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By P. D. Hunt, I. Johnson, M. G. Chasanov, H. M. Feder

The solubilities of the transition metals from scundium to nickel, inclusive, in liquid cadmium were determined by sampling saturated solutions. At 400°C these solubilities (ppm) are:Sc, Co, 22; Ni, 12000. Relative partial molal enthalpies and excess partial molal entropies at infinite dilution for the solutes Cr, Mn, Fe, and Co are compared zoitlz similar data for the post-transition metals. Three new intermetallic phases, ScCd,, TiCd, and Ti,Cd, encozaztered in the course of this work, are reported. Measurements of the solubility of the 3-d transition metals in liquid cadmium have been reported' only for iron. The present measurements for the entire series were made as an aid to the study of the systematics of alloy formation. EXPERIMENTAL The apparatus and sampling techniques used for the solubility determinations were similar to those described by Martin etal.' Temperatures were measured with a Pt/Pt-10 pct Rh thermocouple sheathed in recrystallized alumina and immersed in the solution. The thermocouple was recalibrated periodically during the course of the investigation. Thermocouple voltages were measured to the neares 0.01 mv with a Rubicon model 2732 potentiometer. A scaled-down version of the apparratus, in which the total metal charge was about 90 g, was employed to measure the solubility of scandium. Two-mm ID Vycor filter pipets were used to sample the scandium-cadmiurn solutions; the samples weighed about 2g- Cadmium with a minimum purity of 99.95 pct was used; the only impurities detected spectrochem-ically were C'u and Mg, both less than 10 ppm. The purities of the other metals were: scandium, 99.9 pct; titanium. 99.92 pct; vanadium, 99.9 pct; chromium, 99).99 pct; manganese, 99.9+ pct; iron, 99.90 pct; cobalt, 99.95 pct; and nickel, 99.96 pct. Solidified melts were routinely analyzed spectro-graphically. No significant contamination by the crucible, sampling pipets, or other materials of construction was observed. The entire specimen obtained by sampling was dissolved to preclude analytical errors due to segregation on cooling. Colorimetric methods3 were used for the analyses of cobalt (2-nitroso-l-naphthol), manganese (permanganate), nickel (dimethylglyoxime), titanium (peroxide), and vanadium (thiocyanate).4 Chromium, iron, and scandium were neutron-irradiated to produce The dissolved samples were gamma-counted to determine solute concentration.For the separation of intermediate phases from cadmium-rich alloys selective leaching by saturated ammonium nitrate solutions was employed. The concentration of cadmium in the successive leaches was followed polarographically and the process was terminated when the rate of cadmium dissolution decreased markedly. For the further investigation of intermediate phases 1/4- in. diam powder compacts were pressed at 80,000 psi and annealed in argon at 315" to 330°C for 10 days. Larger quantities of alloys were prepared in sealed tantalum capsules heated in a rocking furnace.

Jan 1, 1962

By G. Sandoz, C. A. Siebert

OIL quenching of steel, in good commercial practice, is carried out using a great deal of agitation in the quenching bath. Many of the tests reported in the literature represent the results obtained on steels quenched into still oil. Scott1 describes three stages of cooling in liquid quenching baths, namely: "State `A'-Vapor Blanket Cooling-In this, the first stage, a thin stable vapor film surrounds the hot metal. Cooling is by conduction and radiation through the gaseous film and is therefore relatively slow. "Stage `B'-Vapor Transport Cooling- Termination of the `A' stage is marked by wetting of the metal surface. Vapor forms copiously in bubbles and is carried away by gravity and convection currents to condense in cooler surrounding liquid. This is the fastest stage of cooling. "Stage `C'-Liquid Cooling--The `B' stage ends as the surface temperature of the metal approaches the boiling point of the quenching liquid. Vapor no longer forms, so cooling is by conduction and convection and the temperature difference is greatly decreased. This mode of cooling is slower than that of the `B' stage." Mechanical agitation of the quenching medium will accelerate all three stages of cooling. The greatest effect, however, will be noted on stage `B' because the removal of the bubbles from the surface of the steel will not be entirely dependent upon gravity and natural convection currents. The method employed in this investigation for evaluating the oils was the end quench test. The various oils were substituted for water as the quenching liquid and hardness determinations were made at various distances from the quenched end. Most of the tests were run using a 3/8-in. orifice with a 2 ½ -in. stream height. However, to check the effect of other velocities two additional conditions were used, namely: (I) A 3/8-in. orifice and 1-in. stream height, and (2) a ½ -in. orifice and a 3 ½ -in. stream height. In all cases the samples were suspended so that the quenched end was ½ -in. above the orifice. The steel used was an NE 9450 having the following analysis: [ ] Some tests were run on an NE 8740, 3312, and a 4340 steel. The results obtained on these steels confirmed those obtained on the NE 9450 and have therefore been omitted' from this paper. The test bars were machined from 1 1/8 -in. stock to 1-in. diam by 4 in. long.

Jan 1, 1948

By Donald B. Gillies

PROBABLY the most critical and difficult period in an engineer's career is that between the completion of his college work and his attainment of professional recognition and accepted status in the industrial world. Upon leaving school the young graduate breaks his immediate ties with his educational institution and in a sense finds himself adrift. At this time in his life a society like our Institute has both the responsibility and the privilege of meeting a vitally important need in his professional life. Some of these young men are Student Associates, in the year after graduation, and some are Junior Members, but all need advice and assistance. In some respects this situation will be accentuated by the war. Not only will thousands of young engineers be mustered out of military service but the process we describe generally as industrial reconversion will make necessary many readjustments in personnel. About two years ago the Institute recognized the opportunity of helping the younger member to help himself by appointing a new standing committee to be known as the Committee on Professional Development of Junior Engineers. Herbert Hoover is Honorary Chairman and it is my privilege to serve as Chairman. The name of the Committee is not entirely satisfactory but it expresses the general objective. The present article is in the nature of a progress report of the work of this Committee.

Jan 1, 1945

By T. H. Alden

In several recent studies of fatigue fracture in single-phase metals, tests have been made using the condition of essentially constant plastic strain amplitude.1-4 This procedure departs from the more common practice of holding the amplitude of stress constant. From these studies have emerged two important generalizations about the behavior of metals during cyclic straining. First, measurements of the stress amplitude, required to impose the fixed plastic strain amplitude, have shown that the rate of cyclic strain hardening in annealed metals is rapid in the early cycles but decays quickly to a very low value.1"5 This behavior is displayed particularly for a range of strain amplitudes below about 2 pct and at low and high temperature. Frequently, the hardening rate becomes so low that one can determine a "saturation" stress. This stress increases with strain amplitude. In addition, an experimental relation between fracture life and plastic strain amplitude was obtained by Coffin and Taternelli,' namely N 1/2 ep = constant. For several metal:;, this equation has been shown to hold down to a strain amplitude of 0.1 pct. Whether it also holds in the "low amplitude" range (lives of more than about 105 cycles) has not been established. The importance of the saturation stress level (a value derived from strain hardening measurements) to the question of fracture life (the usual quantity of interest of fatigue testing) lies in the observation that cracks start to form when the cyclic hardening rate is essentially zero, and not before.4"5 This point suggests immediately a means of relating tests at constant stress and constant strain amplitudes. When making comparison, the stress in a constant stress test is to be identified with the saturation stress in a constant strain test. If these ideas are correct, then it should be possible, using the relation between fracture life and strain amplitude and experimental curves of saturation stress versus strain amplitude, to predict the fracture life as a function of stress, i.e. predict the S -N curve, for low stress fatigue. Saturation stress amplitude-plastic strain amplitude data, obtained in tension-compression, exist only for a few metals and for relatively high amplitudes of strain. Comparable S -N curves (push-pull loading) were known by the author only for OFHC copper. Values for this metal taken from Ref. 2 are shown in Fig. 1. The strain amplitudes, the lowest

Jan 1, 1962

By A. S. Joy

Vacuum flotation tests carried out according to the method of Schuhmann and Prakash1 have shown that the acid limiting edge of the flotation area for a Brazilian hematite, in the presence of dodecylamine, is a straight line of slope approximately unity. The flotation tests and the structure, surface ionization, and electrokinetic properties of this hematite have been fully discussed elsewhere. 2 The numbers of adsorbed H+, and OH- ions and collector molecules have been determined in the range of critical conditions defining the acid limit of the flotation area. The total amine adsorption is shown in Fig. 1 as a set of contours superimposed on the straight part of the flotation area. These were determined by spectro-photometric estimation of the complex formed between residual amine and the anionic dye Orange II.3 The ionic strength of the solutions was kept constant and at a value in sufficient excess of the amine concentration to ensure that the diffuse part of the double layer was populated predominantly by indifferent ions. Adsorption of H+ and OH- in the absence of amine was found by potentiometric acid-base titration in the presence of hematite.4 The form of the adsorption-titration curves suggested that the hematite surface behaves in an amphoteric manner, and that positively charged sites arise through loss of a hydroxyl ion, and negatively charged sites by loss of a hydrogen ion. On this basis, curves 8 and 9, shown in Fig. 2, were calculated from the titration curves. These show the variation of the numbers of positive (s +) and negative (s—) sites with pH. To distinguish between ionic and other modes of adsorption, zeta-potential determinations have also been made using the streaming potential technique. The influence of amine on the zeta-potential of the mineral over a wide pH range is shown in Fig. 3. The change in charge ?s, due to adsorption of amine ions in the Stern layer, was calculated by applying the Gouy-Chapman theory, as modified by Stem, to the results shown in Fig. 3. The validity of this treatment has been shown by Ottewill and Jaycock.5 The three full lines, Nos. (1) through (3), included in Fig. 2 show the relationship between ?s and pH at three amine concentrations. The general conclusion from the zeta-potential curves is that adsorption of amine causes a reduction in the negative charge on the surface. Comparison of the values shown in curves (1) through (3) of Fig. 2 with the - curve shows that the magnitude of the reduction is comparable with that of s - at any given

Jan 1, 1964

The Du Pont Magazine for August and September gives the following interesting information regarding recent progress in the use' of explosives. Blasting -Clay.-"The place where I tried blasting down clay for a brick yard had been worked for some years by old-time pick and shovel method. There was a large shallow pit, irregular in shape, with a perpendicular face at one end. I put down a line of holes 3 ft. deep and 6 ft. back from this face, loading each hole with one and one-half car-tridges of Red Cross Extra 40 per cent. dynamite. The charges were connected up to a blasting machine circuit and fired electrically. "Two of these shots kept the brick yard men very busy for two days taking out the loose clay. "I am convinced that if any brick yard man will try this method he will always have a blasting machine and dynamite on hand thereafter, because it cuts labor cost almost in two to get down the clay in. this way." In some clay pits the practice is to blast a large amount of clay in the fall, allowing it to freeze and thaw through the winter. Such clay is much easier to puddle in the spring than freshly dug or blasted clay. When the clay contains stones, the blasting loosens them and makes their separation-easy. Well-Drill Holes in Quarrying.-The well drill or cable drill method of working a quarry face is now in quite common use. The use of large drills is constantly increasing among quarrymen. In fact the growing tendency is for large machinery of all kinds such as mammoth crushers, steam shovels, etc. Volume is what is wanted nowadays. The advantages of the big drill over the piston driven drill are numerous. By carrying the holes the full depth of the face the stone is loaded and treated on one working floor. It eliminates the cost of bench cleaning. Loading operations are less frequent, thus lessening the danger. Stone can be shot down in greater volume and in better shape, making it economical to use a steam shovel. No bench cleaning makes it safer for the men. It is cheaper and can be used in outlying and temporary operations where the cost of installing a power plant would be out of the question. It permits a greater spacing of bore holes and eliminates the necessity of "squibbing" or springing. In this method usually holes from 4 in. to 6 in. in diameter are drilled the full depth of the face from 15 ft. to 2,0 ft. apart, and as far back and the whole face shot down at one time. The cost of well drilling may vary all the way from 20 cents to 75 cents: per foot, and in extremely hard rocks up to $1.50 per foot.

Jan 10, 1916

Elected Died 1895 *ABBOTT, AI ATTHUR 1908 1882 *ABBOTT, ARTHUR V 1906 1905 * ABE, MASAYOSHI 1909 1903 * ADAMS, CHARLES C. 1905 1905 * ADAMS, WILLAMS 1909 1903 * ADAMS, W. EDWARDS 1910 1884 *ADDY, MATTHEW 1896 1889 * AKERS, WILLIAMS 1906 1894 *ALLEN R B 1896 1905 * ALLEN, R. SCOTT 1906 1874 *AMIOT, H 1892 1886 *AMSLER, CARL 1894 1895 *ÅNGSTROM, CARL 1901 1887 * ARCHBALD, JAMES 1910 1900 * ARLETT, GEORGE H 1906 1895 *ARMSTRONG, JOHN F 1898 1882 *ARNOLDS, HUGO 1886 1875 *ASHBURNER, CHARLES A 1889 1872 *ASIIBURNER, WILLIAM 1887 1883 *ATKINS, C M , JR 1885 1905 * AUSTEN, PETER T 1907

Jan 1, 1917

By I. B. Cadoff, J. C. Bilello, R. Rosenberg

Diffiusion of magnesium into the surface of LiF crystals to controlled depths and subsequent heat treatments provided a wide range of surface zone harahesses and structure, The bend strength of the LiF crystals was increased by as much as an or-dev of magnitude. Ductility was achieved when dislocation generation occurred in the diffusion zone or when dislocations penetrated to the surface from the intevior. A critical surface hardness of 130 to 140 kg per sq mm was found helozu which generation could take place in the diffusion zone and ahoue which the zone was impenetrable, This hardness was obtainable by several methods, among them the aging of quenched MgF2 -LiF solutions to produce MgF, precipitation. Maximum hardness was ohtained in quenched specimens with no visihle evidence of MgF,. Diffusion-zone formation followed a parabolic rate law and an activation energy of 20.9 kcal per mole was obtained for the process. RECENTLY, the properties of ionic crystals as related to surface condition have been receiving much attention, specifically the transitions between ductile and brittle behavior. Originally Joffe 1 showed that NaCl crystals could be made ductile by immersion in water and related this to the elimination of surface microcracks. Aerts and DeKeyser 2 and Gorur 3' have subsequently shown that ionic crystals are inherently ductile and are embrittled through contact with air. Machlin and Murray4 hypothesized that a layer of NaCIO3 produced by contact of ozone with NaCl induced embrittlement by acting as a barrier to outward dislocation flow. westwood,' Rosenberg and Cadoff,9 and Bilello and cadoff' have reported surface strengthening of LiF crystals by coating with a magnesium compound and then heat treating for adherence. The major effect of the coat was to inhibit dislocation-slip lines from reaching the specimen surface. westwoods showed microcrack formation and fracture to be caused by slip-band interactions at the surface. The material presented in this paper is an extension of the work reported earlier by Bilello, Rosenberg, and cadoff'6,7 and illustrates the wide range of surface properties and bulk behavior obtainable by use of heat-treated magnesium-diffused surface regions in LiF crystals. EXPERIMENTAL PROCEDURE The LiF single crystals were obtained from the Harshaw Chemical Co. Some batch to batch variation was observed; therefore all specimens for a given test series were cleaved from the same crystal. The typical dimension used was 1 by 0.1 by 0.40 in. Surface damage resulting from cleavage was removed by chemically polishing in a 2 pct NH4OH solution. Each group of specimens was given a vacuum anneal at 700°C for 4 hr to provide a base standard for measuring comparative effects of various surface treatments. To produce the reacted surface zone, the annealed specimens were immersed in a boiling suspension of MgF, in doubly distilled HzO, agitated slbwly for 30 sec, removed, and dried at room temperature. Uniform coatings of MgF, were deposited with a thickness of approximately 5 mils. It should be noted that this technique can be modified for use with crystals which are soluble in water by using boiling absolute alcohol as the dissolving medium. This was found effective for the coating of NaCl with MgF2. The diffused surface zone was obtained by annealing the coated samples at elevated temperatures in a vacuum of lob4 mm Hg. Penetration depth was controlled by varying the annealing time from 1/2 to 28 hr. After heat treatment, the samples were tested for bend strength and hardness. Load was applied by four-point bending in a hard-beam testing jig. Four-point rather than three-point bending was used to provide a wide area of constant stress and to minimize the effect of localized inhomogenities in the specimen. The deflection rate was 8 x min-' and the distance between knife edges was 1/4 in. Load-time curves were obtained from a chart recorder coupled to the machine and converted to resolved shear stress on the shear plane vs deflection, as plotted in the figures. The unstressed portions of the sample outside of the two outer knife edges were used for the microhardness studies. Microhardness measurements were made with a Bergsman tester attached to a Reichert metallograph. All hardness impres-

Jan 1, 1964

Elected Died 1895 *ABBOTT, AI ATTHUR 1908 1882 *ABBOTT, ARTHUR V 1906 1903 * ADAMS, CHARLES C. 1905 1884 *ADDY, MATTHEW 1896 1889 * AKERS, WILLIAMS 1906 1894 *ALLEN R B 1896 1905 * ALLEN, R. SCOTT 1906 1874 *AMIOT, H 1892 1886 *AMSLER, CARL 1894 1895 *ÅNGSTROM, CARL 1901 1900 * ARLETT, GEORGE H 1906 1895 *ARMSTRONG, JOHN F 1898 1882 *ARNOLDS, HUGO 1886 1875 *ASHBURNER, CHARLES A 1889 1872 *ASIIBURNER, WILLIAM 1887 1883 *ATKINS, C M , JR 1885 1905 * AUDTIN, PETER T 1907 1897 *AYERS, WILLIAM 1898 1885 *BABCOCK, GEO H 1893 1884 *BAILEY, EDWARD 1889 1880 *BAILEY, JACKSON 1887 1900 *BALLOU, FRANKLIN 1903

Jan 1, 1910

Just three years after researchers announced its development, Dravo is putting the finishing touches on a new $60-million Thiosorhic lime mine/kiln complex near Maysville, Ky. Electric utilities in western Pennsylvania and Ohio have already signed long-term contracts for over three-quarters of the projected 907 000-t/v (1-million-stpy) production. Thiosorbic lime, a flue gas desulfurizing agent, proved in industrial testing that at high emission levels (greater than 3000ppm SO2) it could be twice as effective in SO2 capture as conventional lime, while eliminating the major problem of scaling and plugging of scrubber equipment.

Jan 4, 1977

By Theodore B. Counselman

Of all natural resources, iron ore made into steel is the most important both in tonnage and value. The primary reason for the prosperity of the United States in the last century has been its pre-eminence in domestic supplies of iron ore and steel. The depletion of these reserves by two world wars and by the demand for richer blast furnace charges, as well as the constantly growing world- wide demand for steel, has fostered the recent quest for new iron ore mines around the globe. These developments have made a dramatic change in the iron ore picture of the world. It is the purpose here, however, to look briefly at the development of the United States iron ore industry, which has played such an important role in the events leading to the modern day boom in iron ore exploration.

Jan 7, 1965

By E. W. Rouse

THE year 1936 has seen rehabilitation of many plants which had been closed or severely curtailed. The Steptoe smelter of the Nevada Consolidated Copper Co. has been transformed by a rearrangement of the flow of material and utilization of mechanical handling to a maximum. The Phelps Dodge Corp. reports the construction of newer and better reverberatories at the Copper Queen smelter, and of particular interest, a single high-pressure waste-heat boiler placed directly over the uptake. There has also been a complete reconstruction of the smelter at the Laurel Hill plant of the Nichols Copper Co.

Jan 1, 1937

By J. Murray Riddell

The method of treating hazards wherein value is decreased, is cited by R. D. Parks. Quite properly, the theory of probabilities is made use of when multiple hazards are under consideration. E. F. Fitzhugh, Jr. $ deals with the enhancement phase graphically and uses percentage of expectancy as derived by a study of conditions and the selection of a chance factor. It is believed that both of the authors referred to fully recognize the part which human judgment plays, and as coupled with experience, training, and the application of the theory of probabilities; in that respect the composer of this paper is in accord. Within the past year, the task of arriving at a mathematical method for handling the enhancement phase, and, additionally, coupling the negative and positive phases, was explored. In citing the hazard, or negative phase, reference is made to the text by Parks. Types of Items far Consideration On the hazard, or negative, side some of the common items to be considered are: 1. Subsidence and resulting damage. 2. Flo wage of water above that anticipated. 3. Geological. (a) Decline in quality of probable ore, and/or (b) Decline in quantity of probable ore. 4. Depressed economic conditions. 5. Litigation. Similarly, on the enhancement, or positive, side common items to be considered are: 1. Flo wage of water below that estimated. 2. Geological. (a) Increase in quality of probable ore, and/or (b) Increase in quantity of probable ore. 3. Elevated economic conditions. 4. Litigation. 5. Technological advance in the art. Tn all of the above items no consideration is given to placing a value on, or giving consideration to, possibilities. For example, referring to Table 1, the estimated normal present value (Vp) of a property, exclusive of risk consideration, is taken as $100,000. If subsidence affects the usefulness of the shaft, the present value of the property will decrease to $60,000, and it is judged that there is a 1 in 4 chance that the shaft will be impaired;, consequent.ly, if subsidence took place, the present value would be reduced ($100,000-$60,000) $40,000, but since the chance is 1 in 4, the allowable reduction would be only one-fourth of $40,000, or $10,000, or a discount of 10 pct (hazard factor) of the original value; the related safety factor is taken as unity minus 0.10, or 0.90. Thus, the original Vp, $100,000, multiplied by the safety factor ($100,000 X 0.90) gives $90,000, which is the adjusted present value of the property in this single instance. Additionally, there is a water hazard, which, if encountered, will reduce the present value to $85,000. The chance is 1 in 3. Following through with the same reasoning as shown above, the derived safety factor will be 0.95. To arrive at a single multiplying factor which will express the combined risks, the two safety factors are multiplied together, 0.90 X 0.95 = 0.855. That factor when multiplied by the origirial Vp will give the adjusted, and

Jan 1, 1950

By W. H. Fitch

HAVING been asked to make some remarks after the reading of Mr. Dyrssen's paper, I regret that a test started some months ago has not yet been completed, but some of the things which I can tell you at this time seem interesting and shed a little different light on the idea of a recuperator. The device referred to is becoming more than. a recuperator, largely taking the place of a regenerator. I assume there is familiarity with the sketches that I presented in October, 1926, before the Engineers' Society of Western Pennsylvania, describing our re-cuperator combination with checker chambers, and I have additional ones to show at this time. The follow-ing remarks will deal with modifications that have been made. At that time I suggested the gases leaving the regenerators at, say, 1400°, be reduced to 500° F. The opinion of the operating men consulted since that time is that, under the best operating conditions, the tem-perature may be 750° to 800° F. after the recuperator and on entering the stack. While the lowest final temperature of the gases en-tering the stack is important from the economic stand-point of fuel burning, and operating in general, it is not the whole story. The method of getting the heat out of the checkers is important. It is believed by many with whom we have talked that a better way is by a combination of checkers and a carborundum re- cuperator of the type described as it will stand all tem-peratures met in practice and might be called a super-refractory.

Jan 1, 1928

By V. Rajaram, I. P. Nielsen, H. D. Raymond

The Parachute Creek member of the Green River formation in the Piceance Basin, Colorado, contains vast reserves of oil shale, nahcolite, dawsonite, and other accessory minerals. The dry alkali process of sulfur dioxide removal using nahcolite (naturally occurring sodium bicarbonate) has great potential. A room and pillar mining scheme has been designed to extract a nahcolite zone occurring at a depth of 472 m, from the lease application area of the Yankee Gulch joint venture. Geotechnical parameters affecting mine design will be discussed. A preliminary development plan for mining at the rate of 1000 t/d will be described in detail.

Jan 12, 1979

By E. Gybbon Spilsbury

In a paper* read at the last meeting of the Institute, in Scranton, Pa., I referred to the proposed introduction at the Haile gold-mine, South Carolina, of a novel method of chlorination. I have since

Jan 1, 1888

By R. C. Buehl, M. B. Royer

High manganese slags of low phosphorus and iron content are produced by air oxidation of high phosphorus spiegeleisen in a basic-lined converter. Control of phosphorus and iron within specification limits for ferromanganese ore feed is obtained by a unique cyclic operating procedure. Various types of slags, or synthetic manganese ore, can be made. AN affiliated paper' describes the production of high phosphorus spiegeleisen containing 14 to 23 pct Mn and up to 4 pct P in an experimental blast furnace from open-hearth slag or manganiferous iron ore. This phosphorus content is too high for use of the spiegel in normal steel-production operations. Consequently, a preferential separation must be effected whereby the manganese is concentrated in a product that is usable in industrial operations. The preferential separation methods being investigated for this phase of the work are confined to pyrometal-lurgical processes for ready incorporation into steel-plant operations. It is fortunate that manganese is more actively oxidizable than iron or phosphorus, and therein lies a preferential separation method for isolating manganese from these two elements. Silicon is more strongly oxidizable than manganese, and its oxidation precedes, or occurs simultaneously, with manganese. Therefore, manganese and silicon are separable into a high manganese oxide slag phase while the phosphorus and iron remain in the molten metallic state. Complete separation of these elements represents an ideal condition which is not generally attainable in actual operations. This pyro-metallurgical method for separating manganese from phosphorus and iron by preferential oxidation was investigated by blowing 500 lb of metal in a basic-lined vessel to obtain preliminary information on the effectiveness of the procedure. Certain conditions of attainment in the separation process are desirable in any method for removing manganese from high phosphorus spiegeleisen, such as: 1—High recovery of manganese in the oxidation product; 2—the product to be of equal or better quality than ferromanganese-grade ore—48 pct Mn minimum, less than 10 pct SiO2, and Mn-P ratio of 300:1; and 3—attainment of the enumerated objectives in a product amenable to industrial handling, such as a slag of high manganese content that will flow from the processing vessel and of sufficient fluidity for ready separation of metallic granules that may have become mixed with the manganese slag phase. Previous Work Recovery of manganese from low grade ores and industrial byproduct slags by smelting to spiegeleisen, with subsequent oxidation to synthetic ferro-manganese-feed ores, has been a subject for periodic investigation during the past four or five decades in the United States and Germany. Joseph' and associates of the Bureau of Mines North Central Experiment Station, Minneapolis, Minn., smelted manganiferous iron ores of the Cuyuna range, Minn., to spiegeleisen and subsequently tried air and ore oxidation procedures for concentrating the manganese into synthetic ferrograde manganese ore. Joseph's results on the operation of a side-blown basic-lined converter for air oxidation of manganese from molten spiegeleisen were so discouraging that the procedure was abandoned after 11 blowing tests. Much slag was thrown from the converter vessel; phosphorus content was four to five times the maximum allowable for ferro ore; and a manganese-iron ratio of only 2 or 3:1 was obtained in the slag instead of the required 8:1. Oxidation of manganese from spiegeleisen with about 0.5 pct P, by adding iron ore to molten spiegel in an experimental open-hearth furnace, proved moderately successful in Joseph's experiments. The main drawback to the operation was the necessity for over-oreing for effective oxidation of the manganese with consequent too high iron oxide residual in the slag. Furthermore, the phosphorus content was proportional to the iron concentration and therefore much too high, so that several hours of reduction by a carbonaceous material were required to adjust the iron and phosphorus to the desired content of high grade ferro feed. A troublesome feature of the slag product of the spiegel oxidation process was its lack of fluidity if the silica content was less than 10 pct, the concentration considered desirable for the synthetic ore. Approximately twice the desired concentration of silica was required to impart enough fluidity for transfer from the vessel by pouring. The acute shortage of manganese in Germany

Jan 1, 1953

By Joseph P. Hodgson

JOSEPH P. HODGSON.-As to ".Safety First," I did not deal with that, but I will say that in 1913, the number of .men killed was nine, and that year the "safety first" program was commenced; the next year, 1914, the number was reduced to five. In 1915, I am pleased to say that the number was reduced to two in the Copper Queen's entire property, and we have none so far this year. THE CHAIRMAN (G. F. G. HERMAN, Bisbee, Ariz.).-I can say, further, that we have from eight to nineteen men per month incapacitated for more than 14 days. Those are classified in this State as serious accidents. The number of men injured has apparently increased, -but that is clue to our improved method of recording and classifying accidents, no matter how slight. C. W. GOODALE, Butte, Mont.-The importance of cooperation among the members of the staff of an industrial organization is well brought out by Mr..Hodgson's paper.

Jan 12, 1916

By A. W. H. Morris, G. H. Laurie, J. N. Pratt

Using- galvanic cells of the form Sn(liq)/Sn" (LiCl-KC1-SnCl,)/Sn-Ag (alloy), measurements have been made of relative thermodynamic properties of the a, C, E, and liquid phases of the Ag-Sn alloy system. Partial heats of solution of the components in the liquid alloys lzave also been observed by direct cal-orimetric measurement in an isoperibol calorimeter. The thermodynanzic quantities are disczlssed in relation to structural and other properties and the existence of anomalous minor fluctuations in the partial heats and entropies of solution in liquid alloys is tentatively suggested. In the course of a recent electro motive-force study of the thermodynamic properties of Sn-Ag-Pd liquids,' some measurements were also performed on the Ag-Sn binary system. Most previous thermodynamic studies of this system have been concerned with the liquid state. Measurements confined to the limiting heat of solution of silver in liquid tin have been made by many calorimetric workers2 while high-temperature calorimetric measurements of the heats of formation of the full range of liquid alloys are reported in the early work of Kawakami~ (1323°K) and more recently by Wittig and Gehrin~(1248°K). Electromotive-force studies on liquid alloys have been made by Yanko, Drake, and Hovorka' (606" to 686°K; 86 to 99.4 at. pct Sn) and by Frantik and Mc Donald' (900°K; 30 to 90 at. pct Sn). The only known measurements on the solid state are of heats of formation of the a, £, and c phases; these values were obtained using tin-solution calorimetry, at 723"K, by Kleppa,~ whose investigation also yielded heats of formation of liquid alloys containing more than 64 at. pct Sn. The present experiments on the Ag-Sn alloys include a re-examination of the liquid phase and, because of the dearth of free-energy data for the solid state, attempted measurements on the a, c, and E phases. The principal new feature of electromotive-force results obtained for the liquid phase was an indication of anomalous fluctuations in the partial heats and entropies of solution of tin at certain compositions. However, since the values for these thermodynamic quantities were determined from the temperature coefficients of cell potentials, which are commonly subject to considerable error, confirmation by calorimetric measurements was considered desirable. A detailed investigation of the partial heats of solution of the components in the binary liquids was made using a liquid metal solution calorimeter. I) GALVANIC CELL STUDIES a) Experimental Details. Measurements were made, as a function of alloy composition and temperature, of the potentials of reversible galvanic cells of the form: ~n(liq)/~n++/~n-Ag (solid or liquid alloy) Details of the apparatus and experimental techniques have been given elsewhere.' so that a brief account will suffice here. Molten salt, 58 mole pct LiC1-42 mole pct KC1, containing small amounts (1 to 2 mole pct) of stannous chloride was used as the electrolyte. The salts were dehydrated by pre-electrolysis and vacuum -drying techniques. Cells were established under an argon atmosphere by immersing tin and alloy electrodes in the molten salt contained in a large silica tube, heated in a vertical resistance furnace. The tube was sealed at the top by a head plate provided with openings permitting the simultaneous insertion of six electrodes, a central thermocouple sheath, and connections to vacuum and argon lines. Temperatures were controlled to *0.2"C over prolonged periods, with maximum variation over the electrodes at any time of 0.l°C. Temperatures were measured with a standardized Pt/13 pct Rh-Pt couple. The electromotive force of this and the cell potentials were measured on a Cambridge Vernier potentiometer and short-period galvanometer. Alloys were prepared from Pass "S" tin (99.999 pct) and Johnson-Matthey high-purity silver (99.999 pct) by melting in evacuated silica capsules and quenching in cold water. For liquid phase experiments, pieces of the resulting alloys were remelted into prepared silica electrode units, while solid electrodes were prepared by remelting into 3-mm bore tubing, inserting a cleaned molybdenum lead wire, and quenching to produce uniform rods about 3 cm in length, with soundly attached leads. In all cases remelting was done under an argon atmosphere. The solid electrodes were subsequently annealed in evacu ated silica tubes for 14 days at about 20°C below the solidus and quenched. Analyses showed that these techniques produced uniform electrodes with no significant change from weighed out compositions. b) Results and Discussion. Measurements were made on about forty alloys in the solid and liquid states, over varying ranges of temperature between 550" and 1050°K. Stable, mutually consistent, and reproducible electromotive-force data were obtained with most liquid alloys and these are shown in Fig. 1. Investigations were extended below the liquidus tem-

Jan 1, 1967

By J. W. Downey, M. V. Nevitt

MUELLER and Knott' have reported that Ti2Cu has the Si2Mo-type (Cllb) structure. The lattice parameters of Ti2Cu and the positions of the titanium and copper atoms are given by them as follows: ao = 2.944A; co = 10.786A 6 atoms per unit cell: 2 Cu (a) 000; 1/2: 1/2, 1/2 4 Ti (e) 002; 1/2, 1/2, 1/2 + z 00 -2 ; 1/2. 1/2. 1/2- z where z = 0.341 We have found eight other binary compounds which appear to be isostructural with Ti2Cu. All of them involve the combination of a titanium group element with a copper group element or a titanium group element with palladium. The compounds and their lattice parameters are given in Table I. The alloy samples were prepared by arc melting metals having a purity of 99.9 pct or better. They were homogenized for 72 hr at 900°C in evacuated capsules and quenched in tap water. Filings were prepared, and these were reannealed for 4 hr at 700°C, also in evacuated tubes. The lattice parameters were determined by a least squares Bnalysis of the back reflection lines of patterns made with cobalt radiation. It was not possible to make a precise determination of the lattice parameters of Zr2Au because the filings underwent rapid oxidation at room temperature. The evidence supporting the large tetragonal cell containing 6 atoms involves the presence of the reflections 002, 101, 004, 112, 114, 202, and other reflections with higher indices for which I = 3n. Three or more reflections corresponding to these indices, which cannot be indexed on the basis of a small body-centered tetragonal cell containing 2 atoms, are observed in the patterns of all of the compounds listed in Table I. They are strongest and most numerous when the components have large differences in their atomic scattering factors, as is the case in Ti2Pd, Zr2Cu, and Hf2Cu. The values of the z parameter should be regarded as approximate They were selected on the basis of the best agreement between the observed intensities of two pairs of closely spaced powder pattern lines (004): (112) and (114): (202) and the corresponding intensities calculated for several values of z. An ordering scheme was assumed in which titanium, zirconium, or hafnium atoms occupy the titanium positions of Ti2Cu, and copper, silver, palladium, or gold atoms occupy the copper positions. Calculated and observed intensities of the aforementioned lines and the other lines of the patterns are in satisfactory agreement, but a refinement of the z parameters and a final confirmation of the ordering arrangement must await a more detailed study. It is interesting to note that in transition metal systems at A2B stoichiometry the Si2Mo-type structure competes for stability with two other fre-

Jan 1, 1962