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By Anthony Folger, Charles E. Straub

Kansas produced 38,150,878 bbl. of oil in 1928 and 40,658,170 bbl. in 1929, thereby retaining its rank as fourth among the oil-producing states of this country. Production for 1928 was less than that for 1927 (Fig. 1) because of a decrease in the number of completions, but the average initial production per well (Table 1) shows an increase due to the completion of wells of comparatively large capacity in the new Valley Center pool of Sedgwick County. This increase in average initial production per well was further augmented during 1929 by completion of additional wells of comparatively large capacity in the Valley Center pool and the new Greenwich pool of Sedgwick County. Production for 1929 exceeded that for 1928 and threatened to exceed all records except that of 1918, however, production was prorated in

Jan 1, 1930

By T. Airaksinen, R. T. Hukki

A new static pneumatic classifier for the primary separation of the feed material for microclassification is discussed. Pilot plant test results and a novel flowsheet for microclassification at the industrial scale are presented.

Jan 1, 1980

By David LeCount Evans

Not only E. B. Mayo but also W. C. Lacy, who apparently urged the preparation of this analysis, is to be commended. Regional thinking of this type is needed to assure future success in the never-ending search for new mineralized and petroliferous districts. As is usually the case, here is a regional study that will be read by the mining geologist alone. It is ironic that several of the trends established in this study have suggested themselves in northern mid-continent, detailed, and regional studies. These, where established, have offered new keys to petroleum exploration and have provided a possible basis for unraveling a number of broad generalities. The oil geologists, active in Colorado, Kansas, and Oklahoma, would find much food for thought in Mr. Mayo's projections.

Jan 6, 1959

By D. E. Light, J. Y. Somnay

The use of alkyl acid phosphates and their alkali salts as collectors for the uranium minerals brannerite and uranothorite was investigated. In particular a detailed flotation study was carried out using isooctyl acid phosphate as a promoter. Tests were conducted on an Elliot Lake ore analyzing 0.11% U 3 O 8, chiefly as brannerite, and approximately 9% pyrite. Pyrite was floated with conventional reagents; the flotation of brannerite from the sulfide tails was studied to determine the optimum pH and pulp density to employ with isooctyl phosphate. 4 uranium recovery of over 90% was possible with a selectivity index of 8.95 when these tails were floated at 17% solids and a pH of 1.7. The effect of various modifying agents was also investigated. Aluminum sulfate, lactic acid and sodium silicate improved the selectivity of collection yielding selectivity indices of 9.5 to 11.5. Ferric chloride was found to be a depressant for brannerite. A Bancroft ore which analyzed 0.13% U308, and contained uranothorite was also amenable to flotation using isooctyl acid phosphate. The composite uranium concentrate obtained assayed 0.41% U308 at a recovery of 95.3% and a ratio of concentration of 3.24. Previous investigations1,2 on the flotation of brannerite, pitchblende, uraninite and/or uranothorite from various Canadian ores showed that fatty acids, including oleic acid and tall oils, petroleum sulfo-nates and alkyl acid phosphates, were suitable collectors for these uranium minerals. Additional work carried out by the Mines Branch in Ottawa on brannerite ores from the Elliot Lake area3 used the tall oil Acintol FA-1, or FA-2, as a collector. A recovery of 92% of the uranium in a concentrate which contained about 55% of the weight and assayed 0.2% U3O8 was obtained from a feed of 0.1% U308 in this latter instance. Eigeles et a1.4 carried out flotation on pitchblende ores and found that the most promising results were obtained with alkyl acid phosphates and their alkali salts as collectors. Within the homologous series of alkyl phosphates, the best flotation characteristics were displayed by isooctyl phosphates. Further, isooctyl phosphate derivatives were much less sensitive to hardness forming salts than oleic acid, enabling all flotation tests to be made with tap water. This paper describes tests employing alkyl acid phosphates for the flotation of ores containing brannerite and uranothorite. The flotation work described herein was conducted in conjunction with the development of a leaching process for Elliot Lake, Ontario, brannerite ores. In this process pyrite in the ore was concentrated by flotation and roasted, providing sulfur dioxide which was used to produce sulfuric acid in situ in a liquid-solid extraction process. A 40% conversion to sulfuric acid was indicated at a leaching temperature of 80°C; this resulted in the extraction of 93% of the total uranium after a contact period of 6 hr. A rotary kiln was used as a leaching vessel. Preconcentration by flotation was studied in conjunction with the above process to reduce the bulk of solids for leaching and, consequently, capital expenditure. The materials and methods used in this study will be described initially. Then the results will be presented in two sections, the first dealing with the brannerite ore, and the second with the uranothorite. Finally an economic analysis of the results on the brannerite material will be made. MATERIALS AND METHODS The two ore samples examined were from uranium-producing mines. One was a brannerite ore, a uraniferous quartz pebble conglomerate from the Elliot Lake area, which contained 0.11% U3O8, 4.3% S and 4.5% total Fe. Mineralogical studies of similar samples indicated the presence of quartz, microcline, sericite, pyrite and minor quantities of rutile, pyrrho-tite and zircon. The other ore was from a biotite-rich pegmatite in the Bancroft area; feldspar, quartz and biotite formed the major gangue components. Uranothorite was the principal uranium mineral; the head assay was 0.13% U 3 O 8. Preparation of Feed: The ores were crushed to —10

Jan 1, 1963

By Chas. F. Jackson

IN these days the headlines and spotlight have been focused largely upon the new processes developed and new plants erected to meet the multiplied demands for mineral products required for prosecution of the war. By comparison, the less spectacular achievements of the miner, who is meeting the demand for raw material without which these processes and plants would be useless, have received little attention. Attendance at the mining meetings here reported was small, averaging about 35 to 40, but interest was as keen as ever, and evidenced to your reporter that the miner is no less on the job than is the metallurgist. It is evident that the mine operators are not neglecting any improved methods and practices in their struggle to produce more in the face of diminishing labor supply.

Jan 1, 1943

By W. A. Boyer

If the safety factor of a mine hoisting rope is checked for the lowest depth, is the rope then safe for all levels? The answer here is no. A new set of volues is proposed. HOISTS for metal mines are seldom designed for one particular depth. They are intended for an ultimate load and depth with a given speed but are first used to hoist from a shallower depth, gradually working to the ultimate as development progresses. Sometimes the mine is not worked on the upper levels because of the kind and grade of ore, the mining of which depends on market conditions. In this case the hoist may be used in the same working shift to lift ore, for example, from the 1200 and the 4400-ft level. This means that the safety factor of the rope should be considered not only when it hoists from the greatest depth, but also when it hoists from the upper levels. According to present safety factor standards, a hoisting rope can have ample safety margin when hoisting from the lower or lowest level and still be shy of sufficient safety margin when hoisting from the upper levels. This will be shown by curves presented in this paper. The safety factor of a hoisting rope as defined by the U. S. Bureau of Mines' is the ratio of the static load to the tensile strength of the rope. It is calculated by dividing the breaking strength of the rope* In Fig. 1 curves A and B are plotted against the vertical suspended distance, which is the abscissa, and the factor of safety, the ordinates. Curve C is a smooth curve drawn through the midpoints of the steps of curve A and would more closely represent the minimum factor of safety for new rope for any particular depth. Curve D is a smooth curve drawn through the midpoints of the steps of Curve B and would more closely represent the minimum factor of safety when ropes should be discarded for any particular depth. If a new rope were applied with a minimum factor of safety, then the vertical distance or ordinate under curve D for any particular depth, divided by the vertical distance or ordinate under curve C, would represent the minimum percent of remaining area intact that could be allowed before the rope would be discarded. Also, that section of the ordinate between curve C and curve D is proportional to the section of the area of the new rope that could be allowed for wear and broken wires. Considering that point at 2500 ft on the chart, the ratio do to co would be the minimum percent of rope area remaining at the point of discard. The ratio of that portion of the ordinate cd to co would represent maximum percent of area of a new rope available for wear and broken wires.

Jan 1, 1955

During the war period of quicksilver activity there were a number of departures from what may be termed the classical quicksilver metallurgy. Attempts were made to beneficiate low-grade ores by gravity concentration and flotation; mechanical furnaces began to replace the Scott furnace and the vertical coarse-ore furnaces, and condensers of sewer tile and redwood tanks were used in place of the older brick and stone condensing chambers. Other developments that have occurred during the current period of quicksilver activity are mainly in the nature of improvement and further refinement of those started during the war period. Each period of quicksilver activity has been accompanied by the proposal of various new processes, including wet methods for the treatment of quicksilver ores and innovations in furnaces, retorts and condenser equipment. As far as the author knows, nothing of economic significance in the way of "new processes" has been developed. There is in fact no real need for any essentially new process for the treatment of quicksilver ores; the direct furnace treatment is simple and inexpensive. Moreover, with rare exceptions, the quicksilver industry has no complex or refractory ore problems corresponding to those which are receiving more and more attention from metallurgists in other branches of the nonferrous field. Untler these conditions improvements in quicksilver metallurgy must be looked for through the adaptation of current developments in engineering and metallurgy generally to the particular needs of quicksilver practice rather than through the invention of new processes. Preliminary Treatment of Quicksilver Ores At Sulphur Bank, in the treatment of old dump material left by the early operators, wet screening is being used as a preliminary step in concentration ahead of flotation. Power shovels and trucks are used to deliver some 400 tons of ore per day to the lower terminal of a hoist, which in turn discharges the material at the top of the screening plant. Wet screening is carried on in two stages. Depending on the character of the material, 1-in. or 2-in. punched screens are used on the first trommel.

Jan 1, 1930

By G. F. Loughlin

Nearly 55 years have elapsed since the U. S. Geological Survey was organized. During this period the mineral industries have grown from infancy or early childhood to well developed maturity, and some mining industries appear to be declining. Decline in mining is even more conspicuous in certain districts, or even states, than in any mining industry as a whole, and discoveries or developments of important new districts have been very few in recent years. Our reserves of most metals and nonmetals are adequate for many years of normal production, subject to changes in rate of exploitation that may be caused by foreign competition and by changes in technology and market conditions; but the declining production of many districts and the scarcity of important new discoveries to compensate for them is cause for some apprehension. It is likely that future production will depend to a considerable extent on deep exploration and on the thorough examination of places in and adjoining existing districts where significant outcrops are lacking and only apparently insignificant geologic features offer encouraging clues—more so than on the discovery of entirely new districts. Even the possible discovery of new districts, which have escaped the intensive search by the nontechnical prospector, must be dependent on geologic information. There is therefore no need for argument as to the value of geology to the mining industry; and the need of continuing to advance the science. The U. S. Geological Survey's past contributions to mining geology, as expressed in its official reports and other publications, are recognized by Ransome in his historical review of mining geology in the Lindgren volume.' These contributions have helped to form the basis of modern mining geology, which has grown rapidly in the last 25 years. This growth has witnessed the organization and maintenance of geologic staffs by mining companies in several districts, and their detailed work, together with the fact that nearly all of the larger mining districts have

Jan 1, 1935

PRESIDENT AND DIRECTOR CHESTER A. FULTON NEW YORK, N. Y. PAST PRESIDENTS AND DIRECTORS EUCENE MCAULIFFE OMAHA, NEBR. C. H. MATHEWSON NEW HAVEN, CONN. TREASURER AND DIRECTOR ANDREW FLETCHER NEW, YORK, N. Y.

Jan 1, 1944

By Charles Bohdanowicz

Production of crude in 1937 decreased (Tables 1 and 5) by about 2 per cent, while gas production for that period increased by about 6 per cent after a slight decrease in 1936 (0.4 per cent).' As in preceding years, drilling operations were confined principally to extensions of old oil fields in the Jaslo district (fields 1 and 7) and to some extent to such extensions in the Stanislawbw district (field 27). Deepening of old wells to horizons reached more recently by new wells gave on the average better results per well than those attained by new wells (Table 3). Reserves of proved lands have increased some by new oil fields discovered, Targowiska (field 8) and Czarna (field 19) both of which, however, have only small production. The Daszawa gas field (field 25) has not been extended, but two new gas fields were located instead— Opary, distant 25 km. (151/2 miles) northwest of Daszawa, Balicze at 12 km. (7 1/4 miles) southeast of Daszawa, and Kalusz (TESP Company exploiting potassium salts) in the vicinity of the town of that name (field 33). Drilling upon the gas area near Tarnbw and Debica, while gas-bearing sandstone had been found at depths of from 300 to 512 meters (984 to 1680 ft.) (Zdziary No. 2) and at 220 m. (722 ft.) [pressure 11 atmospheres, flow 24 cu. m. per min. (847 cu. ft.)] (Przyborbw No. l), has not as yet ascertained horizons qualified for permanent exploitation. The exploring well near Kos6w remained for the last seven months at the depth of 1420 m. because of the collapse of rotary drilling pipe. Below the 300-m. level no gas sands have been encountered at this well. Gas Reserves In connection with the broad plan of developing industrially the sector of Poland lying between the Vistula and the San Rivers, and extending farther north as far as the city of Radom, there arose the necessity of a more accurate calculation of gas reserves for the fields of

Jan 1, 1938

By D. H. Newland

On the bulk basis New York's contribution to the production of oil is small, representing, as it does, a bare half of one per cent of the annual total for the United States. Yet it has more importance than is implied by such a statement. Petroleum includes a variety of organic compounds, some more and some less valuable. It would be a fairer estimate of the situation to say that New York in recent years has produced around 10 to 12 per cent on the average of all Pennsylvania grade oil, the supply of which is strictly limited and the demand steady even in times of overproduction of other grades. One may not infer from this that New York and other Appalachian states enjoy an independent position in the market with a price structure uninfluenced by that of the Mid-Continent, Gulf or California fields. On the other hand, the recent market demoralization in the South and West brought about by uncontrolled production caused prices to drop to a point where the life of the local industry was seriously threatened. The current cost of producing oil in New York under the methods of water-flooding, by which most of the output is now obtained, has been estimated by competent authority at not less than $2.50 a barrel. The

Jan 1, 1934

THE first session of the Institute was held in the hall of the Washington University, Wednesday evening, May 27th, President Raymond in the chair. After the address of welcome by Hon. Thomas Allen, and the reply of Mr. Raymond, the following names were presented for election as members and associates, duly indorsed by the Council. They were unanimously elected : *Henry Booth, - New York City. *Charles H. Morgan, - Worcester, Mass. *Howard Painter, - West Chester, Pa. *Dr. M. J. Goodfellow, - Eberhardt, White Pine Co., Nevada *Otto Wittelshach, - Eureka, Nevada. *John T. Williams, - New York City. †Charles A. Young, - Philadelphia. *Charles E. Stafford, - Boston, Mass. *Arnold Hague, - Orange, N. J. *Richard Pearcé, - Black Hawk, Colorado. *W. R. Maffet, - Wilkes-Barre, Pa. *Prof. George A. Koenig, - University of Pa., Philadelphia *Prof. R. Nutting, Jr., - Indianapolis, Indiana. *Edwin Mickley, - Hockendauqua, Pa. *G. C. Broadhead, - St. Louis, Mo. *Dr. Adolph Schmidt, - St. Louis, Mo. *Alexander Leonhard, - St. Louis, Mo. *Edward D. Meier, - St. Louis, Mo. *John W. Meier, - St. Louis, Mo. *Prof. Forrest Shepherd, - St. Louis, Mo. *Edward Walsh, - Pilot Knob, Mo. *George Riggs, - St. Louis, Mo. †Col. Chas. B. Parsons, - Cadet, Mo. † W. A. Scott, - Mine La Motte, Mo. *Prof. Paul Schweitzer, - Columbia, Mo. *William E. Guy, - St. Louis, Mo. †William Harris, - St. Louis, Mo. *Henry Black, - Pittsburgh, Pa. †W. Noyes, - New York City. *W. Lorenz, - Philadelphia. †E. A. Whetmore, - New York City. * Members. †Associates.

Jan 1, 1875

By F. Milton Lewis, Edward S. Frohling

The information which is required for' a preliminary feasibility study and the additional information which is required for the final feasibility study on a new mineral deposit are discussed. The preliminary feasibility study is made from very little information and at a minimum cost to the owner. However, the outline for the preliminary report is similar to the one used in the final report. In this manuscript, it is assumed that the results from the preliminary study are favorable and the owner authorizes a final feasibility study by an outside engineering company. The type of organization for completing this final feasibility study is described. The final reports includes all information and data relative to this new mineral deposit. This information is presented so that it may be understood by financial people as well as by technical people.

Jan 1, 1978

By R. C. Edwards, Will Mitchell, T. G. Kirkland

THREE years ago, when the Process Research Laboratory at Allis-Chalmers Manufacturing Co. sought a remedy for the increasing cost of disposing of great quantities of spent sands from foundries, R. C. Edwards developed a continuous inclined paddle scrubber which removed a substantial amount of the charred coatings from the grains with a surprisingly small amount of degradation of the sand itself.1 The satisfactory results obtained on foundry sand, using this piece of equipment in conjunction with classification, suggested that a similar procedure could probably be applied to the cleaning of other sands, such as those required by the glass and chemical industries. This paper describes the flowsheet and the results of tests performed on impure natural sands. The four materials tested were silica sands obtained from widely separated geographical areas. Three of the sands tested contained various amounts of iron oxide and the fourth an excessive amount of calcareous bonding material. The iron oxide was present predominantly in the form of grain coatings, which were scuffed by the paddle scrubber, and in all cases a product was manufactured which would meet one of the sets of specifications imposed by the glass industry' The Edwards paddle scrubber used in these tests consists of a rubber-lined steel cylinder 18 in. in diam and 48 in. long, mounted on a frame so that its slope can be varied 5 ° to 35º from horizontal. This variable slope permits controlled flow of material through the machine. Rubber paddles rotate inside the cylinder and are secured to a center shaft 2 in. square, which extends through the entire length and is turned at both ends so that it can be supported by sleeve bearings centrally fixed in the end plates of the shell. At the upper or feed end it extends through the bearing on the end plate into a sheave, to which the motor drive is connected by means of Texrope transmission. The four sets of paddles mounted on the shaft, two in each set, are made of rubber belting, 1/4 in. thick, 9 in. wide, and 16 in. long. The two paddles in each set are secured on opposite sides of the square shaft, but in the same longitudinal position along the shaft axis. In other words, the two paddles in the set operate 180° apart. Each successive set is mounted 90º from the preceding one. One end of each paddle is bolted to the square shaft and the other weighted by a steel bar, 1x1 ½ x9 in. long, which is attached about 1/ 2 in. from the outer tip of the paddle. By centrifugal force at proper shaft speed, these weights force the paddle surface to rub smoothly against the rubber lining of the cylinder. During operation, the sand forces its way between the paddle face and the surface of the cylinder, providing the necessary abrading action as the pulp flows by gravity down the length of the cylinder. The capacity of the machine is limited by the amount and the hardness of the coating material and by the quality of product desired. The degree of scrubbing is governed by the retention time in the scrubber, which in turn may be changed by varying the feed rate, water content of the feed, and

Jan 1, 1952

ANNUAL MEETING OF THE NEW YORK SECTION - The annual meeting of the New York Section was held at the Machinery Club, May 7. While the dinner, at which fifty attended, was in progress, the names of the nominees for next year's officers were posted. The result of the election was as follows: Chairman, E. P. Mathewson; vice-chairmen, William Y. Westervelt, R. M. Atwater, Jr.; treasurer, Wilber Judson; executive committeemen, Lucius W. Mayer, Edwin S. Berry. The subject for the evening was "Organization and Campaign in France of the 27th Engineers." Colonel O. B. Perry described the many difficulties surmounted, for it was necessary to work with untrained men ALLEN H. ROGERS WALTER S. DICKSON CHAIRMAN OF NEW YORK SECTION SECRETARY OF NEW YORK SECTION and shortage in supplies. He described the unusually fine character and physique of his officers, which made it possible to make the untrained men most efficient. He described in some detail the work of building bridges over the Meuse River and the bringing up of supplies to the first army base, in particular at the Argonne-Meuse sector; General Pershing gave a personal commendation of the work undertaken by this regiment. The Colonel described the methods of operating the transportation of ammunition and supplies to the "army dumps," by which at the time of signing the armistice there had been brought up 600,000 tons of equipment for use in the projected campaigns. An interesting item was that 3,600,000 sand bags had been provided, in case the Germans should be able to turn the line of the American troops. Captain Edwin S. Berry described the methods of sending materials to the front lines and gave figures to indicate the huge quantities required, adding that the order of preference was troops, ammunition, food, and engineers' supplies. The speakers then answered several questions given by the members present. WALTER S. DICKSON, Secretary.

Jan 6, 1919

By R. M. N. Pelloux

This study of aluminum-copper alloys had two aims: 1) To determine the effect of the amount and distribution of a second phase, CuAl2, on the creep-rupture strength, ductility, and fracture characteristics of the alloys. The work of Gemmell and grant' on single-phase aluminum-copper alloys provided a basis for the present study. 2) To attempt to provide a relation between the microstructure and strength of two-phase alloys deformed at comparatively high temperatures (greater than 0.45 T,). The creep behavior of the two-phase magnesium alloys Mg;Ce and Mg-A1, has been treated by Roberts. 9 In work reported by Sully and Hardy4 and by Underwood, Marsh, and Manning~ on A1-Cu two-phase alloys, and also in a portion of the work of Gemmell and grant,' aging took place during the creep tests. 'In the present work, overaged aluminum-copper alloys were subjected to creep deformation at two temperatures, 500 and 700OF. The overaging treatments to produce the precipitate dispersions were performed prior to the test, at temperatures which were the same as the ultimate respective test temperatures. Hence, the present study is concerned with the creep behavior of stable (in contrast to "underaged") two-phase A1-Cu alloys, i.e., alloys in which no depletion of the solid-solution matrix occurred during: creep. MATERIALS AND PROCEDURE A 2 and a 3 pct Cu alloy, supplied by Alcoa, were studied; Table I shows the compositions. The grain size of the specimens, 0.9 to 1.0 mm, was achieved by annealing the machined test bars for 2 hr at 1000°F, followed by furnace-cooling to 900°F, and homogenizing for 4 hr. Both compositions are in the single-phase condition at 900°F. Two types of overaged dispersions, termed "over-aged I" and "overaged 11" were prepared after the grain size and the homogenization anneals. The overaged I alloys were prepared by quenching to room temperature after homogenization, aging at either 500' or 700°F for 72 hr, and air-cooling to room temperature. The overaged I1 alloys were prepared by furnace-cooling after homogenization, to either 500' or 700°F, and holding at the necessary temperature for 72 hr. The times for furnace-cooling from 900°F to 700° and 500°F were, respectively, about 2 and 3.5 hr. The structures of the A1-2 pct Cu alloys are shown in Fig. 1 (overaged I) and in Fig. 2 (overaged 11). A comparison of Figs. 1 and 2 shows that in the overaged I alloys the precipitate particles along the grain boundaries are much more closely spaced and the grain boundaries are straighter than they are in the overaged I1 alloys. Further, the particle size and spacing in the grains are smaller than in the overaged I1 alloys. Microstructures of the A1-3 pct Cu alloys have not been shown; the structures of these alloys differed from those of the A1-2 pct Cu alloys only in that the distribution density of the particles was greater. The creep specimens had a gage section 1 in. long with a diameter of 0.155 to 0.195 in. Before testing, specimens were electropolished in a solution of 100 cc glacial acetic acid, and 30 cc of 60 pct perchloric acid, at 40' to 50°F, at 24 v. The specimens were kept refrigerated prior to testing to avoid precipitation at room temperature. Constant stress creep tests were conducted; the load was applied 75 min after heating of the specimens to test temperature had begun. EXPERIMENTAL RESULTS Creep-Rupture—Fig. 3 shows the log stress-log rupture life plotfor the overaged alloys studied, and also for the underaged A1-2 pct Cu alloy.' At 700°F, the stress-rupture life relationship is nearly independent of both the amount of precipitate (i.e., composition) and of the type of overaging treatment (i.e., precipitate dispersion). At 500°F it is apparent that the increase in rupture life that was ex-

Jan 1, 1960

By J. F. Smith, J. E. Davison

A value for the enthalpy of formation of z2 of -3.14 i 0.21 kcal per g-atom has been measured by the technique of acid solution calorimetry. This result is in quite good agreement with two earlier determinations by tin solution calorimetry and by direct reaction caloriinetry, and averaging of values determined from the three independent calorimetric techniques gives enhanced precision and accuracy with AHh8 (CaMgZ) = - 3.15 i 0.05 kcal per g-atom. For comparison with experimental data, values for the enthalpies of formation of CaMgz, SrMgz, and BaMgz of -9.8, -7.9, and -2.8 kcal per g-atom were estimated from a calculation based on the LVigizer-Seitz approximation as modified by Raimes for polyvalent elements. While complete quantitative accord between these calculated talues and available experimental data is lacking, nonetheless numerical accord is better than might be expected and, more importantly, parallel numerical trends are observed between experimental and calculated vnlues. WITHIN the past decade the enthalpy of formation of CaMg, has been determined a) from measurement of magnesium vapor pressures over binary Ca-Mg alloys,' b) by solution calorimetry with liquid tin as the solvent,' c) from measurement of hydrogen vapor pressures over ternary alloys of calcium, magnesium, and hydrogen,3 and d) by direct reaction alorimetr. The value from tin solution calorimetry is the most precise and is probably the most reliable, and this value is within the quoted uncertainties of the other three experimental results. The overall agreement among the four independent investigations is quite good, particularly so when the diversity of techniques is noted. On the basis of this agreement, CaMgz was chosen as a test material to evaluate the operation of a newly constructed apparatus for the determination of enthalpies of formation of intermetallic phases by acid solution calorimetry. This was believed to be a severe test because of the high chemical reactivity of both calcium and magnesium which reactivity presumably accounts for the fact that an early determination5 of the enthalpies of formation of Ca-Mg alloys by acid solution calorimetry yielded values significantly more negative than the four recent determinations. EXPERIMENTAL APPARATUS AND MATERIALS Experimental Apparatus. The enthalpy of formation of CaMg, was determined by measuring the difference between the heat evolved when dissolving the metallic compound and the heat evolved when dissolving equivalent amounts of unreacted metallic elements in hydro- chloric acid. This was done differentially with an apparatus consisting of twin calorimeters which were constructed to be as nearly identical as possible. The advantage of differential calorimetry is that systematic errors arising from the individual calorimeter design tend to cancel. A schematic representation of the apparatus is shown in Fig. 1. A dead air space around both calorimeters was provided by a large, thermally insulated jacket. Each calorimeter consisted of a 2-liter Dewar flask which was completely enclosed in a copper container. Each Dewar contained 1600 g of 2.5hr HCl to act as the solvent, and thermal effects resulting from solvent evaporation were minimized by covering the acid with 50 g of mineral oil. There was no detectable reaction between the acid and the mineral oil. Equivalent amounts of mechanical energy were added to the calorimeters through twin stirring rods which were driven at the same rpm by a single motor with the intent of the stirring being to maintain thermal equilibrium throughout the solvent. To calibrate the heat capacities of the calorimeters, known amounts of electrical energy could be added by passing measured voltages and currents for known times through submerged heaters, approximately 20 ohms, which were wound noninductively from Manganin wire. A 6-v storage battery was used as a power source, and a dummy heater was used as an exercise circuit to allow the battery to stabilize at a constant electromotive force before energizing one or the other of the calorimetric heaters. A type K-2 potentiometer was used to measure the potential drop across an energized heater while the current was determined from the potential drop across an external standard resistor. Times of energization were measured with an electric timer, and the electrical energy supplied to a heater

Jan 1, 1969

By John W. Wagner, Robert K. Willardson

Single crystals of Pbl-xSnxTe have been grown from nonstoichiometric, cation-rich melts with the objective of producing as-grown, bulk material containing carrier concentrations ranging from 1016 per cu cm to 1018 per cu cm. Three specific crystal composi-tions were investigated in detail; x = 0.00, 0.10, and 0.17. Pull rates of from I to 3 mm per hr were used. Single crystals were successfully pulled from melts containing as little as 30 at. pct Te. Hall coefficients, resistivities, and carrier mobilities of these materials were determined. The relationship between the composition of the melt and the carrier concentration in the as-grown crystal has been studied for the three crystal compositions of interest. BULK single crystals of Pb,-,Sn,Te have previously been grown from stoichiometric melts.1,2 Such crystals are p-type and have relatively high carrier concentrations ranging from -9 x 1018 per cu cm for PbTe to -8 x l020 per cu cm for SnTe at 77°K. These carrier concentrations result from deviations from stoichiometry (lead vacancies) in the as-grown crystals. Since lower carrier concentrations are desirable for electrooptic device applications, these crystals are usually subjected to long-term, isothermal anneals.' This paper reports on the growth of Pbl-xSnxTe single crystals from nonstoichiometric melts with the primary objective of producing as-grown material containing relatively low (1016 to 1018 per cu cm) carrier concentrations and also reports on the general characteristics of these crystals. The phase relationships in the Pbl-xSnxTe systems are such that materials solidifying from nonstoichiometric, cation-rich melts will have smaller deviations from stoichiometry than materials grown from stoichiometric melts. Fig. 1 is the T-x phase diagram for PbTe in the vicinity of the stoichiometric composition.3 A crystal grown from a stoichiometric melt will solidify at a melting point maximum at which the solid will contain -0.5002 atom fraction of tellurium. PbTe single crystals grown in our laboratories from stoichiometric melts have carrier concentrations of 9 x 10" per cu cm, indicating that the excess tellurium in the crystals is as expected from this phase diagram. However, growth of PbTe from a lead-rich melt will result in material having a more nearly stoichiometric composition. Although the addition of Sn to the melt shifts the solidus curve further toward the tellurium-rich side,4 the general discussion given for PbTe applies to the Pbl-xSnxTe systems as well. EXPERIMENTAL Single crystals of Pb1-xSnxTe have been grown in our laboratories from nonstoichiometric, cation-rich melts using the Czochralski technique and boric oxide liquid encapsulation. The details of the growth apparatus and growth technique have been reported in a previous paper on growth of these alloys from stoichiometric melts.2 In the present study, three specific crystal compositions were investigated in detail; x = 0.00, 0.10, and 0.17. Growth of alloy crystals from nonstoichiometric melts requires considerable care, and good quality single crystals were obtained in this study only by optimizing the mechanical and thermal stability of the growth system and by using pull rates of from 1 to 3 mm per hr (Pbl-xSnxTe crystals are easily pulled from stoichiometric melts at rates of from 5 to 10 mm per hr). The liquid encapsulation technique was found to yield near-ideal conditions, since the B2O3 layer increased the thermal stability at the growth interface, permitted easy attainment of near-ideal thermal gradients, and dampened vibrations at the melt surface. The hygroscopic character of the B2O3 was a slight problem and vacuum heat treating was necessary to completely remove the water from the boric oxide. During initial growth, the seed diameter was reduced and a narrow neck (1 to 2 mm diam) of several millimeters length was grown. The latter steps were found to be necessary for the growth of single crystals, i.e., if either of these two requirements were

Jan 1, 1970

By P. R. Hines

Diphenyl guanidine is used as an accelerator in vulcanizing rubber. Other rubber accelerators are also flotation collectors, e.g., dithiocarbamate, thiazole, and the xanthates. Urea and its derivatives are good flotation collectors,' and guanidine is the nitrogen analog of urea. These two characteristics suggested testing diphenyl guanidine as a flotation collector. Diphenyl guanidine has been tried in flotation work previously, but references give no details.'.' Bunker Hill Co. of Kellogg, Idaho, supplied the ore sample used in these tests. The sample was typical of the ore milled in 1949 and contained 4.52 pct Pb and 1.08 pct Zn. A flotation test made by the author with potassium ethyl xanthate as a collector, the same flotation reagents, and the same grind employed in regular Bunker Hill mill practice was the standard for comparing results with the compounds and derivatives of guanidine. The compounds and derivatives of guanidine are only fair collectors of galena. However, if potassium ethyl xanthate were used in the galena float, its presence later in the sphalerite float would make it impossible to introduce another type of collector and be certain which collector contributed the result, so the compound or derivative of guanidine under test was used in both the galena and sphalerite floats in Table I. On both the galena and the sphalerite in the Bunker Hill ore, the depressing action of sodium cyanide and zinc sulfate is much greater with collectors of the guanidine type than with the xanthates. If the depressing agents are left out when a guanidine type of collector is used, but a pH of 8.6 is maintained with either lime or sodium carbonate, the depressing action is approximately the same as in the standard xanthate test. Consequently the depressing agents, sodium cyanide and zinc, were not used in the galena floats of tests 1226, 1228, and 1286, Table I, so the galena floats would be on a comparable basis with the standard xanthate test. As shown by the tests in Table I, the loss in the tail when diphenyl guanidine is used is 8.3 to 9.3 pct, as compared to 17.6 pct with potassium ethyl xanthate, or a recovery of 2.3 to 2.0 lb more zinc. Concentrate grade is 13.7 pct with potassium ethyl xanthate and increases to 22.9 and 31.8 pct with diphenyl guanidine, showing a much higher selectivity. Unless the Barrett's No. 4 coal tar creosote is considered to be a collector, no collector other than diphenyl guanidine is present in the tests, Nos. 1226, 1228, and 1286. Tests 1218, 1253, and 1263 in Table I1 were run to check the effect of the depressing agents used in flotation of the galena (sodium cyanide and zinc sulfate) upon subsequent flotation of sphalerite by diphenyl guanidine. Urea was substituted for potassium ethyl xanthate in tests 1253 and 1263 because it is a good collector for galena and a poor one for sphalerite, and the effect of the depressing agents is more marked with urea than with potassium ethyl xanthate. Test 1205 checks the effect of urea alone without any depressing agents when used for the flotation of galena. Table I1 shows that diphenyl guanidine as a collector for sphalerite is compatible with other flotation reagents used in floating galena. When the depressing agents sodium cyanide and zinc sulfate are used in the galena flotation step, the amount of lime in the sphalerite flotation must be increased (compare 1253 and 1263). Table I11 gives some of the compounds of guanidine which were tested and compared. Some of the compounds and derivatives of guanidine* are solu- * Diphenyl guanidine is in commercial production and is available on the market. ble in water and others are not. Those tested were fed dry. When an organic collector is promising, its compounds and derivatives should be tested and their comparative collecting power recorded. Eventually, in this way, it may be possible to discover some of the essential chemical characteristics of a good collector. For example, it is interesting to compare the diphenyl and dibutyl derivatives in Table IV with those of urea in Table 111, Example 3, U. S. Patent 2,664,198. All are good collectors. Table I shows some of the effects of lime on recovery of sphalerite by diphenyl guanidine. Table V

Jan 1, 1960

By Edward L. Clark

The year 1954 witnessed great activity in the field of geology as applied to mining. The search for in nearly all districts is becoming more and more intensified as established reserves are being depleted. Much geologic work has been directed to finding extensions of known orebodies, but prospecting in new areas has constituted a large part of the program of many operators. The acute need for additional reserves has brought into the search all the tools known to the geologic profession. This is reflected directly by frequent references to geophysical and geochemical methods in the regional reviews that follow. The lone prospector of the early days of metal mining has been eliminated almost completely by modern scientific methods involving surface and subsurface geology, exploratory drilling, geophysics, and geochemistry. Nearly all new exploration is based on long-range programs coupled with studies of regional geology to determine the structural environment of areas of mineralization. The success of this approach has encouraged new operators in the field of exploration to adopt similar policies. Only in the search for uranium ores is the individual prospector still active, but the familiar picture of the burro heavily loaded with grubstake, gold pan, and pick and shovel has been replaced by the Geiger counter and the scintillometer carried by hand, by truck, or by airplane.

Jan 3, 1955