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By B. F. Oliver, F. Garofalo

Gas-metal heterogeneous reactions and zone-lrelting were sinultarneously employed to produce several high-purity irons with low interstitial contents in a levitating- zone melter. Successive zone-tneltitzg pusses were made in carious sequences of atmospheves which included prepuvified tank hy-drogeta, water vapor hydrogen, palladiuril-purified hydrogen, and vacuunm of 2 x 10-6 Torr. Different irons ranging in purity from 99.89 to 99.996 pct with residual curbon contents of 17, 8 to 10, and 3 to 5 ppm have been Drepared. No measuvable gradient in the residual carbon content was observed along the entire zone-melted length (6-10 in.) in I-ilz.-diameter bars. The absence of a carbon-concentration gradient in the solid indicates an apparent distvihution coefficient of 1, an unusual condition. Internal friction, solid-state extraction, and hot-hardness results indicate that the level of mobile carbon in a iron depends on the gas-metal heterogeneous reactions employed. Purification under an oxidizing atmosphere resulted in the immobilization of nearly all of the carbon present at leuels of 10 ppm or less. Continuation of purification in a reducing atmosphere veturued the carbon to a state of mobility which was aguin reversed by further purification in all oxidizing atmosphere. The immobilization of curbon at "vesidual levels " is believed to be associated with a strong interaction between carbon and oxygen atoms. frons with low carbon and nitrogen contetzts which did not exhibit a hot-hardness peak were produced after zone ynelting in vacuum. CARBON, nitrogen, and oxygen have strong and well-known effects on many properties of iron. These effects persist even at concentrations of 5 to 20 ppm. The intent of the present investigation was to establish procedures for the preparation of high-purity iron with concentrations of these elements in the range of 5 to 20 ppm and lower. The results reported here deal with the procedures employed to prepare high-purity iron, and with observations on the behavior of certain elements at "residual levels": particularly carbon. The details of the (levitating) zone melter in which the final purification steps are performed and the necessary control of the pertinent solidification variables have been described previously.1,2 MATERIALS AND PROCEDURES Commercial electrolytic iron was induction vacuum-melted and cast into 30-lb ingots. Melt additions and ingot analyses for carbon, oxygen, and nitrogen are noted in Table I. All ingots were melted in stabilized zirconia crucibles conditioned with one iron wash heat. Middle sections of the ingots were forged to 1-1/4-in. rounds, machined to 1-in.-diameter bars, then cut to 36-in. lengths. The zone-melting operations were performed on six iron bars (A to F) at a freezing velocity of 2 in. per hr with the freezing interface rotating2 at 200, 300, or 400 rpm. Liquid zones were passed through the bars in various sequences of atmospheres, Table 11, including prepurified tank H2, palladium-purified Hz, wet H2, and system vacuum of 2 x 1018 Torr. Wet-Hz atmospheres were obtained by bubbling palladium-purified Hz through water exhibiting a resistance of 3 megohms. This water was heated with a platinum-immersion heater and was degassed prior to use. Zone melting in a wet-HZ atmosphere resulted in oxidation of the elements which are oxi-dizable with respect to iron. Fine oxide particles were observed on the surface of the liquid zone, and were encased in the bar surface with the passage of the molten zone. Between each zone pass, the surface of the bar was removed by filing and deep etching; this was continued until the oxide formation ceased. The filings were magnetically separated and the residues analyzed by optical spectroscopy. These were especially high in silicon and manganese. Samples were removed from the iron bars, with few exceptions, following each zone-melting operation. A 0.08-in.-thick disc was cut with an Al2O3 cut-off wheel at a point 1/2 in. above the beginning of freezing. Material from each disc was used for hot-hardness measurements, resistivity-ratio measurements, and carbon, nitrogen, and oxygen analyses. Analyses for most other elements were

Jan 1, 1965

By R. J. Stoehr, F. Howell

Since the ore mined in the Grants-Ambrosia Lake uranium area is taken from a water-saturated sandstone formation, part of the milling operation includes a drying process. The authors discuss the merits and disadvantages of two methods: natural drying and mechanical gas-fired drying; operating and cost data are included. In the Grants-Ambrosia Lake uranium area, approximately 7000 tons of ore are mined each day from a water-saturated sandstone formation. This ore is sampled and treated at four separate milling operations. Prior to the design and initial construction of the milling facilities, very little was known as to the physical properties of the ore which would be handled in the sampling and crushing facilities at the mills. All four mills initially were constructed without ore-drying facilities. As mining proceeded, it was determined that, even after drying the ore in place by use of drainage development underground, the moisture content of the ore as hoisted averaged approximately 18 pct. Actually, some of the mines produced ores which resembled cream-of-wheat in character and had a moisture content in excess of 24 pct. Each of the four mills had a differently designed sampling and crushing plant; therefore, the moisture content of the ores had varying adverse effects upon the operation of the plants. It was determined after some experience that most of the sampling and crushing facilities could not economically handle ore if the moisture content was greater than 10 pct—one operator considers 12 pct moisture as a maximum. In all of the plants, moisture content over 8 pct increases costs to some extent. In addition to the added sampling and crushing costs, some of the mills were located 15 to 20 miles from the mines and the high moisture content of the ores increased the haulage costs from the mine to the mill. It was generally conceded that it was necessary to employ some method to reduce the moisture content of the ore prior to sampling. Several methods were considered: 1) natural drying at the mine site, 2) mechanical gas-fired drying at the mill site, 3) mechanical gas-fired drying at the mine site, 4) radiant heating on concrete clabs, and 5) infrared shed drying. After preliminary investigation all possibilities but natural drying and mechanical gas-fired drying at the mill site were eliminated. NATURAL DRYING A cooperative feasibility study was conducted on the natural drying method. This study indicated the following: 1) During summer months May through September, ore piled 4-ft deep would dry from +20 to +10 pct HzO in 30 days with no mechanical turning. 2) In the first four days after piling a reduction of 5 to 7 pct total moisture content was accomplished by drainage and absorption of the water into the underlying ground on which the ore was piled, providing the ground surface absorption rates approached 10 gal per sq ft per day. After the first four days the decrease of moisture caused by drainage was practically nonexistent. 3) In the summer months drying by evaporation amounted to approximately 0.1 pct decrease in total moisture per day and mechanical turning of the ore could increase this as much as three times. 4) Climatic conditions of the area indicated that: a) Air temperatures averaged 64' May, June, July, August, September; 41" October, November, December, March, April; 31" January, February. b) Average rain fall was 10 in. with 40 pct of this occurring during July and August. c) Only on very rare occasions were there over five consecutive days with below freezing temperatures. d) The annual evaporation rate was approximately 75 in. On the basis of this study, two of the mill operations decided to attempt to meet the moisture specifications by natural drying supplemented by mechanical turning. The other two operations decided upon rotary gas-fired drying at the mill site. The natural drying method has been quite successful in practice. The ore running approximately 18 pct moisture is trucked from the head frame and piled in rows about 6 ft wide, 3 1/2 ft deep, 5 feet apart during the months of May through September. In approximately 30 days this ore will

Jan 1, 1961

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

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

Jan 1, 1963

By E. Miller, J. M. Eldridge, K. L. Komarek

Activities of magnesium in liquid Mg-Sn alloys have been determined between 5 and 90 at. pct Sn and 990" and 1290°K by an improved isopiestic method wherein tin specimens, heated in a temperature gradient and contained in crucibles of special geometry, were equilibrated with magnesium vapor in a closed titanium system. The crucibles were designed so that the equilibrium compositions of the specimens were satisfactorily preserved on termination of the experimental runs by quenching. The activity values are in excellent agreement with those predicated on the phase diagram and allowed a delineation of the solidus curve of the compound Mg2Sn near its melting point. EQUATIONS have been recently derived relating the chemical potentials of the components to the liquidus and enthalpy data for binary systems exhibiting one congruently melting compound.' The liquidus curve of the Mg-Sn system between the eutectics was carefully redetermined and the thermodynamic properties thus calculated were in reasonably good agreement with values derived from electromotive-force measurements of an,' but differed greatly from the iso-piestically determined values of Ashtakala and Pid-geon.3 The present study was initiated: a) to resolve the discrepancies; b) to develop a method for measuring activities in systems having volatile (and possibly highly reactive) components; and c) to use the method in a general investigation of the thermodynamic properties of the homologous series of Mg-Group IVb systems, i.e., Mg-Pb, Mg-Sn, Mg-Ge, and Mg-Si. This paper describes the results for the Mg-Sn system. An isopiestic technique, originally developed by Herasymenko 4 and adapted for alloys having a component of high reactivity and low volatility,5-8 was modified in this study by using crucibles designed to preserve the equilibrium composition of highly volatile liquid specimens on quenching from high temperatures. Tin specimens, contained in tightly covered graphite crucibles and heated in a temperature gradient, were equilibrated with magnesium vapor of fixed pressure from a magnesium reservoir kept at constant temperature in a previously evacuated and sealed titanium tube. During equilibration magne-

Jan 1, 1967

By T. L. Joseph, G. Bitsianes

THE layered structure of partially reduced iron ore was described in a previous paper.' Reduction by hydrogen was found to take place at well-defined interfaces between layers of the solid phases. In the present investigation, a detailed study was made of the wiistite phase that had formed during the partial reduction of a cylindrical compact of chemically pure hematite. An unusually wide band of wiistite permitted a rather detailed study of this phase. The specimen was made from Baker's C.P. hematite in the form of a cylinder 1.5 cm in diameter and 1.8 cm long. A dense ore structure with about 6 pct porosity was attained by heating the specimen in air at 1100°C for 3 hr. To confine reduction to the top surface, a ceramic coating was applied to the bottom and sides of the cylindrical compact. The specimen was then partially reduced in hydrogen at 850°C and subjected to a coordinated sequence of macro-, micro-, and X-ray examinations. A section of the partially reduced cylinder is shown in the macrograph, Fig. 1. Four layers consisting of metallic iron, wustite, magnetite, and unreduced hematite are clearly shown. The effort to force reduction to proceed downward in topochemi-cal fashion was only partly successful, as some reduction occurred along one side and bottom of the cylinder. A rather wide layer of dark wustite phase had formed, however, and permitted sampling for X-ray studies as indicated. To supplement previous work and to study the wustite layer in more detail, ten separate layers were removed for X-ray examination. Broad and diffuse patterns were obtained with the as-filed powders, especially with those of iron and wiistite, and the condition indicated a cold-working and variable composition effect within the respective layers. This condition was corrected by annealing the entire series of powders at an appropriate temperature. For the annealing treatment, the ten powder samples were wrapped in silver foil, sealed under vacuum in small quartz tubes, and heated at 750°C for 16 hr. The specimens were then drastically quenched in cold water to preserve the annealed condition. These annealed specimens were X-rayed in turn and the compiled patterns are shown in Fig. 2. The standard patterns for iron and its oxides have been interjected at appropriate positions for purposes of comparison and phase identification. All of the patterns obtained were clearcut and concise so that positive identifications could be made for all of the phases. The outermost layers A, B, and C were composed almost entirely of iron with a small amount of wiistite being detectable at the X-ray limit of phase detection. Layer D from the iron-wustite interface showed both of these phases. The next four layers E, F, G, and H were all in the dark phase band which had been tentatively identified as wustite by the macroexamination, Fig. 1. The diffraction data with their single-phase patterns of wiistite for these layers checked the visual evidence. Continuing the X-ray analyses after layer H, the macrograph (Fig. 1) shows that layer I came largely from the magnetite zone but included some fringes of the wiistite-magnetite interface. The diffraction pattern for the sample confirmed this observation. Layer J came from the unreduced core of the specimen and its diffraction pattern indicated a preponderance of hematite phase. The reduction behavior of synthetic compacts has thus been found to be similar to natural dense iron ore. The previous results were supplemented with measurements of the diffraction films and calculations of the respective unit parameters. These X-ray data are summarized in Table I and offer some interesting correlations as to the compositions of the various phases undergoing reduction. The iron layers that were analyzed gave lattice parameters close to that of pure iron at 2.8664A. Evidently this iron was present in layers A through D as a pure phase with little or no oxygen dissolved in its lattice. With the wiistite layers an entirely different situation prevailed in that there was a definite and

Jan 1, 1955

By Hugh D. Pallister, Richard W. Smith

The Alabama flake-graphite industry has flourished only in times of war when importations of foreign graphite for crucible use have been greatly curtailed or cut off. World War I was a boom period and in 1918 some 30 plants produced 7,795,475 lb. of flake graphite. The industry languished following the war and no graphite was produced from 1929 to 1939. The Federal Bureau of Mines began investigating the Alabama graphite deposits in 1940 and worked out modern recovery methods that were applied to production during part of World War II. A prospecting program disclosed reserves of over 25 million tons of graphitic schists. In 1942 the War Production Board authorized the enlargement of the only plant then producing flake graphite and the construction of two new plants. Production of flake graphite from these three plants in 1943 is estimated at 8,100,000 lb. Increased imports from Madagascar late in 1943 shut down one of the new plants and curtailed production at the other. Alabama flake graphite has not yet been able to compete with Madagascar graphite for use in the manufacture of any but small graphite crucibles. The future of the industry must depend on meeting the higher carbon content demanded for other uses.

Jan 1, 1945

By A. M. Gaudin, C. S. Chang

IN general, fatty acids or their alkali salts do not cause clean quartz to float. However, the presence of multivalent ions, such as the alkaline-earth metal ions and heavy-metal ions, can activate quartz and thus make it respond to soap flotation. The mechanism of activation and soap flotation of quartz has been studied.1-4 The problem was attacked by making flotation tests rather than by careful adsorption measurements on suspensions of ground quartz in solutions containing the activator and the collector. Attempts have been made to determine the adsorption of barium ion and calcium ion on quartz. The results have only qualitative value as the analytical methods were not adequately precise. Artificial radioactivity and progress in radioactivity detection have introduced a new analytical tool, which can have a sensitivity several orders of magnitude greater than that of other methods.5-6 In the experimental work described in this paper the radioactive tracers, barium 140 and carbon 14, were employed. Lauric acid was synthesized, having a radioactive carbon atom and was used with Ba140 to study the adsorption of barium and laurate ions from aqueous solution on ground quartz. Flotation tests, using the vacuum flotation technique,4 were run in conjunction with the adsorption experiments. The object of this investigation was to understand better the reaction mechanism of barium activation and soap flotation of quartz. Methods and Materials Quartz Sample Preparation: Lumps of hand picked quartz, washed free of stains, were reduced in size to -20 mesh in laboratory crushers. The product was boiled in concentrated hydrochloric acid to remove the abraded iron. The cleaned product then was ground dry in a laboratory porcelain mill, using siliceous pebbles, to pass through a 200 mesh screen. The ground product was deslimed by sedimentation at 37 microns. This -200 mesh +400 mesh material was subjected again to boiling with concentrated hydrochloric acid, followed by washing with distilled water and further desliming. The cycle was repeated until no trace of iron could be detected in the wash liquor. During the final washing, the pH of the wash water was checked to insure the complete removal of the acid from the mineral. The quartz then' was rinsed with conductivity water. The resulting product was dried in a drying oven and stored in mason jars. The impurities (spectrographic) were as follows: Al, 0.01 to 0.001 pct; Li, Mg, Mn,, Na, each less than 0.001 pct; Fe and Cu not detected. The specific surface of the quartz sample was determined by the krypton gas adsorption method.7 The average of two measurements was 881 sq cm per g. The calculated specific surface for 37/74 micron quartz particles, using a surface factor of 1.96,8 is 900 sq cm per g. This is in good agreement with the measured value of 881 sq cm per g. Beta-Counting Method: The radioactive isotope of barium used in the experimental work was barium 140. It has a sufficiently long half-life, 12.8 days, emits high-energy beta particles (up to 1.0

Jan 1, 1952

By F. W. Archibald

The American Smelting and Refining Co. has standardized its copper converting practice to attain a maximum unit blister production with a minimum of refractory consumption by careful location of the tuyeres and by applying magnetite coatings on the hard-burned magnesite brick linings. THE American Smelting and Refining Co. operates four primary copper smelters in the United States with a total of 17 Peirce-Smith type converters; 15 of them are 13 ft in diameter by 30 ft long, and two are smaller. Some details of operations vary with locale; however, fundamentals of design, operation, and maintenance are common to all plants. All converter shells are l-in. thick except for one new converter with riding rings on the ends which has a shell thickness of 1 1/2 in. More tuyeres can be installed with rings on the ends and hence more air can be used. Welded construction is replacing riveted. Minor shell repairs are made after each campaign. Principal causes of complete shell replacement are warpage and cracking resulting from localized over-heating. A 13x30 ft shell is being replaced after 34 years of operation and a total production of approximately 750,000 tons of blister. Converters are driven by 80 hp DC motors through company-designed worm gear reducers. Rotation is 0.38 rpm which permits the skimmer to spot the converter quite accurately for skimming slag. At three of the plants, protection against unscheduled air or power failures is afforded by the installation of emergency drives, consisting of auxiliary air motors or storage batteries. In order to avoid excessive splash out of the converters, the converter mouths are located as far back on the shells as existing flue facilities will permit. At one plant, the back of the mouth is only 13" to the rear of the vertical center line of the converter,. whereas it is 28" at another plant. Newly-lined mouth areas vary from 36 to 44 sq ft with effective operating areas about 25 pct less. It is important to keep the converter mouths as clean as possible. Dirty mouths create back pressures in the converters and as a consequence the tuyere air volumes are reduced. Mouths are generally cleaned by bumping with an empty ladle. Small mouth-cleaning rams have been used but unless extreme care is exercised the brickwork may be damaged. After considerable experimentation, the plants standardized tuyere elevations at 4 to 4% in. below horizontal center line at the shell with a downward pitch of about 13/16 in. per ft of length. Tuyeres are spaced at 6 in. centers except at the riding rings where there are no tuyeres. With this tuyere location, several of the plants now freeze magnetite slag in the bottoms, fronts, and backs up to the bottom of the tuyeres to control the internal shape of the converter. This has the effect of improving the agitation and mixing so that there is a marked increase in converting speed besides affording protection to the brick lining. Currently, the trend is to increase tuyere diameters from 1% to 2 in. to increase the air flow. At present, all converters are hand-punched but one converter is being equipped with a set of mechanical tuyere punchers. Rods for punching are % in. hexagonal smelter bar upset to ll/s in. and rods for cleaning tuyeres are upset to about 1% in., or larger, depending upon the tuyere diameter. Two of the plants use pneumatic reamers for cleaning the tuyeres between charges to minimize disturbing the coating on the inside of the refractory lining. Most of the puncher's platforms are pneumatically or hydraulically mounted so that a convenient punching position can be maintained regardless of tuyere position. For normal operations, tuyere air pressures vary from 15 to 13.5 psi, although some cycles such as magnetiting require pressures down to 8 psi. Air requirements vary from an average of 25,000 cfm on the newer installations down to 12,000 cfm on the older ones. Converter hoods are designed to protect the punchers from sparks, splash or hood accretions as well as to prevent the escape of objectionable

Jan 1, 1955

By A. L. Jamieson, H. Rosenthal

The action of mercury on stressed brass to produce cracks was known before Moore, Beckinsale and Mallinson1 showed that actual season cracking did not occur spontaneously but could be induced by ammonia. These investigators studied other substances, including diphenylamine, without finding that anything other than ammonia could cause season cracking Grimston2 reported season cracking in cartridge cases stored in wooden boxes wetted with dilute sulphuric acid pickling solution. Season cracking associated with sulphur dioxide, water vapor and air has been reported by Johnston,3 although he reported that trimethylamine and pyridine did not cause cracking. Jevons4 has ascribed season cracking of brass in certain instances to trimethylamine, "aldehyde amine," "ketone amine" and pyridine, but no experimental work was done evidently to prove this definitely. Pyridine was investigated by Morris,5 who found it to have considerable cracking power. In the present investigation, the object was a qualitative evaluation of a number of representative amines with respect to their ability to cause season cracking. Thus it was desired only that an appreciable vapor pressure of each amine be obtained in order to make the test as severe as possible, without attempting to test equivalent concentrations for comparative purposes. MEthods Specimens TWO types of specimen were used: 1. Unannealed 70-30 brass CUPs formed from 0.040-in. thick sheet. Height of cup Was 13/8 in. and diameter was 17/8 inches. 2. First draw pieces of caliber .50 cartridge cases in the unannealed condition (70-30 brass)- The cups were representative of a thin wall and thin base specimen, whereas the draw pieces have a thick base (1/4 in.) and a thick wall (approximately 3/32 in.). Both types of specimens contained high residual stress and cracked in less than one minute in a solution of I per cent mercurous nitrate and I per cent nitric acid provided that this was receded by a 30-sec. pickle in 40 per cent nitric acid. Specimens were prepared as follows: (1) degreased in trichlorethylene, (2) rinsed in H2O, (3) pickled 5 min. in 10 per cent by volume H2SO4 (1.84 SP. gr.), (4) rinsed in H2O, and (5) dried. Amirtes Tested In selecting the amines, representatives of the three series of amines, and one series of substituted amines were chosen. The aliphatic series was represented by the methyl and ethyl primary, secondary and tertiary amines. These are the simplest aliphatic amines. For the aromatic series, the phenyl primary, secondary and tertiary amines were selected as being the simplest. The heterocyclic series was represented by pyridine, which is a simple heterocyclic base (tertiary amine).

Jan 1, 1944

By Henry Howe

W. E. RUDER, Schenectady, N. Y.-In 1913 I presented a paper before this society on Grain Growth, and at that time it seemed to me that the only explanation for grain growth was that of critical strain. I do not think I published the photographs at the time, but I made some experiments on the effect of stretching sheets of metal. This allowed for fairly accurate determinations of the amount of cold deformation, At the time I worked-with silicon steel because one could see the change in grain growth with the naked eye. I stretched about 10-samples from 0.5 per cent. to 10 per cent., and, after heating to 1,050° C., I found that the maximum grain growth occurred at about 2 ½ per cent. cold deformation. This I designated "the critical strain" for maximum grain growth. About a year ago I talked with Prof. Jeffries, who explained to me his ideas of grain growth. It occurred to me that it would be a very easy thing to check the strain hypothesis against the strain and temperature hypothesis, if we took a certain number of these strips, strained exactly alike and heated to different temperatures; in that case the maximum grain growth ought to appear at a different percentage of deformation for each temperature. These experiments showed that there was, as Mr. Jeffries shows in his present paper, a decrease in germinative temperature with increased cold deformation. The samples were stretched from ½ to 8 per cent. and heated for 10 hr. in hydrogen. Samples were introduced into a furnace previously heated to temperature. A maximum grain growth was obtained at 5 per cent. deformation, when heated to 750° C.; at 2 ½ per cent. when heated to 800' C.; at 1 1/4 per cent., if heated at 950°C.; and at 5/8 per cent.. when heated at 1,100° C. This shows very clearly that the germinative temperature decreases with the increase in cold deformation. The growth was very much more marked, however, at the high temperature, i.e., the grain grew more rapidly and attained a much larger size than at lower temperature. In considering the photographs (Fig. A) those along the lateral edges should be ignored because.

Jan 4, 1917

By Michel T. Halbouty

The area for which oil and gas developments in South Texas are reported for 1940 in this paper covers the same counties that were included in the reports for 1938 and 1939, with the addition of LaSalle County. LaSalle County is includcd in the Laredo district of South Texas, which totals seven counties for that district. The Corpus Christi district remains the same, with nine counties. The two districts together comprise what is known as the South Texas area for this report. Continued exploration along established trends and beyond proven field limits during 1940 provided South Texas with new fields and new producing levels at a rate of discovery fairly comparable with the high records set during recent years. The wells drilled in the counties within this district (including LaSalle) numbered 1656, approximately 8 per cent below the 1801 figure of last year. However, rank wildcats totaIed 336, an increase of 17.5 per cent compared to the 286 drilled in 1939. Therefore, since new field discoveries numbered 25 in 1940 against 29 in 1939, the rate of new field discoveries in 1940, based upon rank wildcats drilled, was I/I3.4 while that of 1939 was I/9.86, which shows a decrease of about 25 per cent in the rate of new fields. The rank wildcat tests in 1940 gave the following results: 18 produced oil, 4 produced distillate with gas, 3 produced. only gas, and 3r1 were dry holes (Table 5). Of the 1320 tests drilled in already proven fields or as extensions to pro+en areas (representing a decline of 12.8 per cent from last year's total of 1515 tests), 1048 produced oil or distillate, 60 produced gas and 212 were dry holes (Table 4). Of the producers, 50 found new sands or crude-in-distillate-sands in existing fields. Among the several fields subjected to extensive development were: Colorado, Jim Hogg County; East White Point, San Patricio and Nueces County; Rincon and Sun, Starr County; Glen, Webb and Zapata Counties; Wade City and Orange Grove, Jim Wells County; Stratton and South Clara Driscoll, Nueces County, and Aransas Pass, San Patricio and Aransas Counties. The development of important crude reserves on structures formerly considered primarily distillate fields has probably been the most important phase of the year's operations in South Texas. The Rincon, Stratton, Agua Dulce, Wade City, Odem and Robston fields provided the new crude sand discoveries. At some places crude production was opened by exploratory wells that found new sand horizons; in others by flank wells that found already discovered distillate sands sufficiently low to provide crude production. Rincon, Starr County, with its multiple sands, is now believed to be one of South Texas' largest crude-oil reserves. Offshore drilling showed important results during the year, including the discovery of two new submerged fields and the extension of the East White Point field into offshore Nueces County. The new marine fields are: East Flour Bluff) 76

Jan 1, 1941

By Michel T. Halbouty

The area for which oil and gas developments in South Texas are reported for 1940 in this paper covers the same counties that were included in the reports for 1938 and 1939, with the addition of LaSalle County. LaSalle County is includcd in the Laredo district of South Texas, which totals seven counties for that district. The Corpus Christi district remains the same, with nine counties. The two districts together comprise what is known as the South Texas area for this report. Continued exploration along established trends and beyond proven field limits during 1940 provided South Texas with new fields and new producing levels at a rate of discovery fairly comparable with the high records set during recent years. The wells drilled in the counties within this district (including LaSalle) numbered 1656, approximately 8 per cent below the 1801 figure of last year. However, rank wildcats totaIed 336, an increase of 17.5 per cent compared to the 286 drilled in 1939. Therefore, since new field discoveries numbered 25 in 1940 against 29 in 1939, the rate of new field discoveries in 1940, based upon rank wildcats drilled, was I/I3.4 while that of 1939 was I/9.86, which shows a decrease of about 25 per cent in the rate of new fields. The rank wildcat tests in 1940 gave the following results: 18 produced oil, 4 produced distillate with gas, 3 produced. only gas, and 3r1 were dry holes (Table 5). Of the 1320 tests drilled in already proven fields or as extensions to pro+en areas (representing a decline of 12.8 per cent from last year's total of 1515 tests), 1048 produced oil or distillate, 60 produced gas and 212 were dry holes (Table 4). Of the producers, 50 found new sands or crude-in-distillate-sands in existing fields. Among the several fields subjected to extensive development were: Colorado, Jim Hogg County; East White Point, San Patricio and Nueces County; Rincon and Sun, Starr County; Glen, Webb and Zapata Counties; Wade City and Orange Grove, Jim Wells County; Stratton and South Clara Driscoll, Nueces County, and Aransas Pass, San Patricio and Aransas Counties. The development of important crude reserves on structures formerly considered primarily distillate fields has probably been the most important phase of the year's operations in South Texas. The Rincon, Stratton, Agua Dulce, Wade City, Odem and Robston fields provided the new crude sand discoveries. At some places crude production was opened by exploratory wells that found new sand horizons; in others by flank wells that found already discovered distillate sands sufficiently low to provide crude production. Rincon, Starr County, with its multiple sands, is now believed to be one of South Texas' largest crude-oil reserves. Offshore drilling showed important results during the year, including the discovery of two new submerged fields and the extension of the East White Point field into offshore Nueces County. The new marine fields are: East Flour Bluff) 76

Jan 1, 1941

By C. H. Aldrich

For many years the City of Prescot, about 8 miles northeast of Liverpool, has been the home of British Insulated Cables, Ltd., one of the largest wire mills and manufacturers of electrical equipment in England. Since this location is close to the industrial center of the country and the seaboard, with good railroad transportation facilities, it was a logical site for the new refinery. Early in April, 1932, the writer was called upon to prepare a preliminary layout and estimate of cost of the proposed plant, and shortly afterward, following a discussion of these figures with officials of British Insulated Cables, in England, the decision was reached to proceed immediately with construction of the plant. The refinery was built by British Insulated Cables, Ltd. Designing of the plant was started early in May, 1932, orders for equipment being placed as rapidly as possible. On July 18 the first steel was erected and the first charge was cast on Jan. 5, 1933. No difficulties of any consequence were experienced in starting the plant and the grade of copper produced was quite satisfactory after the first charge. The initial capacity desired was 2500 tons of refined copper per month. Since only one furnace was to be built, it was necessary that it should have sufficient reserve capacity to catch up after unavoidable shutdowns. It was also necessary to lay out the plant so that it would operate efficiently at this tonnage and at the same time permit expansion in the future, if necessary, to several times its original capacity. In order to meet these conditions and also to take full advantage of the space available, the layout shown in Fig. 1 was adopted. The principal plant structures are a blister storage aisle, casting building, wire-bar storage building and a coal-pulverizing building. Additional smaller structures include a brick and charcoal shed, pumphouse, drill room, water-cooling tower, clay-preparation shed, substation and plant office. Incoming blister is received in either broad-gage railway cars or steam motor lorries in the blister storage aisle, unloaded by overhead electric crane to narrow-gage cars, weighed and sampled, then either sent directly to the furnace or placed in storage. After refining, the copper is cast on the wheel, passes through the cooling bosh and is

Jan 1, 1934

By W. D. Keller

THE high-alumina clays of Missouri are interesting for several reasons. They are the only sedimentary deposits in North America of first grade (over 70 pct A1,0,) diaspore and boehmite sufficiently large to be mined commercially. Mineralogically, they are composed of diaspore and boehmite in intimate coexistence, but gibbsite, the common hydrated alumina mineral in bauxite and laterite, is absent, or is exceedingly scanty if present.* Therefore, the Missouri high-alumina clays do not represent typical laterization. The physical chemistry leading to their mineral genesis, and the geolbgical setting for their formation, present important problems for scientific study. The origin of the Missouri high-alumina clays has been discussed in earlier reports by Allen1 (1935) and McQueen 8, 9 (1929, 1943). These investigations were made under difficult conditions, however, because no diaspore deposit had been opened where a Paleozoic (Pennsylvanian) rock cover lay undisturbed over the high-alumina clay. The relationship of the clay to only the underlying rocks could actually be observed. Lacking the guidance of critical postdepositional geologic evidence, undue and erroneous emphasis was placed on the postdepositional leaching of the deposits in the theories on the origin of diaspore and boehmite from clay (hydrous aluminosilicates) . With new geologic evidence at hand, a clearer picture can be made for the origin of the Missouri high-alumina deposits. In this paper the geology of a diaspore deposit whose original Paleozoic cover had not been eroded will be described and interpreted genetically. The close relationship of boehmite and diaspore (also with kaolinite and a chloritic mineral), will be established. A theory of origin for the high-alumina clays, consistent with the new data, will be postulated.

Jan 1, 1952

By A. S. Eve

In the spring of 1930, the question was raised as to the possibility of estimating the depth to which the pyrrhotite-nickel deposit at the Falconbridge mine extended in the earth. This body is 7500 ft. long, it dips at 80° to the north, and it is fairly straight with slight sinuosities. Dr. F. W. Lee suggested that it might be possible to solve the problem by measuring the vertical magnetic intensity, with a good magnetometer, both near the surface of the earth and also at a level a few feet higher in the air. The writer regarded this suggestion with some scepticism, but it was decided to put the scheme to a practical test. In July, 1930, Dr. Lee, Dr. Keys and the writer, with Mr. Joyce and Mr. Belloc as assistants, made a firm, light wooden platform (Fig. 1) measuring 4 by 4 ft. on the top, which was 10 ft. above ground. This platform could be moved easily a few yards by four men, and carried across country in a wagon or by motor truck. Some iron nails were used in its construction, but we were not able to detect their influence on the Askania magnetometer. Nevertheless, in future work, the use of iron should be completely avoided. Readings were taken along a traverse at right angles to the orebody, at several stations, both on the ground and on the platform. The excess readings, over the dike, as compared with those about 800 ft. away, are shown in Table 1. The largest reading, 6.8, is open to suspicion and should be rejected. The depth of the top of the orebody is known by electrical survey, and by actual drilling, to be about 112 to 123 ft., and the covering is sandy glacial drift. Similar readings were taken over a long straight magnetic diabase dike. These also are shown in Table 1. The magnetic vertical intensity is consistently less at the higher level, which is 10 ft. above the lower level.

Jan 1, 1932

By C. L. Sollenbeger, R. B. Greenwalt

PERHAPS the most widely used dispersants or gangue depressants in nonmetallic flotation are sodium silicates, which vary in silica-to-soda ratio from 1 to 3.75. Typical manufactured silicates in order of decreasing solubility and increasing amounts of silica are Metso, silica-to-soda ratio of 1.00; D, 2.00; RU, 2.40; K, 2.90; N, 3.22; and S-35, 3.75.* References in flotation literature1,2 to the use of sodium silicates are often weak because they fail to mention the type of silicate used. Metso and silicate N have occasionally been mentioned, but when the type of silicate is not mentioned, it is usually assumed to be N, the cheapest of the soluble silicates and the one recommended by sodium silicate manufacturers as a flotation agent. In the All is-Chalmers Research Laboratories a systematic study was made of the effect of different alkali-silica ratios on the concentration by flotation of two scheelite ores. One of these was a high grade ore from the Sang Dong mine in Korea. The effect of such factors as pH; addition agents; and conditioning time, temperature, and pulp density on the flotation efficiency of this ore have been described previously. The other ore was a low grade ore from Getchell Mines Inc., Nevada. The mineralogy and techniques of concentrating this ore have been described by Kunze. Hereafter these ores will be referred to as the Korean and Nevada ores. Experiments were made with both to determine the effect of three factors—-type of silicate, concentration of silicate, and pH of the pulp—on recovery and grade of tungsten in a rougher concentrate. Average WO, content of the Korean ore was 1.50 pct and of the Nevada ore 0.27 pct. The predominant tungsten mineral in both ores was scheelite, which was accompanied by a small amount of powellite. The powellite and scheelite were finely disseminated through both ores and required a —200 mesh grind for liberation. Major gangue minerals in the Korean ore, in decreasing order of abundance, were amphi-boles, quartz, biotite, garnet, fluorite, and calcite. Bulk sulfides composed about 3 pct of the total weight. Gangue in the Nevada ore, in descending order of abundance, was garnet, alpha quartz, calcite, phlogopite, wollastonite, and amphiboles. Sulfide minerals were 3 to 4 pct of total weight. Batch flotation experiments were made with 500-g samples of ore, each sample wet-ground to 90 pct passing 200 mesh. The finely ground ore was floated in a Fagergren batch cell at 25 pct solids. The natural pH of the Nevada ore was 8.9 and of the Korean ore, 8.5. The D, RU, K, N, and S-35 sodium silicates were obtained in colloidal dispersions with varying amounts of water. The most alkaline, Metso, was in dry powdered form. For convenience in addition, 5 pct solutions by weight were prepared from each of the silicates, on the basis of dry sodium silicate dissolved in the correct amount of distilled water. Chemical analyses of the various silicates are given in Table I, together with the pH of the 5 pct solutions. A preliminary bulk sulfide float was made with secondary butyl xanthate as the collector and pine oil as the frother. The WO] analysis of the sulfide concentrate was nearly 1 pct for the Korean ore and about 0.1 pct for the Nevada ore. The tungsten contained in the sulfide concentrate constituted about 3 pct of the total tungsten in each ore. No effort was made to recover these tungsten values. The scheelite was floated with oleic acid. Adjustments in pH were made with sulfuric acid or sodium carbonate. A 1 pct solution of 85 pct Aerosol OT was sprayed on the froth and sides of the cell during the scheelite float to aid in dispersing the minerals and to decrease the entrapment of gangue particles. Six tests were planned for each of the six types of silicate in which concentrations of 1, 2, and 4 1b of silicate per ton of dry ore were investigated at both 6.5 and 10 pH. All tests were made at room temperature. The performance of each silicate was judged from the grade and recovery of WO, in the scheelite rougher concentrate. Tungsten recovery was calculated on the basis of the scheelite remaining in the ore after the preliminary sulfide float. Testing of each silicate at three levels of concentration and two levels of pH required 36 tests with each scheelite ore. Variance analyses were performed on the concentrate grades and recoveries to determine whether or not the type of sodium silicate, the concentration of sodium silicate, or the pH significantly affected recovery or grade. Results Concentrate Grade: A variance analysis of the concentrate grades for the Korean ore showed that concentration of the silicate and pH of the ore pulp were major factors in producing a high grade concentrate. Also, the silica- to-so da ratio was important as an interaction with pH. The concentrate grade vs silica-to-soda ratio is plotted in Fig. 1. The curves show that the concentrate grade improved with an increase in concentration of sodium silicate and also

Jan 1, 1959

By Craig S. Hartley

An approximate expression is obtained for the energy of a closed dislocation loop in equi1ibriu)n with a constant net stress. The result obtained is valid for loops in isotropic or anisotropzc materials provided that they are suJficiently large that the energy per unit length of a segment of the loop can be approximated by that of an infinite straight dislocation tangent to the loop. It is shown that this approximation leads to very close agreement with a more rigorous calculation of the elastic energy of a circular glide loop. The Gibbs-Wulff Form, GWF, of a dislocation is the closed planar loop which has the smallest elastic self-energy of all possible loops having the same Burgers vector and enclosing a fixed area, A.' The energy of such a loop is related to the net resolved shear stress* required to expand the loop and to the stress required to activate a Frank-Read source.223 In the following sectiorls the problem of determining the form of the GWF is discussed and an approximate method for calculating its elastic self-energy is presented. It is demonstrated that the approximations employed lead to no serious errors when applied to a calculation of the elastic energy of a circular glide loop. This method is then used to obtain a closed form expression for the energy of GWFs in isotropic and anisotropic materials. THEORY Burton, Frank, and cabrera4 have proved that the relationship of the equilibrium shape of a two-dimensional array of atoms under the influence of the Gibbs free energy associated with unit length of its boundary, G(O), is that the polar plot of G(0) vs 0 is proportional to the pedal of the GWF.* The angle 0 is measured "The pedal of the polar graph ofG(0) vs0 is the envelope of tangents to the eraph.relative to some crystallographic reference direction. The difficulty in applying this result to a closed dislocation loop arises from the self-interaction of the loop. For a dislocation the energy analogous to G(0) is a function of the total configurati~n.~ Consequently the relation which determines the GWF is an integro-differential equation rather than the simple differen- tial equation which results when G(8) is a function of 0 alone. Mitchell and smialek3 and Brown~ have used the self-stress concept introduced by ~rown' to calculate the shapes of dislocations in equilibrium with an applied stress. In this approach the glide force on an element of the dislocation loop due to the interaction of the element with the rest of the loop is equated to the glide force exerted by the local applied stress. The shape of the loop is then adjusted so that the two forces above are equal at all points on the loop. It is possible to calculate the energies of such loops by noting that, for equilibrium with an applied stress, the energy is equal to pijbiAj (summation convention) where bi is the Burgers vector, p.. is the local net stress tensor, and Ai is a vector directed perpendicular to the plane of thd loop with magnitude equal to the area of the loop. Also Brown' has calculated the energy of a hypothetical polygonal GWF using the above technique and anisotropic elasticity. However, his indicated solution for the energy in the general case of an arbitrary GWF is only slightly less involved than an iterative solution of the integrodifferential equation referred to earlier. In the present work the approximation employed by DeWit and Koehler' is used to calculate the energy of a closed loop in equilibrium with an applied stress. That is, the energy of a loop segment, ds, is approximated by the product of ds and the energy per unit length of an infinite, straight dislocation in a cylinder coaxial with the tangent to the loop at the angular position of the segment. This is known as the "line tension" approximation. The inner cutoff radius of the elastic solution defines the core radius, while the outer cutoff radius is determined by some characteristic dimension of the loop. Actually, both of these radii vary with the edge-screw character of the segment. The effective core radius changes because of the orientation dependence of the Peierls width of a dislocation,8 and the outer radius should be the radial distance from the circumference of the loop to the center of symmetry of the area enclosed by the loop.g However, since the energy varies logarithmically with the ratio of these radii while depending directly on the effective elastic constants, only the effect of the latter is considered. This approximation also neglects the self-interaction of the loop segments. For small loops this will doubtless be extremely important, but for large glide loops produced by plastic deformation the self-interaction is not nearly so important in determining the energy of the loop. This point is illustrated by the following calculation of the energy of a circular loop. Consider a circular loop of radius R which lies in the XI - x, plane of an infinite isotropic continuum and whose Burgers vector makes an angle $ with xs. The first-order solution for the elastic self-energy is:'

Jan 1, 1970

By J. G. Faller, L. P. Skolnick

The distribution of cobalt and vanadium over non-equivalent crystallographic sites in C14-type Zr(VCo), alloys has been investigated. An anomalous X-ray scattering technique developed by Skolnick, Kondo. and lavine7 by which the separation in the scattering factors of two similar atoms can be enhanced was employed. Six alloys spanning the pseudobinary section ZrV1.6Co0.4-ZrVO.6CO1.4 at 10pct steps showed a nonrandom compositionally dependent distribution. Specifically, at high vanadium content cobalt preferentially occupied sites of type (6h) and vanadium, sites of type (2a; at low vanadium content the reverse was observed. In addition to the distribution fraction the structural parameters x and z were obtained. There was no significant deviation of these parameters from those obtained in the ideal C14 structure. Certain suggestions are made to account for the observed nonrandomness in the distribution of atoms on the two types of sites. INTERMETALLIC compounds of formula AB2 iso-morphous with MgCu2, MgZn2, and MgNi2 are known as Laves phases. Because Laves phases exhibit high symmetry and coordination numbers, the highest possible for an AB2-type compound,1 they are among the most frequently observed compounds in nature. In recent years interest has centered about the purely transition metal Laves phases2-' in efforts to understand the function of atomic size and electronic structure in the formation of these compounds. It has been observed that pseudobinary Laves phase systems often show a variation of structure across the phase diagram. Such a system is the ZrV2-ZrCo2 in which the structure varies from cubic MgCu2 to hexagonal MgZn2 to cubic MgCu2.4 Some understanding about the conditions under which the second modification is stable can perhaps be gained by studying the distribution of cobalt and vanadium atoms on lattice sites in the MgZn2 modification of the system ZrV2-ZrCo2. In both the MgZn2 and MgNi2-types there exist nonequivalent positions open to occupancy by the B element, whereas in the MgCu2 prototype all sites are equivalent. Skolnick, Kondo, and La-vine7 have developed an anomalous scattering technique suitable for this type of investigation. Whereas the influence of size on the formation of a Laves phase is well recognized, no substantial evidence has been put forth in support of the size ratio dependence of a particular prototype. Berry and Raynor8 suggested that RA /RB ratio does indeed affect the type of structure that is chosen, MgZn2 compounds tending to cluster about 1.225 while MgCu2 compounds were found at larger deviations from this ratio. Dwight,3 however, from a study of 164 Laves phases does not believe this generalization to be justified. Electronic effects are certain to play a part in the stability of Laves phases in general and in the choice of a structure type in particular. For example, size along would favor the formation of Laves compounds of Ti, Zr, Hf, Ta, or Nb as the A element with nickel or copper as the B element. The absence of such is attributed to an unfavorable electron : atom ratio by Elliott and rostoker.4 Early experiments of Laves and witte9 with pseudobinary and pseudoternary systems of the three prototypes established the dependence of crystal structure upon electron: atom ratios. They observed that the MgCu2 structure dissolved elements of higher valency until the electron: atom ratio of =1.8 was reached; the MgZn2 likewise dissolved elements of lower valency replacing zinc. witte,6 from calculations of the electron : atom volumes of Brillouin Zones, obtained limits of stability for the prototypes MgCu2 and MgZn2. Elliott and Rostoker4 used these limits with considerable success in the all-transition element Laves phases they investigated. According to witte,6 compounds between the electron :atom ratios of 1.80 and 2.32 were of the MgZn2 type; those above and below exhibited the MgCu2-type structure. On the basis of these limits and an assumed valency of zirconium based upon the near tetra-valence of titanium, Elliott and Rostoker obtained valencies for the first transition series elements. For the Laves phases with which this investigation is concerned, ZrV2 and ZrCo2, the authors calculated electron :atom ratios of 2.54 and 1.56, respectively. These ratios are for the MgCu2-type structure and straddle the stability band of the MgZn2 modification. One could, therefore, predict that a pseudobinary system ZrV2-ZrCo2 should pass through the MgZn2 modification in traversing the composition diagram from one end to the other. Implicit in this assumption is a smooth change of the electron: atom ratio from 2'54 to 1.56. MOSS10 states that his finding the low temperature structure of ZrCr2 to be C15 instead of C14 alters greatly Elliott's valency of zirconium and hence the assumed valencies of the other metals. Such a quantitative correlation of structure with electron : atom

Jan 1, 1963

By S. Luszcz, R. W. Vook, Fred Witt

In situ X-ray investigations were made on polycrys-talline silver films deposited by vacuum evaporation on (111) CaF2 and (100) NaCl single-crystal substrates at 80°K. The films were evaporated and annealed in an X-ray diffractometer attachment having a residual gas pressure of 2 x lo-' Torr. All measurements were made without exposing the films to the atmosphere. Measurements were made on the films in the as-deposited state and after various annealing treatments. The intrinsic stacking and twin fault densities, the magnitudes of the uniform and nonuniform strains, and the crystallite sizes were determined. In addition the textures in the films were measured qualitatively. The results obtained for the as-deposited films on single-crystal substrates are in substantial agreement with previously reported results for silver films deposited on glass. Intrinsic stacking and twin faults, as well as uniform and nonuniform strains, were present in these films. During the various annealing treatments (up to 350°C) the faults and nonuniform strains annealed out. Considerable grain growth and texture changes occurred also. The effects were much greater for the NaCl substrate than for the CaFz substrate. The relative magnitudes of the grain growth in the variously oriented grains could be explained qualitatively in terms of the thermal strains and strain energies introduced into the differently oriented grains during the initial, irreversible anneal. These strains were due to the different thermal expansion coefficients of the film and substrate. X-RAY diffraction measurements on evaporated films deposited on substrates at low temperature have the advantage that many of the imperfections introduced into the film during deposition are "frozen in". Thus, the influence of a very important experimental variable, substrate temperature, on the imperfection structure of evaporated metal films may be studied. Moreover, the effects of annealing such films makes possible the study of thermally activated recovery processes in these films. The present study was designed to determine the influence of single-crystal substrates on the resultant film structure relative to the previous results obtained using glass substrates.' To this end great care was taken to keep the experimental variables the same in the two cases. Different experimental conditions would, of course, result in films having different physical properties. Again the initial substrate temperature was in the neighborhood of 80°K and the films were subsequently annealed to 350°C. The pure metal silver was chosen for evaporation, primarily because of its relatively low stacking fault energy and consequent high fault density in the as-deposited state. The silver films were formed by evaporation onto air-cleaved {ill} CaF, and (100) NaCl surfaces cooled to 80°K in an X-ray diffractometer attachment2 having a base residual gas pressure of 2 X l0-' Torr. The films were not exposed to the atmosphere until all of the X-ray data had been recorded. In this way one of the most important experimental variables, environment, could be well-controlled and reproduced. X-ray measurements were made at the temperature of deposition and included determinations of the diffraction line peak positions, line shapes, and integrated intensities. The peak position measurements were used to determine the intrinsic stacking fault densities and the average uniform strain in the film. The shapes of the diffraction lines provided information on the twin fault density, true crystallite size, and average nonuniform strain. The preferred orientation in the film was determined qualitatively from the integrated intensities. I) EXPERIMENTAL PROCEDURE The evaporator attachmentZ was charged with 99.999 pct Ag pellets positioned in a tantalum filament which had been outgassed previously at l0-8 Torr. The CaFz and NaCl single crystals were cleaved in air and then placed in position in the chamber so that their cleavage surfaces were on the diffractometer axis. The chamber was prepumped using a sorption pump, sealed off, and then baked at 150°C for 24 hr. The ion pump operated during the bakeout cycle. The substrate was then heated to 500° C by means of an auxiliary heater and kept hot until the rest of the chamber was cooled slowly to room temperature. This bakeout procedure consistently resulted in an ultimate pressure in the low lo-' Torr range. The substrate was then cooled down on 80°K. Its temperature was monitored by a thermocouple wedged into the rear of the copper substrate holder. The diffracted intensity and peak position of the 111, 222, and 333 CaF, lines were measured prior to evaporation. Nickel-filtered, pulse-height-discriminated copper radiation was used. Similar measurements were made for the 200 and 400 lines from NaC1. These measurements were used as a lattice parameter check and to determine the thickness of the evaporated silver films from the attenuation of the substrate lines. The evaporation rates were approximately 3A per sec for both films while the maximum pressures during evaporation were 3 x lo- ' and 7 x 10"8 Torr for the CaF, and NaCl cases, respectively. The film thickness was measured by the attenuation of the CaF, and NaCl substrate lines and by at optical interference method. Values of 1700 and 1500A, respectively, were obtained for the silver

Jan 1, 1969

By Edward Steidle

Those who have followed the rapid progress in rock-dusting bituminous-coal mines must admit that opinion crystallized during the year just closed in support of this preventive of coal-dust explosions. Up to 1924 only one mining company in America practiced rock-dusting on a large scale, but during 1924 forty-two companies had adopted this safety measure, and the "boom" is expected to extend over the next two or three years. Alabama is represented by 1 company, Colorado by 3, Illinois by 4, Kentucky by 1, New Mexico by 4, Pennsylvania by 20, Utah by 8, and Wyoming by 1. A total of about 500 miles of entry has been dusted. Illinois leads with 275 miles of dusted entries and Pennsylvania holds second place with about 175 miles. In each case there is a sense of great security, not only on the part of the operator but by the miner as well. It is also interesting to note that during 1924 the compensation rating or inspection bureaus in twelve of our coal-producing states revised their rating schedules so that a credit would be given for rock-dusting. This credit ranges from 10 to 20 cents per $100 payroll. Recent drastic federal and state regulations approved by mine operators made rock-dusting compulsory in bituminous coal mines in Utah, beginning July 1, 1924. Legislative action favorable to rock-dusting may be expected in other states. Colorado has already proposed a change in its laws, and Pennsylvania, Maryland, Washington, and West Virginia are giving the matter consideration. If the rock-dusting problem is handled properly and proves to be entirely successful, no mining man of any standing will delay applying it in his mine. State legislation regarding this matter may or may not solve the problem. At present, the mining companies that are rock-dusting of their own choice are doing it carefully and thoroughly. In Utah, some are doing it conscientiously, trying to get what benefits can be obtained while others are reported to be doing it only to keep within state regulations. In any event, if we are to have new legislation, it is essential that the various states know what they are about and then, if possible, work for uniform regulations.

Jan 1, 1925