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By R. H. Schnitzel

Internal-friction peaks have been observed in tungsten single crystals at about 300° and 400°C. The characteristics of these peaks are similar to interstitial peaks observed in other bee metals; therefore, the origin of these peaks appears to he the Snoek mechanism. The interstitial responsible for the peak at about 300°C has not been identified. Carburizing increases the magnitude of the peak at about 400°C; consequently, it appears reasonable to suppose that the specific interstitial associated with this peak is carbon. The activation energies associated with the 300° and 400°Cpeaks are about 35,000 and 45,000 cal per mole, respectively. INTERNAL - friction peaks resulting from the stress-induced diffusion of interstitials (Snoek relaxation peaks) have been frequently observed in bee metals.1-5 Attempts to detect Snoek relaxation peaks in tungsten have, however, not been fruitful.' Failure to find Snoek peaks in sintered tungsten can perhaps be attributed to one or more of the following difficulties: a) the relatively low purity of the sintered tungsten; b) the lack of extensive metallurgical knowledge about tungsten-interstitial alloys, such as suitable interstitial dosing and quenching procedures; and c) the inconsistency of some of the interstitial analyses of tungsten, which reflects itself in one's inability to be sure of the nature of the specimens. This present investigation did not overcome all of these difficulties for successful tungsten internal-friction measurements. Some of these difficulties still persist and new difficulties were encountered during the course of this investigation. Nevertheless, the use of electron-beam tungsten single crystals having somewhat greater purity levels than sintered tungsten combined with appropriate carburizing and quenching procedures permitted a reasonable attempt to be made. As a consequence, internal-friction peaks were observed in these tungsten single crystals at about 300° and 400°C. These peaks were found to be unstable, since they annealed rapidly away during a sequence of internal-friction measurements. Hence, it was necessary to construct an apparatus having a faster heating rate to study some of the details of these peaks. From the behavior of these peaks as well as our knowledge of similar peaks in other bee metals, one can reasonably conclude that these peaks are caused by residual interstitial impurities within these crystals. Further investigation of these peaks after the application of various metallurgical treatments lent credence to this supposition. EXPERIMENTAL TECHNIQUE The internal friction of tungsten single crystals was measured using two different pieces of apparatus both of which are of essentially the same conventional design, namely the KE type of torsion pendulum. The important difference between these two types of apparatus was in the attainable heating rate and method of protection of the specimen from atmospheric contamination. The apparatus designated "number 1" was enclosed in a vacuum chamber which was heated by an externally mounted furnace. It had a slow rate of heating which was estimated to be about 4°C per min from room temperature to about 350°C and then about 1°C per min to 600°C. The internal friction of tantalum was measured with this apparatus and the established Snoek peaks were found.' These tantalum peaks in the temperature range from room temperature to 400° C served as a check for the apparatus. The apparatus designated "number 2" having a faster heating rate than number 1 was not elaborate. It consisted of a mounted nickel tube to which split heating elements were attached. Argon was used as the protective atmosphere. The measured heating rate was about 12° to 15°C per min whereas the cooling rate was somewhat slower at about 10° C per min because of the increased difficulty encountered in stabilizing the temperature. No surface oxidation of the specimen was noted after any test. This apparatus was also checked with the known peaks of tantalum.1 The preparation of the single-crystal specimens for internal-friction measurements consisted of centerless grinding the crystals from an approximate 0.200 in. diameter to 0.030 to 0.040 in. in diameter, and then electropolishing them to about 0.020 in. in diameter. Single crystals processed in this manner are designated as being in the virgin condition. Since the length of crystal varied from 3 to 9 in., the test frequency varied from about 1 to 2 cps. The frequencies of measurement, axial orientations, and chemical analyses for the various crystals are listed in Table I. The controlled addition of carbon into tungsten is a difficult problem. Attempts to find the critical conditions necessary for an equilibrium treatment were not fruitful. Therefore, a simple nonequi-librium method was used. The addition of carbon to these crystals consisted of appropriately combining three treatments—carburizing to achieve a case, annealing to partially dissolve the carbon into the

Jan 1, 1965

By A. S. Emanuel

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

Jan 1, 1969

By B. Otto Pixler

Mud-analysis logging provides identification of the fluid content of formations drilled by the rotary method and permits the accurate correlation of oil and gas shows with the depth. Mud-analysis logging eliminates much coring and has an especially important application in drilling programs when coring is particularly hazardous or the electric log is difficult to interpret correctly. An appreciation of the factors that influence the results of the mud analysis, such as rate of penetration, mud properties, coring, and characteristics of reservoir rock as related to the "flushing effect," permits a better understanding of the mud-analysis log. Recent studies of the relationship of the two gas readings obtained by the gas-detector instrument have proved significant. The difference between the total combustible gas reading and the higher molecular weight gas reading indicates the presence of methane. With few exceptions, zones not showing an increase of methane probably can be condemned. Mud-analysis logging furnishes valuable information, which generally cannot be obtained by other methods. Introduction Logging by mud analysis of wells drilled with rotary tools is a direct method of locating oil-and-gas-bearing formations. The use of this method of logging has increased each year until now more than 20 field units are being used in 13 oil-producing states and in some foreign countries. Several papers1-9 have been published in the petroleum trade journals describing in detail the equipment and the application of mud-analysis logging. This paper will discuss briefly the method and review its application and some of the late developments. Method As the drilling of a well progresses, the drilling bit dislodges and disintegrates a cylindrical section of the formation. If oil or gas is contained in the pore spaces of the cylinder, some of the contents of these porous spaces will be entrained in the drilling fluid. In wall logging by mud analysis, the mud is continuously examined for oil and gas on its return to the surface, and the results are correlated back to the actual depth of the hole at the time the mud was clearing the eyes of the bit. The test for gas is made by diverting a portion of the circulating mud from the flow line to a separator or gas trap, where the mud is thoroughly mixed with air and a portion of the gas entrained in the mud is removed. A stream of air is drawn coun-tercurrent to the flow of mud in the gas trap, thus materially assisting the separation of the gas from the mud. The air-gas mixture is then drawn into a "hot-wire" gas-detector instrument where the percentage of the combustible gas is determined. The presence of oil in the formation drilled is detected by a physical examination of the drilling mud under ultraviolet light. A sample of the mud is treated to reduce the surface tension and gel strength, after which it is placed in a viewing box. This box is so constructed that all external light is excluded and so that the sample may be subjected selectively to either ultra-

Jan 1, 1946

By B. Otto Pixler

Mud-analysis logging provides identification of the fluid content of formations drilled by the rotary method and permits the accurate correlation of oil and gas shows with the depth. Mud-analysis logging eliminates much coring and has an especially important application in drilling programs when coring is particularly hazardous or the electric log is difficult to interpret correctly. An appreciation of the factors that influence the results of the mud analysis, such as rate of penetration, mud properties, coring, and characteristics of reservoir rock as related to the "flushing effect," permits a better understanding of the mud-analysis log. Recent studies of the relationship of the two gas readings obtained by the gas-detector instrument have proved significant. The difference between the total combustible gas reading and the higher molecular weight gas reading indicates the presence of methane. With few exceptions, zones not showing an increase of methane probably can be condemned. Mud-analysis logging furnishes valuable information, which generally cannot be obtained by other methods. Introduction Logging by mud analysis of wells drilled with rotary tools is a direct method of locating oil-and-gas-bearing formations. The use of this method of logging has increased each year until now more than 20 field units are being used in 13 oil-producing states and in some foreign countries. Several papers1-9 have been published in the petroleum trade journals describing in detail the equipment and the application of mud-analysis logging. This paper will discuss briefly the method and review its application and some of the late developments. Method As the drilling of a well progresses, the drilling bit dislodges and disintegrates a cylindrical section of the formation. If oil or gas is contained in the pore spaces of the cylinder, some of the contents of these porous spaces will be entrained in the drilling fluid. In wall logging by mud analysis, the mud is continuously examined for oil and gas on its return to the surface, and the results are correlated back to the actual depth of the hole at the time the mud was clearing the eyes of the bit. The test for gas is made by diverting a portion of the circulating mud from the flow line to a separator or gas trap, where the mud is thoroughly mixed with air and a portion of the gas entrained in the mud is removed. A stream of air is drawn coun-tercurrent to the flow of mud in the gas trap, thus materially assisting the separation of the gas from the mud. The air-gas mixture is then drawn into a "hot-wire" gas-detector instrument where the percentage of the combustible gas is determined. The presence of oil in the formation drilled is detected by a physical examination of the drilling mud under ultraviolet light. A sample of the mud is treated to reduce the surface tension and gel strength, after which it is placed in a viewing box. This box is so constructed that all external light is excluded and so that the sample may be subjected selectively to either ultra-

Jan 1, 1946

By Howard N. Eavenson

ALL of the matters so far taken up by the Institute Committee on Stabilization of the Coal Industry will be of help, but it seems to be that under present conditions not very much can be expected until the railroad situation has been improved. As an instance of this, I would cite the fact of our experience at our mines in West Virginia and Kentucky. During 1917 and 1918 at our West Virginia plants we produced for our own consumption, practically entirely in the Chicago district, about 4,750,000 net tons of coal. In 1919 our output was reduced to 3,500,000 tons, this being caused partly by the shortage of orders in the few months following the armistice, but more particularly by The car shortage which began last September and continued throughout the remainder of the year, with the exception of December. This car shortage has been more acute since the first of the year, and while we now have an actual capacity here of 20,000 tons daily and have the equipment to produce it, with the possible exception of a few houses, we are able to average only about 12,000 tons, and in consequence, about 30 per cent. of our by-product ovens in the Chicago district are idle, and a number of blast furnaces are down for the want of coke. These figures, of course, refer to conditions before the strike of switchmen in April was started.

Jan 1, 1920

By E. A. Peretti

BEFORE embarking on a detailed investigation of the system indium-antimony-bismuth, experiments were carried out to determine the existence of quasi-binary sections. The bordering binary systems are known1 and show the occurrence of three intermetallic binary species corresponding closely to InSb, InBi and In2Bi. Attention was focused on the low-indium end of the ternary diagram where the possible quasi-binary sections, excluding ternary compound formation, would involve the pairs: InSb-Bi, InBi-Sb and InSb-InBi. The latter pair revealed itself as a true quasi-binary, so it was investigated fully by thermal analysis, x-ray and microscopic examinations. All compositions were made by proper combination of three elements involved. The indium had a guaranteed purity of 99.97 pet; the antimony contained 99.99 pet Sb, and the bismuth had a purity of 99.99 pet. Alloys were made by melting together antimony, bismuth and indium in evacuated, sealed pyrex-glass tubes at a temperature of 600°C with vigorous agitation. The melts, weighing about 80 grams, were allowed to freeze in the sealed tubes and finally were transferred to glass tubes for the taking of cooling and heating curves. A protective atmosphere of helium was used, and the melts were stirred mechanically while cooling at rates of from 0.5 to 3°C per min. Temperatures were measured with a calibrated chromel-alumel thermocouple and were recorded graphically on a Minneapolis-Honeywell extended-range recorder working in conjunction with a Leeds and Northrup type K-2 potentiometer. Conventional polishing techniques gave satisfactory results in preparing specimens for microscopic examination. Etching was carried out with Vilella's reagent or aqueous mixtures of chromic oxide with either nitric acid or sulfuric acid plus dichromate. Conclusions deduced from the thermal analysis and microscopic examinations were confirmed by X-ray photograms using Co-K alpha radiation. The phase diagram is shown in Fig. 1. The liqui-dus consists of an uninterrupted line running from the freezing point of InSb (525°C) to a eutectic point experimentally indistinguishable from the freezing point of InBi (110°C). X-ray patterns of the InSb show a slight expansion of the lattice with the addition of InBi, and microscopic work indicated the solid solubility of InBi in InSb to be less than 0.5 pet at room temperature. Acknowledgment We wish to thank the Indium Corporation of America for the loan of the indium used in this investigation. References 1 E. A. Peretti and S. C. Carapella, Jr.: Trans. ASM., 1949, vol. 41, P. 947. T. S. Liu and E. A. Peretti: Trans. ASM, 1952, vol. 44, p. 539. Metals Reference Book, vol. 1, 2nd ed., AIME, p. 345.

Jan 1, 1959

By Owen Rice

CHANGES in coke hardness affect the working of the blast furnace, for soft coke is an obstacle to proper furnace operation. Soft coke is due to a low hydrogen-oxygen ratio in the coal charged; increasing this ratio increases the hardness of the coke. The best means of determining the hardness of coke is the combined tumbler and ball-mill. Soft coke is a great hindrance to proper blast-furnace operation and changes in coke hardness affect the working of the furnace. The best method of determining the hardness of coke is by using a combination tumbler-ball-mill. Soft coke is due to a low hydrogen-oxygen ratio in the coal charged. An increase of this ratio improves the hardness of the resulting coke. WHAT IS GOOD COKE? It is not always appreciated that the correct answer may be such a reliable forecast to the physical condition of the blast furnace, and incidentally its entire operation, that among the ordinary variations in other raw materials and also in operating conditions, it assumes a position of primary significance. Inasmuch as coke forms two-thirds of the total bulk of material charged, this assertion will not seem exaggerated, and in the subsequent discussion its applicability will be presented. Coke is the ideal blast-furnace fuel because it is strong and hard enough to resist the crushing and grinding effects of the furnace burden, and its porosity allows the ready passage of gas upward through the charge, and rapid combustion before the tuyeres. Coke deprived of its strength and with a cell structure physically frail and chemically susceptible to solution by carbon dioxide, has its chief asset eliminated. When the melting zones are approached the fluid cinder trickling toward the hearth will envelope the small pieces of coke and form a sticky mass that will retard the free passage of gas. Blast pressure will then rise, driving

Jan 1, 1921

By R. S. Shoemaker, F. W. McQuiston

REFINERY SECURITY "Highgrading, " a polite word for stealing gold and silver, has been a way of life since the metals in native form have been mined or produced. Unfortunately, in the past, highgraders were not always severely prosecuted or even looked upon unfavorably in their communities. Recent high metal prices with attendent world wide publicity, however, has made highgrading or thievery again a serious problem in mines and plants. When a small button of gold the size of the end of ones little finger has a value equal to about one week's wages, the safe-guarding of gold production by enforcing tight security measures becomes a prime responsibility of management. The higher the gold price, coupled with unrestricted owner- ship, the greater the temptation to “get-your-cut”, and diligence by management must become an integral part of plant security. Primary security begins by knowing the expected gold production and the sampling of a gold ore mill feed for this determination has proved not reliable. However, solution flows can be accurately sampled and measured thereby closely predicting the gold recovered each day as precipitate. The progressive record of total ounces of gold contained in the precipitation press, referred to in cyanidation plants as I1solution calll1 predicts the accumulated production. The "callH is an important adjunct to security and extreme caution must be used so that the pregnant solution meter and sample are confined in a security area. It should be recognized that this key sample may be the target for Ifdoctoring" by trusted insiders (assay office employees) as a preliminary step for stealing precipitates and/or metal. Security measures similar to the following were adopted after one operation experienced a sizeable theft of gold precipitate and metal by trusted employees. The refinery area where precipitates are handled and melted to bullion and all other gold products are kept should be completely enclosed with a tight security fence preferably of solid construction. Access to this enclosure should be through one of two electrically controlled gates, one for personnel and another for occasional truck entrance. Admittance should be restricted to essential personnel who are required to sign a register in and out with the date and time. I£ there is a "back gate" to the restricted fenced area, it should remain locked except in an emergency and then opened only by a supervisor. Television monitoring cameras viewing the gate entrance and other sensitive areas connected to a viewing screen located in the general office afford visual observation at all times.

Jan 1, 1975

By Jasper Stuckey

THE object of this paper is to record and interpret field and laboratory observations made by the writers during five years of study of the barite deposits of North Carolina. Deposits of barite are known to occur in three localities in North Carolina (Fig. 1) two of which-the Hot Springs and Kings Mountain -contain material of economic value. The Hot Springs area begins near Bluff, some 6 miles south of Hot Springs, and continues northeast by Stackhouse; a total length of 7 miles. The Kings Mountain deposits lie along a belt that extends from the north end of Crowders Mountain in a southwestward direction, along the east side of this and Kings Mountain, to Kings Creek, South Carolina. The third locality is 3 1/2 miles southeast of Hillsboro, Orange County, a short distance west of the highway leading from Hillsboro to Chapel Hill. It is not known when barite was first discovered in North Carolina, but production from the Hot Springs area began some 50 years ago. The state has never produced large quantities of barite-usually there have been less than three producers-and definite figures are not available, but reasonably reliable estimates indicate a total production of 300,000 tons. From 1901 through 1920 barite mining was on a seemingly prosperous basis and a large tonnage. was shipped from the Hot Springs and Kings Mountain areas. With the depression of 1920 the industry began to decline and production practically ceased in 1926.

Jan 1, 1933

By C. M. EYE

IN the spring of 1905 I was employed by Messrs. Bradley and Requa, under our fellow member, Thomas Cox, on the mill plans for the Nevada Consolidated, when an opportunity came to go to the Philippines to erect a small mill on the property of the Benguet Consolidated. This I accepted, expecting to be away eight months or so, but it was seven years before I got back. .I sailed in May, on the Coptic, having as room-mate as far as Kobe, A. E. Drucker, who was going out to Korea for the Oriental Consolidated. It was the first trans-ocean trip for either of us, and we had some rather unusual experiences. This was toward the close of the Russo-Japanese war and the Russian fleet was known to be on the way from Suez to Asiatic waters, but it was a matter of doubt whether they would risk a passage between Japan and the mainland, or take the longer but obviously safer route outside of Japan. The Coptic carried much contraband of war for Japan, so naturally did not care to meet this fleet. No definite word being available at Honolulu, we went to the Midway Islands, but the cable station there had very little information to offer, so we proceeded cautiously toward Japan. On the last afternoon out, we steamed due north at half speed for several hours, and finally sneaked into Yokohama at night, to learn that ' the Russian fleet had met the Japanese the day before and had been annihilated. We sailed over the spot in the Sea of Japan a week later, and when we got to Manila we found three of the Russian boats interned and being guarded by the monitor Monadnock and a cruiser. This was only a matter of form, as the Russians were only too glad to be there for the rest of the war, and the boats could not have gone far anyway, for they were literally shot to pieces. The Admiral's flagship had a hole within 3 ft. of the water line, for ward, through which a man could enter by stooping.

Jan 1, 1929

By R. K. Datta

Eluropium -activated yttrium vanadate, excited by short- and long-wavelength ultraviolet radiations, shows enzission lines near 6100A, the principal ones correspondirzg to transitions of EU+3 ions from 5Do to the F2 energy level. The ~neclmlallistns of absorption and etnissiorz of this phosphor have been empirically studied. The absorption is caused by two separate processes in the matrix. The phosphor YVO4:Eu and tlie matrix YVO, haue essentially the same resectance spectra in the region 2500 to 4000if. There are two broat ah~o?~ption bands: natnely, around 2600 and 3600A regions. Whet? compared with the reflectance spectra of the constituent oxides, namely, Y2O3, V205, Eu2 03, the absorption bands of the tnatvix and the phosphor in the short- and long-wavelength ultraviolet regions can be interpreted as due to charge-transfer processes involving i) Y-O and ii) 17-0, respecti~~ely. The excitation spectrum' of the phosphor has two broad bands with peaks at about 2600 and 3600A regions. U can be postulated that enevgy absorbed under short- crud long-wavelength ultraziolet excitatzon, respectzcely, by Y-0 and V-O parts of the niatrix is transferred by radcatio~zless process to EU+3 ions. Thzs postulate can empirically be proved on the basis of the spectra of the systems (YVO4,-YPO4,):Eu. PO? ~ons do not have' any appreciable absorption in the short or long uv regions. When P0't3 ions are substitlited for v0i3 ions in YVO,:Eu phosphors, the absorption and excitation in the lo~zg uv region are gradually reduced. Ailoreover, the £«+3 emission under 3650A excitation is decreased zuitlz increase in PO^ content, lt~lzereas the emission under 253711 excitation remains esserztially constant with as IILUCIL as 60 mole pct of YPO, in YVO,:En. EUROPIUM-activated yttrium vanadate (YV04:Eu) is a well-known phosptor.'-3 When excited by cathode rays, 2537, or 3650A radiations, YV04:Eu emits typical narrow-band spectrum of EU'3 fluorescence in the region of 5900 to 7100A, a very strong maximum occurring at about 6190A. This emission is considered to be due to 5Do — 7F2 transition of excite: EU*3 in 4f state. Moreover, the emission under 3650A excitation increases with temperature markedly. Because of these properties, YV04:Eu phosphor finds wide application in industries, namely, in color television tube, laser, and high-pressure mercury-vapor lamps. It is the purpose of this paper 1) to present the empirical study of the mechanism of absorption and excitation of YV04:Eu phosphor by ultraviolet radiation, and 2) to offer an explanation for the process of emission. It should be mentioned that a theoretical discussion on the mechanism of absorption in terms of the crystal or ligand field theory is beyond the scope of this paper. Empirical studies presented here are based primarily on spectroscopic and crystal-chemical investigations. EXPERIMENTAL i) Preparation of Materials. The synthesis of vanadate phosphorinvolves preparation of (Yi-.tEuj^Oj, blending the mixed oxide with an oxidic compound of vanadium, such as V205 or NH4V03, and firing the mixture at about 1000°C for several hours when YVO4:Eu forms as a primary phase. (Y1-xEux)203 compositions are prepared by coprecipitation of oxalates, and igniting them at about 1000°C. The vanadium compound is added in excess of the stoichiometric proportion for fluxing purposes. The charge is cooled, ground, and the excess of vanadium is removed by a hot wash (-80°C) of alkali or ammonia. Y(VP)04:Eu samples are prepared by mixing (Yi-xEux)203 with stoichio-metric proportions of (NH4)2HP04 and the vanadium compound. The mixtures are prefired at 700" to 800°C for 1 or 2 hr, then ground and refired at 1150°C. The firings of the phosphors are done in silica crucibles, and the homogeneity of the final products checked by X-ray diffraction analysis. ii) Spectroscopic Measurements. Diffuse reflectance sqectra of the samples within the range 2500 to 7000A are obtained by using CaF2 as standard in Cary Recording Spectrophotometer, Model No. 14. The emission spectra from phosphor plaques, excited under different ultraviolet sources, are obtained by a direct-recording spectroradiometer4 adapted with a grating monochromator with nearly constant dispersion. Maximym sensitivity in the spectral region from 2500 to 7000A is obtained with a quartz-windowed, S-20 response p$otomultiplier. The total' band pass is kept about 30A. The spectra are calibrated against the light from a standard tungsten filament lamp reflected from a magnesium-oxide plaque. Brightness data given throughout this report $re measured from the height of the main peak (6190A) of the emission spectra. The excitation spectra are measured using sodium salicy-late as standard. RESULTS AND DISCUSSION The diffuse reflectance spectra of both pure and activated YV04, along with their constituent components, are shown in Fig. 1. YVO4 shows two broad absorption bands, namely, around 2500 and 3600A, respectively. Since there is little difference between the reflectance spectraoof YVO4 and YVO,:Eu in the uv region (2500 to 4000A), it can be postulated that excitation of the phosphor is mainly due to absorption by the matrix, i.e., YVO4. The question, now, is whether the matrix (Yv04) is excited as a whole, or different components are responsible for the two absorption bands. The characteristic absorption spectra of molecular ions involving transition metal ions, both in aqueous solutions and in crystals, are due to electronic transi-

Jan 1, 1968

By J. E. Lawrence

Copper-decorated lattice disorders in silicon have been analyzed by electron transmission microscopy, chemical etching, and P-N junction reverse current measurements before and following different gettering treatments. Lattice disorders acted as the nucleating sites for copper precipitation. Copper precipitates in silicon resist chemical etching, absorb electron beams more than silicon, and cause excess reverse currents. Totally gettered disorders will chemically etch rapidly, be transparent to electron beams at extinction contrast, and not contribute to excess reverse currents. Three different gettering procedures were performed to determine the effectiveness of different EXTRANEOUS metal contamination can alter the minority carrier lifetime and resistivity of bulk silicon as well as cause excessive reverse currents in semiconductor devices. Previous workers have reported such activity for gold,1,2 copper,'-* iron,' and rnanganese.2,5 Gettering is a method employed to render these impurities electrically inactive. However, some property of the junction-degrading metals prevents gettering procedures from being wholly reliable. The comparative effectiveness of gettering with different agents has been the topic of earlier publications.2,3,6-11 Two mechanisms for gettering metallic impurities have been proposed: the distribution coefficient mechanism by Thurmond and Logan7 and the compound formation mechanism by Goetzberger and Shockley.2 Both of these models evolved from data gettering mechanisms. First, phosphorus was allowed to enter a protective SiO2 film but remain away from the Si-SiO2 interface to test the effectiveness of the compound formation gettering mechanism. Second, phosphorus was allowed to enter the backside of silicon wafers to test the effectiveness of the lattice strain gettering mechanism. Finally, nickel was diffused into the backside of silicon wafers to test the effectiveness of the distribution coefficient gettering mechanism. In each case, copper precipitates dissolved as a result of the gettering treatment. Tightly packed precipitates will resist gettering more than loosely packed copper precipitates. acquired by the electrical analyses of gettered semiconductor materials. An electrical analysis, however, cannot identify the fate of the gettered metals. The radiotracer technique has recently been applied to determine the redistribution of metals following different gettering treatments.3,9,10 The spatial resolu tion of the radiotracer technique prevented the analysis of metal precipitates which contribute to the excessive reverse currents of P-N junctions. The gettering processes employed by the earlier workers, almost without exception, allowed the gettering agent to enter the silicon lattice. This procedure makes it quite difficult to differentiate between the distribution coefficient and the compound formation mechanisms. The metallographic analysis of gettered copper precipitates discussed in this work supplements the earlier work by obtaining direct evidence of silicon lattice defects decorated with copper before and following different gettering treatments. The effectiveness of a process which restricts the gettering agent, phosphorus, to a dielectric film and thus away from the silicon lattice is discussed in addition to the ef-

Jan 1, 1969

By L. E. Mannion

Sodium carbonate or soda ash is one of the two principal alkalis of commerce, the other being sodium hydroxide. The use of sodium carbonate is recorded in ancient Egypt, where naturally occurring brines or solid salts were the source of impure soda for glass manufacture. In early modern times until the 19th century, soda ash, as well as potash, was recovered mainly by leaching the ashes of plants. In Europe, during the 18th century, a brown lye for laundering was produced by pouring hot water over burned seaweed. One of the better grades of this kind of material was a product from Spain termed "barilla," which analyzed 24 to 30% Na2CO3 (Hou, 1942). The birth of the modern chemical industry may be said to start with the LeBlanc process for making sodium carbonate from salt, sulfuric acid, and lime. Although invented in France in 1691, England made the most extensive use of it. In 1863 Ernst Solvay devised the ammonia-soda or Solvay process, and by 1874 the first of many Solvay plants was built. These were to supplant the LeBlanc method and dominate soda-ash production until the present time. Although of lesser importance, natural sodium carbonate deposits continued to support operations in various parts of the world. Shortages during World War II stimulated production of "natural" soda ash, particularly at Searles Lake, Calif., and at Lake Magadi, Kenya. Within the last ten years in the United States, a notable surge in production has occurred based on the vast trona deposits in Wyoming. Table 1 lists some principal producers of natural soda ash and the character of the source deposits. Uses and Specifications Sodium carbonate (Na2CO3) is a white, crystalline hygroscopic powder, an aqueous solution of which is strongly alkaline. Most commercial soda ash is a product that must meet high standards of purity and uniformity. Two forms are commonly sold: a fine, powdery material called light ash, and a more coarsely crystalline dense ash; these weigh 32 to 39 and 60 to 66 lb per cu ft, respectively. Dense ash may be produced by adding a little calcium chloride to the sodium carbonate solution to control crystal size and prevent agglomeration. Specifications and typical analyses of light and dense ash in the United States are shown in [Table 2]. Sizing generally achieves about 75% of light ash and 90% of dense ash between +30 and -100 U.S. screen mesh. World use of sodium carbonate now exceeds 24 million tpy, of which the United States produces more than 7 million tons. The market for soda ash is dominated by the glass industry, which uses almost half the supply. Inorganic chemicals, including phosphates and silicates, consume about 30%. Other principal uses include the manufacture of soaps and detergents, petroleum, caustic soda, organic chemicals, and paper; and nonferrous and ferrous metallurgy. [Fig. 1] shows the percent consumption by use of soda ash in Europe, Japan, and the United States. The price of soda ash in the United States remained relatively stable during the 1960s at about $33 per ton; in 1972 it reached $35 per ton. The price in 1975 was $42 per ton. Geology Mineralogy [Table 3] is a list of the more common sodium carbonate-bearing minerals. Anhydrous sodium carbonate is almost never found in nature; only natron, thermonatrite, and trona have been used directly as sources of sodium carbonate. At Searles Lake, burkeite and hanksite are important in the reconstitution of

Jan 1, 1975

By AIME AIME

BUSINESS forecasting may be an inexact science, if it is a science at all, but in the opinion of the statisticians of the American Telephone & Telegraph Co. it is a valuable aid to the making of future business plans, whether it be used by a telephone system, a manufacturer whose distribution is country-wide or, one whose trade is confined to certain sections. Whatever the defects of business forecasting may be; the American Telephone & Telegraph Co: has employed it since 1921, not only for charting the probable; course of telephone traffic over long-distance lines, but' to determine the needs for new plant and equipment: caused by shifting tides in business or increases in population or general industrial expansion.

Jan 1, 1929

By H. Doi, Y. Fujiwara, K. Miyake

In order to throw light on the mechanism of plastic deformation of WC-Co alloys, compressive tests of WC-(7 to 43) vol pct Co alloys have been carried out at room temperature, and stress-micro strain relation has been investigated in detail. The analysis of the factors affecting the yield stresses reveals that the yield stresses can be predicted by modified Oro-wan's theory if one properly estimates the planar in-terfiarticle spacings. Conzpressive straining of some of the alloys by 0.066 to 0.17pct increases the decrements by a factor of as much as 3.4 to 14, whereas the corresponding increase in the electrical resistivities is less than 10 pct. The analysis of the decrement data in terms of -Gramto and Lücke theory shows that the marked increase is attributed to increased dislocation darnping itt the binder (cobalt) phase. By cornbilling the decrement data and the conzjwession duta, one obtains the relation between flow stress in shear (?t) and increase in dislocation density (p): At = const . v6 . This is interHeted to mean that the mechanism of strain hardening of CirC-Co alloys is essentially sarne as the one for dispersion strengthened alloys. The possible effect of bridge formations between the carbide particles has also been examined. OWING to the combination of hardness, strength, and other physical and chemical properties, WC-Co alloys have opened the way for unique fields of applications, the recent ones being, for instance, anvils for super-high-pressure generation apparatuses. In such applications, the alloys are frequently subjected to very high compressive stresses: these stresses may cause the alloys to deform plastically and eventually to fail. However, much remains obscure regarding the nature of the plasticity of the alloys. Evidently, the alloys owe their high strength to the hard carbide particles which frequently occupy as much as 80 to 90 pct in volume fraction, whereas the ductility required for practical applications is provided by the small amount of the binder phase between the carbide particles. When the volume fraction of the carbide phase is not very large, deformation behavior of the alloys may be described by some of the current dispersion strengthening theories. However, greatly increasing the carbide phase is thought to lead to some carbide skeleton structure or bridge formations owing to the increased chances for direct contacts between the carbide particles;1,2 this may appreciably affect the plasticity of the alloys. Regarding the effect of formation of the carbide skeleton structure, it is interesting to note the work by Ivensen et al.3 on compression tests of the alloys containing somewhat large carbide particles; they observe extensive generation of slip bands in the carbide particles after application of some preliminary compressive stresses. They interpret the results in terms of plastic deformatiot: of the carbide particles which are supposed to have formed a skeleton structure; the binder phase plays only a passive role, at least in the early stages of the deformation. That carbide crystals exhibit microplasticity at room temperature is apparent from the work of Takahashi and Freise4 and French and Thomas5 on indentation of WC single crystals. On the other hand, Dawihl and coworkers6-10 maintain that even when volume fraction of the carbide phase is very large (for instance, more than 90 pet), a very thin binder layer generally exists between the carbide particles. They interpret the results of the extensive mechanical tests in terms of the plasticity of such a layer. Gurland and Bardzil11 point out that decrease in ductility of the alloys with increase in the carbide phase is caused by the effect of plastic constraint exerted by the dispersed carbide particles. Drucker12 further develops this concept from a continuum-mechanics approach on an assumption that a continuous thin binder layer separates the carbide particles. A common feature of the studies reported so far on the plasticity of the alloys is that the information deduced is invariably qualitative in nature. Thus, very few systematic experiments for obtaining reliable and sufficiently detailed stress-strain curves of the alloys varying widely in the microstructural features have been carried out. In particular, it may be of special interest to investigate in detail the early stages of the plastic deformation of the alloys in order to shed light on the strengthening mechanism. However, such work appears to be extremely rare. Doi et al.13 recently reported a first brief account of the results of some quantitative analysis of the plasticity of the alloys in terms of dislocation theory. Their experiment was rather limited in the composition range covered (volume fraction occupied by the carbide phase: 79 to 83 pct), and thus they could not necessarily elucidate the controlling mechanism of plastic deformation of the alloys of a more general composition range. Consequently, in the present investigation, deformation behavior and some other physical properties of the alloys were investigated and discussed in more detail over a much wider composition range. SPECIMEN PREPARATION WC-Co alloys used in this experiment were prepared in cylindrical or rectangular form by sintering in vacuo compressed mixtures of tungsten carbide and cobalt

Jan 1, 1970

By T. P. Clendenin

THE northerly two thirds of Mexico falls into five main physiographic divisions, illustrated on the accompanying map. In form, these divisions are a series of strips, paralleling the northwest-southeast axis of the country.

Jan 10, 1951

By R. D. Longyear

[Some Problems Involved in the Interpretation of Diamond-drill-hole Sampling and Surve ing (paper by J. J. Collins, Mining Tech., Jan. 1946). ............... I Geologic Interpretation of Magnetic Exploration on the Mesabi Range, Minnesota (paper by R. H. B. Jones, Mining Tech., July 1946) ................... 2] DISCUSSION R. D. LONGYEAR.*-Mr. Collins is to be commended very highly for the brief summary he has made of the currently used methods of taking diamond-drill sludge samples and the principles involved in evaluating the results. This paper should stimulate further discussion and research on this vitally important problem. It is particularly imperative that geologists and engineers know when assay results on sludge recovery can be accepted quantitatively and when they must be considered only qualitatively. In most cases where the sludge recovery is less than 95 per cent or more than 125 per cent, it is safest to consider the assays as of qualitative value only. Certain cases, however, are known where a relatively small proportion of the sludge sampling will give a reasonably accurate measure of the value of the total sample. One such case is ore in which the valuable mineral is of approximately the same specific gravity as the waste mineral, such as chalcopyrite in a massive pyrite body. The essential point is to determine the degree of accuracy of sludge sampling in any given drilling project and to weigh the results accordingly. It should be emphasized, however, that sludge sampling can be made reliable in many localities where careless practice produces unreliable results. In many instances, it is desirable to empty the core barrel in the core shack instead of at the drill, so that the engineer can examine the core as it first comes from the core barrel. It should be pointed out, however, that the drill * E. J. Longyear Co., Minneapolis, Minnesota. runner should be permitted to study the core to guide his future drilling. It is hoped that with the return of more normal conditions after the war geologists, engineers, contractors, and manufacturers will be able to carry on more research along the lines of improved core-barrel design and drilling technique with the objective of increasing core recovery so as to eliminate as far as possible the necessity of relying upon sludge samples. H. M. ROBERTS.*-Whoever in the future will have to do with the search for ore bodies and their exploration will have frequent occasion to refer to the clear and comprehensive summary on diamond-drilling methods by John Collins. His review of the experience of the last 40 years in this technique is invaluable. As Dr. L. D. Ricketts wrote in 1932, "The principles on which an art is founded are usually few and necessarily basic in nature, but he who wishes to achieve the power to select his aides and give success to important undertakings that may be intrusted to him in the future must ordinarily undergo years of drudgery in order to gain the experience that will enable him to distinguish such fundamentals through the haze of reinforcing detail that clothes and tends to disguise them."[t] Ricketts went on to say that since the beginning of the century there has been much

Jan 1, 1946

By K. A. Gschneidner, O. D. McMasters

DgIel-ential thermal, nretallographic, and X-ray paramzetric methods were used to establish the Yb-Pb phase dingram. The terminal solid solubilities in the system are less than 0.2 at. pct. Lead additions lower the 792°C transformation tewzperature of pure ytterbiun~ at 787°C by means of an inverted peritectic veaction. Ytterbium additions raise the 327oC melting point of lead to 329°C by means of a perilectic reaction. Three intermetallic compounds Yb2Pb, YbPb, and YbPb, melt congruerttly at 1246", 1116o, and 740°C. respectively. YbsPb3 forms by a peritectic reacliorz at 1250°C. YbzPb crystallizes in the PbCh (C23) type structure and the orthorhombic latliceo constants are a, = 7.478. bo = 5.225, aud C0 = 9.549A. YbsPbs crystallizes in the hfnsSi3 (D8a) type structure. The hexa~nal lattice constants for this phase are a, = 9.325 and co = 6.92d. YbPbl crystallizes in the cubic AuCU3 (Ll2) type structure with a: = 4.8628 + 0.0008A. YbPb is diwrorphic with the structure change occurring al 507°C upon healing. The crystal structures of the two forttzs were not determined. Eulectic reactions occur at 5.1 at. pct Pb and 769oC, 41.5 at. pct Pb and 1086oC, and G8.0 at. pct Ph and 717°C: RELIABLE information concerning the alloying behavior of most of the rare-earth metals is scarce. A systematic study of the rare earth-lead alloy systems now in progress is an effort to supply such information. Determination of the phase diagram of the Yb-Pb alloys is the first step of this study. Variations in the valence of normally divalent ytterbium may be studied by comparing the characteristics of the Yb-Pb alloys to those of the trivalent rare earth-lead and of the divalent alkaline-earth-lead systems. Of particular interest are the melting temperatures of the intermetal-lic compounds since these are known to be high relative to the melting points of the constituent metals. Crys-tallographic and magnetic susceptibility data for the rare earth-lead alloys are to be included in the comparative study. Results from this and subsequent investigations should provide a better understanding of alloy formation. EXPERIMENTAL PROCEDURE Materials. The major impurities in the ytterbium and lead used in this investigation are listed in Table I. The lead was obtained from Cominco Products, Inc., and was specified to be 99.99 pct pure. The ytterbium was prepared in this laboratory by the lanthanum reduction of the oxide followed by a distillation of the ytterbium. Alloy Preparation. The alloys were prepared by

Jan 1, 1968

By Tony B. Szwilski, K. Unrug

INTRODUCTION Since the introduction of longwall coal mining systems, reliable predictions of roof support requirements at the face and the roof caveability in the gob area have been major contributors to the success of the longwall face by means of safety and face productivity. That is, the successful operation of a longwall is well-served by good regular caving of the gob. In recent times, with the advent of increased coal face mechanization and capital investment, the evaluation of the feasibility of longwall mining has become essential. In the United States, where a face unit for a face length of about 150 metres may cost around $6 million, a quantitative system that would assist in selecting the best equipment for the coal would prove extremely beneficial. There have been many such varied investigations in the past few years. A vast -amount of work has been invested principally by West Germany [3, 7, 8, 91 , Poland [I, 101 , United Kingdom [4, 5, lo], France [4], and South Africa [4]. It is the object of this paper to review this previous research work and give an outline that may be used as guidelines for long- wall evaluation. Essentially, for the initial design phase for a longwall system, account must be taken of the geometry of the coal panel, its position relative to the surface (depth), direction of the coal cleat system, faults and in-situ stresses and other neighboring workings in the same coal seam and other seams both above and below. The advance of the coal panel disturbs the stress field and in doing so creates an abutment zone around the face. At this stage the condition of homogeneity of the surrounding rock mass does not apply. The magnitude of the rock strata pressure may exceed the ultimate strength of the rocks and create zones of clastic, plastic and elastic material, the limits of which are difficult to determine. The collapse of the gob and resulting expansion of the displaced waste roof rock, create a statically undefined support complicating an already unclear rock structure. For example, it is often a point of debate whether, indeed, the vertical strata pressure develops to regain the original magnitude of virgin stress. Under these post-failure circumstances an analytical approach based on simplified and idealized assumptions can only be considered a very general approximation. Theoretical concepts, however, may be adequately supplemented by empirical methods that are based on numerous underground observations and surveys [3, 4, 7, 8]. These methods employ the use of rock indices that very handily correspond to the competence of the roof rock mass. Scale model work [3, 41 , using equivalent materials representing the surrounding rock mass within the coal seam zone, have given valuable qualitative and sometimes quantitative data in addressing the behaviour of the rock mass around longwall panels. To characterize the state of art of caveability predictioqthe principal concepts will be reviewed with special emphasis placed on practicality for the planning of longwall operation. It has been the general observation of the authors that many of the literature surveys published in English often neglect reference to other international mining literature. It is with this point in mind that an overall review has been written including mining concepts identified with the principal coal mining countries. THEORETICAL CONCEPTS Arching Theory For the development of this theory, assumption has been made that an extracted height, h, in a coal seam results in an extracted panel of width, w . Also, the coal seam is horizontal and the rock strata of both the roof and floor are homogeneous. The primary (virgin) stress distribution will change in the roof as well as the floor. As a result of lack of support caused by the excavation (in the gob area) an additional load is developed due to the redistribution of the load around the sides of the panel, referred to as the abutment, R, where: [ ]

Jan 1, 1982

By Brooks J. Klimley, Daniel M. Higgins, Grover R. Castle

Measuring The Economic Viability Of Resource Projects (A Western Surface Coal Project) The bankers approach to the analysis of a new "green fields" mining project is similar but different from the approach that the pining company might take. The purpose of this paper shall be to discuss the techniques that are used by mining companies and bankers as they try to measure the economic viability of mining projects. The analysis of these new projects (by both the mining companies and the banker) is based on a projected revenue stream and not on historical earnings or past perfomance because these projects are start up situations with no history to look to. The starting point in the analysis of these projections is the choice of the assumptions to be used in preparing these projections. After the assumptions have been determined and the projections are prepared then the projections are submitted to various tests in order to determine whether the project measures up to previously agreed upon minimum standards. In order to illustrate the analytical procedures used in evaluating a mineral project the writer has constructed a hypothetical case involving the development of a western surface coal mine (Property). The basic data in connection with this hypothetical new project is described in the next section of this paper. After the Description of the Project is a section which shows the type of analysis that a mining company might prepare in order to approach a bank for a loan and the final section illustrates the type of analysis that a bank might prepare in evaluating this loan request. Description Of The Project or Basic Data In Connection With Undeveloped Western Surface Coal Property An independent mining/geological Consultant's report has been completed on the Property which confirms that the Property contains 175 million tons of economically recoverable coal subdivided into the following reserve categories in accordance with U.S. Bureau of Mines and U.S. Geological Survey definitions: Measured or Proven 90,000,000 Indicated or Probable 50,000,000 Inferred or Possible 35,000,000 The owners of the reserves have chosen to drill up those reserves that are nearest to the subcrop and have not spent as much time on those portions of the Property which are on the fringes of the deposit where the overburden is thicker because the stripping ratio and hence the operating costs and capital requirements are higher down dip. The proven reserves are based on an average thickness of 80 feet, of which a mining recovery of 90% is projected. The overburden thickness varies from 0' to 280' with an average thickness of 127'. The overburden consists mainly of scoria, sandstone, gravel, shale and silty clay. 134 holes were cored (and analysis done on five foot increments) in the measured reserve on the following spacing: 100 foot centers to define the burn line; 1,320 foot centers to define the early mining areas; 2,640 foot centers to identify the later mining areas.

Jan 1, 1985