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By Don L. Kendall, Martin G. Buehler

A simple physical model has been developed to fit carrier-removal data in silicon irradiated near room temperature with reactor spectrum neutrons. Commonly observed donor and acceptor defect energy levels are assumed to be introduced linearly with neutron fluence. The donor levels (in ev) are Ev + 0.16, Ev + 0.27, and Ev + 0.31 and the acceptor levels are Ec - 0.55, Ec - 0.40, and Ec - 0.1 7, where Ev and Ec are the valence and conduction band energies, respectively. The introduction rates of each level are adjusted to fit literature initial carrier-removal rate data. When normalized with respect to the Ev +0.27 level, the relative values of introduction rates are 5.3, 1.0, 3.1, 1.0, 2.0, and 20.0, respectively for the six levels indicated above. To fit p-f (hole concentration vs neutron fluence) and n-f (electron concentration us neutron fluence) data, the introduction rates are multiplied by a factor which preserves the relative values given above. This factor depends upon irradiation temperature, reactor energy spectrum, neutron fluence calibration, and oxygen content of silicon. An extensive study of the effect of neutrons on carrier-removal in silicon irradiated with reactor spectrum neutrons (E > 10 kev) has been given by Stein and Gereth1 (SG) and Curtis, Bass, and Germano' (CBG). They measured initial carrier-removal rates for both p- and n-type silicon over an impurity range typical of silicon devices. In this work, we attempt to fit a simple theory to this data to establish a usable relationship between hole and electron concentration, p and n, respectively, and neutron fluence f. The p-f and n-f relations are needed to assist in the design of neutron tolerant silicon devices and are needed to clarify presently used empirical resistivity-fluence relationships.3 Neutron damage in silicon produces a variety of defects ranging from simple point defects to defect clusters. For the purpose of this treatment, we assume that simple point defects dominate carrier-removal effects. In contrast to this view, stein4 has proposed that defect clusters are responsible for a significant portion of carrier-removal effects. In the following section, it is shown that the carrier-removal effect in n-type silicon with an electron concentration less than 1015 cm-3 can be explained adequately by assuming that the divacancy is the dominant defect and that its introduction rate is independent of the electron concentration. For electron concentrations greater than 1015 cm-= an additional acceptor defect center is needed, and for simplicity the A-center (vacancy-oxygen pair) has been chosen. Although the E-center (vacancy-phosphorus pair) can account for some of the results, the A-center was chosen because the E-center requires a more involved treatment which the presently available data do not justify. In p-type silicon three radiation-induced donor levels are assumed, namely the divacancy and two other centers of unspecified nature located at Ev + 0.16 ev and Ev to 0.31 ev. The donor divacancy at Ev + 0.27 ev is assumed to be introduced at the same rate in p-type as in n-type. However, this rate is too low to fit p-type initial carrier-removal data. The dominant centers in p-type silicon are assumed to be the Ev + 0.16 ev and Ev + 0.31 ev levels where the latter is not the divacancy. The introduction rates are chosen to fit initial carrier-removal rate data. Assuming that the introduction rates are independent of Fermi level, the ratio between them is fixed for subsequent p-f and n-f calculations. Using the same ratios, the initial carrier-removal rate data1,2 as well as p-f and n-f data1,5 can be fit provided the absolute value of the introduction rates are adjusted to account for irradiation temperature, reactor energy spectrum, neutron fluence calculation, and the oxygen content of silicon. THEORETICAL ANALYSIS This analysis is basically the same as that used by Hi116 to analyze electron damage in silicon except we express the degree to which an impurity level is ionized not in terms of the Fermi level, but in terms of carrier concentration. Landis and pearson7 have used the latter approach to analyze y-damage in silicon. Neutron-induced defects responsible for carrier-removal at room temperature are assumed to be simple point defects with no interaction between defects so that they may be represented by discrete energy levels. It is also assumed that no constituent of a defect complex is used up and defects stabilize shortly after irradiation. Defects are assumed to be introduced linearly with fluence according to the product Rtf where Rt is the defect introduction rate and f the neutron fluence. Taking into account the ionization of defects according to Fermi statistics, and considering charge neutrality where minority carriers are neglected, the n-f relation is where no is the preirradiation electron concentration. The parameter Nt is the electron concentration at which the ionized defect concentration is one-half the total defect concentration (Rtf) or where Et is the defect energy level. For silicon at 300°K, ni = 1.45 X 1010 cm-3 and Ei = Ev+ 0.542 ev which was determined using Ec — Ev = 1.11 ev and me* = 1.07 mo and mh* = 0.558m0. The spin degeneracy factor, which usually appears as a number multiplying the Nt/n term of Eq. [1], is taken as unity. In effect, this factor has been incorporated into the defect en-

Jan 1, 1970

By E. Miller, K. L. Komarek, M. Ettenberg

The activity of aluminum in solid Co-A1 alloys has been measured by an isopiestic technique between 850° and 1200°C from 45 to 80 at. pct Al. The activity shows a Precipitous decrease around the stoichzornetric composition of CoAl. Free energies of mixing have been calculated over a limited composition range. Considering an antistructure-vacancy defect mechanism, the degree of intrinsic disorder, a , in CoAl was related to the alunminum activity. Excellent agreement between the calculated and experimental activity curves was obtained for a = 1.25 x 10-4. ThERMODYNAMIC properties of solid aluminum-transition metal alloy are being studied in an investigation of disordering in ordered compounds. In a continuing series of investigations, activities of solid Fe-1,' Ni-A1, kd r-A13 alloys have been measured. From the results for Fe-A1 and Ni-A1, the degree of intrinsic disorder for the equiatomic compounds was calculated2 using equations derived by Wagner and chottk. From the results for Cr-A1 the degree of intrinsic disorder was calculated from equations derived by Orr.' In this paper, the results of the study of Co-A1 alloys are described. Published activity data in the Co-A1 system has been limited to liquid alloys at 1600°C.° A heat capacity study7 of stoichiometric CoAl indicated that a second-order phase transformation occurs at 790° C, attributed to an order-disorder reaction. Oelsen and Middel,' employing the calorimetric mixing of pure liquid metals, obtained heats of formation for compositions from 6 to 90 at. pct Co. Heats of formation for 50 and 78 at. pct Co alloys have also been measured by acid solution calrimetr. The Co-A1 phase diagram, as compiled by Hansen and Anderko,lo is in good agreement with more recent X-ray evidence. The method for measuring activities of aluminum in this study is essentially that employed in the studies of the Fe-1,' i-Al, and r-A13 systems. This isopiestic method entails placing cobalt specimens, in a temperature gradient, in a sealed alumina system containing a pure liquid aluminum source of fixed vapor pressure. The specimens are equilibrated, cooled to room temperature, and their final compositions determined. From the measured temperature of the specimens and the known vapor pressure of pure aluminum the activities of aluminum in the alloy can be calculated. EXPERIMENTAL PROCEDURE The cobalt was 3-mil-thick sheet of 99.9 pct purity (herritt Gordon Mines Ltd., anada). The major impurities were 0.1 pct Ni, 0.014 pct C, 0.018 pct Fe, 0.004 pct S, and 0.005 pct Cu. The aluminum metal had a purity of 99.99 pct (Aluminum Corp. of America) and all alumina parts were 99.7 pct A1,O3 (Triangle RR Grade, Morganite Refractories, Inc.) with major impurities 0.05 pct SiOz, 0.1 pct Fe203, 0.2 pct NazO, and 0.05 pCt K20. Runs 1 to 3 were made with annular cobalt specimens (12 mm ID by 21 mm OD) punched from the sheet. The specimens were deburred and degreased in carbon tetrachloride and in acetone. The samples, each weighing about 150 mg, were then positioned along an alumina rod, a in. OD by 14 in. long, separated by alumina spacers, i in. ID by | in. OD by & in. long. The lower end of the rod was placed in a hole drilled in the center of an 80-g aluminum cylinder. This assembly was put into an alumina crucible, 1+ in. ID by 13 in. OD by 3+ in. high, and the position of each sample was measured to within 50.5 mm relative to the bottom of the crucible. An alumina tube, 28.5 mm ID by 35.5 mm OD by 14 in. long, closed at the top, was slipped over the whole assembly, so that it fitted snugly into the bottom crucible. The entire reaction assembly was tied with molybdenum wire and lowered into a mullite tube, closed at the bottom. A quartz thermocouple tube, closed at one end, containing a t/Pt-10 pct Rh thermocouple, calibrated according to the specifications of the National Bureau of standards,'' was placed along the reaction assembly inside the mullite tube. The temperature of each specimen could be determined by gradually raising the thermocouple and measuring the temperature gradient along the reaction assembly. The combined error in temperature measurement and sample position resulted in a total error of Q°C in the recorded temperature of each sample. The mullite tube was sealed at the top by a water-cooled brass head, connected to a conventional glass vacuum system. The aluminum reservoir is heated to its melting point sealing the alumina system containing the samples. During this process the pressure is maintained below 0.01 li Hg. During subsequent heating to establish the proper temperature gradient and throughout the entire run the pressure is maintained below 2 1 Hg by means of a two-stage mechanical pump. Equilibration runs lasted from 4 to 6 weeks and were terminated by air cooling. The temperature of the liquid aluminum reservoir was brought below its melting point in less than 20 min. For runs 4 and 5, alloy buttons with 49 and 69 at. pct A1 were prepared from the initial high-purity metals by arc melting under purified argon. The alloy buttons were comminuted to powder with an alumina mortar and pestle until the powder passed through a 400-mesh screen, particle size 0.0014 in. Portions of this powder weighing between 50 and 200 mg were placed in small alumina trays, 25 by 15 by 5 mm, which were then

Jan 1, 1969

K. T. Aust and J. W. Rutter (General Electric Research Laboratory)—We find it difficult to reconcile the activation energies determined by Gifkins with his general conclusion that "migration during both creep and grain growth can thus be treated on the basis of the same model" (that of Lucke and Detert). Gifkins finds the activation energy for grain boundary migration during creep to be 24.5 kcal per rnol and that for grain boundary migration during grain growth to be 7.5 kcal per mol. The calculation carried out by Gifkins of the activation energy for grain boundary migration during grain growth, using the Lucke and Detert model, gives a value of 20 to 24.5 kcal per mol, rather than his experimental value of 7.5 kcal per mol. The theory of Lucke and Detert was developed to account for the rates of migration of grain boundaries in the presence of impurities during grain growth. The theory does not take into account the effect on the boundary migration of another, simultaneous process such as creep deformation and would be expected, therefore, to be applicable only to migration during grain growth. The fact that Gifkins measured a different activation energy for boundary migration during grain growth (7.5 kcal per mol) from that during creep (24.5 kcal per mol), although the specimens were of the same composition, shows clearly that such an effect exists under his experimental conditions; the presence of a simultaneous creep deformation markedly affects the boundary migration process in comparison with what would be observed under the same conditions but without the creep deformation. The failure of McLean's equation (Eq. [4] of Gifkins' paper) to give a satisfactory dislocation density difference for boundary migration during creep is not surprising, since the activation energy which must be used in this equation refers only to the elementary atom transfer process of grain boundary migration. This activation energy value is approximately 6 kcal per mol for zone-refined lead, as determined in both the grain boundary migration experiments of Aust and Rutter31, 32 and the grain growth experiments of Bolling and Winegard.33 Using this activation energy value, McLean's equation gives reasonable agreement with observed migration rates for grain boundaries moving free of the influence of impurities.31, 32 The value of 24.5 kcal per mol is probably associated with the presence of impurity atoms, as Gifkins suggests. It should be noted, however, that this value was obtained using lead of only one composition and measurements at only two temperatures. The work of Aust and Rutter3"' on the effects of tin, silver, and gold on grain boundary migration in zone-refined lead in the temperature range from 320" to 200°C, as well as the work of Bolling and Winegard34 on the effect of silver and gold on grain growth in zone-refined lead, shows that the measured activation energy is markedly dependent upon the kind and amount of solute present. Gifkins' work does not permit evaluation of the effect of the 8 ppm of impurities other than oxygen present in his specimens. One incidental point: the symbols used to designate the experimental points of Fig. 6 appear to be in incorrect order in the figure caption. As the caption is printed, it would indicate that larger grain sizes were obtained after annealing at 47°C than at 100°C, which does not agree with the text (point M, p. 1019). Finally, it seems clear from Gifkins' results that any serious attempt to determine whether grain boundary migration and grain boundary sliding during creep occur with the same activation energy, as Gifkins suggests and McLean rejects, must take into account the effects of impurities on these two processes, Although the work of Weinberg35 indicated that adding small amounts of copper, iron and silicon to aluminum did not affect the grain boundary shear behavior, it should be noted that his starting material contained approximately 60 ppm of impurities. Gifkins' results indicate impurity effects at an impurity level of 8 ppm, suggesting strongly that the most significant impurity range to be investigated lies substantially below that value. R. C. Gifkins (author's reply) — As Drs. Aust and Rutter suggest, the results under discussion may have to be reinterpreted in the light of their own work on grain boundary migration, which was not available to me when the paper was written. Because of their work, Aust and Rutter attach more importance than I did to the activation energy for grain boundary migration during annealing (7.5 kcal per mol) obtained from a "direct" plot of log-rate against the reciprocal of absolute temperature. At the time it was obtained, this value seemed rather low, although it was similar to the value obtained by Bolling and Winegard.36 It was then, and still is, difficult to accept this value because of the low value of the index in the power law for grain growth, which seemed to indicate the influence of impurities. It was also concluded that the low value of the activation energy might have arisen from the manner of selecting rates of grain growth which were truly comparable at the two temperatures. There were many other indications in these experiments and those on recrystallization during creep3? that an impurity, probably oxygen, was of importance. The model for grain-boundary migration which Lucke and Detert had proposed was an obvious possibility and its use yielded an activation energy for boundary migration during annealing of 20 to 25 kcal per mol.

Jan 1, 1961

By E. T. Turkdogan

The activity of sulfur was determined as a function of composition of ferrous sulfide by equilibrating with hydrogen sulfide-hydrogen gas mixtures at 670° , 800°, and 900". The present results supplement the available data over the composition range from 36.6 to 39.5 pct S. The X-ray lattice spacing measurements made are in accord with the available data and indicate that the limiting composition FeSl.008 may be taken for the iron-iron sulfide equilibrium. The growth rate of ferrous sulfide on iron was measured by reacting iron strips or blocks in hydrogen sulfide-hydrogen gas mixtures. Owing to the slow approach to equilibrium between the gas phase and the surface of the sulfide layer, The sulfidation experiments were carried out for several days. It is shown that the growth rate ullimately proceeds in accordance wilh the parabolic rate law. From the parabolic rate constants and the thermodynamic data on iron sulfide the self-difiusivity and chemical diffusivity of iron in ferrous bisulfide are evalualed. The self-diffusivity of iron thus derived zs found to increase with increasing sulfur content. THE ferrous sulfide known as "pyrrhotite" is a non-stoichiometric phase having a wide composition range from about 50 to about 58 or 60 at. pct, depending on the sulfur activity. RosenQvistl studied the thermodynamics of this phase over wide ranges of temperature and composition. Hauffe and Rahmel' and Meussner and ~irchenall~ studied the parabolic rate of sulfidation of iron in sulfur vapor. By using markers, these investigators showed that the iron cations were the predominant diffusing species in iron sulfide. This is confirmed decisively by the self-diffusivity measurements of condit4 who showed that the self-diffusivity of sulfur in ferrous sulfide is several orders of magnitude lower than the self-diffusivity of iron. Although much has been learned from these studies about the Fe-S system, further research on this subject was considered desirable for better understanding of the physical chemistry of iron sulfide. This work was confined to the study of the kinetics of sulfidation of iron in hydrogen sulfide-hydrogen gas mixtures. The results of this study are given in two consecutive parts. Part I, the present paper, is on the parabolic rate of sulfidation of iron and the diffusivity of iron in ferrous sulfide. The second paper, Part 11, is on the kinetics of the surface reaction between hydrogen sulfide and ferrous sulfide. EXPERIMENTAL Three types of experiments were carried out: i) equilibration of ferrous sulfide with gas of known E. T. TURKDOGAN, member AIME, is Manager,Chemical Metallurgy Division, Edgar C. Bain Laboratory for Fundamental Research, U. S. Steel Corp., Research Center, Monroeville, Pa. Manuscript submitted March 6. 1968. ISD sulfur potential; ii) X-ray studies of ferrous sulfide; and iii) measurements of the parabolic rate of sulfidation of iron. Equilibrium Studies. About 1 g of iron powder or foil. contained in a small recrystallized alumina crucible ind suspended from a calibrated silica spring, was reacted with a hydrogen sulfide-hydrogen mixture of known ratio until no further change in weight was observed. %hen the gas composition was changed and the new state of equilibrium was established after several hours of reaction time. The composition of the sulfide was obtained from the initial weight of the sample and the weight after equilibration. X-Ray Studies. The lattice parameters of some of the equilibrated samples were determined using the General Electric XRD-5 diffractometer with a cobalt tube (no filter) set at 40 kv apd 10 ma; the CoK, radiation was taken as 1.79020A. Observed 220 and 311 diffraction peaks of silicon served as an internal comparison standard to correct for possible misalignment of the goniometer. The lattice parameters of the sulfide phase were calculated from the corrected Bragg angles of the 110 and 102 peaks. Rate Studies. In the initial experiments attempts were made to measure the parabolic rate of sulfidation by measuring the gain in weight of a thin iron strip, -0.05 cm thick, suspended from a silica spring in the reacting atmosphere. The preliminary experiments showed that this technique was not reliable for the measurement of the parabolic growth rate of the iron sulfide layer. In the subsequent experiments the data on growth rate were obtained by measuring, on a microscope stage, change in the thickness of the sample after reaction for a specified time in a hydrogen sulfide-hydrogen mixture of known sulfur activity. For each reaction time a new sample was used. Precision-machined iron blocks, 0.5 by 2 by 5 cu cm, were de-greased and annealed in hydrogen for several hours prior to the sulfidation rate measurements. The experiments were carried out at 670°, 800°, and 900°C in gas mixtures having the ratios, and 1.0 for periods of times from a few hours up to 8 days. Apparatus and Materials. A vertical globar tube furnace with a 3-in.-long uniform temperature zone was used. The glass tube fittings were fused on the zircon reaction tube, 1.5 in. diam. The temperature was measured with a Pt-10 pct Rh/Pt thermocouple placed in the hot zone of the furnace inside the reaction tube (an alumina thermocouple sheath was used). A separate thermocouple was used for the temperature controller which maintained the furnace temperature constant within about 2°C. Anhydrous liquid hydrogen sulfide and oxygen-free dry hydrogen from gas tanks were used in preparing the gas mixtures by the constant head capillary flow-meters. In all cases volume flow rate was 1000 cu cm per min at stp, corresponding to a linear velocity of about 6 cm per sec at 800°C; under these conditions

Jan 1, 1969

By K. P. Gupta, P. C. Panigrahy

The stabilization of the R, a-Mn, and 0-Mn phases have been studied in the Mn-Ti-Fe and Mn-Ti-Co systems. Iron and cobalt both appear to stabilize the (Mn-Ti) R phase to almost the sarne extent. The R-phase region was found to extend from the lowest e/a to slightly beyond the maximunz e/a limit known for this phase. But, while iron appears to stabilize the a-Mn phase, cobalt tends to stabilize the p-Mn phase. In the two systems manganese appears to get replaced by iron and cobalt in each of the mentioned phases. The instability of the a-Mn phase in the Mn-Ti-Co system and the /3 -Mn phase in the Mn-Ti-Fe system cannot be explained on the basis of adverse size effects because atomic diameters for both iron and cobalt (C.N. 12 at. diam) are ziery similnr and not much different from manganese which they replace. Qualitatively, the reason for the stability of the a-Mn and the p-Mn phases can be traced to the more favorable e/a ratio prevailing in the respective systems and to a competing tendency between the two phases. In transition metal alloy systems the o, p,P, R, a- Mn,' and p-Mn2 phases have been claimed as electron compounds. A large volume of work has been done to establish the criterion for the formation of the o phase but until very recently practically no systematic work was done on the a-Mn and the /3-Mn phases. A recent investigation on the P-Mn phase3 indicates the e/a criterion for p-Mn phase stabilization. Since the R phase was first known to appear only in certain ternary systems1 no detailed work was then possible for this phase. The R phase has been recently discovered as a binary intermetallic compound in the Mn-Ti~ and Mn-si~-' binary systems. The existence of binary R phases opens up the possibilities of studying the effect of alloying elements on the stabilization of the R phase. Of the two binary systems possessing an R phase, the Mn-Ti system appears to be more interesting because at a suitable high temperature it is possible to find the three electron compounds, the a-Mn, p-Mn, and R phases, side by side and it is possible to study the effect of a third transition element on these three electron compounds. For the present investigation iron and cobalt, so called B elements for the formation of electron compounds, have been used as the third element to study the stabilization of the a-Mn, P-Mn, and R phases. EXPERIMENTAL PROCEDURE The alloys were prepared by using 99.9 pct pure electrolytic Fe and Mn, 99.5 pct Co, and crystal bar titanium, supplied by Semi Elements Inc., New York and Gallard Schelsinger Mfg. Co., New York. Weighed amounts of the components were melted in recrystal-lized alumina crucibles in an inert atmosphere (argon) high-frequency induction melting unit. Titanium was made into fine chips for easy dissolution and a special charging procedure was adopted to avoid contacts of titanium chips with the alumina crucibles. Up to 20 at. pct Ti, the maximum titanium content in the investigated alloys, there was no visible sign of reaction of titanium with the alumina crucibles. With a careful control of melting time and temperature the losses were minimized and were always found to be below 0.1 pct. Because of such small and almost constant weight losses, the alloys were not finally analyzed. The alloys were wrapped in molybdenum foil and annealed in evacuated and sealed silica capsules at 1000" * 2°C for 72 hr and subsequently quenched in cold tap water. Annealed samples were examined metallographically and by X-ray diffraction. For all high manganese alloys oxalic acid solutions of various concentrations and 1.0 pct HN03 solution were found suitable as etching reagents. Best contrast between the a-Mn and the R phases could be obtained by using freshly prepared 60 pct glycerine + 20 pct HN03 + 20 pct HF solution. For high iron and cobalt containing alloys, especially for alloys containing the a-Fe, y-Fe, and P-Co phases, 15 cc HNOJ + 60 cc HC1 + 15 cc acetic acid + 15 cc water solution was found to be the best etching reagent. All X-ray diffraction work was carried out (using specimens prepared from annealed powders) with a 114.6 mm diam Debye-Scherrer camera using unfiltered FeK radiation at 25 kv and 10 ma. All calculations for X-ray diffraction work were carried out using an IBM 7044 digital computer RESULTS AND DISCUSSION The two ternary systems, MnTiFe and MnTiCo, were investigated near the manganese rich end, Figs. 1 and 2, and show some common features. In both alloy systems large extensions of narrow R phase regions occur at almost constant titanium contents. At titanium contents higher than that of the single phase R-phase alloys, the same unidentified X phase was found in both ternary systems. The extensions of the X phase close to the Mn-Ti binary indicate that this phase could be the TiMns phase. Too few X phase diffraction lines were present in the diffraction patterns to make positive identification of the X phase. In contrast to this similarity the two systems show opposite behavior in the extensions of the a-Mn and 8-Mn phase regions; while iron tends to stabilize the a-Mn phase, cobalt

Jan 1, 1970

By H. Udin

G. KUCZYNSKI* and B. H. ALEXANDER*—This paper represents a most noteworthy attempt to evaluate experimentally the surface tension of a solid metal. Because of the great importance of such measurements, any proposed method should receive the closest scrutiny before the results can be considered reliable. In regard to the experimental method, we think that the marking of the gauge length by means of tieing knots in the wire may be the cause of some of the spread in the results. Such a knot may be expected to tighten slightly, and thus increase the gauge length, when placed under stress at high temperature. Although this effect would be very small, amounting at most to only a few times the wire diameter. A fairly tight knot in a wire will decrease the wire length by about ten times the wire diameter, thus only a slight tightening of the knot would cause considerable spread in the results. Upon plotting the stress strain curves from the authors' data, the writers found that there was a fairly consistent tendency towards an S-shaped curve, instead of a straight line. Such an effect could be caused by the tightening of the knots. The writers think, however, that the experimental results are fairly reliable, but that there may be other methods of interpreting them depending upon what mechanism is assumed to be responsible for the shrinkage of the wires. The authors have assumed that the stress due to surface tension results in viscous flow. It should be made clear that it has never been demonstrated that viscous flow can occur in metal crystals even at very high temperatures. The experiments of Chalmers13 on tin, which are so frequently quoted as giving evidence of viscous flow at low stresses are by no means satisfactory. In his experiments, Chalmers found that only the initial rate of flow was approximately proportional to stress. He also found that the rate of flow varied markedly with time which, in his experiments, was less than 2 hr. Inasmuch as there is no proof of viscous flow in metals, and the authors have brought forth no conclusive evidence on this point, it may be worth while to investigate other possible mechanisms of material transport which would account for the shrinkage of the wires. The writers wish to point out that in these experiments the shrinkage of the wires can be adequately explained, according to a self diffusion mechanism. Thus, if we assume a concentration gradient for self diffusion which is a function of the radius of curvature of the wires, and assume that diffusion will occur so that the total surface area is decreased, we find the following expression for the self diffusion coefficient: where k = Boltzmann constant r0 = initial radius of the wire T = absolute temperature ? = surface energy 8 = interatomic spacing t = time e = strain at zero applied stress Eq 19 may be used to evaluate the self diffusion coefficient of copper, using the strain measurements obtained by the authors for zero stress as obtained by extrapolating their curves for 5 rail wires. By inserting a reasonable value for the surface energy (1500 ergs per cm2) we find: -66,000 D = 5 X 10e RT [20] The activation energy is of the correct order of magnitude, but the frequency coefficient is much too high, indicating that surface diffusion may be playing an important role. This discrepancy in the action constant is much smaller than the corresponding discrepancy obtained by the authors for the viscosity coefficient. The writers by no means propose that this proves that the shrinkage of the wires is due to self diffusion but we merely wish to point out that there are explanations other than that given by the authors. In this, as in any kinetic phenomena, it is necessary to study the rate of the process before anything can be said about the mechanism. The determination of surface tension given by the authors is based upon an interpretation of the data which embody the concept of viscous flow. The final proof of this concept will be obtained only after the time relationships confirming the authors' Eq 15 have been conclusively established. The rough linearity of the stress strain curves obtained by the authors for experiments run the same length of time should not be considered as proving that viscous flow is occurring. H. UDIN (authors' reply)—All of the test specimens were annealed at 1000°C for an hour or more before preliminary measurements were made. During this anneal the wires recrystallize, and the greatest part of grain growth takes place. Also, the knots sinter at the cross-over points. This does not in itself eliminate the possibility of end errors, although it greatly decreases their probable magnitude. It is still possible that some extension occurs due to creep in shear at the sintered points. If so, this effect would be quite independent of and superimposed on the normal shrinkage or extension of the wire itself. Within the precision of the experimental results, straight lines satisfy the data as well as do any other simple curves. Until data of greater precision are obtained, it is futile to discuss any possible trends away from linearity. The disagreement between Kuczynski and Alexander's Eq 19 and our Eq 18 is one of semantics and mathematics, not mechanism of flow, since Eq 18 is based on the self-diffusion concept of viscous flow. It would be interesting to learn how the mathematics leading to Eq 19 deviates from that of Eyring and of

Jan 1, 1950

RUSSIA was the United States Number One source of manganese ore in 1948 when 34 pet of imports were received from that source, stated Norwood B. Melcher, assistant chief, ferrous metals and alloys branch, Bureau of Mines. In 1949, this country received only 20 pet of 1948 shipments from Russia, and only token amounts are now being received. Aggressive programming by industry and government resulted in prompt increases in shipments from major, producing sources; India, Gold Coast, and the Union of South Africa all increased exports to fill the vacuum left by Russia and provided an excess adequate to increase total imports approximately 290,000 short tons in 1949. Again in 1950, and with, even less ore from Russia, imports increased another 290,000 short tons. Since the shift from Russia as a source of manganese, the United States has received in total about 85 pet of its imports from India, Union of South Africa, Gold Coast, and Brazil in that order of importance. Producers of both home consumed and merchant ferromanganese have been able to adjust downward the manganese content of the home-consumed product and so obtain partial relief. Millions of tons of steel were produced in 1951 with a relatively low grade ferromanganese. This adjustment has been made without decreasing the quality of the steel, although with some increase in cost through introduction of new problems, including increased hand- . ding of material and additional removal of carbon. Forced into a pattern of price and grade structure such as exists today, the producer of ferromanganese must adopt one of three possible courses as a short-range program: 1-He may continue to deplete his stocks by producing standard (78 pet) ferromanganese and hope that the future will bring some form of relief; 2-he may attempt to produce 78 pet ferromanganese by paying higher prices for premium ores; or 3-he may drop the grade of ferromanganese and stretch stocks and future supplies of ore as far as possible. The present rundown condition of Indian railroads is attributed to the fact that the service has had no opportunity to recuperate since the beginning of World War II, while the demand for the movement of commodities has probably increased. The Union of South Africa has expanded its exports to the United States greatly since 1948, but, the showing of that country in 1951 was disappointing. Efforts have been made for some time by firms in the United States, at the urging of the manganese miners in the Union, to prevail on the railroad authority to grant and make available larger allocations of cars for manganese ore movement. As a whole, such efforts have been unsuccessful. Although the allocation of rail shipping has been the obvious factor in the decreased movement of ore, many other less determinate factors appear to be involved. Brazil, long an important supplier of manganese to the United States, has important manganese deposits in three areas, all of which are significant to this country. The Gold Coast is an important source of supply. Its metallurgical ore is particularly of significance because of its unusually high grade which permits considerable latitude in blending with the lower grade materials of South Africa and India. The Belgian Congo should have an output of 100,000 tons or more annually beginning this year. R. S. Dean presented two papers. One with K. M. Leute on hydrometallurgical methods for recovery of manganese from domestic ores and one as sole author on the so-called carbamate or Dean process. The two papers tied into each other. In the first mentioned he reviewed the various processes applicable to oxidized, and nonoxidized and reduced ores. The advantages of each .were pointed out. So far the only process tried on a substantial scale on oxidized ores was the SO2 process used at Las Vegas, Nev., on Three Kids ore during World War II. Many problems were encountered. Some of them were whipped while some of those remaining perhaps would have been whipped had time permitted. Since then work has been done elsewhere to avoid the formation of the troublesome thionates encountered at the Three Kids plant. Dean discussed the thionate and NO, processes as applied to oxidized ores. The only commercially used process on reduced ores is that of making electrolytic manganese. Among others that have been considered are the nitric acid process, the Bradley-Fitch ammonium sulphate process, and Dean's ammonium carbamate process. Dean's thesis was that extremely large tonnages of so-called low grade manganese ores are available, and that these should not be depleted in attempting to simulate a foreign metallurgical grade ore. He pointed out that the grade of the domestic manganese ores would be considered high if the same grade were found in copper ores. The selling price of electrolytic manganese and electrolytic copper are roughly the same. In addition to electrolytic manganese, he believes that domestic ores should be used to make exceptionally high grade products. These might be battery grade oxide or substantially pure oxide sinter, which might be used for high manganese alloys or for upgrading metallurgical grade manganese to produce a high manganese ferroalloy. The carbamate process is based on the fact that manganous oxide is readily soluble in concentrated ammonia solutions containing ammonium salts. In solutions of sufficiently high concentration the manganese exists as an anion. Lixiviants of ammonia and ammonium carbonate permit extraction of the manganese from reduced ores and the manganese can be recovered as carbonate by heating or by driving off ammonia. R. V. Lundquist presented a paper on upgrading high-silica ores or concentrates with sodium hydroxide to extract silica and to yield a product with a more favorable manganese: silica ratio. The NaOH is, regenerated in part by CaO.

Jan 1, 1952

By C. F. Allen, G. B. Walker

K. F. TROMP*—In dealing with the question of the most suitable kind of solid media for heavy density suspension processes Walker and Allen point out that the particle size of the solid media should not be taken too fine, as the viscosity increases with the area of the solid media and a low viscosity is essential lor high tonnage and accurate separation. A coarser particle size of the solid media will, in their opinion, of necessity give rise to a differential density in the bath (higher gravity at the bottom of the bath than at the top) but they advocate acceptance of the differential density rather than a higher viscosity. Though I fully agree with the choice the authors have made, I cannot subscribe to their view that only by accepting a differential density in the bath a coarse particle size of the solid media can be used. There certainly is another alternative: stronger agitation. Applying sufficiently strong vertical currents, a uniform gravity can be obtained quite well in a suspension of a coarse solid media. Of course, this is not a very attractive solution, for it means a degradation of the true gravity separation and a step backwards to hydraulic classification, which makes the washing dependent on size and shape of the particles. However, to a greater or lesser extent, this is what actually takes place in all the heavy density suspension processes relying on a uniform gravity in the bath. The so-called "stable" suspension processes make no exception. They all "stabilize" their suspensions by introducing or creating vertical currents, be it upwards or downwards or both, be it by hydraulic or by mechanical means. In fact, there is no such thing as a "stable" suspension in gravity separation, as the very reason for the use of suspensions in this field is the property that the solid media is able to settle and so facilitate the recovery. I have been enlarging on this point because the characteristics of the various processes can only be well understood and viewed from the same angle (from Bar-voys up to Chance) when the fact is recognized that mechanical or hydraulic agitation is a condition sine qua non for obtaining a uniform density from top to bottom in a suspension. Is a Cone-slraped Vessel Essenlial? Of the two alternatives for getting a low viscosity Walker and Allen have preferred correctly the sacrifice of uniform gravity in the bath instead of increasing further their vertical current arid agitation. The resulting differential density of the bath brings the problem of bow to prevent accumulation of intermediate gravity products in the bath, an accumulation which, if not prevented, would ultimately plug their cone. According to the authors an open-top cone combined with a downdraft current of the bath liquid would he the only suitable way to cope with such suspensions and they assume as a fact that "in any vessel other than a cone, such a differential density could not be tolerated." My experience is quilt: different. In my process, which has been in successful operation for more than a decade, differ-ential density of the suspension is applied ranging from values below 0.1 up to differentials above 0.5, according to the prevailing requirements of the individual plant. In this process, which is charac-terized by the use of horizontal currents in a suspension of differential density, the form of the vessel is of secondary importance and different types are in operation. It so happens that none of these are in the, form of a cone. The fact that 24 washboxes on my process have been installed and 12 others are under construction may constitute sufficient proof against the opinion that only a cone-shaped separator would be suited for differential density separation. Horizontal Currents in Differentia1 Den-sity Sepparation I myself have some doubts as to the suitability of a cone with downdraft for dealing with differential density (or, for that matter, any other washbox relying on vertical currents for removing the intermediate gravity products). It ap-pears to me that it is restricted to feed of small size only and even then with watch-fulness. If we take, for example, a piece of 2 in., the draft necessary to pull such a piece down to a zone wherein the den-sity of the suspension is, say, 0.03 higher, is quite considerable. For a suspension of, say, 1.6 sp gr the downdraft will have to be in the region of 3 in. per second. Unfortunately. most of the differential in density is in the part immediately below the reach of the top current which transports the floats. Consequently, we need the downdraft where we like it least: in the upper part of the cone. This entails the risk that light float particles are carried away with the downward current. This current of, say again, 3 in. per second would carry particles up to 1.3 sp gr and 3/8 in. size into the 1.6 gravity zone. This is prohibitive. It is also prohibitive because a downdraft of 3 in. per second in the upper part of the cone would require a tremendous circulation of medium. IIalf way up a 20 ft diam cone, a downdraft of 3 in. per second would correspond with 8500 gpm. With the downward current following the way of least resistance, the strength of the downdraft will not be exactly the same at different places of a cross area. If, as I anticipate, the center of the cone is favored, the strength of the downdraft will fall below the critical value near the

Jan 1, 1950

By Karl A. Bauer, Cornelis Bezemer

The deposition of calcium carbonate scale on surface and subsurface production equipment creates an operation problem in many oil fields. The formation water in which the carbonate-scale-forming components are initially dissolved becomes supersaturated with calcium carbonate as a result of the drop in pressure during production. The continuous flow of a supersaturated solution through the production equipment results in the growth of a dense layer of calcium-carbonate crystals. For a scale layer to be built up, the supersaturated formation water should contact the walls of the production equipment. The tendency for scale to be deposited, therefore, will be low, if the crude has a low water cut and if the water is finely dispersed in the oil. A scale problem will occur, if at a high water cut part of the water is present as free water. The rate of scale deposition will then be approximately proportional to the rate of free water production. Depending upon where the formation water becomes supersaturated, scale may be deposited in the flow line only, in both flow line and tubing, and in some cases even in the perforations and in the formation near the wellbore. In the South Sumatran fields (Indonesia) the main difficulties encountered due to the deposition of calcium-carbonate scale have been restriction of flow through tubings and flow lines, wear and abrasion of plungers and liners, and stuck plungers or wellhead valves. So far, the only methods of combating the *Presently associated with Brunei Shell Petroleum Co., Ltd.. Seria. scale problem have been routine acidizing and additional well pulling. As for the pumping wells, it was estimated that some 50 percent of the total well-pulling effort was directly attributable to scale deposition. The most promising alternative was to prevent the deposition of calcium carbonate scale by means of chemicals. Inorganic polyphosphates such as sodium hexametaphosphate and trisodium polyphosphate are known to retard the formation of scale by the "threshold action". They are adsorbed on specific faces of the crystal nuclei and thus prevent crystal growth, thereby stabilizing supersaturation. Polyphosphates are effective at very low concentrations ( a few ppm), and far less than stoichiometric quantities are required to keep the scaling ions in solution. Recent investigations on barium sulfate scale1 have confirmed this mechanism. The types of polyphosphate mentioned can be applied as concentrated aqueous solutions either squeezed into the formation, lubricated down the annulus or injected via macaroni string. Several squeeze jobs with polyphosphate solutions have been carried out in the South Sumatran fields, however, with disappointing results. Lubrication down the annulus and injection through a macaroni string were not considered attractive in this area because of the kind of equipment and the degree of supervision these techniques require. Polyphosphates are also available in a granular, glassy form, which, in contrast with the readily soluble types already mentioned, show an extremely low

Jan 1, 1970

By Charles H. Jacoby

The solution mining of evaporites has a history of approximately 5,000 years. The insitu leaching of metalliferous ore will have many of the same characteristic problems which have confronted industry for years in the production of evaporite minerals. Basically we will be converting the less soluble forms of valuable metals into their more soluble salts and producing these in much the same manner as, for example, sodium chloride. There are a number of problems which we are faced with that are more complex and complicated and, therefore, will require a higher degree of sophistication than previously employed. One of our most important undertakings will be the clearcut definition of the problems involved. While a great deal of expertise can be drawn from the solution mining of evaporites and the oil industry, problems peculiar to the hydrometallurgical field will need to be solved. One of these is the introduction of permeability into an impermeable rock so as to expose the sought after values of metals which by volume are infinitesimal when compared with sodium chloride, potash or other type water soluble mineralization. After establishing this permeability which will be miniscule when compared to a solution cavity, there will be the maintenance of this permeability. In general, salt deposits are of a somewhat uniform chemical composition and thus their chemistry was relatively simple. Each metalliferous ore body is somewhat unique in its chemistry and will need to be treated accordingly.

Jan 1, 1974

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

Jan 1, 1965

By James C. M. Li, J. Weertman

James C. M. Li (United States Steel Covp.)—The author has discovered a single analytical relation between the minimum, or the steady-state, creep rate and the applied stress confirming a statement made earlier by orn" that such relation should exist and should reduce to the power law at low-stress levels and to the exponential law at high-stress levels. However, as pointed out by the author, all the available theories of creep are not adequate to explain such a single relation. Inspired by such a statement, I have made a suggestion concerning a possible explanation13 of the new relation. This is based on the concept that the rate-controlling step is the cooperative motion of a short dislocation segment. The nature of and the reason for the cooperation have been discussed13 as well as the reason why the motion of the dislocation could be controlled by the mobility of the short segments. A natural short segment has been proposed13 to be the node formed at the intersection of two dislocations. The reason why the node may contain only a few atoms has not been discussed and the application of the proposed model to all the metals and alloys reported in this paper has not been attempted. It seems appropriate to include these in this discussion. The model was partly inspired by the substructure recently observed in the electron microscope on creep specimens. One such example is shown in Fig. 48 in Darken's Campbell Memorial Lecture. The substructure is a collection of dislocation intersections and irregular networks. No pileups have ever been observed in such specimens. A closer look at the network indicates that one set of dislocations is more straight than the other set sug- gesting that the other set may be mobile in the plane of the net. Since, for the network to survive the creep deformation, some dislocation reaction has to take place at the intersection of the two sets of dislocations, the mobile dislocation, even if it can slip in the plane of the net, will have difficulty in moving at these intersections. To illustrate, an idealized network is shown in Fig. 9. The thin lines represent the set of dislocations which are mobile and can slip in the plane of the net except at the nodes which are formed at the intersection of the two sets of dislocations. The other set of dislocations, represented by the thick lines, may have a Burgers vector which is not parallel to the plane of the net, and therefore may be immobile. Because of this nonparallel Burgers vector, the Burgers vector of the node, which is avectorial sum of the Burgers vectors of the two sets of dislocations, will also be nonparallel to the plane of the net. Therefore, the node cannot slip in the plane of the net and the set of mobile dislocations will have to drag the node along as indicated in Fig. 9. Now the problem is how many atoms could be involved in the nodes. Exact calculation of the length of the node is a difficult task especially since the length should be a steady-state length and not an equilibrium length. An estimate of the equilibrium length can be made by balancing the line tension of all the dislocations. The results would be a small fraction of the length 1 between nodes as shown in Fig. 10. In some instances such a calculation shows that the node will not be formed. But, since the calculation is only approximate, it does not rule out the possibility of the formation of a short node. In other instances the equilibrium length of the node is an appreciable fraction of I. Such a node would

Jan 1, 1963

By W. T. Malone, J. R. Williams, R. L. Tiner, J. M. Tinsley

Hydraulic fracturing methods for production stimulation have become a common procedure in the oil and gas industry. Fracturing treatments are performed on wells of various potentials to help increase the production rate. In addition to the desire for increased production is the need to predict what increase might be expected. This knowledge is useful in economical treatment planning to accomplish the desired production goals for the well. Theoretical production increases due to horizontal radial fractures may be calculated using equations developed from mathematical analyses and electrical models.1,2,6 It also is possible to predict theoretical production increases due to vertical fractures using curves developed from electrical3 and mathematical models.8 However, these studies assumed that the vertical fracture height and the formation height were equal, which may not be true." In addition, the final fracture height through which fluid is produced may not be equal to the created height. The development of vertical fracture proppant transport relationships has made unrealistic the assumption that propped fracture height is equal to created fracture height. Through the use of published proppant transport equations,4'12 it is possible to calculate the height of a bed of propping agent deposited in a fracture of a given height. Assuming that the fluid flowing in the fracture moves through only the propped portion of that fracture (i.e., that the un-propped part of the fracture heals) it becomes essential to know how production increase varies with the ratio of propped fracture height to formation height. It should be recognized that future investigation may determine that the fracture does not heal completely and that a highly permeable channel exists over the deposited bed of proppant. The effect of this channel was not considered for the present study. The following analysis of experimental data allowed development of curves to determine theoretical production increases considering fracture height as a variable. Discussion In designing a fracturing stimulation treatment a number of variables must be considered. The size of the treatment, type of proppant used, proppant concentration, treatment fluid properties and well conditions are all factors affecting the dimensions and permeability of the fracture. Production increase due to a vertical fracture is affected by propped length, height, width and permeability of the fracture for a given set of formation conditions. Production increase may be defined as the ratio of production rate after fracturing to the production rate before fracturing at the same pressure differential, pe — pw. The producing rate in an

Jan 1, 1970

By E. F. Koppe

The Upper Freeport coal in the Freeport and New Kensington quadrangles, Pennsylvania, varies from a bony streak to a thick coal deposit often exceeding ninety inches, the "Double" or "Thick Freeport". Distinctive basal partings, a central bone layer, and a canneloid top bench may be present. The appearance of a sandstone roof, sandstone rolls, and bony coal at the top of the main coal bench can be anticipated in thin Freeport areas when basal partings are absent. When the two basal partings are present, a shale roof is normal. These effects are correlated with the original topography upon which the coal was deposited. The original depositional high areas tend to coincide with present structural highs. Preliminary data indicate that coal quality, in part, is affected by the deposi-tional setting. In "high" areas, a tendency exists for the main coal bench to contain higher percentages of fusain and mineral matter. Within limits, some-what higher ash fusion temperatures appear to correlate with paleotopographic highs. As a result of these findings, critical examination of the paleotopography and related sediments is indicated in other areas and other coals. The Upper Freeport coal is quite variable both in thickness and composition in the Freeport and New Kensington quadrangles of Pennsylvania (Figure 1). The coal horizon in these quadrangles is marked either by a thin carbonaceous shale bed or by a single bed containing a variable number of partings (binders). The complex coal zone known locally as the "Double" or "Thick Freeport" contains the Upper Freeport Coal Bed at the base; but in addition, it has an overlying bone layer and an upper coal bed occasionally capped with a canneloid layer. The "Thick Freeport" often exceeds 90 inches in thickness, whereas the normal Upper Freeport coal usually varies between 34 and 50 inches.

Jan 1, 1961

By Job Goostray

IN THIS paper, as in so many other discussions of historical nature, there is little chance for original material and much has had to be rewritten from older papers, documents, accounts, reports, and the like, some of which are of doubtful authorship or contain conflicting statistics. Fully aware of these little historical pitfalls, the authors have tried to quote the origin where possible, and also to seek further confirmation when the statement warranted it, but cannot assume responsibility for certain facts and dates. The Encyclopedia Britannica was frequently consulted. The authors wish to acknowledge assistance from MacKintosh-Hemphill Co.-formerly the Fort Pitt Works-and also from officials of the Watertown Arsenal who loaned valuable books and gave much necessary information. They are particularly indebted to Colonel Dixon of that institution. The data on modern guns were furnished by Mr. F. Brauer of the Watertown Arsenal; Mr. H. S. Chaffee assisted by obtaining records and data of work carried on by the Builders' Iron Foundry of Providence, R. I.

Jan 3, 1925

By D. R. Cook

This paper is a case history of an exploration venture for base metals, begun by the Rocky Mountain District of Bear Creek Mining Company in 1952 and completed in 1954. The project was based on the idea of W. S. Burbank, U. S. Geological Survey, that commercial deposits of base metals might occur in Paleozoic sediments beneath hydrothermally altered volcanic rocks in the Southern Bonanza mining district, Colorado. Here, an area of andesitic rocks, four square miles in extent, has been argillized, pyritized, chloritized and silicified. Geological, geophysical and geochemical studies were followed by the diamond drilling of three holes totalling 6,220 feet. Further alteration ang geochemical studies were made on the cores from these holes. A brief review of the alteration and geologic mapping, colored aerial photograph interpretation, geochemical soil and rock sampling, magnetic, gravity and radio-metric surveys are presented together with some conclusions regarding this work. This paper is a case history of an exploration venture for base metals, begun by the Rocky Mountain District of Bear Creek Mining Company in 1952 and completed in 1954. Important contributions were made to the project by personnel of the Rocky Mountain District and the Geophysics Division. Individual acknowledgements to these people are made at the end of the paper. BASIS FOR THE PROJECT The project was based on the idea of W. S. Burbank (1947, p. 444) that commercial deposits of base metals might occur in Paleozoic sediments beneath hydrothermally altered volcanic rocks in the Southern Bonanza mining district, Colorado. Paleozoic sedimentary rocks, including the favorable Leadville limestone, are exposed three miles south of the altered area, and reason exists to believe that they might underlie it within a reasonable depth. Alteration of pre-mineral volcanic rocks has been used successfully as a guide to concealed orebodies in the Main Tintic and East Tin tic mining districts, Utah (Bill-ingsley, 1933, p. 120-122; Lovering et al, 1949; Howd, 1957, p. 124-134; Cook, 1957, p. 73) and could be a useful guide here. GENERAL GEOLOGY AND STRUCTURE The Northern and Southern Bonanza mining districts are northwest of the San Luis Valley in southern Colorado, just within the northeastern edge of the San Juan volcanic province. The districts are1ocated on the southern extension of the Sawatch uplift, a prorninent northwest-trending structural high. The highly productive mining camp. of Leadville, Gilman and Aspen are on the northeastern and northwestern flanks of this uplift where Paleozoic limestones have

Jan 1, 1961

By J. C. Osmond

One of the least known geologic regions in the U.S. is the area now called the Basin and Range Province. It is paradoxical that so little geologic information has been compiled for a province that has yielded billions of dollars worth of metals and is currently producing a small amount of oil. Regional stratigraphic studies of parts of this large territory have been published only recently, and regional structural interpretations of even parts of the province are rare in the literature. This, of course, does great injustice to the earliest workers: Gilbert,1,2 Russell,9 Le Conte,4 Spurr,5 Louderback,8 and others, who recognized the area as distinctively different from the rest of North America. Their simplified picture of the structure of the ranges and the province as a whole is the groundwork for present understanding and has never been superseded. Since their early works, however, geologic data from the province has consisted largely of detailed reports of widely scattered mining districts. Each district has been described as though it were an island in an unknown sea. More recent syntheses of the geologic history have been prepared by Lindgren,7 Ransome,8 Nolan,9 Bill-ingsley and Locke,30 Longwell,11 and Eardley.12 The tentative nature of the present interpretation, which treats the structural evolution of the Utah and Nevada area, must be considered in light of the scarcity of geologic information from the province as a whole. The methods of interpreting tectonic history from stratigraphy are based largely on the concepts of Marshal Kay.23 Discussions with Hoover Mackin also have aided in organizing the Tertiary history. TECTONIC AND STRATIGRAPHIC SETTING Two approaches to the subject of the tectonic history are possible; they correspond to looking through opposite ends of a pair of binoculars. One involves an expansion and extension of detailed work and the other an interpretation based on regional geological relationships. It is believed that the second approach, used here, is not in disagreement with detailed observations. The area of the Basin and Range Province is shown in Fig. 1. Within this area middle Tertiary to Recent high-angle faulting has controlled development of mountain ranges and valleys. Only the part of the area north of Las Vegas, Nev., and south of the Snake River in Idaho will be considered in this article. Within this part of the province most of the ranges trend north-south. Approximately two thirds of the area is covered by late Tertiary to Recent valley fill and lake deposits.

Jan 1, 1961

By Martin Rubenstein

CdS crystals have been grown from a number of metallic solvents such as bismuth, tin, lead, and cadmium. Etching studies have shown that plastic deformation occurs if the crystals are not removed from the solvent prior to the solidification of the solvent, on cooling. The deformed crystals show a umique exciton fluorescence as a function of edge dislocation density. If one grows the CdS in the eutectic alloy of the above four metals (commonly called Wood's metal) the crystals can be removed from the solvent with hot water and no plastic deformation occurs. In this paper, the liquidus solubility measurements of CdS, as a function of temperature, are presented. The data were obtained using a high -temperature filtration technique. CADMIUM-SULFIDE crystals have been grown from a number of metallic solvents1 such as cadmium, bismuth, tin, and lead. Liquidus solubilities of CdS in cadmium,2 bismuth,3 and tin4 have already been measured. Crystals of CdS, in all four metals, have been grown by solution growth: 1) by cooling a saturated solution and 2) by a solution transport method.1'"1 CdS crystals grown in these four solvents have a few characteristics in common: 1) 1.8°K photolumines-cent emission consisted mainly of the radiative recombination of the bound exciton commonly known as I,, 2) slip lines which could easily be seen by the naked eye, and 3) edge dislocation densities in the order of l05 per cu cm.1 It was decided that these slip lines and the high edge dislocation densities were caused by a plastic deformation of the CdS crystals. It was felt that this plastic deformation did not occur during the growth of the crystals nor during the cooling of the solution, but did occur when the solvent which was in contact with the crystals froze. If these assumptions were valid, the slip lines and the high number of dislocations could be reduced or eliminated by removing the crystals from the solvent before the solvent froze. Since crystals of CdS had already been grown separately in such solvents as bismuth, lead, tin, and cadmium, it was felt that crystals could be grown in a eutectic mixture of these four metals. In this work a eutectic (or near eutectic) mixture of bismuth, lead, tin and cadmium in the proportion 50, 26.5, 13.5, and 10 wt pct, respectively, was used to grow CdS crystals. Such a mixture has a melting point of about 70°C and is close in composition to the alloy commonly known as Wood's metals. If the crystals could be grown from this mixture of solvents, and if hot water (>75°C) could be used to separate the crystals of CdS from the metallic solvent, it was hoped that CdS crystals could be grown with little or no plastic deformation which had been ob- served when crystals were grown from these solvents uncombined. CdS crystals were grown from this low melting eutectic mixture of bismuth, lead, tin, and cadmium using the solvent transport method. CdS powder and the appropriate amount of metals were sealed in a quartz tube under a pressure of about 5 X 10-6 torr. This ampule was then placed in a vertical position in a furnace. The temperature was raised to about 900°C. The furnace was designed so that the top of the liquid column within the ampule was between 10° to 40°C higher than the bottom of the liquid column. These temperatures were measured on the outside of the quartz ampule. The ampule was maintained at temperature for 7 to 14 days (depending on the temperature at which transport was taking place) and then the furnace temperature was lowered until the temperature was about 125°C. The ampule was then removed from the furnace, placed in water maintained at about 90°C, and opened in this 90°C environment. The crystals could then be removed from this two-phase liquid (Wood's metal and water) by mechanically picking them out. Alternatively, the crystals could be quantitatively removed by adding an excess of mercury to the mixture of metals, crystals, and hot water. The hot solution of metals and the hot water could be evacuated using a small diameter tube connected to a vacuum. Small amounts of mercury and water could be removed by heating the crystals in vacuum. Crystals prepared using this technique showed no evidence of slip. However, some of these crystals did show edge dislocation densities as high as l04 per cu cm. Some few selected crystals showed no dislocations. Single crystals of CdS were grown as large as 5 by 5 by 0.5 mm. The ampules for the growth of these crystals were 13 mm O.D., 11 mm I.D., 150 mm! LIQUIDUS SOLUBILITY MEASUREMENTS The CdS starting materials was G.E. 118-8-2 powder which was fired in H2S at 1000°C, and then a vapor transport technique5 was applied to produce a "sound" mass of CdS. The Wood's metal was prepared by weighing out bismuth, lead, tin, and cadmium in the proportions of 50, 26.5, 13.5, and 10 wt pct, respectively. The bismuth, cadmium, and lead were from the American Smelting and Refining Co. (ASARCO) and all had purities of 99.999+ pct. The tin was 99.9999 pct spectroscopic grade from the Vulcan Materials Co. The appropriate mixture was placed in a quartz tube, evacuated to a pressure of 5 X 10-6 torr, melted to a liquid, cooled to room temperature under this same vacuum. This ingot was then placed in another quartz tube, evacuated to 5 x l0-6 torr, and sealed off under vacuum. The ampule was then horizontally placed in a furnace. The temperature was raised to 600°C, and over a period of several hours the ampule was vigorously shaken several times. The ampule was then removed from the furnace, and the metallic liquid was

Jan 1, 1970

By J. J. Forbes

'"THE Federal Coal Mine Safety Act (public Law T. 552. 82nd Congress) was approved oil July 16, 1952. It incorporates, as Title I, the Coal Mine Inspectio1.1 and Investigation Act of May 7. 1941 (Public Law 49, 77th Congress), which gave Federal inspectors only the right to enter. coal mines for inspection and investigation purposes but no power to require compliance with their recommendations. Title 11 contains the enforcement provisions of the act; its purpose is to prevent major disasters in coal mines from explosions, fires. inundations. and man-trip 01. man-hoist accidents. At this point a brief account of events that preceded the enactment of the Federal Coal Mine Safety Act seems appropriate. The hazardous nature of coal mining was recognized by the Federal Govermment as long ago as 1865, when a bill to create a Federal Mining Bureau was introduced in Congress. Little was done, however, until a series of appalling coalmine disasters during the first decade of this century provoked a demand for Federal action. As a result an act of Congress established a Bureau of Mines in the Department of the Interior on July 1, 1910. The act made it clear that one of the foremost activities of the Bureau should be to improve health and safety in the mineral industries. One of the first projects selected by the small folce of engineers and technicians then employed was to determine the causes of coal-mine explosions and the means to prevent them. By investigations aftel mine disasters the fundamental causes and means of prevention were soon discovered, and the coal mining industry was informed accordingly. However, despite this knowledge and the enactment of State laws and the Federal Coal Mine Inspection and Investigation Act of 1941, mine disasters continued to occur with disheartening frequency and staggering loss of life. The devastating explosion at the Orient No. 2 mine on December 21, 1951, resulted in the death of 119 men. The Orient disaster rekindled the memory of the Centralia. Ill., disaster of March 25. 1947, which caused the death of 111 coal miners. These two tragedies ultimately brought about enactment of the Federal Coal Mine Safety Act. The act is a compromise measure. Senator Matthew M. Neely of West Virginia and Congressman Melvin Priec of Illinois introduced almost identical versions in the 82nd Congress, but they were considered too drastic. The final version was introduced by Congressman Samuel K. McConnel, Jr., of Pennsylvania, after considerable discussion and amendment in committee hearings. It was passed by the Congress and became effective when signed by the President on July 16, 1952. The act is somewhat limited in scope because it applies only to approximately 2000 coal mines in the United States and Alaska that employ regularly 15 or more individuals underground. It exempts approximately 5300 mines employing regularly fewer than 15 individuals underground and all strip mines, of which there are about 800. Moreover, it covers only conditions and practices that may lead to major disasters from explosion, fire, inundation, or man-trip or man-hoist accidents. According to Bureau records, such accidents have resulted in less than 10 pct of all the fatalities in coal mines. It is important to mention that the law is not designed to prevent the day-to-day type of accidents that have caused the remaining 90 pct or more of the fatalities, because it was the specific intention of the Congress to reserve the hazards which caused them to the jurisdiction of the coal-producing states. Many who opposed any Federal legislation that would give the Federal inspectors authority to require compliance with mine safety regulations claimed that such legislation would usurp or infringe upon States' rights. To assure that the principle of States' rights would be preserved, the act provides for joint Federal-State inspections when a state desires to cooperate in such activities. The Director of the Bureau of Mines is required by the act to cooperate with the official mine-inspection or safety agencies of the coal-producing states. The act provides further that any state desiring to cooperate in making joint inspections may submit a State plan for carrying out the purposes of this part of the act. Certain requirements are listed: these must be met by a state before the plan can be accepted. The Director of the Bureau of Mines, however, is required to approve any State plan which complies with the specified provisions. The Director may withdraw his approval and declare such a plan inoperative if he finds that the State agency is not complying with the spirit and intent of any provision of the State plan. When this paper was prepared, agreements for joint Federal-State inspections had been entered into with Wyoming and Washington. A few other states have indicated their desire to submit a State plan and negotiations toward that end are now under way. Reluctance to enter into such agreements may be due to the mine operators' knowledge that in the states that adopt a cooperative plan they are prohibited from applying to the Director of the Bureau of Mines for annulment or revision of an order issued by a Federal inspector and must appeal directly to the Federal Coal Mine Safety Board of Review for such action. Experience has proved that review by the Director as provided in the act is a less expensive and time-consuming procedure to all concerned than applying to the Board. Reluctance also may stem from the fact that joint Federal-State inspections somewhat restrict the movements of the State mine inspectors and tend to reduce the number of inspections of mines. Where a State plan is not adopted, the Federal coal mine inspector is responsible under the law to take one of two courses of action if he finds certain hazardous conditions during his inspections. The first action involves imminent danger. If a Federal inspector finds danger that a mine explosion, mine fire, mine inundation, or man-trip or man-hoist accident will occur in a mine immediately or before the imminence of such danger can be elim-

Jan 1, 1955

By J. F. Elliott

PRESENT knowledge of the usual metallurgical slags indicates that they are, for the most part, rather complex in behavior and as yet there is no ready means for describing, in a simple manner, the behavior of any one of them. One of the best known slag systems is the iron oxide-silica-lime ternary which is the basic "solvent" in a number of important metallurgical refining operations, the basic open hearth being one of the most important. In this operation, the slag dissolves such components as sulphur, phosphorus, manganese oxide, and magnesia. Considerable study of this slag system and the behavior of these additions has been carried out in the past by a number of authors, as has been summarized in several critical reviews.','2 However, except for determination of the activity of iron oxide, only a limited amount of effort has been directed towards developing, from these data, an understanding of the general behavior of the basic solvent. Reported here are the results from a series of calculations based on data from the literature which permit a semiquantitative evaluation of the activities of iron oxide, silica, and lime (plus magnesia) in the ternary system at 1600°C. The preliminary results, which were reported briefly at a symposium held by AIME in 1953, have been revised and are completed. The steps in the calculation are as follows:* I—establish the activity curves and the curve of the excess molar free energy of mixing at 1600°C for each of the binary systems, 2—construct the activity surface of iron oxide for the ternary from the data on the binary systems and information available in the literature for the ternary area, 3—determine the surface of excess molar free energy of mixing for the ternary system from the activity surface of iron oxide and from the molar curves obtained for the binary system, and 4—differentiate the ternary surface of the molar excess free energy of mixing to obtain the ternary surfaces for the logarithm of the activity coefficients for silica and lime (log rslo, and log rc.~). Si0,-Fe,O: Schuhmann and Ensio have measured the activity of iron oxide in simple iron oxide-silica slags when in equilibrium with y iron. Their data recalculated to 1600°C are shown in Fig. 1. Also included is a point representing a measurement by Gokcen and Chipmana of the activity of iron oxide at 1600°C at the point of saturation with solid silica. For convenience and in accordance with other treatments,' the calculations are based on the hypothetical component, FelO, which is obtained by converting all the analyzed iron in the slag to FeO. In spite of Schuhmann and Ensio's conclusion that the activity of iron oxide in the system does not vary with temperature over the experimental range of 1258" to 1407"C, the data are corrected to 1600°C assuming that temperature does have an effect. It was felt to be most reasonable to assume that the term log rr.10 is a linear function of the reciprocal of the temperature. Reyu has indicated that an effect of temperature on the activities in this system is to be expected from the Schuhmann and Ensio data. In essence, the correction consists of multiplying the experimental value of log rf,,o by the ratio of the experimental temperature in Kelvin to 1873°K. The magnitude of the correction is not large, being approximately 11.5 pct of the experimental value of log rve10. A very minor correction was necessary to compensate for the fact that the slags were in equilibrium with y iron in the experiment, while at steel-making temperatures they would be in equilibrium with liquid iron. Data for the correction were obtained from Darken and Gurry. The standard states established are pure liquid iron oxide (FelO) in equilibrium with pure liquid iron (with the appropriate amount of oxygen in solution) and pure liquid silica. The method of plotting in Fig. 1 is convenient for the calculation of the activity of liquid silica and permits a reasonable extrapolation for the activity of Fe,O in the ranges where no experimental data are available. The uncertainty in the extrapolation to infinity at one terminal where Nvelo = 1 for the usual Gibbs-Duhem integration is reduced considerably by this method. The region of two coexisting liquid phases is estimated to range from 1.8 to 41.7 mol pct Fe,O. The nature of the activity curve for the single-phase region indicates that the activity of iron oxide across the two-phase region is very close to 0.39. Computation of the function log ~F,,o/(1— NF,,o)' for this region (dashed line) in conjunction with the curve through the adjusted experimental data indicate the best probable value of 0.382 for alPe,o in the two-phase area. The line from 0 to 0.018 Nf~~o is obtained by assuming that the component follows Henry's law. In this range, the value for log rveto is 2.59. Appropriate mathematical manipulation of the plotted linet yields the activity curves for the The curve AF", the excess molar free energy of mixing (actual minus ideal), as shown in Fig. 3 is also computed from Fig. 1. This curve is required for subsequent calculations. CaO-Fe,O: The phase diagram for the lime-iron oxide system when in equilibrium with liquid iron is not well known but there appears to be no intermediate compound present. This fact as well as the activity values for Fe,O extrapolated to the CaO-Fe,O binary from Taylor and Chipman' tend to indicate somewhat negative deviations from ideality for the activity curves for the two components. Strong indication of this is evident in Fig. 1 where are plotted the points computed from the estimated activities of Fe,O for the binary system.' It appears that the best line through the data is a horizontal straight line. Because of the general indication of the slight negative departure from ideality, the line is extrapolated horizontally to NF~,o = 0. It is con-

Jan 1, 1956