effect of annealing was evidenced by a rearrangement of the dislocations into low-angle boundaries and hexagonal networks. ETCH pit techniques have been used extensively to study dislocations in both deformed and annealed bulk metal crystals. Ideally one hopes to obtain a one-to-one correspondence between the etch pits and the points of emergence of the dislocations at the surface. One then attempts to deduce the way in which dislocations are arranged in the bulk crystal from the arrangement of etch pits on the surface. It is clear that one can obtain only limited information of the dislocation configurations inside the crystal from etch pit studies of single surfaces. Considerably more information is obtained if one is able to follow the course of the dislocations through the crystal using progressive etching technique. Techniques of this sort were used by Gilmanl to study dislocations on the slip planes of NaCl crystals and by Damiano and Tint2 to study dislocation arrangement in zinc crystals grown from the melt. The present paper makes use of a technique first described by Tint and Damiano3 to observe and continuously record the dislocation structures which appear while a crystal surface was being progressively etched. Studies were made on cleaved (0001) surfaces to reveal the dislocations along their length on the surface closely parallel to the slip plane. The technique for revealing segments of dislocations along their length by etching is well known. Wilsdorf and Kuhlmann-wilsdorf4 revealed disloca- tions along their length in aluminum containing a few percent copper, when precipitates segregated along the dislocations. The technique was used by Low and Guard5 to study dislocation configurations on the slip plane in Fe-Si alloys containing carbon. In the present work the technique was applied to zinc containing cadmium since it was shown by Gil-man6 that a cadmium-rich phase could be made to precipitate from supersaturated solutions along dislocations in zinc. Segments of dislocations delineated by the precipitates were revealed by etching a surface prepared by cleaving the crystal. The three-dimensional nature of dislocations and substructures was thus studied from the cinephotomicro-graphic record of the continuous etching process. EXPERIMENTAL Single crystals of zinc containing the order of 0.1 pct Cd were prepared by slowly lowering a graphite crucible containing the melt through a temperature gradient of 15°C per cm at a rate of 1.5 X 10-3 cm per sec. "As grown" crystals were aged for periods of 1 month at room temperature, then cleaved in liquid nitrogen, and etched according to the procedure used by Gilman.' The etchant containing 32 g of CrO3, 6 g of hydrated Na2SO3 in 100 ml of water behaved as a chemical polish for zinc and etch pits were produced at the site of precipitates or inclusions. After the precipitates or inclusions were removed from the surface, the etch pits left behind were eventually polished smooth. This behavior enabled one to continuously observe the surface while the specimen was immersed in the etchant. Best results were obtained when the specimen surface was vertical and the reaction products of polishing were continuously removed by gravitational convection. Some crystals were heavily deformed in excess of 25 pct strain, others were lightly deformed the order of a few pct by compression such that the deformation occurred essentially by basal glide. Some crystals were etched immediately after deformation, others were allowed to age at room temperature for several weeks prior to etching. Heavily deformed crystals were annealed at various temperatures and etched on the cleavage plane immediately after annealing, others were allowed to age at room temperature for several weeks prior to etching. The etched structures of deformed and annealed structures were studied. Similar experiments were conducted on 99.9999 pct pure zone refined Tadanac zinc crystals which

Jan 1, 1963

By E. J. Fasiska, H. Wagenblast

The dilalion of a ivon by interslilial carbon was measured by two independent techniques —dilatometric mesurements at 719 c and X-ray measurments of the urlil cell parameters a1 room temperature after quenching. The relative expansion per increase in cavbon content by both methods is (2.9 + 0.3) x 10-3 pev at. pcl C nrzd is temperature- independent within experimental error. This corresponds to (6.3 5 0.6) cu cm per g-atom for the partial gram-atomic volume of carbon in a iron-only slightly smaller than the atomic volume for iron in the same temperature vange. THE only previous quantitative study of the dilational effect of carbon dissolved in a iron was performed in 1934 by Burns1 which, at the time, generated some discussion of possible sources of experimental error.2 For a system of such widespread importance, we felt that a new investigation was merited. Both X-ray diffraction and dilation measurements were used to determine the expansion of the a iron lattice by dissolved carbon, avoiding as much as possible any previous experimental problems and deficiencies. The dilation method at solution temperature offers not only measurements which are free of residual strain but also, in conjunction with the room-temperature X-ray measurements, a method to detect any large temperature dependence of the partial gram-atomic volume of carbon. To insure that quenching strains did not affect the room-temperature X-ray measurements, wire specimens of constant carbon content but different diameter were examined for such an effect. SPECIMEN PREPARATION The material used for both experimental techniques was "Ferrovac E" iron received in the form of 19-mm-diam rod and stated as having the following impurity contents: C, Cr, Cu, Mn, P, and V, each in the range of 10 to 50 ppm; Co, O, Mo, S, and Si, 60 to 100 ppm; W, 200 ppm; Ni, 230 ppm; N, 4 ppm. The stock material was cold-swaged to 0.71 mm diam for the Debye-Scherrer X-ray camera specimens and portions were cold-rolled from 6.3 mm diam to 0.79- and 0.25-mm sheet for X-ray diffractometer and dilation measurements. The wires were annealed in wet hydrogen for 6 hr at 840°C and 15 hr at 720°C, and then quenched into 0°C water. A chemical analysis for carbon after this treatment gave 0.0046 + 0.0014 at. pct C. Three portions of these wires were subsequently held at 719°C in three different hydrogen + methane mixtures and then quenched, resulting in carbon concentrations of 0.0283, 0.0598, and 0.1067 at. pct C by chemical analysis. After carburizing, the wires were swaged to 0.48 mm and electroplated with silver to prevent carbon loss during subsequent heat treatment. The final heat treatment consisted of holding the wires at 72 1°C for 5 min in a He-2 pct H mixture followed by quenching into 0°C brine. The wires were held at room temperature for a few minutes to remove the silver plating using a phosphoric acid-hydrogen peroxide solution, and then stored in liquid nitrogen until the measurements were made. EXPERIMENTAL TECHNIQUE A) Dilation Measurement. The dilatometer consisted of a gas-atmosphere vertical tube furnace modified so that length changes of a ribbon-shaped specimen could be measured externally. This was done by installing a gas-tight mercury seal at the top of the furnace as shown schematically in Fig. 1. The specimen (21.0 cm long, 1.27 cm wide, and 0.25 mm thick) was suspended in the center of the furnace by 3-mm-diam quartz rods with the upper one passing through the cap of the mercury seal. Above the cap, the upper quartz rod was coupled to a lever exerting a load of about 25 g (-12 lb per sq in.) on the specimen and having a 10 times mechanical magnification. The vertical position of a marker at the other end of the beam was read with a traveling microscope with a precision of 0.01 mm. The temperature gradient of the furnace was meas-

Jan 1, 1968

By H. E. Swanson

A description of the field apparatus has been published by D. G. Brubaker. Data from laboratory model studies of the in-line and broadside methods of operation are detailed. The conductor models include a single sheet conductor at several strike and dip angles and a schistose-type conductor. In addition, data on the effects of the strike length and of the depth of the conductor are presented for the broadside method of operation. All of the data show that the inclintion reverses direction over the top edge of dipping single sheet conductors. Differences between anomalies over conductors dipping between 90" and 30" are subtle,but flat-lying sheets can be readily distinguished from steeply dipping sheets. Schistose conductors are easily distinguished from single sheet conductors, and a procedure is given for determing the direction of schistosity. The depth of penetration under ideal conditions is 0.7 of the coil separation. In 1950, The New Jersey Zinc Co. (of Pa.) developed a lightweight apparatus for electromagnetic prospecting. A description of this apparatus has been published by D. G. Brubaker.1 It consists of a small, battery-powered vertical source coil and a direction-finding receiving coil. Source and receiver are kept a fixed distance apart and move as a unit along the survey lines. At each receiver station the inclination of the magnetic field created by the source is measured. Two methods of operation are used, in each of which measurements are taken with a constant source-to-receiver distance and with the plane of the source oriented to pass through the receiver station. In one procedure, called the in-line method, source and receiver travel in tandem along the same line. In the other procedure, called the broadside method, source and receiver move along adjacent lines, with the source-to-receiver direction oriented parallel to the assumed strike direction. The data recorded in either case are the inclinations, measured in degrees from the horizontal, of the magnetic field created by the source. These data are plotted at the receiver stations on a map. Scale-model studies of both methods of operation have been conducted in the laboratory and are reported in this paper. APPARATUS Small source and receiving coils wound with many turns of fine copper wire were used to produce and measure an alternating magnetic field in the same manner as the field apparatus. The model source coil was mounted in a vertical position and oriented so that the receiving coil was in the plane of the source. The receiving coil was mounted in a frame so it could be rotated to obtain the inclination measurements. The source coil was excited by a 100-kc signal generator. A tuned amplifier and a voltmeter were used to detect the null position of the receiving coil. The coils used in the field apparatus are usually spaced about 400 ft. The coils used in the model work were spaced from 4 in. to 4 ft apart. Thus the scale of the model work ranges between 1/1200 to 1/100 natural size. The model conductors were aluminum-coated building paper supported on wooden frames. The conductivity-thickness product was measured using a four-electrode system and was found to be about 300 ohms-'. CONDUCTIVITY CONSIDERATIONS The electromagnetic response from a thin sheet conductor is a function of the product of the conductivity of the sheet times the thickness of the sheet times the frequency of the alternating electromagnetic field times some linear dimension of the system such as the coil separation which indicates scale. The secondary electromagnetic field produced by the conductor increases in amplitude from zero at zero conductivity to a maximum value for infinite conductivity, while the phase of the secondary field with respect to the primary field shifts from 90" at zero conductivity to 0" at infinite conductivity. Several authors2-' have shown that most of both the increase in amplitude and the change in phase of the secondary field takes place over a three-decade range of the conductivity-thickness-frequency product. Only small changes in the amplitude and

Jan 1, 1961

By Bryan J. Travis, Thomas L. Cook

INTRODUCTION Our growing concern for adequate and secure sources of energy and minerals has stimulated vigorous exploration for new sources, research toward a better understanding of geological processes, and development of new extraction technologies. The need for control, or at least prediction, of subsurface fluid flow is important for many of these technologies for example: primary, secondary and tertiary recovery of oil; ground water and waste management; in-situ fossil energy extraction (oil shale, coal, tar sands); and solution mining of uranium, copper and other minerals. These technologies, especially the last two, are characterized by highly complex systems. A partial list of the physical processes occurring would include flow in porous/fractured media, multi-phase and multi-component flow with heat transport, chemically active fluids and soils, tracers, diffusion and dispersion, fracturing and dissolution. A great deal of understanding of how these processes behave and interact can be obtained from models. MODELS Theoretical models are valuable because they: 1) provide a frame of reference for interpreting results of laboratory and field experiments; 2) once validated by experiments, allow a variety of geometries, injection/production strategies, etc., to be examined (at relatively low cost) for efficiency and stability; 3) can provide guidance to the design of experiments and field operations. Most models are based on the fundamental principles of mass, momentum and energy balance. But from this starting point, many paths can be taken. For example, there is the theory of Payatakes (1973) which concentrates on the microscale dynamics. In this approach, the rock or soil matrix is represented by a complex of characteristic channels (such as periodically constricted smooth tubes). Detail of flow within the characteristic channel is calculated very accurately. A difficulty with this model is that description of a representative channel can require several parameters which may not be easily measured. Also, it is not clear how the channels can be combined practically to model a large scale flow. Another type of model is the "global" one described by Bear (1972). Here, the continuum equations for conservation of mass, momentum and energy are averaged over a distribution of pore channels, resulting in a set of conservation equations in which the small scale structure of the medium is replaced by quantities such as porosity, permeability, dispersion coefficients and tortuosity. This approach allows computation of large scale flows. However, additional constitutive equations are needed which relate averaged quantities such as permeability to observables such as local saturation, particle size distributions, and others. An important difference between models is the way they handle the momentum equation. Payatakes' model solves the full equation. In others, it is replaced by a simpler relation such as Darcy's law (valid for slow flow rates) or by Forchheimer's equation which extends Darcy's law to higher flow rates. These simple relations can nevertheless match a great deal of experimental data (Dullien 1975). The permeability term which appears in Darcy's law and in Forchheimer's expression has been related to other quantities such as porosity and particle surface area. The Kozeny-Carmen equation is a well-known example, valid for some ranges of porosity and particle sizes and for some materials. Several other semi-theoretical, semi-empirical formulations have been devised, none of which are entirely satisfactory. One goal of researchers has been the ability to predict permeability of a porous material from basic measurable quantities such as grain size distributions without recourse to adjustable parameters. This effort has proceeded from consideration of distributions of idealized, non-intersecting channels, to intersecting channels, to consideration of both distributed pore radii and pore neck radii. This last approach has been used successfully to predict permeabilities (ranging over several orders of magnitude) in sandstones (Dullien 1975). Additionally, studies on explicit networks of channels (e.g., Fatt 1956) and percolation theory (e.g., Larson et. al. 1981) have been used to examine interconnectivity effects in porous media with the hope of eventually being able to predict permeability accurately. To be of more than theoretical interest, a model must be compared s controlled laboratory conditions where boundary and initial conditions and relevant material properties can be accurately determined. Also, extraneous forces can be eliminated so that the interactions between processes of interest can be clearly seen and flow models can be vigorously tested. In contrast to the well-defined environment and

Jan 1, 1982

By Raynor Linzey, Karl M. Busen

The formation of thin films of silicon oxide by anodic oxidation of silicon and the subsequent removal of these films by an etch is a process often used for the evaluation of concentration distributions Profiles) in silicon layers by the differential sheet conductance method. The accuracy of the resulting profile is very strongly influenced by the uniformity of the thickness of the reacted silicon. Normally, it would be expected that for a constant number of coulombs passed the thickness would be the same from oxidation to oxidation. Investigations show that in certain electrolytes, for a given number of coulombs passed through an n-type silicon sample, the thickness of the reacted silicon increased with increasing resistivity. Even for the same resistivity the thickness varied sometimes by a factor of 1.5. When an electrolyte was used which consisted of 10 pct water by volume in ethylene glycol with 4.0 g KNO per 1000 ml of solution, anodiza-tion at 5 ma per sq cm led to satisfying results. Short-time anodizations gave oxide layers of a higher apparent density than those experienced from thermally gown silicon oxides. THE functioning and the electrical characteristics of semiconductor devices are based upon the incorporation of "impurities" into a single-crystalline body of suitable material and on the concentration distribution (profile) of this impurity. The incorporation can be achieved by well-known processes as, for example, by diffusion, epitaxial growth, alloying, or ion implantation. Often the profile resulting from these processes is not known. A powerful tool to learn about a concentration distribution is given by the method of differential sheet conductance which employs successive four-probe measurements on a layer subjected to stepwise removal of thin sublayers. Differential sheet conductance vs position (or penetration depth) of a sublayer is plotted and a smooth curve is drawn through the data. From this curve the profile is then calculated. When the semiconductor material is silicon, the sublayers are removed suitably by anodic oxidation of the silicon and subsequent dissolving of the formed silicon oxide by an etch. The accuracy of the resulting profile is very strongly influenced by the uniformity of the sublayer thickness. Normally, it would be expected that, for a constant number of coulombs passed, the thickness would be constant from oxidation to oxidation. Investigations showed that for sublayers several hundred angstroms thick the reproducibility can be rather poor. Therefore, efforts were made to obtain a reliable technique for uniform removal. The present paper describes such a technique and certain phenomena which were encountered during the investigations. APPARATUS AND TECHNIQUE The first report on the investigation of concentration distributions, where for differential sheet conductance measurements thin silicon sublayers were removed from a diffused layer by anodic oxidation, was given by Tannenbaum. The author reports the removal of sublayers which for the most part were 400 thick. More advanced device designs now require much narrower layers. When it was tried in these laboratories to determine profiles within such layers, difficulties were encountered with respect to sublayers which by necessity had to be thinner than the ones reported by Tannenbaum. The apparatus used for the investigations is sketched in Fig. 1. Two cylindrical containers connected by a wide tube are filled with an electrolyte. The left container receives the cathode whereas the right container is closed at the bottom end by a sample support consisting of a Teflon base and a copper pedestal. The silicon sample (1 by 1 cm) is mounted to the pedestal embedded flush in the Teflon base using silver paint (Degussa) for electrical contact. Pyseal is applied to the edges of the sample to protect the copper pedestal from the electrolyte. The base is mounted to the container using a water-tight silicon rubber gasket. Fig. 2 gives a view of the sample support. The copper pedestal is connected to the positive side of a power supply operating at a constant current output (Kepco Model ABC 425M). The electrolyte which has been reported by Duffek et al. consisted of either 2 or 10 pct water by volume in ethylene glycol and 4.0 g KNO3 in 1000-ml solution. The electrolyte is best prepared

Jan 1, 1967

By P. Martinez, A. F. Hoyte, F. E. Senftle

The possibility of applying a neutron activation technique for silver exploration is considered. A mobile positive-ion accelerator type neutron source is used to irradiate a small area of rock or soil in situ. By using a short period of irradiation and gamma ray spectral analysis, a technique is shown for silver exploration. Two different mobile units are described. Laboratory and preliminary field tests both indicate that a sensitivity of less than 1 oz of silver per ton of ore can be achieved. The increasing consumption of silver for industrial uses and also for coinage has caused a serious shortage of silver in this country. The silver shortage has been reviewed and analyzed by kiilsgaard1 who concludes that, "The best hope for meeting future demands for silver is through accelerated exploration for precious ores." As almost all the exposed "bonanza" type silver deposits evidently have been found, it is urgent that some sensitive geophysical technique be found to detect large, extended, but generally low-grade, secondary ores, as well as hidden vein deposits. Silver is easily made radioactive by exposure to slow neutrons; hence a neutron activation method appears promising for locating silver deposits. The principles of mineral beneficiation using neutron activation techniques were discussed some years ago.2-4 Using the same approach, a preliminary description5 has been published of neutron activation as a mineral exploration tool. An exploration technique is described in which silver is made radioactive in situ and detected with a gamma radiation counter. The technique is similar to the well-known method used for uranium exploration. THEORETICAL CONSIDERATIONS Elemental silver consists of two isotopes, Ag107 and Ag109, having naturally occurring isotopic abundances of 51.4% and 48.6%, respectively. For short periods of irradiation of silver by thermal neutrons, the long-lived 250 day, half-life isotope, Ag110m, is not produced in significant quantities. However, significant quantities of 2.3 min half-life Ag108 and 24.5 sec half-life Agl10 are formed by the following reactions. Ag108 and Agl10 emit a 0.44 Mev (million electron volts) and a 0.66 Mev gamma ray, respectively. Ag107 + n + Ag108 (2.3 min) Ag109 + n + Ag110 (24.5 sec). Because of the large capture cross section (110 barns) of Ag109, and short half-life of Ag110 (24.5 sec), the 0.66-Mev gamma ray is the most prominent emission from silver for neutron activation periods of about a minute's duration.* The 0.44-Mev gamma ray from Ag108 will also be present, but will be one or two orders of magnitude lower in intensity. The decay scheme of Ag110 is shown in Fig. 1. If the neutron irradiation time is limited to about 100 sec, the Ag110 activity will essentially reach saturation and can be used to detect the presence of silver. In a neutron flux of 10 8 neutrons/cm2/set, the induced 0.66-Mev activity in 1 g of silver will be about 2 x 107 disintegrations per sec. This is about 1000 times the measurable gamma activity of 1 g of uranium in equilibrium with all its decay products; hence there is ample activity for detection. Under the same conditions of activation, most of the other elements do not reach this relatively high disintegration rate. Although this is in favor of the proposed technique, other problems must be considered. For mobile operation, it is desirable to obtain the largest neutron flux to weight ratio. Hence we have used a small 150-kev accelerator-type neutron source rather than an isotopic source such as an americium-beryllium neutron source. By use of remote control system, an accelerator-type neutron source can be safely used without the massive shield required for an isotopic source. Moreover, an accelerator-type source is more versatile in that it allows one to use a flux of either 14-Mev or 3-Mev neutrons, depending on whether a tritium or a deuterium target is used. With a 14-Mev generator, one can obtain a flux of 10 9 neutrons/cm 2/sec, and with a 3-Mev generator, the flux is generally two orders of magnitude less. Although silver will become activated with either generator using proper moderation, detection may be

Jan 1, 1968

By V. Koump, T. F. Perzak, R. G. Olsson

The rate of dissolution of recrystallized alumina in molten iron oxide in equilibrium with iron at 1450°C was studied by rotating alumina disks in the melt. The samples were rotated from 1 to 12 min at speeds from 54 to 3270 rpm. It is concluded from the experimental results that the process is limited by diffusion in the liquid boundary layer. The interdiffusion coefficient for the dissolution of alumina disks in pure molten iron oxide was estimated to be about 3 xl0-5= sq cm per sec. THE erosion of refractory materials is of considerable importance in iron- and steelmaking processes. Since many refractories contain alumina, this investigation was undertaken to develop a further understanding of the erosion mechanism. Shurygin et al.1-3 have investigated the rate of dissolution of alumina in molten silicates and molten fluorides by rotating alumina disks in various melts. The rates were reported to be limited by diffusion in the liquid boundary layer. In the present investigation the rate of dissolution of alumina in molten iron oxide in equilibrium with iron was studied in a similar manner; alumina disks were rotated at different speeds in molten iron oxide at 1450°C. The relationship between the rate of dissolution of the flat surface of the disk and the speed of rotation was used to determine whether the process is limited by diffusion in the liquid boundary layer or by some chemical reaction mechanism. APPARATUS AND EXPERIMENTAL PROCEDURE A schematic diagram of the experimental apparatus is shown in Fig. 1. The iron oxide melts were contained in 2-in.-diam high-purity iron crucibles that were centered in a cylindrical graphite susceptor. Prior to each sequence of experiments, sufficient reagent-grade ferric oxide was added to a crucible to form approximately 350 g of molten iron oxide; the depth of the melt was about 11/2 in. To prevent excessive erosion of the crucible, about 70 pct of the required iron was added to the crucible in the form of iron powder. The mixture was melted in an atmosphere of purified argon by induction heating with a 250-kc generator. After the oxide was molten, a Pt/Pt-10 pct Rh thermocouple at the exterior of the crucible was calibrated against an iron-sheathed thermocouple immersed in the melt and was thereafter used to regulate the melt temperature. All experiments were conducted at 1450°C with a probable error of 10°C. The alumina disks were constructed from pure re-crystallized alumina having a density of 3.7 g per cu cm (porosity approximately 6 pct). For each disk sample a 1-cm-diam alumina cylinder of known length (0.9 to 1.0 cm) was cemented into a ground seat at the end of a 1.27-cm-OD centerless ground alumina tube. The ends of the tube and cylinder were flush and served as the disk surface. When mounted in the apparatus the alumina tube was guided by tungsten carbide bearings and rotated by a variable-speed motor. The bearing and drive assembly could be raised and lowered in order to allow the sample to be quickly moved in and out of the melt. At the start of an experiment, a sample was preheated for several minutes directly above the melt, and then immersed in the middle of the melt to a depth of a in. and rotated for 1 to 12 min at speeds of 64 to 3270 rpm. The speed of rotation was measured by a hand tachometer. At the start and completion of each experiment, a melt sample was withdrawn with a cold copper rod and the alumina content was determined by chemical analysis. During individual experiments the alumina concentration of the melt changed by the order of 0.25 wt pct. Average melt compositions for individual experiments were used in the subsequent computations and were in the range between 0.12 and 4.3 wt pct alumina. The extent of dissolution was determined by sectioning the end of the sample and measuring the final length of the alumina cylinder with a microscope. Since the exposed end of the cylinder, i.e., the disk surface, was etched in a manner characteristic of this geometry, a number of measurements were made on

Jan 1, 1969

By R. J. Wasilewski

Electrical resistivity variation with temperature was measured on a series of alloys containting up to 33 at. pct of oxygen over the range 77° to1500°K. The resistivity behavior is highly anomalous and itzconsistent with simple metallic conduction. Both composition and temperature-depended resistivity singularities were observed. A few experiments carried out on Ti-N and Zr-O alloys indicate the presence of similar anomalies. These observations, together with the published data on effects of substi-tutional alloying on the resistiuity of titanium, suggest that the anomalies are inhevent in the electron structure of this group oj metals. The existence of two-band conduction, and a significant shift of bands relative to each other with temperature and/or the electron concentration are suggested. CONSIDERABLE advances have been made in recent years in the alloy theory of simple metals. Very little, however, is known about the bonding in transition metals and their alloys.&apos; Titanium, with its relatively few electrons, may be expected to show simpler alloying behavior than the more complex transition elements. Its alloys with the interstitial elements appear particularly attractive in an investigation of bonding characteristics because of a) the simple nature of the solute elements, b) the remarkable similarity between the equiatomic structures Tic, TiN, and TiO, and c) the extensive solid solubility ranges of oxygen and nitrogen in a titanium reported.2,3 The Ti-O system was chosen for the most extensive investigation because of the relative ease of preparation of suitable specimens. Since the main object of the work was to obtain data on the bonding and its changes on alloying, electron-sensitive properties were primarily investigated. The present work describes the investigation on the electrical resistivity-temperature-oxygen content relationships. A few experiments were also carried out at selected compositions in the Ti-N and Zr-O systems. EXPERIMENTAL Materials and Method. Polycrystalline specimens were prepared in the form of hairpin strips some 50 by 5 by 0.15 to 0.50 mm by direct metal-gas reaction. This was carried out by controlled oxidation followed by a homogenizing anneal at a higher temperature. All the test specimens were fully homogenized as judged from the uniform microstructure and microhardness. To avoid preferred orientation, each strip specimen was annealed in the ß range prior to the oxidation, this procedure assuring random orientation in the strip;4 hence any texture resulting from the oxidation reaction itself affected all the specimens to a similar extent. Titanium used was of high purity (66 DPN, 10 Kg load; major impurities 0,-43G ppm, N,-70 ppm, C-25 ppm, Fe-14G ppm). The solute content of the alloys was determined by weighing, after the reaction with a known amount of oxygen. The specimens in which the discrepancy between the volumetric and gravimetric measurements exceeded 2 pct (or 0.2 mg for the low oxygen alloys) were rejected. The mean between the two measurements was then taken as the oxygen content of the alloy. Check analyses showed no measurable nitrogen contamination. All oxygen contents are given in atomic percent. Zr-O alloys were prepared in identical manner from hafnium-free crystal bar metal, cold-rolled to strip 0.25 mm thick. Ti-N alloys required very long reaction times at the maximum temperature available (1250°C). In order, therefore, to detect possible oxygen contamination, duplicate specimens were reacted in every experimental run, and one of these was analyzed both for oxygen (vacuum fusion) and for nitrogen (Kjeldahl). Only the specimens in which the check analysis showed < 1000 ppm O were then used for resistivity investigation. Since only relatively high nitrogen alloys (7.1 at. pct; i.e., 2 wt pct N,) were investigated, this oxygen contamination was considered permissible. Dc resistance was measured by the four-probe method as previously described.= The temperature was determined with a calibrated thermocouple placed in the center of the specimen hairpin. The errors in the specimen resistance values thus obtained were estimated at 1 pct due almost exclusively to the finite thickness of the potential wires and the consequent uncertainty as regards the true resistance length of the specimen. For the calculation of the specific resistance, however, no dimensional measurements could be carried out on most of the

Jan 1, 1962

By H. H. Klepfer, M. E. Snyder

UNTIL very recently, the commercial availability of the rare earths as metals has been very limited. Fabrication of mill products from these metals has not been studied in most cases. This note reports the results of the development of fabrication techniques for thulium. Thulium has a melting point of about 1550°C and a hexagonal close-packed crystal structure. It oxidizes in air to give a black oxide (TmzO,). The procedures for producing thin thulium foil were developed on one ingot weighing about 220 g and were subsequently applied in processing about a pound of metal to foil. Several alternates for the various fabrication steps were investigated and will be discussed. The metal fabricated was in the form of commercial chill-cast ingots 1 in. in diam and 2 in. long weighing approximately 220 g. Impurities in the ingots were reported by the vendor to be 4000 ppni tantalum, 2000 ppm calcium, 200 ppm nickel, 100 to 200 ppm iron, 100 ppm europium, and less than 100 ppm copper, lutetium, and ytterbium. In addition to these impurities, several salt-like inclusions as large as l/8 in. in diam were revealed along the center line of the one ingot sectioned. Preliminary tests indicated that small wafers cut from the as-cast ingot would not fabricate readily by rolling. Forging of copper-jacketed wafers was therefore attempted. At 1550"F forging was satisfactory but an apparent reaction of copper with thulium demanded investigation of lower temperatures. Therefore, the remainder of the test ingot was forged at 1450°F—with only minor cracking. All ingots forged were inserted into copper tubes of 1 in. 1D and 0.125-in. wall thickness. The jackets were sealed by flattening the ends of the tubes and welding under helium. Heating time at 1450°F was 30 min. Press forgings of 1/8 in. per pass were used, followed by 10 min reheats. When the ingots had been squared and reduced to 0.250 in. in thickness, the original copper jacket was stripped off and replaced by a new jacket in preparation for hot rolling. Hot rolling at 1450" F without edge cracking was readily accomplished after forging. Excellent results were obtained with 10 pct reductions of thickness followed by 5 to 10 min reheats. After reduction of thickness from 0.250 to 0.100 in. the copper jacket was removed. It was found, in fact, that hot rolling in air was possible. A tenacious black oxide similar to that seen on zirconium was formed during 3 min reheats at 1450°F. Reduction in air to 0.010 in. foil was possible taking 10 pct reductions per pass. The oxide coat formed during hot rolling in air could best be removed by sand blasting and pickling. Common pickling solutions containing polar solvents were found to attack the metal too rapidly and a concentrated nitric-hydrofluoric acid mixture attacked neither the oxide nor the metal. The most satisfactory pickling solution was 52 vol pct concentrated nitric acid-48 vol pct glacial acetic acid. After forging to 0.250 in., vacuum annealing and cold rolling was found to be another satisfactory alternate to hot rolling in copper jackets. After forging. a hardness of Rockwell B76 was found. Annealing in vacuum (2 X l0-5 mm of Hg) for 1 hr at 1200"F did not alter this value. Annealing at 1470"F for 1 hr brought the hardness down to R;]63. With cold rolling (5 pct per pass) the hardness returned to about R,1:76 after 20 pct reduction and edge cracking became noticeable. However, cold rolling to a total of 40 pct reduction in thickness (RI,,83) was possible before edge crack propagation became serious. Good surface finish was obtained, and the metal loss due to oxidation was minimized by cold rolling and vacuum annealing. Using this procedure the yield of 1.25 in. wide by 0.010 in. thick foil from a 1-in. diam ingot was about 40 pct.

Jan 1, 1961

By A. W. Sommer, H. H. Kellogg

It is shown that SO3-O2 mixtures react with sphalerite at an appreciable rate ill the temperature range of 361° to 527°C to fornz ZnSO4. The rate of reaction follows a parabolle lax. Oxygen, or O2-SO2 mixtures, have a negligible effect on sphalcrite in the same temperatuee range. PRACTICAL roasting of sphalerite is usually performed at 800°C or higher. The calcine is composed of zinc oxide unless the roaster atmosphere contains relatively large amounts of SO2 and the temperature is held to 800oC or lower, in which case zinc sul-fate may also form. Ong, Wadsworth, and assell&apos; have made a careful kinetic study of sphalerite oxidation under these "normal conditions" and have concluded that the rate of the reaction is controlled by the decomposition of an activated complex adsorbed on the sphalerite surface. They found the rate of oxidation to be small at 700°C. Extrapolation of their data to 400°C would indicate an almost negligible rate at this temperature. In our work sphalerite was reacted with air, mixtures of SO2, O2, and N2, and mixtures of SO3, O2, and N2 in the temperature range 361o to 527OC. Negligible rates of oxidation were found, except for the gas mixtures containing SOs. With this latter gas, the oxidation of finely divided sphalerite was fairly rapid and zinc sulfate was the product. Based on the limited evidence available, the rate of sphalerite oxidation by SO3 is postulated to be controlled by gaseous diffusion through pores or cracks in the zinc-sulfate coating. This evidence for the direct reaction of sphalerite and SO, at low temperature may prove of importance to the understanding of zinc-sulfate formation in the dust-collecting equipment usually associated with zinc roasters. The roaster gas carries off fine dust, much of which may be unreacted sphalerite. The temperature in dust-collecting equipment drops from the roaster temperature (about 800°C) through the range of temperature we studied, to ambient temperature. Such dusts are known to contain far larger amounts of zinc sulfate than the primary calcine. It has been assumed in the past that this sulfate is formed by reaction of ZnO dust with SO3 (or SO, plus 0,) in the partly cooled gases. Our work shows that an alternative possibility exists—the direct reaction of SO3 with ZnS dust. EXPERIMENTAL Reaction rates for sphalerite at 350° to 600°C are relatively small so that it was necessary to use finely divided material with a relatively large surface area in order to obtain measureable amounts of reaction. In the preliminary experiments, pure mineral sphalerite, ground to pass a 325-mesh sieve, and chemically precipitated ZnS (in the form of an impalpable powder) were used. In the quantitative rate experiments the ground mineral sphalerite was processed in an Infrasizer to obtain a product with particle size between 9 and 18 µ. The analysis of this material was 66.7 pct Zn, 0.09 pct Fe, and 32.7 pct S (theoretical sphalerite is 67.1 pct Zn, 32.9 pct S). The sized powder was carefully mixed and divided into l-g samples. The apparatus used for the quantitative rate measurements is shown in Fig. 1. For the preliminary experiments the following change was made: The external catalyst furnace (B, C)* was not used. *Letters refer to Fig._______1 .___- Rather, when catalysis of the SO2 + O2 reaction was desired, the glass beads in basket M were replaced by vanadium-oxide pellets. Procedure—A l-g sample of ZnS was placed on a shallow stainless-steel tray, I, and spread evenly to a depth of about 1mm. The tray was placed in the reaction assembly and the assembly inserted in the cold furnace. The furnace tube was flushed with dry argon and then heated to the desired reaction temperature. The temperature was controlled to ±0.5oC. Gas mixtures (O2 + N2 or O2 + SO2) were prepared from tank gases by means of a mixing device identical to that employed by Darken and Gurry.2 The total flow rate of gas was 205 ml per min to point A of Fig. 1. The accuracy of the individual and

Jan 1, 1960

By Alan Stanley

THE Maclntyre Development of National Lead Co. is located at Tahawus, N. Y., in the heart of the Adirondack Mountains. Operations involve the mining and concentrating of a titaniferous iron ore to produce ilmenite and magnetite concentrates. A general description of the operation and metallurgy has been given by Frank R. Milliken.1 Pigment plant production demands that the MacIntyre mill produce a 44.7 pct. TiO2 ilmenite concentrate. To achieve the required ilmenite grade and tonnage it is important that the table concentrate grade be closely controlled. Unfortunately, however, the titaniferous orebody which feeds the Maclntyre mill is not uniform. Ore dressing characteristics vary from one end of the orebody to the other, and from one level to the next.. The changeable nature of the mill feed precludes a single adjustment of the equipment for long periods of time. Thus the operators must constantly watch the equipment to insure a uniform concentrate from the fine and coarse tables and Wetherills, or dry magnetic separators. Chemical assaying of mill products requires about 4 hr from the time the sample is taken until assay results are obtained, and this is available only on a two-shift basis. The ore may change rapidly, even several times during a shift, so that assay results lose most of their control value by the time they are reported to the mill operating crew. Members of the crew have therefore tried to evaluate the table and Wetherill concentrate by visual inspection, since through long experience the shift operators, under most circumstances, can gage closely the grade of the mill products. However, there are times when the, physical nature of the ore is radically different from normal. Under these conditions visual inspection is of no value, and at such times final ilmenite as low as 43 pct TiO2 has been produced and shipped before the assay results have been received. The specific gravity method of assaying for TiO2 has been attempted to eliminate the shipping of ilmenite below normal grade as well as to help control day to day and hour to hour mill production. Table I shows the minerals found in the Maclntyre ore along with their average weight proportions and specific gravities. The first two products considered for the specific gravity method were fine and coarse table concentrates. It was reasoned that these products were essentially ilmenite with the higher specific gravity gangue minerals. Since they were always produced the same way, and the desired grade of TiO2 was always constant, the specific gravity of these materials would increase or decrease as the amount of ilmenite increased or decreased. Thus for table concentrates which assayed 40 pct TiO2 a constant gravity would invariably be obtained, and as the TiO2 value changed the specific gravity would change in direct proportion. The third product considered was Wetherill ilmenite. It was assumed that a desired grade of 44.7 pct TiO2 would also always contain the same amount and type of gangue minerals along with the ilmenite, and thus would always have the same specific gravity. As the TiO2 value of the ilmenite concentrate changed so would its specific gravity. Dr. Kenneth Vincent, chief metallurgist of the Baroid Division of National Lead Co. at Magnet Grove, Ark., ran specific gravity tests on 17 samples of the desired products. The lowest specific gravity reading assayed the lowest in TiO2 and as the specific gravity increased the trend was for the TiO2 assay to increase, see Fig. 1. Since these results warranted further investigation, a 500-g capacity Torsion balance and 250 ml Le Chatelier specific gravity bottles were obtained. [ ] Shift samples of fine table concentrate, coarse table concentrate, and final ilmenite were tested. Each sample was split and 85 g weighed on the Torsion balance. The Le Chatelier bottle was filled with water to a zero mark. To avoid wetting the neck of the bottle it was found necessary to do this

Jan 1, 1952

By D. B. Hunter, H. W. Rosenberg

The titanium-rich portion of the Ti-Pd system was investigated from 0 to 75 wt pct Pd by metallo-graphic and X-ray techniques. A 0 eutectoid occurs at 24 wt pct Pd and 1190°F. Two compoutzds are indicated in the region below 75 wt pct Pd, Ti,Pd and Ti2Pd3. The solubility of palladium its a titanium is low, probably less than 1 pct. In 1960 Rudnitskii and Birunl published a complete version of the Ti-Pd phase diagram. However, their work was in disagreement with the earlier literature in that they reported only one inter metallic compound, whereas three had been reported earlier. In view of these discrepancies, it was therefore necessary to redetermine those portions of the diagram of immediate interest. The following account describes our work on the system over the range of 0 to 75 wt pct Pd. MATERIALS AND METHODS Distilled titanium sponge and elemental palladium were used in the formulation of the alloys; the chemistry of these materials is detailed in Table I. The alloys were prepared as 10 to 50 g blended compacts that were melted into buttons by arc melting under gettered argon on a water-cooled copper hearth. Weighing of the ingredients before and after melting showed that negligible weight changes occurred. Therefore, no analyses were undertaken and the compositions of all alloys are nominal. All alloys were fabricated by hot rolling at 1700°F to 0.070-in.-thick sheet. Scale was removed by sandblasting and pickling in a 5 pct HF-35 pct HNO,, balance H20 solution. For metallographic examination, specimens were mounted after heat treatment transverse to the rolling direction, ground on silicon carbide papers of increasing fineness to 600 grit, and then electro-polished using a solution containing 600 ml me-thanol, 60 ml perchloric acid, 360 ml butyl cello-solve, and 2 ml "Solvent X". Unless otherwise specified, etching of alloys containing up to 42 pct Pd was carried out by swabbing with a 12 pct HN03-1 pct HF aqueous etch where a bright etch was required, or by a 1 pct hydrofluoric in saturated oxalic acid solution where contrast between phases was required. The Ti-52.8 Pd alloy was etched with a solution of 25 ml HF, 40 ml glycerine, 35 ml methanol, and 18 g benzalkonium chloride. For X-ray examination, 1/2-in.-square speci- mens of sheet were mounted flat in a standard 1-in. metallographic mount and ground and polished as above. X-ray diffraction was performed using a Norelco type 12045 Diffractometer, employing CuKa radiation with a nickel filter at 40 kv and 20 ma. Specimens were rotated about the sheet normal during exposure. Although this procedure did not remove the effects of sheet texture from the relative intensities, it had the advantage that oxidation or contaminants entering during preparation of powder samples could not confuse the patterns obtained. RESULTS AND DISCUSSION Fig. 1 illustrates the Ti-Pd phase diagram according to Rudnitskii and Birunl with the work of the present authors superimposed. Both interpretations agree that the system is of the 0 -eutectoid type with an extensive 0-phase field, and that the eutectoid temperature is just below 1200°F. There is also agreement that the solubility of palladium in a titanium is restricted. Our work would indicate that the a solubility of palladium is low, probably less than 1 pct. However, whereas Rudnitskii and Birunl place the eutectoid composition at 41 wt pct Pd, this investigation shows it to be at about 24 wt pct Pd. Moreover, this investigation confirms the existence of compounds at Ti2Pd and Ti2Pd3, whereas Rudnitskii and Birun report only a single Berthol-lide phase covering the TiPd to TiPd, range. Laves et a1.&apos; and Wallbaum, whose work was summarized by Maykuth , reported the existence of Ti2Pd3 and TiPd, in addition to Ti2Pd. More recently, Nevitt and Downe~&apos; have reported the structure of

Jan 1, 1965

By D. W. Mitchell

INE operators have a choice of several classi- fications of mechanical loaders. Within each classification there are many types and makes available. Table I lists loaders on which manufacturing data as to operating characteristics are available. This paper discusses the conditions met in a mine as they affect these characteristics. It is assumed that management will provide satisfactory engineering, supervision, power, maintenance, loader service within a concentration of workings, and a balanced working cycle served by balanced production equipment. These are factors which affect the optimum operational efficiency of a loader. The conditions which determine loader choice are: Height of Vein—The main limitation to the use of a loading machine is the height to which the vein is mined; i.e. a loader cannot be higher than the place in which it is to work unless rock is taken. Since there are several low vein loaders being developed and successfully applied, this does not appear to be a requisite of an efficient mining operation. The maximum useable height of a loader should be equal to the working seam thickness less a working clearance for travel and operation. A—Working seam thickness = B—Artificial roof support thickness = C—Safe headroom below support = (generally about 6 in.) D—Height of roadway = E—Total of B + C f D =_______________________ A—E = maximum loader height F—Distance from top of roadway to bottom of roof support = G—-Height of loader&apos;s coal or ore line (see Table I) = H—Difference between F and G = Size of largest broken particle + a safety factor of 2 to 3 in. H is a loadability factor and is important because the clearance over the top of the conveyor chain to the roof or roof support must be greater than the largest broken particle or else the particle and/or the conveyor chain may be broken. From this standpoint it might be desirable to use a lower height machine even though it may have a smaller capacity, though this is warranted only when increased lump realization offsets lower man-day and machine pro- duction rates. Ivan Given has stated, "Loading should not be handicapped by securing lump only to grind it in the breaker." Width of Working Place—The width of a working place is the greatest width a place may be safely driven. The working place includes not only the face but the roads the loader must tram when mucking out more than one face. The width is limited by the system of placing props with sufficient room between them for the machine runner (about 2 ft). Maximum width of place in which the loader will operate at maximum efficiency is determined by the type of mounting. With track-mounted loaders, maximum width of place is determined by maximum angular swing of the loading head and proximity of track to the face. The use of double track leads to added expense and operational complexities. Several mines that have used double-track systems have found that a substantial saving is made by the use of machines that load out wider places. Trackless loaders may work in rooms of any maximum width. Minimum width of place in which a loader will operate is determined by width of the loader plus a safe movement area for the operator. Often a barodynamic study of the mine will show that either an increase in room width and/or a change in the system of propping may be made by using roof bolting, full or part-width room timbers, removable aluminum I-beams at the face, etc. Increasing the width of a working place will, in general, increase loader operating efficiency by providing more material per fall and by decreasing the preparation and moving time per ton. A change in the system of propping that would increase the minimum width might permit the use of a higher capacity loader with safer working conditions. Proper face tirnbering is necessary to insure safety from roof falls and because the speed of preparation and loading generally increases since the men work with greater assurance and there is less chance of kicking out posts. Maximum Room Length—With the exception of the scraper and the duckbill, the limit to room

Jan 1, 1952

By A. E. Wraith, N. J. Petch, J. D. Embury, E. S. Wright

The two most important parameters controlling the fracture behavior of a solid are its intrinsic properties, e.g.,grain size, and the operative stress system. The latter may be modified in laminates by the presence of weak interfaces. This is studied in notch-impact tests on a mode1 system of mild steel laminates containing a variety of interfaces. The effect of these is evaluated in terms of the ductile/cleavage transition. Two laminate geometries are distinguished, here called "crack-arrester " and "crack-divider". In both, cleavage is inhibited. This arises because of relaxation of a state of triaxial tension. In the crack-avrester laminates, cleavage initiated at a notch is confined to the layer containing the notch. In crack-cliuider laminates, a thick specimen behaves as the Sum of a number of thinner ones. Additional benefit may derive from improved intritnsic propevties of- the lanlinate layers arising from greater deformation in their manufacture. It has long been recognized that the two most important parameters controlling the fracture behavior of solids are their intrinsic properties (e.g., grain size friction stress,3 distribution of second phase particles4) and the operative stress system under which fracture occurs. In solids that show a ductile/cleavage transition, cleavage is favored by the presence of a notch. This is because triaxial tensions, generated by the localized plastic constraint at the notch, are operative when fracture occurs.= Anything that suppresses these triaxial tensions will be unfavorable to cleavage. Such suppression may possibly occur in laminates containing weak interfaces and the purpose of the present paper is to explore this possibility. Two basic laminate geometries, here termed "crack-avrester" and "cvack-divider", are examined. They are illustrated in Fig. 1. With the crack-arrester laminates, there is the possibility that, when the fracture crack approaches the interface, this, if weak, may delaminate due to the tensile stress acting parallel to the plane of the crack.= If this happens, energy will be used in delamination, the crack will be completely blunted, and the triaxial tension associated with the crack will be relaxed. To fracture the second portion of the laminate, crack reinitiation will be necessary and, because of the relaxation of the triaxial tension, this reinitiation will occur under conditions of nearly uniaxial tension, which are unfavorable to cleavage. Thus there is the possibility of cleavage suppression in the second and subsequent subunits of a crack-arrester laminate. With the crack-divider geometry, there is again the possibility of delamination at the interfaces. This will divide the crack into a series of cracks propagating through the individual laminate subunits. If these are sufficiently thin, the triaxial tension will be relaxed towards a state of biaxial tension in each of them. Thus, with the crack-divider laminates, there is again the possibility of cleavage inhibition. In the present work, these possibilities are explored using a notched impact test on mild steel laminates bonded with soft solder, silver solder or copper. Even if delamination does not occur, it is still possible that cleavage may be inhibited in laminates. With the crack-arrester geometry, the cleavage crack in the first layer may be blunted and arrested by plastic deformation in the laminate bond, if this is ductile. Partial relaxation of the stress transmitted ahead of the crack into the second layer will then result and this will reduce the significance of this stress in the fracture of the second layer. With the crack-divider geometry, there cannot be much effect in the absence of delamination unless a large amount of energy is absorbed in rupturing the ductile material. EXPERIMENTAL DETAILS The composition of the mild steel (wt pet) was: 0.04 C, 0.29 Mn, 0.01 Si, 0.006 P, 0.008 S. "As-received" plate was annealed for 2 hr at 900°C and slowly cooled to give a grain size of 0.04 mm. The laminates were made by brazing or soldering together mild steel plates 8 by 3 in. by various thicknesses. These were obtained from the annealed plate by machining, so that the intrinsic material properties were .kept constant. Laminates containing two to six steel layers were studied using standard Charpy V-notch specimens cut from the bonded plates. Standard homogeneous specimens from the annealed plate and subsize ones from the laminate components

Jan 1, 1968

By Alan Stanley

THE MacIntyre Development of National Lead Co. is located at Tahawus, N. Y., in the heart of the Adirondack Mountains. Operations involve the mining and concentrating of a titaniferous iron ore to produce ilmenite and magnetite concentrates. A general description of the operation and metallurgy has been given by Frank R. Milliken.&apos; Pigment plant production demands that the MacIntyre mill produce a 44.7 pct TiO, ilmenite concentrate. To achieve the required ilmenite grade and tonnage it is important that the table concentrate grade be closely controlled. Unfortunately, however, the titaniferous orebody which feeds the MacIntyre mill is not uniform. Ore dressing characteristics vary from one end of the orebody to the other, and from • one level to the next. The changeable nature of the mill feed precludes a single adjustment of the equipment for long periods of time. Thus the operators must constantly watch the equipment to insure a uniform concentrate from the fine and coarse tables and Wetherills, or dry magnetic separators. Chemical assaying of mill products requires about 4 hr from the time the sample is taken until assay results are obtained, and this is available only on a two-shift basis. The ore may change rapidly, even several times during a shift, so that assay results lose most of their control value by the time they are reported to the mill operating crew. Members of the crew have therefore tried to evaluate the table and Wetherill concentrate by visual inspection, since through long experience the shift operators, under most circumstances, can gage closely the grade of the mill products. However, there are times when the physical nature of the ore is radically different from normal. Under these conditions visual inspection is of no value, and at such times final ilmenite as low as 43 pct TiO, has been produced and shipped before the assay results have been received. The specific gravity method of assaying for TiO, has been attempted to eliminate the shipping of ilmenite below normal grade as well as to help control day to day and hour to hour mill production. Table I shows the minerals found in the MacIntyre ore along with their average weight proportions and specific gravities. The first two products considered for the specific gravity method were fine and coarse table concentrates. It was reasoned that these products were essentially ilmenite with the higher specific gravity gangue minerals. Since they were always produced the same way, and the desired grade of TiO, was always constant, the specific gravity of these materials would increase or decrease as the amount of ilmenite increased or decreased. Thus for table concentrates which assayed 40 pct TiOz a constant gravity would invariably be obtained, and as the TiO, value changed the specific gravity would change in direct proportion. The third product considered was Wetherill ilmenite. It was assumed that a desired grade of 44.7 pct Ti02 would also always contain the same amount and type of gangue minerals along with the ilmenite, and thus would always have the same specific gravity. As the TiO, value of the ilmenite concentrate changed so would its specific gravity. Dr. Kenneth Vincent, chief metallurgist of the Baroid Division of National Lead Co. at Magnet Grove, Ark., ran specific gravity tests on 17 samples of the desired products. The lowest specific gravity reading assayed the lowest in TiO, and as the specific gravity increased the trend was for the TiO, assay to increase, see Fig. 1. Since these results warranted further investigation, a 500-g capacity Torsion balance and 250 ml Le Chatelier specific gravity bottles were obtained. Shift samples of fine table concentrate, coarse table concentrate, and final ilmenite were tested. Each sample was split and 85 g weighed on the Torsion balance. The Le Chatelier bottle was filled with water to a zero mark. To avoid wetting the neck of the bottle it was found necessary to do this

Jan 1, 1953

By Alan Stanley

THE MacIntyre Development of National Lead Co. is located at Tahawus, N. Y., in the heart of the Adirondack Mountains. Operations involve the mining and concentrating of a titaniferous iron ore to produce ilmenite and magnetite concentrates. A general description of the operation and metallurgy has been given by Frank R. Milliken.&apos; Pigment plant production demands that the MacIntyre mill produce a 44.7 pct TiO, ilmenite concentrate. To achieve the required ilmenite grade and tonnage it is important that the table concentrate grade be closely controlled. Unfortunately, however, the titaniferous orebody which feeds the MacIntyre mill is not uniform. Ore dressing characteristics vary from one end of the orebody to the other, and from • one level to the next. The changeable nature of the mill feed precludes a single adjustment of the equipment for long periods of time. Thus the operators must constantly watch the equipment to insure a uniform concentrate from the fine and coarse tables and Wetherills, or dry magnetic separators. Chemical assaying of mill products requires about 4 hr from the time the sample is taken until assay results are obtained, and this is available only on a two-shift basis. The ore may change rapidly, even several times during a shift, so that assay results lose most of their control value by the time they are reported to the mill operating crew. Members of the crew have therefore tried to evaluate the table and Wetherill concentrate by visual inspection, since through long experience the shift operators, under most circumstances, can gage closely the grade of the mill products. However, there are times when the physical nature of the ore is radically different from normal. Under these conditions visual inspection is of no value, and at such times final ilmenite as low as 43 pct TiO, has been produced and shipped before the assay results have been received. The specific gravity method of assaying for TiO, has been attempted to eliminate the shipping of ilmenite below normal grade as well as to help control day to day and hour to hour mill production. Table I shows the minerals found in the MacIntyre ore along with their average weight proportions and specific gravities. The first two products considered for the specific gravity method were fine and coarse table concentrates. It was reasoned that these products were essentially ilmenite with the higher specific gravity gangue minerals. Since they were always produced the same way, and the desired grade of TiO, was always constant, the specific gravity of these materials would increase or decrease as the amount of ilmenite increased or decreased. Thus for table concentrates which assayed 40 pct TiOz a constant gravity would invariably be obtained, and as the TiO, value changed the specific gravity would change in direct proportion. The third product considered was Wetherill ilmenite. It was assumed that a desired grade of 44.7 pct Ti02 would also always contain the same amount and type of gangue minerals along with the ilmenite, and thus would always have the same specific gravity. As the TiO, value of the ilmenite concentrate changed so would its specific gravity. Dr. Kenneth Vincent, chief metallurgist of the Baroid Division of National Lead Co. at Magnet Grove, Ark., ran specific gravity tests on 17 samples of the desired products. The lowest specific gravity reading assayed the lowest in TiO, and as the specific gravity increased the trend was for the TiO, assay to increase, see Fig. 1. Since these results warranted further investigation, a 500-g capacity Torsion balance and 250 ml Le Chatelier specific gravity bottles were obtained. Shift samples of fine table concentrate, coarse table concentrate, and final ilmenite were tested. Each sample was split and 85 g weighed on the Torsion balance. The Le Chatelier bottle was filled with water to a zero mark. To avoid wetting the neck of the bottle it was found necessary to do this

Jan 1, 1953