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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 H. H. Podgurski, J. C. M. Li, Y. T. Chou, F. N. Davis, R. A. Oriani

When an Fe-2 pct A1 alloy is nitrogemted at 500ºC with a gus tnixture (NH3-H2) in which the nitrogen activity has been kept Lou] enough to avoid the formation of iron nitride, a two-phase alloy is generuled which consists of AlN particles and a ferrite phase cotaining a heavy network of dislocations. The amount of nitrogen contained in such an alloy, when equilibrated with the nitrogenating atmosphere, far exceeds both that needed to satisfy the normal solution requirements of a Fe and that needed to convert all of the aluninuwi to AlN. This excess nitrogen is accounted for as being trapped on dislocations, adsorbed at the ferrite -AlN interface, and as an en-Iuznced lattice solubility in strained ferrite. This excessive uptake of nitrogen had previously been attribuled by other investigators to the formation of a nonstoichiornetric aluminum nitride. Isotope exchange experiments revealed various amomts of exchargeable N14 present in the originally nitrided samples that could not be removed by reduction with HS at 500ºC. This exchangeable nitrogen has been identified us that bound to the AlN -ferrite interface. Estimates of inter facial areas in alloys containing -3 pct by weight of A1N are as high as 10 sq m per g of alloy. ThE first1 of this series of papers described the experiments forming the basis for the elucidation of the mechanism of the formation of aluminum nitride particles within an Fe-A1 alloy. It was found that not only are dislocations necessary for the nucleation of the AlN particles but also the nitriding reaction in turn produces a dense network of dislocations in the ferrite matrix. It was also observed that nitrogen in excess of that needed for the formation of stoichiometric AIN is taken up by the alloy without the formation of an iron nitride. The present paper is an analysis of the excess nitrogen sorbed by the nitrided Fe-A1 alloy which considers the structure generated by the formation of the aluminum nitride particles. Because of the high density of dislocations, this system has proved to be quite useful in studying nitrogen-dislocation interactions. Wriedt and Darken2 have already reported such studies in a cold-worked ferritic steel. EXPERIMENTAL Nitrogen Sorption. The specimens of this alloy were cold worked (50 pct reduction) to 0.011 in. thickness and chemically cleaned in a 2:1 concentrated phosphoric acid-50 pct hydrogen peroxide solution before nitrogenation. The flowing nitrogenating atmosphere (11 pct NH3-89 pct H2) was established before the ni- trogenating temperature was reached. The same gravimetric and gas-flow equipment described in an earlier paper1 was also used in this investigation. Changes in nitrogen concentration were followed gravimetrically when establishing the isotherms. In the isotope exchange experiments, concentration changes were followed volumetrically. In some instances chemical analyses (Kjeldahl method) were used to check for material balances in both the gravimetric and volumetric procedures. Our objective was to obtain reversible nitrogen sorption isotherms for alloys equilibrated with NH3-H2 gas mixtures over a large range of nitrogen activity* and temperature. The *Defined as equal to PN H /P3/2 ,where P corresponds to partial pressure in atmospheres. Actually the nitrogen activity, aN, in the alloy equals K PNH3 /p3/2H2, where K is the equilibrium constant for the reaction NH3 = N + 3/2H2. upper limit for nitrogen activity was below that which would produce iron nitride; for reasons which will become apparent later, most of the sorption studies were made in the temperature range between 400" and 500'C. The alloy sample studied most extensively in this investigation was given a series of successive reductions (100 pct H2) and nitrogenating treatments at 500°C to attain a stabilized structure. Presumably some dislocations were lost during these treatments. Throughout most of the sorption studies, temperature was held at ± 1°C and the gas-phase composition was held to k0.2 pet NH3. Based upon the results of numerous diffusion experiments with this alloy* the 'Results to be published in a third paper of this series. times chosen for equilibration were considered more than adequate, Nitrogen Isotope Exchange. The first exchange experiments were carried out by circulating a measured quantity of H2 and NH3* (with a predetermined isotopic *The NH3 was synthesized over a synthetic ammonia iron catalyst using H2, and N2, enriched with N15. AS the NH3 was formed it was removed continuously from the gas phase by circulating the mixture through a refrigerated (78ºK) trap. When most of the nitrogen had been converted to NH3, it was distilled from the trap into a glass storage vessel. composition, N15/N14) over a nitrided specimen at 450°C in a closed glass system. Attempts to reach the exchange limit isothermally, i.e., an isotopic ratio (N15/N14) in the gas phase identical with the extractable nitrogen in the nitrided alloy, were futile. The exchange rate between the gas phase and the alloy was too slow, involving many days. To circumvent the slow exchange with the gas phase, measured amounts of N15 and N14 were introduced into the alloy by nitrogenating with an NH3-H2, mixture at 500°C containing an N15/N14 ratio of 7.76; the charged specimens were then sealed by allowing an oxide film to form over them in air, and in this final condition the specimens were subjected to 500°C in vacuum for various times during which isotope exchange was allowed to proceed within the specimen. It was estab-

Jan 1, 1970

By M. M. Wong, D. E. Couch, G. M. Martinez

The Bureau of Mines electrowon hafnium metal with an average oxygen content of' 150 ppm at 700°C from an electrolyte containing 27 wt pct LiCl, 62 wt pct RbCl, and 11 wt pct HfC14. The average anode and cathode current efficiencies were 90 pct at anode and initial cathode current densities of 86 amp per sq ft. Haf-nium metal with an average oxygen content of 440 ppm was electrowon at 800oC from an electrolyte containing 90 wt pct KC1 and 10 wt pct HfCl4. The average anode and cathode current efficiencies were similar to those obtained in the LiCL-RbCl-HfCl, electrolyte. The chlorine gas given off at the graphite anode was vented through either a silica or a graphite tube to prevent cell corrosion. THE current method for the commercial production of high-purity hafnium is the thermal decomposition of Hfl4.1 The iodide method is not adaptable to continuous process techniques. Nettle, Hiegel, and Baker2 studied the electrorefining of hafnium from hafnium sponge containing 800 ppm oxygen. They failed to obtain hafnium with 600 ppm oxygen in their initial deposits and obtained AEC specification for oxygen only after 75 pct of the soluble hafnium had been removed from the electrolyte. Calculations using their data indicated this was approximately 4 lb of hafnium. The electrolyte was then used to produce approximately 3 lb of hafnium with a low oxygen content. However, no data are shown concerning the amount of anode material initially used or what percent of it was dissolved, therefore, results are not suitable for evaluation of a continuous operation. In general, it was not possible to consistently obtain low oxygen content metal with the electrolytes described by Nettle, Hiegel, and Baker. Wong, Hiegel, and Martinez3 investigated the electrorefining process for hafnium and showed that even by strict control of electrolyte composition only relatively low oxygen reduction could be obtained. The oxygen contained in the hafnium anode material tended to transfer to the cathode deposit and only a limited purification was possible. Both the "iodide" and the "electrorefining" processes depend upon hafnium sponge as a starting material. The sponge is normally produced by magnesium reduction of HfC14 ' and does not meet AEC specifications for hafnium metal. Since only 30 pct of the anode feed could be utilized3 in the electrorefining cells, the Bureau of Mines developed an electrowinning process. HfC14 was used as the feed material for the electro-winning process described in this report. Many of the electrolytes used in the electrorefining studies3 ap- peared to be suitable carrier-electrolytes for HfC14. However, in the initial studies on electrowinning, it was desirable to use electrolytes that had low solidus temperatures and could be operated over a wide temperature range to investigate parameters of the process. Therefore, electrolytes containing LiC1, NaC1, KC1, RbC1, CsC1, and HfC14, in various combinations were explored. EQUIPMENT Chlorinator. Hafnium carbide was chlorinated to produce HfC14 in the batch-type chlorination shown in Fig. 1. Chlorination temperatures were measured with a thermocouple placed in the center of the HfC charge. A flow meter was used to monitor the helium and chlorine. The exhaust side of the silica chlorina-tor tube was equipped with a flask for collecting organic material released during the initial heating of the HfC. The temperature of an internal heater, which extended from the HfC14 condensing flask to the hot end of the chlorinator, was adjusted to prevent the HfC14 from condensing before entering the collection flask. Helium and excess chlorine were exhausted through the lid of the collection flask to an aqueous NaOH solution. Sublimer. Initial studies were conducted using a sublimer, Fig. 2, made by placing a 13/8-in. OD nickel thimble 11 in. long, inside a 11/2-in. ID nickel bell 12 in. long, and locking it in place. This unit was loaded with HfC14 and partially immersed in the molten electrolyte for sublimation directly into the electrolyte. In another sublimer shown in Fig. 3, the HfC14 was contained in a "resin reaction flask". Quartz wool, previously heated to 600aC, secured between two nickel wire screens, was placed just above the HfC14 powder. The lid contained a vacuum outlet, a gage, an argon inlet, and an air-cooled pipe for condensing the HfC14. This sublimer was evacuated and heated. The sublimation temperature was not critical and the sublimer operated satisfactorily at all temperatures between 250" and 350°C. Electrolytic Cell. The electrolyte chamber, Fig. 4, was made of mild steel 8-in. schedule 20 pipe, 30 in. long. The exterior was metallized with a Ni-Cr alloy. The electrolytes were contained in a 16 gage nickel or iron liner with a nickel heat shield on top. The cell was heated by a resistance furnace. A 21/2-in. ID by 25 in. long air lock was connected to one port of a two-port cell cover assembly through a slide valve. The cover assembly of the air lock was electrically insulated from the cell and was equipped with a rubber sleeve that provided for the passage of the cathode lead. This allowed the cathode deposits to be removed and a new nickel cathode to be introduced without allowing air to enter the cell. A tube-rod assembly was bolted to the other port on the cell cover assembly and was sealed by a packing seal. The tube-rod assembly consists of a graphite

Jan 1, 1970

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 Y. Baskin

Solid-solubility relationships in the Pseudobinary systems UAS-UP, UAs-US. UAS-UC, aid UAs-UN were investigated. The first two systems exhibit complete mutual solubility, whereas the component compounds in the other two systenzs are immiscible. The above information, together with solid-solubility data joy six additional pseudobinary systems , were analyzed for compliance wilh the Hurrze-Rothery rules for rnetallic systems. The relative size difference of the component nonmetal atoms was found to be the dopainant jactor determining the extent of solid solubility between the NaC1-type uranium compounds. The anionic and covalent radii of the nonmetal atoms appear to be inadequate for these systems, but compuled radii based on rare earth compounds yield consistent results for the uranium compounds. THE actinide elements, like metallic elements of the transition and rare earth series, readily form binary compounds with nonmetallic elements of groups IV, V, and VI of the periodic table. Of particular importance are the NaC1-type equiatomic compounds with carbon, nitrogen, sulfur, phosphorus, and arsenic. The uranium members of this family of compounds have high melting points, are essentially stoichiometric, and exhibit various amounts of mutual solubility. Thus, they are of interest for investigating the factors governing the extent of solid solubility. Previous investigators have determined the solid-solubility limits in the pseudobinary systems between the compounds UC, UN, US, and UP. Anselin et a1 .' reported complete miscibility in the system UC-UN. Baskin and shalek 2 and Allbutt et a1.3 reported that UP and US exhibit complete mutual solubility. Shalek and white4 reported partial miscibility in the system US-UC. At 1800°C the maximum solubility of UC in US is 40 mol pct, but that of US in UC is 4 rnol pct. shalek5 found limited solubility in the system US-UN; the maximum solubility of UN in US is 11 rnol pct at 1800°C, while that of US in UN is only 0.3 mol pct. White and askin 6 found very limited miscibility in the system UP-UC at 1800°C. Approximately 7 mol pct UC is soluble in UP, but there is no solubility of UP in the monocarbide. Phase relations in the pseudo-binary system UN-UP were investigated by askin.' Approximately 0.7 mol pct UN is soluble in UP at 1800°C, while UP is immiscible in UN. The present study was carried out to explore the extent of terminal solubility in the systems UAs-UC, UAs-UN, UAs-US, and UAs-UP. This information, combined with existing data, provided a sufficient basis on which to determine the factors governing solid solubility in pseudobinary systems containing NaC1-type uranium conpounds. I) EXPERIMENTAL 1) Materials. The compounds UC and UN were obtained from the Kerr-McGee Corp. and United Nuclear Co., respectively. The US, UP, and UAs were synthesized by reacting finely divided uranium with H2 S, pH3, or AsH3 gas at low temperature (300° to 500°C), followed by homogenization in a vacuum at moderately high temperatures (1400° to 1700°c).8-10 The materials were essentially stoichiometric, with the exception of UC, which exhibited a C/U ratio of 1.05. Oxygen was the major contaminant in these compounds, ranging from 0.05 wt pct in US to 0.30 wt pct in UC, and it was generally combined with uranium to form UO2. The UO2 content in these materials was usually of the order of 1 wt pct, and did not exceed 2 wt pct. Furthermore, no evidence was found for a high-temperature reaction between uranium dioxide and any of the compounds. Chemical analyses of equilibrated compositions in the systems UAs-UP and UAs-US showed that the non-metal atom to uranium ratios averaged about 1.01, and that the oxygen contents ranged from 0.06 to 0.22 pct. However, the small deviations from stoichiome-try or the presence of minor oxygen impurities do not invalidate the conclusions to be drawn from this study. 2) Experimental Procedures. The component compounds in powdered from were blended in the desired proportions for 5 hr in the ball mill that consisted of stainless-steel balls in a plastic container. Chemical analyses indicated very little metallic pickup from the blending operation and virtually no increase in oxygen content. The pellets were pressed in a 0.270-in.-diam steel die under 40,000 psi pressure. One wt pct of stearic acid dissolved in CCl 4 served both as a binder and as a die lubricant. Chemical analyses revealed that the stearic acid left no carbon residue in the sintered samples. The pellets were sintered in vacuum in an unsealed tantalum crucible. The temperature, measured with a calibrated optical pyrometer, was maintained at 1800" + 30°C for 3 hr. This was sufficient time for attaining equilibrium as no change occurred in either the lattice parameters or the sharpness of the X-ray patterns when samples were annealed for longer periods of time. The pellets were cooled with the furnace. Debye-Scherrer powder patterns were taken at room temperature with a 114.59-mm-diam Norelco powder camera and CuKor radiation (CuGI = 1.5405A). Unit cell dimensions were determined from a Nelson-Riley extrapolation to the high-angle reflections. The values for were precise to k 0.001A. 11) RESULTS X-ray and met allographic investigation revealed that complete mutual solid solubility exists in the pseudobinary systems UAs-UP and UAs-US. The lattice parameter vs composition plots, Fig. 1, show a

Jan 1, 1968

By G. D. Rieck, M. M. P. Janssen

Chemical diffusion coefficients and heats of activation for diffusion in the NizAh fy), NiAl (6), and Ni3A1 (E) intermetallic phases and the solid solution of aluminum in nickel (( phase) were calculated from layer growth experiments. No finite diffusion coefficient for the NiAl3 ((3) inter metallic phase could be calculated. The values of the diffusion coefficients are dependent both on the method of calculation and the type of diffusion couple. The heat of activation for diffusion in the y phase was found to be 47 kcal per mole in the temperature range oj 428" to 610°C. Heats of activation of 41, 12, and 48 kcal per mole were found for diffusion in the 6, E, and ( phases, respectively , in the temperature range of 655" to 1000°C. Experiments with markers in the diffusion zone demonstrate a very pronounced Kirkendall effect. It appears that only aluminum atoms take an active part in the diffusion process during the formation of the 0 and y phases at temperatures of about 600°C. During the formation of the 6, E, and < phases at higher temperatures only nickel atoms are moving. It is suggested that the great stability of the intermetallic compounds in the Ni-A1 system governs the Kirkendall effect. SOME factors controlling layer growth during inter-diffusion in the Ni-A1 system (phase diagram, see Fig. 1) were studied by Castleman and Seig1e.l&apos;~ They found the NiA1, ((3) and NiAl3 (y) intermetallic compounds to appear in the diffusion zone of Ni-A1 couples at annealing temperatures of 400" to 625°C; the NiAl (6) and Ni3A1 (E) intermetallic compounds appeared in y-Ni couples at annealing temperatures of 800" to 1050°C. These authors carefully examined metallographically Ni-A1 couples after 340 hr annealing at 600°C. Besides the (3 and y phases they found very thin layers of the 6 and E phases. ~n~erman~ and Castleman and Froot4 observed a much more rapid growth of the 5 and E phases at 600°C in Ni-A1 couples in case a crack was present at the /3-A1 interface. Numerous layer thickness measurements carried out by Castleman and Seigle on the y phase prove that the layer growth of this phase obeys the parabolic law after a certain transient period. From this they concluded that the layer growth of the y phase is controlled by volume diffusion. The growth of the 13, 6, and E phases appeared to be volume-diffusion-controlled also. The authors estimated that at 600°C and at atmospheric pressure Dp was 1.8 x lo-"ll sq cm per sec, D, 9.1 x 10" ™ sq cm per sec, Qp 27 kcal per mole, and Qy 31 kcal per mole. The present work was carried out to obtain more quantitative data about the kinetics of growth of the phases of the Ni-A1 system and the reactions that occur during the formation of these phases. Because in this system the diffusion process results in the formation of several distinct intermetallic compounds, the current term reaction diffusion is used in the title of this paper. In order to obtain layers of the fl phase compound of uniform thickness, a new technique for preparing diffusion couples was developed. The kinetics of growth of the y phase in 6-Al, E-Al, and Ni-A1 diffusion couples was studied at different temperatures. The kinetics of growth of the 6, c, and ( phases in Ni-y, Ni-6, and Ni-c diffusion couples was also studied at different temperatures. The calculation of the diffusion coefficients Dp and Dy by Castleman and Seigle are critically considered in this paper; by means of a revised method of calculation more reliable val-ues of , and Dg were found. These values are in good agreement with the values of the diffusion coefficients obtained by the method of Boltzmann-Matano. From the temperature dependence of the diffusion coefficients the heats of activation for diffusion were calculated by means of an Arrhenius-type equation. The investigation of the Kirkendall effect has been used to obtain information about the ratio of the intrinsic diffusion coefficients of the separate atoms5 and the mechanism of diffusion. Moreover porosity as a result of a distinct Kirkendall effect would be of practical importance in connection with the bonding of diffusion coatings. The analyses of the diffusion couples were carried out by metallographic methods. The values of the concentrations at the phase boundaries and the concentration profile in each of the phases, which are needed for the calculation of diffusion coefficients, were obtained by electron-pro be X-ray microanalysis. EXPERIMENTAL PROCEDURE A) Materials for Diffusion Couples. The intermetallic compounds 6 (50 at. pct Ni) and E (74 at. pct Ni) were prepared from the pure metals by high-frequency induction melting in argon atmosphere. Use was made of aluminum wire (99.99 wt pct Al) and nickel sheet (99.95 wt pct Ni). The 6 and E phase melts and the nickel shiet (thickness 0.1 and 0.5 mm) used for preparing diffusion couples were annealed for 64 hr at 1200°~ for homogenization and grain coarsening (final crystal size 1 to 3 mm). composition and homogeneity of the intermetallic compounds were checked by mi-crohardness measurements and X-ray diffraction. From the 6 and E phase melts discs of 0.5 mm thickness were prepared by means of a water-cooled rotat-

Jan 1, 1968

By W. S. Owen, T. Bell

The variation ox the M, temperature with nitrogen concentration has been determined experinzentally. The free-energy difference between martensite and the parent y Phase at the M, temperature,is computed for Fe-C and Fe-N alloys using recent solubility data fm the Fe-N system and new data for the variatim of the activity of the interstitial solute in the y phase with concentration. The "geometric model" is considered also, and the importance of Zener ordering is noted. It is shown that, although at any chosen concentration the M, temperature and the activity are significantly different in the two alloy systems, the free-energy duference is the same within the limits of experimental error, thus Providing further evidence of the very close similarity between the martensite transformations in Fe-C and Fe-N alloys. TO estimate the free-energy change accompanying the martensite transformation in binary interstitial alloys it is necessary to know the variation of the Ms temperature with interstitial solute concentration and some thermodynamic data. To date, only the Fe-C system has been discussed because this was the only system for which relevant experimental measurements had been made, but even in this case the data available are insufficient to permit the free-energy change to be calculated without the assumption of a thermodynamic model for the y and a solid solutions. The last comprehensive discussion of the topic was by Kaufman, Radcliffe, and Cohen in 1.960.&apos; Since that time Ellis, Davidson, and Bodsworth2 have redeter mined the activity of carbon in y iron as a function of carbon content and Atkinson3 has measured the activity of nitrogen in Fe-N austenite. The M, temperature of Fe-N is reported in the present paper. Thus, it is now possible to assess the free-energy change accompanying the martensite transformation in Fe-N alloys on the same basis as that used to assess the change in Fe-C alloys. This comparison is of interest because it has been shown recently4 that the structure of the martensite formed in Fe-N alloys changes with nitrogen content in a manner exactly parallel to the changes in structure in the Fe-C series and that the strain associated with the distortion of the iron lattice in either the y or the a phase by a nitrogen atom is the same as that produced by a carbon atom. The work to be described tests whether or not this close similarity between the two systems extends to the thermodynamics of the martensitic transformations. THE Ms TEMPERATURES FOR Fe-N MARTENSITE Bose and Hawkes5 found the M, temperature of a eutectoid Fe-N alloy (2.35 wt pct N) to be 35°C. This single determination appears to be the only reported measurement of the M, temperature of an Fe-N alloy. In the present work a series of more than fifteen different specimens containing between 0 and 2.7 wt pct N were prepared by controlled nitriding of pure iron wire 0.010 in. diam. The iron was supplied by B.I.S.R.A. and was designated ACN2. The nitriding procedure, all aspects of which are critical, has been described in detail elsewhere.&apos; Each specimen was quenched from the austenitizing temperature into brine at 20°C without removing the specimen from the ammonia-hydrogen atmosphere in which it was ni-trided. Alloys containing up to 0.7 wt pct N were fully martensitic. More concentrated alloys contained progressively more retained austenite. At 2.34 wt pct N the specimen was completely austenitic after quenching to 20°C. The M, temperature of specimens with M, temperature above 20°C (those containing less than 2.35 wt pct N) was determined by a thermal arrest technique. For the more concentrated alloys (2.35 to 2.70 wt pct N) the variation of electrical resistance with temperature down to -196°C was used. Unlike Fe-C alloys, Fe-N alloys cannot be reaus-tenitized in vacuum or in an inert atmosphere because excessive loss of nitrogen occurs, even in short times, at high temperatures. Consequently, the alloys were reaustenitized in the ammonia-hydrogen mixture corresponding to nitrogen equilibrium at the temperatures used. The specimens were quenched in a blast of cold hydrogen gas and the temperature, measured by a thermocouple welded to the 2.5-in.-long specimen, was recorded on a high-speed recorder. In the first experiments 0.002-in.-diam chromel-alumel wire thermocouples were used but it was found that these gave erroneous readings due to contamination by nitrogen pickup. Pt-Pt 13 pct Rh wires of 0.002 in. diam were found to be satisfactory. Further details of the experiments are available in the original thesis.7 The cooling rate was controlled between 400° and 4000°C per sec by adjusting the hydrogen pressure. At least three cooling curves were obtained for each composition. Each specimen was analyzed for nitrogen after quenching. To aid in the accurate location of the martensite arrest points a series of cooling curves of 0.010-in.-diam platinum wire were recorded and these, which did not contain an arrest, were used as comparison standards. Four specimens, each in the form of a 3-in. loop, were prepared from each of the four alloys containing more than 2.35 wt pct N. One specimen was used for nitrogen analysis, one for X-ray diffraction, and two for resistance measurements below 20°C. The latter specimens were quenched from 20°C into constant-temperature baths at selected lower temperatures.

Jan 1, 1968

By R. E. Reed-Hill

The shear continuity conditions under which one mechanical twin may cross another are considered. Twin intersections usually involve various types of slip deformation in addition to twinning. Because the shear of the crossing twin may be partly transmitted through the crossed twin by slip mechanisms, continuity of the twinning shear vectors is not required at a twin intersection. It is concluded that analyses based on twin intersections should not he used as an independent method for deducing twinning elements in newly observed twinning modes. WHEN one mechanical twin passes through another, a twin intersection is said to occur. In the simplest form of intersection, Fig. 1, the crossing of one twin by another is accomplished with the aid of a second-order twin induced, in the twin that is crossed, by the crossing twin. The subject of twin intersections is significant to the field of deformation studies because it has been postulated by cahn1 that twin intersections should occur only under the following continuity conditions: 1) the traces of the primary and second-order twin must be parallel to each other in the plane of the crossed twin; 2) the direction 771 and magnitude, S, of the twinning shear must be identical in the crossing and second-order twins; also, the sense of shear must be the same. If these postulates are valid they constitute a valuable tool for determining twinning elements of newly observed twinning modes in metals. In his classic paper in 1953 on the plastic deformation of a uranium, Cahn1 used these continuity conditions to deduce twinning elements for several uranium modes. However, in the same year, pratt2 showed that both of Cahn&apos;s continuity equations were violated for (1012) twin intersections in zinc. Later, Kiho and Maruyama3, 4 showed that Cahn&apos;s second postulate was violated in {301) and (101) twinning in tin and (101) twinning in bismuth. In spite of this documentation that Cahn&apos;s second postulate is often violated, several recent papers5&apos;6 have been published which have attempted to use the condition of continuity of twinning shear vectors for the evaluation of twinning elements. The primary purpose of this paper is to call attention to the possible ambiguity inherent in applications of Cahn&apos;s postulate, and to present additional information concerning the nature of twin intersections.

Jan 1, 1964

The Library belonging to the Institute is now administered as part of that of the United Engineering Society, the members of the Library Committee representing the Institute on the Library Board of the United Engineering Society. The main collection now consists of 115,900 books, 3680 pamphlets, 5811 maps, and 4402 searches, making a total of 129,793, a net gain of 7701 within the year. There is in addition a lending collection of 1004 volumes and one of duplicates amounting to 11,310. The library grows steadily both by gift and purchase. The cataloging is now substantially current covering 124,100 items represented by 362,145 cards. There are many rare and notable books, especially those relating to early engineering. It is truly a great treasure house of knowledge. While no severe effort is made to record all visitors the books showed 23,470 to have used the Library in 1928. In addition 5102 telephone requests for information were answered, 202 searches and 196 translations made and 34,964 photo prints furnished. The service department is maintained by small fees which cover the cost. The total amount appropriated for operating expense for the year was $46,300, of which $8,240.02 was furnished by the Institute, $5,399.45 being derived as income from the Douglas Library Fund and the remainder from current receipts. Within the year a slight change was made in the method of meeting the expenses of the Library, a flat charge of $5,000 per year being made against each of the four Founder Societies and this being supplemented by a surcharge based upon membership. The effect of this has been for the present to decrease slightly the amount that the Institute would otherwise need to pay. Placing in one collection all the books of the four societies greatly increases the number of books accessible to the members of each and opening the Library to the public is an important factor in keeping the tax exemption privilege enjoyed for the building. The Director and Staff of the Library make every effort not only to accommodate those who come in person to consult the collection but members resident elsewhere who communicate by letter or wire. The facilities of the Library are truly available to all.

Jan 1, 1929

By Roscoe C. Clark

In October 1945. R. F. Farris. in an AIME paper entitled Method For Drtermining Minimum Waiting OIL Cenzent Time, presented a method for caiculating the minimum WOC* time required in oil well cementing operations. Briefly. this method consisted of shutting in a well. after the cement had been placed and noting the time required fur the wellhead pressure to reach a. maximum. This time was then multiplied by a factor of 1.5 to determine when the cement had reached sufficient strength to support the weight of the casing. As a result of this work, a number of areas have reduced their WOC time ~Wuirements with the subsequent saving of considerable rig time. The tests conducted by Farris were, for the most part, conducted under cementing temperatures in excess of 70°F. This was done because in the overwhelming majority of cases. cementing temperatures are in excess of 70°F (only in tile northern part of the country. primarily in the Rocky Mountain ares. in cementing surface casing are temperatures below 70° F. encountered, and such temperatures occur only during the winter months). The Stano-lind Research Laboratory since that time has performed a number of tests both in the laboratory and in the field to evaluate this WOC factor when cemeriting temperatures are lower than 70°F. The results of these tests indicated the need for greater WOC time in areas affeaed by abnormally low cementing temperatures. These tests indi.cated that a woc factor of 2 (Time from start to mix cement to maximum wellhead pressure x 2 = Time to drill plug) will allow sufficient time for the cement to develop adequate strength. A field test under abnormally low cementing temperatures (surface temyerature 35°F., mud discharge temperature <70°F. and cementing depth 500 ft.) in the Rangely Field, "* using the WOC factor of 2, indicated the time to drill the plug as 45 hours. Well conditions preventing getting back into the well until a 48-hour WOC time had elapsed. At this time, the plug drilled firm to hard indicating that the cement had reached its final set. It is contemplated that during next winter additional field tests will be performed to further check the results of the laboratory and field tests conducted to date,

Jan 1, 1949

By W. M. Small

Austria.—Austria produced some 430 cisterns of 10,000 kg. each of crude oil of a 0.9428 sp. gr. during 1934. Gosting II well near Zis-tersdorf was placed on the pump in August and at the end of the year was still producing about three cisterns daily. This well is owned by the Erdöl-Produktionsgesellschaft while Gösting I is owned by Raky-Danubia. Only five wells were completed in the republic during the year. These accounted for 1783.5 meters of the 2225 meters drilled. The only producer completed was Gosting 11. At the close of the year, four rigs were in operation and one rigging up. At least 8 or 10 new wells are planned in Lower Austria for 1935. The European Gas & Electric Co. put its 6-km. gas line into operation in May and has sold 12,301,550 cu. m. of gas to the Vienna City Electric Works. A 2-km. pipe line was built from Gösting II to the railway loading rack near Zistersdorf. Hungary.—No oil or gas was produced except a small amount of gas trapped from flowing artesian wells. The Government completed and abandoned a 1500-m. hole at Tisztaberek in northeastern Hungary and is drilling at 967 m. near Bogáes, 120 km. northeast of Budapest. It is unofficially reported it plans to drill two new wells in 1935. The European Gas & Electric Co. has a rig up for a test at Mihalyi in Transdanubia. Czechoslovakia.—In Gbely (Egbell) there were produced 1283 cisterns of 10,000 kg. of 0.935 sp. gr. oil and a small amount of gas used for fuel. This field is operated by the Government; 17 shallow producing wells and three dry holes were drilled, with a total of 3351 m. of hole completed. In Hodonin (Goding) there were produced approximately 1300 cisterns of 10,000 kg. each of 0.91 sp. gr. oil and a small amount of gas used for fuel. The field is operated by the Apollo, which drilled four producing wells averaging 460 m. in depth, one small gas well of 550 m., one small gas well 260, and one dry hole 230 m. Two wells were deepened a total of 80 meters. The Government is drilling below 800 m. in a wildcat test in eastern Czechoslovakia near the Rumanian frontier.

Jan 1, 1935

The Ashanti mine is located in the Gold Coast region of West Africa in Ghana, where gold is found over a wide area of about 105,000 sq km (40,000 sq miles). Ashanti has been the most productive of all the lode mines and has been one of the world&apos;s notable gold producers for over 50 years. The mine is located at Obuasi, 113 km (70 miles) north and east of Tarkwa, which is 80 km (50 miles) inland from the coast. The Ashanti lode is worked on 300 m (1,000 ft) of strike length over a width of 12 m (40 ft), and by 1934 it had attained a depth of 700 m (2, 300 ft). The lode is in pre-Cambrian granite intruding a system- of shists, phyllites, etc., containing fragments of the wall rock with quartz, carbonates, sericite and small amounts of pyrite, arsenopyrite, sphalerite, galena, and gold. The shattered quartz fractures carry sulfides and gold, most of which are invisible. (William Harvey Emmons, "Gold Deposits of the World," McGraw -Hill, 1937.) Because the mill treats an ore composed of refractory sulfides - chiefly arsenopyrite and fine free gold - the flowsheet reflects the complex ore characteristics. Plane tables are used in the grinding, circuit for free gold recovery. After roasting the sulfide flotation concentrates, additional free gold is recovered from the calcines with a rotary belt concentrator and the two concentrates are combined for feed to the amalgamation pans, with the resulting gold amalgam being retorted. Following four-stage crushing to minus 9. 5 mm (318 in.) with two stages of grinding, the cyclone overflow is floated for sulfide recovery. The flotation concentrate is roasted with the calcine reground and roughly cyanided to scalp out the gold readily dissolved in one of two cyanidation circuits. The cyanide residue joins the thickened flotation tailing for cyanidation in a complete CCD circuit using filters. The gold precipitates are calcined before melting in pot-type furnaces. The tonnage to the mill of 3,175 mtpd (3,500 s tpd) with a content of over 14.7 g per mt (0.43 oz per st) places the Ashanti production as one of the top producers in the world; and with its past long life, the total production rates it as one of the world&apos;s great mines.

Jan 1, 1981

By Roscoe C. Clark

In October 1945. R. F. Farris. in an AIME paper entitled Method For Drtermining Minimum Waiting OIL Cenzent Time, presented a method for caiculating the minimum WOC* time required in oil well cementing operations. Briefly. this method consisted of shutting in a well. after the cement had been placed and noting the time required fur the wellhead pressure to reach a. maximum. This time was then multiplied by a factor of 1.5 to determine when the cement had reached sufficient strength to support the weight of the casing. As a result of this work, a number of areas have reduced their WOC time ~Wuirements with the subsequent saving of considerable rig time. The tests conducted by Farris were, for the most part, conducted under cementing temperatures in excess of 70°F. This was done because in the overwhelming majority of cases. cementing temperatures are in excess of 70°F (only in tile northern part of the country. primarily in the Rocky Mountain ares. in cementing surface casing are temperatures below 70° F. encountered, and such temperatures occur only during the winter months). The Stano-lind Research Laboratory since that time has performed a number of tests both in the laboratory and in the field to evaluate this WOC factor when cemeriting temperatures are lower than 70°F. The results of these tests indicated the need for greater WOC time in areas affeaed by abnormally low cementing temperatures. These tests indi.cated that a woc factor of 2 (Time from start to mix cement to maximum wellhead pressure x 2 = Time to drill plug) will allow sufficient time for the cement to develop adequate strength. A field test under abnormally low cementing temperatures (surface temyerature 35°F., mud discharge temperature <70°F. and cementing depth 500 ft.) in the Rangely Field, "* using the WOC factor of 2, indicated the time to drill the plug as 45 hours. Well conditions preventing getting back into the well until a 48-hour WOC time had elapsed. At this time, the plug drilled firm to hard indicating that the cement had reached its final set. It is contemplated that during next winter additional field tests will be performed to further check the results of the laboratory and field tests conducted to date,

Jan 1, 1949

By Frank A. Wardlaw

MY subject covers the effect that recent metallurgy has had on operations at the Utah-Delaware mine. This mine is the old Highland Boy mine of Bingham Canyon, Utah, one that has now been in operation for about 30 years. It was first operated by Messrs. Weir and Newhouse as a gold mine, under direction of the Highland Boy Gold Mining Co. The ore was oxidized gold ore and it was treated on the property in a cyanidation plant. During the process of development, sulfide ore was found assaying about 5 per cent copper. It proved to be the discovery of what is yet the largest sulfide copper orebody in the State. The first shipment was made in December, 1896. A smelter was built in Salt Lake Valley to treat this ore and not long after the property was sold to the Utah Consolidated Mining Co. From 1900 to 1924, the mine was a large producer of direct-smelting ore which averaged for many years 4.5 per cent. copper, then later dropped to 2 per cent. copper. During the years 1912 to 1920, direct-smelting lead ore was also mined. In 1918&apos;and 1919 ore developments at depth showed a decided increase in silica content and a porphyry sill so closely associated with the ore that it was impossible to mine the ore clean and it was found necessary to build a copper flotation Eoncentrator at Tooele. The mill had a capacity of 1000 tons a day and made a recovery of 90 per cent., and would have been responsible for a continuance of profitable operations had it not been for a slump in the copper market and the necessary high cost of mining ore on the lower levels. RESULTS OF SELECTIVE FLOTATION In 1924 the mine was on the point of a shutdown which had all the earmarks of being permanent; it was being operated at a heavy loss and preparations were made to pull the pumps and salvage the machinery. The plant at Tooele was remodelled for selective flotation by the Inter- national Smelting Co. in order to treat custom ores, and incidentally to clean up a possible 10,000 tons of lead-zinc ore which it was thought possible to get in the Utah-Delaware before shutting the mine down. Results were so encouraging that an effort was made to develop more lead-

Jan 1, 1928

By Frank A. Wardlaw

My subject covers the effect that recent metallurgy has had on operations at the Utah-Delaware mine. This mine is the old Highland Boy mine of Bingham Canyon, Utah, one that has now been in operation for about 30 years. It was first operated by Messrs. Weir and Newhouse as a gold mine, under direction of the Highland Boy Gold Mining Co. The ore was oxidized gold ore and it was treated on the property in a cyanida-tion plant. During the process of development, sulfide ore was found assaying about 5 per cent. copper. It proved to be the discovery of what is yet the largest sulfide copper orebody in the State. The first shipment was made in December, 1896. A smelter was built in Salt Lake Valley to treat this ore and not long after the property was sold to the Utah Consolidated Mining Co. From 1900 to 1924, the mine was a large producer of direct-smelting ore which averaged for many years 4.5 per cent. copper, then later dropped to 2 per cent. copper. During the years 1912 to 1920, direet-smelting lead ore was also mined. In 1918 and 1919 ore developments at depth showed a decided increase in silica content and a porphyry sill so closely associated with the ore that it was impossible to mine the ore clean and it was found necessary to build a copper flotation concentrator at Tooele. The mill had a capacity of 1000 tons a day and made a recovery of 90 per cent., and would have been responsible for a continuance of profitable operations had it not been for a slump in the copper market and the necessary high cost of mining ore on the lower levels. Results of Selective Flotation In 1924 the mine was on the point of a shutadown which had all the earmarks of being permanent; it was being operated at a heavy loss and preparations were made to pull the pumps and salvage the machinery. The plant at Tooele was remodelled for selective flotation by the International Smelting Co. in order to treat custom ores, and incidentally to clean up a possible 10,000 tons of lead-zinc ore which it was thought possible to get in the Utah-Delaware before shutting the mine down. Results were so encouraging that an effort was made to develop more lead-

Jan 1, 1928

The U. S. Navy Department has perfected plans for the enrollment and training of considerable numbers of engineering officers. A school for this purpose, the U. S. Navy Steam Engineering School, has been established by the Department at Hoboken, N. J. The school is open to men between the ages of 21 and 40 who meet the physical requirements of the Navy, who are of thorough ability and officer-like character and who have completed the mechanical or electrical engineering course at certain recognized technical schools, or who possess an education and experience adjudged to be an equivalent thereof. Enrollment in the U. Naval Reserve Force of men properly qualified may be made at any Naval enrolling office, notation being made of the applicant&apos;s qualifications and desire to be detailed to this school. Applicants will be enrolled as Chief Machinist Mates, and during the course of instruction will draw the pay of this rating, $83 per month, plus $60 per month paid as subsistence. Upon graduation, men will be commissioned as Ensigns in the U. S. Naval Reserve, with a salary of $1700 per year. The duty to which a graduate of this school will be assigned will be that of an engineer officer in the auxiliary service of the Navy. Special provision has been made for the continuance of the school with proper material by a Navy regulation which permits undergraduates of the Freshman, Sophomore, and Junior Classes in recognized engineering schools to enroll in the Naval Reserve Force with the rating of Seaman 2d Class, and continue their courses at the institutions where they have matriculated. Such men will be called into active service after their graduation, and can at that time, if they are qualified to pass an officers&apos; physical examination, apply for admission to the U. S. Navy Steam Engineering School. Men who are registered in the draft, either graduates or undergraduates, may enroll with the proper enrolling officer by securing from their draft board a letter of release, which in all probability can be obtained for this purpose. The aim of this school is not simply to produce engineers, but to produce naval engineering officers in the true sense of the word. The course of instruction covers a period of five months, arranged in four periods.

Jan 10, 1918

By Felix B. Shay

THE Agua Fria mine is in eastern Honduras at Lat. 140° 06&apos; N., Long. 86° 36’ W. Danli, the seat of the local municipal government, is the nearest town. The property is approximately 44 miles east of Tegucigalpa, the terminus of a truck road from the Pacific coast. The mine lies at an altitude of 3300 ft. with surrounding elevations as high as 6000 feet. For 20 years the oxidized croppings of the Agua Fria vein had been worked intermittently when in 1927 an attempt was made to open the property. A shaft was sunk 300 ft. and considerable ore was blocked out, but before a mill could be installed financial difficulties arose and the mine reverted to the original owners. Erle P. Halliburton, of Los Angeles, purchased the property in 1934. At that time a careful consideration of all factors involved showed that air transport was the only practical method of moving the equipment and machinery necessary to commence production. The other alternative was by muleback, which required sectionalizing all equipment to a maximum load of 200 lb., and during the rainy season this type of freighting was subject to serious delays. It was decided to purchase a trimotor Ford powered by three Pratt and Whitney Wasp B motors developing 400 hp. each. There were several reasons for the choice: (1) this type of plane was available at a reasonable price, owing to its replacement by faster models on most of the airlines in the United States; (2) the ship was capable of carrying a pay load of 3000 lb. over the required distance; (3) since this airplane had been widely used there would be no difficulty in securing competent personnel or in purchasing spare parts. It was necessary to rebuild the plane for cargo service. The windows were removed and the fuselage was entirely covered. A hatch was cut in the top of the fuselage to receive heavy crane loads and pieces of freight that were too large or too long to go through the rear door. The seats were removed and the interior of the plane was lined with Duralumin sheets. A heavy-duty landing gear was installed and the floor was reinforced. The nearest site for an airport was two miles north of the mine. The necessary grading was done by a small track-type tractor with a wheeled grader, which was brought in overland. Six weeks was required for bring-

Jan 1, 1940

A national budget system, which engineers have long regarded as essential to the proper conduct of our fiscal affairs is at last being seriously considered by. Congress and seems likely to be adopted in some form. Several, bills and joint resolutions have already- been introduced but the measure that seems how to attract the &apos;most attention is H. R. 1201 introduced by. Representative Good, Chairman of the House Committee on Appropriations. This ,bill provides for the creation of a Bureau of the Budget in the office of the President, to which full information shall be furnished by all Departments and other Governmental agencies concerning powers, duties, financial transactions, business method&apos;s, etc. A change, is made in the fiscal regulations in that the Departments shall hereafter submit their fiscal estimates to the President instead of to the Secretary of the Treasury, while the latter official shall submit estimates of the public revenues and the condition of the Treasury. Two budgets are, provided for:, The first, or regular, budget shall contain a balanced statement of the resources and liabilities of the Government and the revenues and expenditures, actual or estimated as the case may be, for the preceding, current, and ensuing fiscal years. The President is further, authorized to submit his recommendations as&apos; to how the heeds of the Government should be met, and such further data regarding the financial affairs of the, Government as he deems proper. The second or alternative budget shall make known the essential facts regarding the condition of the Treasury and what, in the opinion of the President. are the revenue, and expenditure needs for the ensuing fiscal year, to be prepared in such form as the President shall deem most appropriate. The bill&apos; abolishes-the offices. of Comptroller of the Treasury and all -the Auditors for the several Departments, and substitutes therefore an Accounting Department, an establishment independent of the Executive Departments, under the direction of newly created officer to be known as the "Comptroller General of the United States" whose powers shall comprise all those now conferred on the Comptroller of the Treasury and the several Auditors and, in addition thereto, the investigation at the seat of Government or elsewhere of all matters relating to the receipt or disbursement of public funds, concerning which report shall be made to Congress at the beginning of each regular session, containing recommendations concerning the legislation deemed necessary to the accurate rendition and settlement of accounts.

Jan 8, 1919

By Francis Donaldson

THE direct injection of cement grout into water-bearing fissures as a means of checking or stopping the flow of water into shafts and tunnels has been experimented with for a decade or longer and seems to have been first attempted in Europe. The earliest application of which the writer has found a record was at a shaft sunk by the Mining Society of Lens; this is described by C. Dinoire in the Transactions of the Institution of Mining Engineers.1. It is only lately, however, that the process has been entirely successful. This success has been accomplished on the Catskill Aqueduct, now under construction by the city of New York. This aqueduct includes a number of deep pressure tunnels, reached by shafts for both waterway and construction purposes. In portions of these shafts and tunnels considerable underground water was met. The contract for the first of these deep pressure tunnels was let to the T. A. Gillespie Co.; this section is known as the Rondout Siphon. It leads under the Rondout valley at a depth of from 400 to 800 ft. and is about 5 miles long. The engineers expected that considerable water would be encountered, but fortunately this was not the case except at one shaft, known as No. 4, which penetrated the rock at a junction between limestone and conglomerate. Water-bearing fissures were encountered almost immediately. At a depth of about 200 ft. a flow of 1,500 gal. per minute was struck. The shaft then contained as many pumps as could be used, and it seemed impossible to sink it further. After vain efforts had been made to proceed, John P. Hogan, a division engineer of the Board of Water Supply, suggested that cementation of the fissures be tried. The process was attempted for the first time in this country. Since the shaft was partly full of water it was necessary to drill grout holes with a diamond drill. Platforms were placed on the timbers at the water level, the diamond drill was installed and six 90-ft. holes were drilled in the bottom of the shaft. Several car loads of cement were pumped through these holes into the fissures, the drill casings being used for grout pipes. This largely cut off the flow of water from the bottom and sinking could then

Jan 1, 1914

By Alexander Knoll, Dwight L. Baker

THIS paper is a report on work undertaken to investigate the results and conclusions of Ravitz and Porter1,2 that galena freed of surface oxidation products and lead carbonate ("clean" galena) is waterrepellent, and that the action of xanthates in flotation is the action of a cleansing agent, enabling oxidized galena particles to expose a pure lead sulphide, water-repellent surface. The apparatus, in construction and use, was essentially that of Ravitz and Porter. The only significant modification introduced by the present authors was the substitution of a three-necked flask for the flotation cell as the "reaction vessel." Our procedure was to place 50 grams of freshly ground, minus 200-mesh galena in the reaction vessel, sweep out all molecular oxygen from the system with oxygen-free nitrogen, and proceed to wash the galena surface free of its oxidation products with repeated small portions of (I) ammonium acetate (500 c.c. of water, 200 grams of ammonium acetate) or (2) ammonium chloride, hydrochloric acid (2 liters containing 200 grams of ammonium chloride and 25 c.c. Of 1.18 sp. gr hydrochloric acid). The galena was next washed with many 100-c.c. portions of oxygen-free, distilled water. The galena was finally considered free of soluble salts when wash water that had been in contact with the mineral for at least 48 hr.* gave negative tests for: (x) lead ion with sulphide; (2) chloride with silver ion; (3) acetate with cuprous chloride, sodium chloride; and (4) ammonium ion with Nessler&apos;s reagent. Next 500 c.c. of potassium ethyl xanthate solution, free of dissolved oxygen, was run onto the "clean" galena particles. For this system there were determined: I. The wetting properties of the clean galena particles by shaking the reaction flask and noting the degree of mineral collection at the liquid-air interface. This was, of course, simply a qualitative test, but it proved adequate for our purpose. 2. The removal of xanthate ion from the potassium xanthate solution on being shaken with the "cleansed" mineral. Xanthate concentrations were determined by iodine titration according to the methods of Taylor and Knoll.3 3. The pH of the xanthate solution after having been shaken with the "cleansed" galena. The pH was determined colorimetrically.4 The results of five experiments of the type mentioned above are given in Table x.

Jan 1, 1941