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Knowledge of coalfield geology has evolved rapidly over the past few years. Recent advances ranging between exploration, mining geology and seam variation studies have enabled application of geological techniques commensurate with technological changes in the coal industry.

Jan 1, 1969

By R. W. Gould, B. G. LeFevre, A. G. Guy

The resistivity anomaly known as the K state was studied in Ni-Mo alloys containing 10.5 and 14.0 at. pct Mo. Both these alloys exhibit a large K effect which depends on the mechanical and thermal treatment. On the basis of X-ray diffuse scattering studies which were correlated with resistivity measurements, it appears that the K state in dilute Ni-Mo alloys can be associated with changes in the degree of short-range order within the a phase. An interesting phenomenon that has received much attention in recent years is the K state. The K state is marked by anomalous changes in some of the physical properties of certain alloys without the occurrence of observable microscopic structural changes. One of the early pieces of work in this area was by Thomas' who studied alloys of Ni-Cr, Ni-Cu, Ni-Cu-Zn, Fe-A1, Fe-Si, and Ni-A1. Upon annealing specimens which had been previously cold-worked or quenched from an elevated temperature he found an anomalous increase in resistivity over a certain temperature range. He also found that specimens which had been appropriately annealed to develop the K state showed a decrease in resistivity upon subsequent cold working. These effects are opposite to those found in normal alloys. Although the resistivity anomaly has been rather arbitrarily taken as the "definition" of the K state, there are several other interesting effects which accompany the resistivity increase. In Ni-Cr alloys,2, 3 for example, it was found that the hardness increases with increasing resistivity. It was also found that specimens which have been treated to develop the K state can be cold-worked for as much as an 80 pct reduction of area without an increase in the hardness. In Fe-A1 and Fe-Si alloys4 the K state is accompanied by an increase in flow stress and by a lattice contraction. In Ni-A1 alloys,5 specimens which have been treated to develop the K state also show an increase in elastic modulus. In Ag-Pd alloys6 the increased resistivity observed on annealing a cold-worked specimen is accompanied by an increase in the thermoelectric power and an increase in the Hall coefficient. The explanations of the K state phenomena are varied and depend upon the particular alloy in question. Several theories have been advanced to explain the increased conductivity with cold work on the basis of changes in the electronic configuration of the alloy as a result of local lattice distortions.7"9 Most investigators, however, believe that some type of local order in the solid solution, either short-range order (SRO) or clustering, is responsible for this effect. Theories concerning the relationship between ordering and the K state have for the most part been speculative, since there is little direct X-ray evidence that can be correlated with the above property changes. Much of the previous work on the K state was done in the Ni-Cr system where the small difference in the X-ray atomic scattering factors of the components nickel and chromium makes it very difficult to use X-ray diffuse-scattering measurements to determine the role of local order. In the Ni-A1 system, however, Starke et al.10 succeeded in detecting a connection between local order and the K state. It was found that a small but measurable K effect correlated with increasing SRO in the nickel-rich a phase. The manner in which local order might increase the resistivity of K state alloys is not completely clear. Since most of the known K state alloys contain at least one transition element, significance has frequently been attached to the presence of an unfilled d shell. It has been suggested that during the formation of the K state the number of conduction electrons decreases as a result of the transfer of s electrons to the d shell where they are more tightly bound.1'11'12 Koster and Rocholl13 have proposed that SRO can cause an increase in resistivity for alloy systems in which the number and mobility of charge carriers are reduced when the percent solute is increased. According to this hypothesis, the local environment of a given solvent atom changes in the same manner with increasing percent solute as it does with an increasing degree of SRO; hence the change in physical properties should tend in the same direction. In this hypothesis, SRO is considered only in a statistical sense, and the increased resistivity of the K state is attributed to a change in the mean distribution of electrons and holes in the s and d states as a result of SRO. From the work of Chen and Nicholson on Ag-Pd alloys,6 it appears that the K state can occur in systems for which the d shell is completely filled. These investigators explained the increased resistivity by picturing the SRO as small domains of some form of long-range order (LRO). According to ~ibson,'~ the number of effective electrons can be reduced by the creation of a new Brillouin zone boundary near the Fermi surface of an alloy as a result of the changing crystallographic symmetry that accompanies the formation of a superlattice. This idea may be expressed in terms of the superzone concept.15 In the present work the role of local order in the formation of the K state in Ni-Mo alloys was investigated. The principal tools used in this study were X-ray diffuse scattering and electrical resistivity measurements; however, these data were supplemented by electron microscopic and field-ion microscopic data. The purpose of the work was to determine whether or not the K state in Ni-Mo alloys can indeed be attributed to the formation of SRO as has been proposed by previous investigators.

Jan 1, 1969

By Rodney L. Stone, David S. Cahn

As part of an over-all laboratory and plant test program to determine mixing ad other techniques for a more economic use of bentonite as an iron ore pellet binder, a settling test for measuring the bentonite content within a pellet or a batch of pellets has been developed. Through this test, it has been shown that dry fracture load is directly proportional to bentonite content in batches of pellets, but inversely propor tional to bentonite content in individual pellets of the same batch. This apparent paradox is explained by a negative correlation between a pellet's size and its bentonite content and the fact that large pellets can withstand a higher fracture load than small pellets. In past attempts to characterize green and dry iron ore pellets, the authors found large variations in the results of strength tests on closely sized pellets from the same batch.' Reasons advanced for such variations in the quality of pellets in which the binder is bentonite were the presence of internal flaws and the nonuniform distribution of the binder. Even when resulting pellet strength is good, there is still the question of whether the same strength could have been attained through a more effective use of a smaller amount of bentonite. The authors' own and other studies 2-3 have pointed out the strong dependence of pellet strength on the degree of "mixedness" of the iron ore concentrate and the bentonite binder. However, before such a relationship could serve as a guide for the development of better mixing techniques and the associated economy of

Jan 1, 1969

By M. A. Rigdon, R. E. Grace

The dissociation of cupric oxide to cuprous oxide and oxygen was studied with a microbalmce technique at 700" to 750°C. In this temperature range the dissociation pressure of the reaction 2CuO= Cu2O + 1/2 O2 was: The theory of near-equilibriwm reaction rates predicts a linear relationship between reaction rate and the Gibbs free-energy change for small values of AF/RT. This correlation is found to be valid for AF/RT = -0.1 or approximately 200 cal per mole away from equilibrium. THE theory of reaction rates near equilibrium as developed from classical thermodynamics suggests a small range of linear behavior between the overall reaction rate and the free-energy change accompanying the process. The extent of this linear correlation is generally unknown, even to the order of magnitude. The idea of linearity is also found in the formal mathematics of coupled transport phenomena, e.g., chemical diffusion, thermal diffusion, thermoelectricity, and so forth. The linear array of forces and fluxes which leads to various main and cross coefficients is predicated upon linearity between reaction rates and the bulk thermodynamics which govern the process. The general case in reaction kinetics is well-known: the magnitude of the free-energy change does not cor- relate with observed reaction kinetics, irrespective of whether the process occurs by diffusion or chemical reaction or both. The real need is to investigate specific reaction paths near equilibrium in order to learn of the limitations in attempting to correlate reaction rates and thermodynamics. It is the main purpose of this paper to examine the dissociation kinetics of cupric oxide under conditions of known driving force where the dissociation process is likely to occur by chemical reaction. A secondary objective is to obtain equilibrium data for the CuO-Cu20-O2 system. In a prior paper Edmiston and race' investigated reduction kinetics of wustite in H2-H2O gas mixtures. The present study was carried out in oxygen according to the following reaction:

Jan 1, 1969

By C. L. Magee, H. W. Paxton

The effects of testing temperature, frorn 77" to 420" K, and volume fraction of martensite on the micro-plastic response of unaged Fe-31Ni martensite-austenite aggregates have been determined. The kinetics of the aging phenomena which lead to a decrease in the microplastic response were also characterized. These determinations, supplemented by other experimental results, show that at least two mechanisms of plastic deformation give rise to the apparent softness of the quenched structures. Only one of these mechanisms is fully discussed in this paper The transformation of retained austenite to martensite during the application of stress leads, in specified conditions, to large microplastic strains. This deformation behavior cannot be described by normal transformation plasticity theory but is shown to result from the fact that stress-assisted formation of martensite is a possible deformation mode. The present results and further considerations of previous work lead to the conclusion that it is unnecessary to postulate a special work-hardening mechanism to explain the mechanical properties of unaged martensite. It is now generally accepted that dislocation motion can occur in many solids at stresses very much below the L'macroscpic" yield stress, e.g., 0.1 pct offset. This phenomenon has been investigated by a variety of techniques including measurements of elastic limit,' effective static elastic modulus,~ and irreversible deformation following stressing at low levels.3"5 Of particular interest to the work to be described are exper -iments conducted on the deformation of martensite in attempts to decide whether freshly quenched ferrous martensites are "hard" or "soft".6 Muir, Averbach, and cohenl and McEvily, Ku, and ~ohnston' have shown that as-quenched ferrous rnartensites can be plastically deformed at relatively low stresses. A difference between these two sets of experiments exists in that some diffusion of carbon would take place before testing in the experiments of Muir et a1. because the plain Fe-C alloys which they have tested transform to martensite well above room temperature. McEvily et a1. examined Fe-Ni-C alloys with Ms of about -30"~ and tested the alloys directly after quenching to — 195" ~ —a technique which obviates any appreciable carbon diffusion. Unfortunately, a characteristic of the alloys which transform below room temperature is that they do not transform entirely to martensite. The results discussed below will show that, because the transformation of this retained austenite under stress leads to plastic deformation, one cannot investigate the properties of martensite by such experiments. The existence of a second deformation phenomenon, which is not caused by retained austenite, is also established in the present work. In line with a previous suggestion,' it is believed that the second microdefor-mation mode is principally due to the internal stresses generated by the formation of martensite. To avoid confusion in the present report, the evidence we have found for this interpretation will be discussed separately in a brief note.7 EXPERIMENTAL Materials. The alloys were induction-melted and cast under vacuum; the resulting compositions are given in Table I. The ingots were hot-swaged to 2-in.-diam bar and further cold-swaged and/or cold-rolled prior to specimen preparation. The standard tensile specimens were machined from sheet. The gage section was 0.05 by 0.2 by 5 in.; 0.75-in.-wide ends had 0.2 5-in. centered holes for pinloading. The three-point bend samples were 0.075-in. thick and 0.6 in. bide. The distance between the outer loading points was 5.5 in. In order to establish a standard starting condition, all specimens were quenched to 77°K prior to annealing in vacuo for austenitizing. The temperature of the austenitizing anneal was controlled to + 5"~. The testing and aging temperatures were maintained by various liquid baths (nitrogen, 77"~; freon, 130° to 200°K; acetone, 200 to 300°K; silicone oil, 300' to 450°K) to better than il°K. Strain Measurement. The results herein were derived from both uniaxial tension and three-point bending experiments. For bending tests, the stresses and strains reported are those corresponding to the maximum fiber values. Normally, because of the small strains involved, very sensitive strain measurements are necessary to make microplastic measurements. However, because of the magnitude of the dilatation and shear involved in the martensitic transformation, the requirements in the present experiments proved to be less rigorous. In most experiments the plastic strain was evaluated by measuring stress relaxation and modulus defects. In this method, specimens are loaded rapidly to some predetermined load on an In-

Jan 1, 1969

By Peter Chmara

The measurement of dust concentration in Ontario mines since 1926 has been accomplished by konimetry, based on South African experience and methods. The introduction of a voluntary program of semi-annual surveys of air conditions at all operations throughout Ontario mines created a need for an instrument that would assess konimeter spots rapidly and accurately. The development of the Electronic Scanner, it is felt, answers this need. A program whereby all konimeter spot samples taken at Ontario mines will be counted at the MAP AO field offices in North Bay is described.

Jan 1, 1969

By Richard Birk

Rf sputtered quartz has been successfully used in multilayer interconnects for MOS devices. The target potential was 2000 v peak to peak with a frequency of 13.56 Mc per sec. The sputtering rate was approximately 60A per min with an operating pressure of argon gas at 10 to 15 p. The dielectric strength is 8.0 x 10' v per cm and the pinhole density is less than 2 x 10-2 per sq mm. Infrared absorption peaks for the Si-O vibrational bands we at 9.4, 12.4, and at 22.5 p. The etch rate of the sputtered SiO2 is 1200A per min. MOS devices have been fabricated using multilayer interconnects with no degradation of electrical characteristics. MULTILAYER interconnects require an insdating film between the metal layers which can be deposited below any potential eutectic temperature. Sputtered Si4, which can be deposited with substrate temperatures below 200°C, satisfactorily meets the multilayer insulation requirements and has been used to prepare MOS circuits with multilayer interconnects. The physical and electrical properties of rf sput-

Jan 1, 1969

By D. R. Rice

Separation of valuable constituents from a complex mineral mixture was examined. Nitric acid leaching produced a solution containing copper, zinc, iron and a large proportion of silver. The residue contained antimony, lead, the remaining silver and elemental sulfur. A caustic sodium sulfide leach dissolved the antimony from the residue, producing an insoluble, high-grade silver-lead product and a filtrate for electrolytic recovery of antimony. The pH of the primary filtrate was raised, precipitating the iron and leaving a solution containing the copper, zinc and the soluble portion of the silver, which would be recovered by conventional means.

Jan 1, 1969

By C. F. Starr

This paper deals with the various types of cable in use in mines, with special attention paid to their construction. There will be a few comments regarding the different insulants, jacketing materials and armouring used, depending on their application. Governing standards and the differences therein will also be discussed.

Jan 1, 1969

By Stephen D. Antolovich

RECENTLY, much interest has been generated in materials that undergo martensitic phase transformations on straining.')' While it is undoubtedly true that a large amount of ductility can be obtained at rather high strength levels, the question of the general way in which the phase transformation affects the plane strai fracture toughness, as measured by the parameter KIC, has yet to be answered. Let us consider a material that contains a sharp crack as shown in Fig. 1, and is subjected to a tensile stress 00. It is known that the presence of a crack tends to multiply the stress in the area of the crack according to the following equations:3

Jan 1, 1969

By M. J. Marcinkowski, A. S. Sastri

A detailed compressive stress-strain analysis and transmission electron microscopy investigation has been made of the deformation behavior occurring in a 50 at. pct Ni-Ti (hypoeutectoid) alloy and a 54.5 at. pct Ni-Ti (hypereutectoid) alloy. In the case of the hypoeutectoid alloy, three stages of work hardening are observed. Stage I occurs at a very low stress and is associated with plastic deformation via martensite formation. Stage 11 is characterized by very rapid work hardening and is due to difficulties in causing further deformation in the fine martensite aggregate produced in Stage I. Stage III which occurs at very high stress levels is characterized by smaller work hardening rates and is due to the plastic deformation arising from alternate reconversions of the original martensites to martensites of varying orientation. Rapid quenching of the hypereutectoid alloy leads to very high yield strengths and is related to a fine precipitate dispersion that such treatment brings about. The present investigation represents the final phase of a three-part study directed toward an understanding of the solid-state transformations in near equi-atomic Ni-Ti alloys as well as the deformation mechanisms associated with these alloys. In the first part,"2 to be henceforth referred to as I, it was found that alternate simple shears on {112} planes and in (111) directions convert the parent B2 structure in the equiatomic NiTi alloy into two distinct close-packed monoclinic martensites. All of the marten-sites were of this type, whether they were formed by cooling or by plastic deformation, whether induced to form in bulk samples or in thin foils, or whether examined in the electron microscope at room temperature or below. On the other hand, in the second part of this investigation,3 to be reffered to as 11, it was shown that upon slow cooling to about 640°C. alloys in the neighborhood of NiTi which possess the B2 structure transform eutectoidally into their equilibrium phases Ti2Ni and TiNi3. However, preceding the formation of these equilibrium phases a series of metastable intermediate phases are formed. This paper will set as its goal the elucidation of the remarkable deformation behavior exhibited by NiTi. In particular, Buehler and Wiley4 have found equiatomic NiTi to be surprisingly soft, while Buehler et al.5 have shown this alloy to possess a memory effect: i.e., upon bending at room temperature it will revert to its original shape when heated to above about 50°C. In I it was shown that NiTi was soft in the sense that the yield stress was low; nevertheless, the alloy work-hardened at an extremely rapid rate to very high stress levels. On the other hand, the hypereutectoid alloys with somewhat higher nickel, say 54.5 at. pct (60 wt pct) have enormously increased yield strengths compared to those of the equiatomic alloys. In order to determine the atomistic processes giving rise to the above behavior, it was decided to examine samples that were wafered from bulk specimens deformed in compression to various strains using the techniques of transmission electron microscopy. EXPERIMENTAL TECHNIQUE All of the alloys used in the present investigation contained either 50 at. pct Ni (55.06 wt pct) or 54.5 at. pct Ni (60 wt pct) and were arc-melted in the form of a finger using the same techniques described in I and II. The finger was capsulated in a stainless-steel jacket and swaged at 850°C into rods. Compression specimens 0.300 in, long and 0.200 in. in diam were machined from these rods. In order to completely re-crystallize the samples and remove residual stresses, all of them were capsulated in evacuated quartz, annealed for 1/2 at 1050°C. and then furnace-cooled. Compression tests were carried out in an Instron tensile testing machine covering a range of temperatures from —196° to 200°C using procedures described previously.6'7 In all cases crosshead speed was 0.02 in. per min. Wafers 0.015 in. thick were spark-cut from the cylindrical samples at 45 deg to the compression axes after they had been deformed to the desired strain. These specimens were then spark-planed to about 0.005 in. and then electrochemically thinned for examination by transmission electron microscopy as described in I.

Jan 1, 1969

By R. W. Armstrong, P. C. Jindal

WE should like to point out that Hu and cline.1 in their study of the recrystallization of titanium, have obtained data which appear very important for accurately determining the dependence of hardness on grain size for this material. It has been proposed2,3 that the macrohardness. H. of a poly crystalline material should depend on its average grain diameter, l. in accordance with the relationship: H =H0 + kHl-1/2 [1] where Ho and kH are experimental constants. This relationship follows from the hardness dependence on yield stress or flow stress4 and. thence. the Hall-Petch stress-grain size relations.5'6 Fig. 1 shows the Diamond Pyramid Hardness. Dph. values vs the reciprocal square root of the average diameter of the recrystallized grains, taken from the titanium data reported by Hu and Cline. The data in this figure give a linear relationship for the hardness over a wider range of grain diameters than anyone has previously measured. The data are not linear, for example. on an I-1 or l-1/3 scale. At the very large grain sizes the data are in reasonable agreement with measurements earlier reported by Holden, Ogden, and Jaffee.7 For the grain sizes smaller than 1 µ, which correspond in Fig. 1 to hardness values greater than 150, the material was reported as not being completely recrystallized and, therefore, these data appear less meaningful as far as the hardness dependence on grain size is concerned. However. it has been suggested by other investigators that deformed materials exhibit strengthening due to an effective grain size refinement even in the unrecrys-tallized condition.8-10 Also. Hu and Cline have shown that a change in texture occurs for titanium during the recrystallization process and. especially. following it. The influence of this texture change on the hardness-grain size relation would be expected to be less than that reflected in the unidirectional stress-strain behavior, even for an hcp material. because of the actual combined stress system which applies for the hardness test. For, at least, certain combined stresses, average values of the orientation factors should still occur in the stress-grain size analysis of a material exhibiting a preferred orientation.' We previously suggested3 that the experimental constants. H0 and kH. from the Meyer hardness-grain size relation should be correlated with the Hall-Petch constants, uoy and ky.5,6 Our recent study" of the Hall-Petch relation and the hardness-grain size results which obtain for a number of polycrystalline materials shows that: The inequality [2] is explained by noting that the hardness should be correlated. perhaps, with the flow stress at some value of strain, as suggested by Dugdale,12 and. also, that the influence of strain on the Hall-Petch relation is to increase uo and not change k very much." Normally. Dph values and Brinell hardness values are nearly equivalent to each other and to the Meyer hardness number. For the case of titanium, then. the inequality [2] may be evaluated using the experimental values of ao = 8.0 kg per sq mm and ky = 1.3 kg per mm3/2 obtained from the experiment of Guard.6,13 Thus, (Ho/uo) = 12 and (kH/k3) = 1.3. This research has been supported at the University of Maryland through the Center of Materials Research by the Advanced Research Projects Agency of the U.S. Government.

Jan 1, 1969

By L. C. George

The Bureau of Mines measured the vapor pressures of selected mixtures in the binary systems CdCl2 ?SnCl2, CdCl2 -ZnC12, PbCl2 ?SnCl2, and PbCl2 -ZnCl2 by the static pressure method. These data were evaluated by the second-law (sigma-plot) method. Equations expressing the vapor pressures and the heats and free energies of vaporization as functions of temperature are given.

Jan 1, 1969

By E. N. Pugh, J. V. Craig

WhILE it has been established that well-defined microhardness impressions can be produced in germanium by room-temperature indentation,1-3 the role of dislocations in the process is the subject of continuing discussion.4-7 Recently, Carroll and ~anaka'

Jan 1, 1969

The authors describe two stratiform intrusions within a two miles thick ophiolite belt, one of the many ophiolite (serpentine) belts of the eugeosynclinal sequences of the Kalgoorlie System (metamorphic age c.2700 million years). Unusually good evidence of gravitational differentiation involving cumulates for an Alpine type peridotite-gabbro intrusion has been obtained, in spite of modifications of the original igneous rocks imposed by regional metamorphism. Unmetamorphosed relics of cumulate rocks are a surprising feature of this occurIfence.'fhe differentiation process reflected in the layered sequences is compared to that of the Stillwater Intrusion, Montana. Phase, cryptic and rhythmic layering are recognized. The economic significance of this study lies not only in the possibility of nickel mineralization in this ophiolite belt, but also in that much detailed information on the nature of these belts, which is difficult to obtain in the case of the more altered and sheared rocks of the belts carrying gold and nickel ore deposits nearby, is gathered from the Yilmia occurrences.

Jan 1, 1969

By Foster Fraas

This Bureau of Mines report describes a method for separating minerals at magnetic susceptibilities within the diamagnetic susceptibility range. The maximum feed rate varies directly with the square root of the lower limit of permissible susceptibility, while the lower limit of permissible susceptibility varies inversely as the square of the magnetic field strength. Minerals may be separated at particle sizes smaller than possible on conventional dry-type magnetic separators.

Jan 1, 1969

By J. A. R. Faucher

"Autogenous grinding may be an efficient and economical solution to your ore comminution problem.An important potential economic advantage of autogenous mills results from the availability of very large capacity units.Autogenous grinding could be more economical in terms of both capital and operating costs.Satisfactory pilot plant testing and thorough economic evaluation are required for a sound decision in comminution plant selection.INTRODUCTIONMankind's first weapon was probably the wooden club, but men soon learned to shape, smooth and polish stone for tools and weapons by pounding and rubbing them with sand and water. It was only about four thousand years ago that rocks were first broken to concentrate, smelt and return the metals they contained. In spite of our recent great technological advances we still break rock in essentially the same manner that was used thousands of years ago - by pounding, rubbing and squeezing - and we still waste much energy and metal in the process"

Jan 1, 1969

By J. H. Swisher

The rate of internal sulfidation of austenitic Fe-Ti alloys in H2S-H2 gas mixtures is controlled primarily by sulfur diffusion, with counterdiffusion of titanium playing a minor role. At temperatures below 1100°C, enhanced diffusion along grain boundaries becomes important. The rate of internal sulfidation at 1300°C is approximately equal to the rate computed from the sulfur diffusion coefficient. The diffusion coefficient of titanium in y iron has been determined from electron microprobe traces in the base alloy near the subscale interface. The solubility of sulfur in Fe-Ti alloys has been measured in the temperature range from 1150° to 1300°C. The equilibrium sulfur content is found to increase with titanium content, due to the large effect of titanium on the activity coefficient of sulfur. The Ti-S interaction becomes stronger as the temperature decreases. TITANIUM as an alloying element in stainless steels is an effective scavenger for interstitial impurities, carbon in particular. Titanium is known to form stable sulfides; however extensive thermodynamic data on the Ti-S system are not available. Schindlerova and Buzek1 have shown that the Ti-S interaction in liquid iron is moderately strong. There have been no previous studies of the Ti-S interaction in solid iron. Internal sulfidation of Fe-Mn alloys was the subject of a recent investigation by Herrnstein.2 He found the rate of internal sulfidation to be an order of magnitude greater than predicted from available solubility and diffusivity data. A satisfactory explanation for the discrepancy could not be given. In the present study, the solubility of sulfur in austenitic Fe-Ti alloys was measured using a standard gas equilibration technique. Fe-Ti alloy specimens were also internally sulfidized. The rate of internal sulfidation was measured as a function of temperature and alloy composition. Supplementary electron micro-probe measurements were made to provide additional information on the nature of the internal sulfidation process. EXPERIMENTAL The starting materials were alloys containing 0.12, 0.24, 0.38, and 0.54 wt pct Ti. The alloys were made in an induction furnace by adding titanium to electrolytic iron that previously had been vacuum-carbon-deoxidized. The major impurity in the alloys as determined by chemical analysis was carbon. The carbon content of the alloys averaged about 100 ppm; metallic impurities were presented in concentrations of 50 ppm or less. Specimens were made in the form of flat plates, 0.03 by 2 by 4 cm for the equilibrium measurements and 0.5 by 1.5 by 3 cm for the rate measurements. The experiments were performed in a vertical resistance furnace wound with molybdenum wire and containing a recrystallized alumina reaction tube. In the gas train, flow rates of the reacting gases were measured using capillary flow meters. The source of H2S was a mixture of approximately 2 pct H2S in H2, which was obtained in cylinders from the Matheson Co. A chemical analysis was provided with each cylinder. The H2-H2S mixture was diluted with additional hydrogen to obtain the desired ratio of H2S to H2, and the resulting mixture was diluted with 30 pct Ar to minimize thermal segregation of H2S in the furnace. Argon was purified by passage over copper chips at 350°C and subsequently over anhydrone. Hydrogen was purified by passage over platinized asbestos at 450°C and then over anhydrone. The H2-H2S mixture was purified by passage over platinized asbestos and then over Pas. The samples used in the solubility measurements were analyzed for sulfur by combustion and iodometric titration. The subscale thickness in the internally sulfidized samples was measured on a polished cross section, using a microscope with a micrometer stage. Electron microprobe traces for titanium in solution were made on several samples that had been internally sulfidized. A Cambridge microanalyzer was used, and the known titanium content at the center of the specimen was used as a calibration standard. The procedure for the microprobe measurements will be described further when the results are presented. RESULTS AND DISCUSSION Equilibrium Data. Fig. 1 shows the sulfur concentration as a function of gas composition for three alloys equilibrated at 1300°C. The dashed line is based on data published by Turkdogan, Ignatowicz, and pearson3 for pure iron. The breaks in the curves are the saturation points for the alloys. The fact that the initial slope decreases with increasing titanium content indicates that titanium interacts strongly with sulfur in solution. To obtain information on the composition of the precipitating sulfide phase, the measurements described in Fig. 1 were extended to higher sulfur partial pressures. These results are shown in Fig. 2. (The initial portions of the curves are reproduced from Fig. 1.) The highest PH2s /pH2 ratio used is believed to be below the ratio required for the formation of a liquid sulfide phase. Time series experiments were used to study the approach to equilibrium in the samples. It was found that equilibrium with the gas phase was reached in less than 4 hr at 1300°C.

Jan 1, 1969

By A. S. Emanuel

A correlation has been developed for calculating the phase behavior of, gas-condensate systems at reservoir conditions. The correlation is based on the principle of corresponding states and has been coded for an IBM 7094. Experimental K-values were determined for several gas-condensate systems at reservoir conditions to evaluate various semi-empirical parameters of the correlation. The approximate range of application of the correlation is 150 to 300F and 1,500 to 6,000 psi. INTRODUCTION The rapid development of digital computers during the past several years has made feasible the calculation of hydrocarbon phase behavior by methods based on rigorous thermodynamic principles. Good correlationsl have been developed for low to moderate pressures, but these techniques have not yet been extended successfully to reservoir fluids at high pressures. Consequently, the determination of phase behavior of oil and gas systems at reservoir conditions is still based almost entirely on generalized data correlations or on experimental studies of the fluid in question. While these methods have been used successfully many times, they do have inherent limitations that restrict their applicability. Generalized correlations, such as the NGShlA K-charts, are limited to the range of pressure, temperature and components for which the data were determined. The accuracy of these correlations is often questionable because the effect of total system composition is not well defined. Experimental studies offer a reliable method for determining phase behavior, but usually the studies are costly and time consuming. Recently, Leland and co-workers presented a new approach to calculating phase behavior from the principles of corresponding states.6-8 Corresponding states methods determine the thermodynamics properties of a given system by comparison with a reference substance whose properties are known. The accuracy of this approach depends on close chemical and structural similarity between the reference substance and the system in question and between components within the system itself. For high accuracy, it is usually necessary to correct for chemical and structural dissimilarities. In principle, however, the corresponding states method should be no less accurate at high pressures than at low pressures, provided reference substance properties are known. This paper describes an empirical modification of the basic correlation proposed by Leland, et al.6 for the specific purpose of calculating the phase behavior of gas-condensate fluids at reservoir conditions. The modified correlation, which has been programmed for an IBM 7094, may be used for either approximate or precise determination of fluid behavior depending on the amount of analytical and, experimental data available for the system. BASIC THEORY The basic theory of the corresponding states phase equilibria correlation was first published by Leland, Chappelear and Gamson.6 Subsequently, Leland, Chappelear and Leach published methods for improving the accuracy of the original theory.7-9 The aim of the correlation is to calculate the K-value of each component of a given system as a function of pressure, temperature, and over-all composition, where Once the K-values are known, the phase behavior may be determined directly by an appropriate flash calculation. The basic equation for calculating component K-values was taken from the work of Joffe. 4 For any component i of a mixture, the K-value is given by

Jan 1, 1969

By Donald M. Hausen

Microscopic evaluation of trace quantities of metalliferous phases in flotation products requires counting large numbers of particles. Particle counts of many thousands may be required for precision, but not obtained practically by conventional microscopic techniques. A less tedious microscopic method for evaluating trace sulfides in mill tailings was developed for the O'okiep Mining Company in South Africa. Hundreds of thousands of particles were evaluated by this method called "gross-counting." Gross-counting consists of counting microscopic fields rather than point-counting individual particles. Total counts are calculated by multiplying the average number of particles per field by the total number of fields examined over the entire mount. Total gross-counts range from about 20,000 particles for +200 to 100,000 or more for -400 mesh size material in lucite mounts. Sulfides and metallic particles in each field are identified and tallied along with field counts. Totals for each type of metallic particle are divided by the total gross-count to give volume percent which is corrected to weight percent by specific gravity factors.

Jan 1, 1969