Search Documents

By R. Schuhmann, J. Th. Overbeek, P. L. De Bruyn

W. E. Ewers (Commonwealth Scientific and Industrial Research organization, Melbourne, Australia)— Any attempt to elucidate further the meaning of the contact angle, particularly if it deals with the magnitudes of those mysterious quantities rsa and YRL, is certain to receive attention from those interested in the fundamentals of flotation. It is imperative, therefore, that attention should be drawn to a serious defect in the treatment by de Bruyn, Overbeek, and Schuhmann. Their Eq. 5 dy = — ld/u — Th2odiH2n states correctly the relationship between the change in surface free energy dy, the surface excesses Tx and Th2o of the components x and H2O and the changes du, and dph2o in the chemical potentials of these components. This equation applies for constant pressure and con- stant temperature and for the interface of the solid in contact with the solution of X. The relation remains valid when 1.1 is defined so that TH2O becomes zero and the equation becomes dr = — r:dur [17] From this equation de Bruyn et al. correctly concluded that increased adsorption of the collector at the liquid solid interface would reduce the interfacial energy ysl. Their second conclusion, however, that an increase in the contact angle, corresponding to a greater decrease in rsa than in rsL can be attributed to greater adsorption of X at the solid-air interface than at the solid-liquid interface is quite unjustified. The portion of the solid surface from which the collector solution has been displaced by air must be considered in terms of the equilibria between the gaseous phase and the surface. If the pressure and temperature

Jan 1, 1955

By H. A. McKinstry, F. F. Lange

A vector analysis of orientating single crystals using the Laue back-reflection X-ray technique is given. Briefly, the analysis involves using a few data taken from a Laue photography and defining the crystal co- ordinate axes in a reference coordinate system. After a few matrix multiplications, the proper goniometer angles can then be determined to orient the crystal coincident with the reference frame. This analysis is easily programed for a digital computer to provide a fast, precise, and efficient method of orienting many crystals which are identical. The general procedure is as follows. The crystal is mounted on a goniometer. Laue photographs are taken until an array of diffraction spots is observed that includes a Laue spot that represents a rotational axis of symmetry. The rotation angles of goniometer are recorded. These angles are defined as positive for a counterclockwise rotation. When the axis of symmetry is located on the Laue photograph, the crystal coordinate axes can be defined in the reference coordinate system* as follows. Two Laue spots are chosen, one of which corresponds to the rotational axis of symmetry and the other to a set of planes whose zone axis is a known crystallographic direction and normal to the rotation axis of symmetry. The Laue spots are used to determine these two crystal directions in the reference coordinate frame. This is done by placing the Laue photograph on a sheet of polar coordinate graph paper and determining the polar coordinates (r, o) of these two diffraction spots in the reference coordinate frame. Their third coordinate is the distance between the crystal and the film (-D). The coordinates Xni of the two crystal directions Nn, (n = 1, 2) in the reference frame are then calculated by the following equations: Xn1 = -D X2n = Ancos on X3n = A, sin on where -tan- 1 rn/D An =Dtan(tan-1rp/D/2) By taking the proper cross products of these two directions (normalized to unit vectors), the crystal coordinate axes 3 (i = 1, 2, 3) can be determined in the reference frame. This is illustrated in Fig. 1. The next step is to determine the relation between

Jan 1, 1969

By W. E. Remmers

The defect in wire known as "cuppiness" has appeared and disappeared from time to time but the exact cause of its appearance or disappearance has not heretofore been known definitely. This defect is not limited to one particular metal or alloy but seems to be found at various times in all of the materials that are drawn into wire. Fig. 1 represents cuppy wire made from an aluminum alloy and Fig. 2 illustrates copper wire that became cuppy in drawing without intermediate annealing. Differences of opinion are current among the manufacturers of wire and in the literature (see bibliography at end of paper), some believing that the source of the trouble lies in segregation in the wire rod, oxides, sulfides, slag, etc.; others that the trouble is created by an unevenness of stress distribution across the section of the wire, usually thought of as being a function of die shape. All of the published work is of a qualitative rather than a quantitative nature. With this in mind, it was deemed advisable to make a study of the shape of the wire-drawing dies, as well as the oxygen content of the copper to be drawn. Experimental After several methods were tried, it was found that by studying the contour of the butt-end of the rod after drawing a measure of the "working" across the section of the wire could be made. The butt-end of the annealed rod was not sheared but was sawed off. The end was then smoothed with a fine file so that the plane of filing was perpendicular to the drawing axis. It is to be noted that this method is not an absolute measure of the distribution of cold working but is a very good indicative means of studying comparative values. The method of examining a tension break in wire was found to be the most sensitive in detecting cuppiness. Other methods, such as microscopic examination of longitudinal sections, X-ray radiographic studies, etching away of outer layers with nitric acid, and fracture by bending, can all be used to identify cuppy wire but the tension break will give the fracture characteristic of cuppiness before any of the other methods can

Jan 1, 1930

By Rodney P. Smith

THE solubility of columbium nitride in ? iron has been determined for the temperature range 1191o to 1336°C from the nitrogen content and metallogra-phic examination of a series of Fe-Nb alloys.* (0.0 to 0.92 pct Nb) equilibrated with a purified gas mixture of 1 pct hydrogen in nitrogen. The method is the same as that used by Darken, Smith, and Filer' to determine the solubility of aluminum nitride in y iron. The variation in the furnace temperature during an equilibration period was about ± 2.0°C. Each sample was approximately 1/2 in. wide, 2 in. long, and 1/16 in. thick. A time series at 1200°C using samples of highest columbium content indicated that one day was sufficient for equilibrium; however, to be on the safe side all samples were left in the furnace for either two or three days. Afterequilibration, the samples were brought to room temperature by quenching in water. The experimental results are shown in Fig. 1. To be in accord with the values reported by Wriedt and Gonzalez2 and the temperature coefficient of our results at higher temperatures, the nitrogen content of iron at 1191oC is assumed to be slightly lower than our experimental value. Our data for the single-phase regions are not sufficiently accurate to establish an interaction coefficient for nitrogen in these alloys. However, the change in nitrogen content with change in alloy content for a number of systems (Fe-N-A1;3,1 Fe-N-Ni;372 Fe-N-Si.3949 Fe-N-V;3,5 Fe-N-Cr;3,6 Fe-N-Mo3,7) has practically the same value for the liquid alloy at a temperature near 1600°C as for the solid alloy at temperatures near 1200oC when the alloy content is below a few percent. On this basis the lines through the single-phase regions have been drawn with a slope corresponding to an increase in nitrogen of 0.0013 pct per 0.1 pct Nb.3 The straight lines through the two-phase regions were drawn with a slope corresponding to a one-to-one atom ratio of nitrogen to columbium in the nitride. The X-ray

Jan 1, 1962

By Frank W. Harris

The strength of hard drawn copper wire is a question of considerable importance to both manufacturer and consumer. Unlike steel and alloy wires, in which strength is governed by both chcniical and physical considerations, t,he high conductivity required for copper wire in the clcc-trical industry generally precludes the possibility of obt,aining tensile strength through the use of alloys. Consequently, this strenglh is largely a rnatter of the ~hysical structure, and all factors known to affect this structure, such as rolling temperature, die contours, lubricants, drawing speeds, etc., arc matters of prime importance. The experiments described here have becn carried out dl~ring the past year at the Baltimore plant of the American Smelting & Refining Co., in connection with a general investigat,ion of sorne of the questions mentioned above, with the object of studying thc physical ~t~ructure of hard drawn copper wire and the influence of ccrtain factors on t,hat st'ruct.ure. The work has been of an exploratory nature, rather than con~prehensivc., but it was thought that the result,s might prove of sr~fficient general interest tjo warrant their publicatlion. The bulk of the hard drawn coppcr wire used in places where strength is an important factor is rnanufacturcd to strict specification, based USU-ally in the United States on thab of t,he Arrlerican Society for Tcst'ing Materials (B-1-23). This specification calls for almost as high a, valuc of t,ensilc strength, consistent with elongation, as it is possible pract'icnlly to obtain, and only physically perfect mlaterial can be relied on to lliect such a specification. Obvious defects, such as laminat'ions protluc:etl through fins in bhe original rods or brittleness duo lo ovt~rdrawing, arc. usually recognized and need only passing refercncc. Laminatlions can be detected by twisting and untwisting the wircx several times; they will show up on the surface in the form of fins. Pig. 1 shows a very bad example of this defect. Thc wire may bc perfectly smooth before twisting hut, when such larrlinations arc3 prcstmt they will readily show up under this treatrncnt. This trouble is caliscd by sirriilar defects in the original rod produced by overfills in rolling. Fig. 2 shows the cross-section of the rod from which thc wire in Fig. 1 was drawn.

By E. A. von Hahn, T. R. lngraham

The rates of cementation of pd11 on electropolislzed copper cylinders were studied in aqueous perchloric acid solutions at pdII concentrations from 0.02 to 0.1 mM. The cylinders were rotated at various high speeds to reduce the diffusion layer to a minimum thickness. In 0.1 M HClO4 solutions, the cemented palladium is dense, adherent, and shiny. The rate data indicate that there are two stages in the deposition. In the initial stage, the rate of cementation is first order with respect to the pd11 concentration. The second stage is much slower. The first stage is consistent with rate control by the diffusion of pd11 ions to the copper surface, and/or chemical reaction at the surface, and the second stage is consistent with rate control by the diffusion of copper ions from the cop-per surface through the deposit of cemented palladium, out to the main body of solution. In 0.001 M HClO4 solution, only the first stage is evident and the rate is more rapid than at higher acidities. This rate enhancement is attributed to PdOH+ ions that predominate at low acidity and aye more reactive than unhydrolyzed pdII. The deposit is porous and loose. All of the cemented deposits are Pd-Cu alloys rather than pure palladium. Activation energies are 9.5 kcal per mole in 0.1 M HClO4 and 7.4 kcal per mole in 0.001 M HClO4. CEMENTATION or displacement reactions occur between aqueous solutions of metal salts and immersed metals according to the general equation: where M1 is electrochemically the more noble metal. Although these reactions find considerable application in metals recovery processes (e.g., the cementation of copper192 or gold3), in electrorefining processes (e.g., solution purification before electrolysis4,5), and in plating and metal finishing processes,6 few studies have been made of the kinetics of such reactions.7-9 The rates of cementation reactions will depend on one or more of the following factors: a) chemical reactions at the metal-solution interface; b) ionic transport to or away from the interface;'-' and c) the character and adherence of the cemented deposit on the substrate metal,6a,10 because the deposit will inhibit the rate of transport of dissolving ions (M2m+) into the solution. In this investigation, the kinetics of the early stages of cementation were studied to obtain an understanding of the reaction mechanism under conditions in which the deposit was sufficiently thin that its inhibiting effect could be disregarded. To achieve this, very dilute solutions in Mn+ were used. Cementation rates are often fast in the initial stages and transport-contr01led.9 To find conditions under which transport control would shift to chemical control, very high stirring velocities were used to minimize the diffusion-layer thickness. Of the many possible cementation reaction systems, the palladous perchlorate-copper system was chosen for this investigation because it was believed to involve simple ion-for-ion exchange. In addition, there are no interfering side reactions, such as the reduction of hydrogen ions, and anion effects are usually absent in perchlorate solutions. EXPERIMENTAL Materials. Reagent-grade chemicals and redistilled water were used in all experiments. Palladous perchlorate stock solutions (0.02 M) were prepared by dissolving 99.5 pct Pd sponge (Johnson Matthey and Mallory Ltd.) in concentrated nitric acid, adding concentrated perchloric acid, evaporating twice slowly (to prevent PdO precipitation) to a small volume, and diluting in a volumetric flask. To prevent gradual hydrolysis of PdII, the stock solutions were made 0.4 M in HC104. Tests for pdIV (Ref. 11) and C1- were negative. Copper strips were cut accurately from 0.025-in. electrolytic tough pitch sheet, Sample 1 (Mines Branch stock or Canadian Copper Refineries Ltd., Montreal), or from oxygen-free, high-conductivity sheet, Sample 2 (American Metal Climax O.F.H.C. brand, sold by Utility Brass and Copper Corp., Brooklyn). The strips were annealed for 1 hr at 335°C in a stream of purified nitrogen (Union Carbide, Linde Division) which had

Jan 1, 1967

By Alfred Boyles

"Heredity"1 in cast iron has been a subject of much discussion. Numerous experimenters have found that the properties of gray iron may vary greatly without corresponding variations in composition or thermal treatment. The main structural difference in such cases is in the size and distribution of the graphite flakes and the explanations given usually attribute this difference to some chemical element not shown by ordinary analysis or to some physical factor, such as inclusions in the melt. It cannot be said that any of these theories is completely satisfactory. Much remains to be learned about cast iron and for this reason a study of the material was undertaken as a part of the program of fundamental research at Battelle Memorial Institute. A review of the literature indicated that very little systematic work had been done on the mechanism of freezing in cast iron. The experiments described below are largely concerned with that problem. Normal and "Dendritic" Cast Iron As examples of variation in type of structure, photomicrographs of two test bars of cast iron are shown (Figs. 1 and 2) and the composition and properties are given in Table 1. Both are common, unalloyed gray iron. Test bar No. 13 has normal graphite flakes while No. 49 has very fine, lacy graphite arranged in a dendritic pattern, the matrix in both being pearlite. These two types of cast iron are well known to foundry-men and need no detailed description.

Jan 1, 1937

Jan 1, 1968

By E. A. Gulbransen, K. F. Andrew

THIS paper. will present the results of our studies on the kinetics of the gas phase reactions of co-lumbium and tantalum with O2, N2 and H2. Studies on zirconium and titanium have been previously reported.9,11 Due to their high melting points and their many excellent physical and chemical properties, colurn-bium and tantalum have been finding their places as useful metals in science and industry. Chemically the metals are very inert to gas and liquid phase corrosion at room temperature. However, at moderate temperatures of 250°C and higher the metals react readily with oxygen and hydrogen. It is of interest to study the gas phase reactions of these metals for the following reasons: (1) to compare the rates of the several reactions with those of other metals and to correlate the rate data with theory and structure predictions, (2) to add basic information on the practical difficulties of the reduction, refining and working of columbium and tantalum, (3) to anticipate new uses for the metals and (4) to understand the role that the metals play as components in high temperature alloys. Literature Survey A number of papers exist in the literature on the gas phase reactions of columbium and tantalum with O2, N2 and H2; however, only fragmentary data have been reported on the kinetics of these reactions. Although the free energy of formation of the oxide Ta2O520at 25°C has been determined and some thermodynamic work has been reported on columbium and its oxides, the data are not sufficient to make equilibria calculations at elevated temperatures. Oxidation: 1. Kinetics: The rate of oxidation of columbium and tantalum has been studied by McAdam and Geil23 using the interference color method. Tantalum is reported to oxidize more slowly than columbium, zirconium and iron. The amounts of oxidation of columbium after 20 hr in air for several temperatures are reported by the Fansteel Metallurgical Corporation.36 Columbium starts to oxidize in air at about 200°C. The oxide is said to be adherent and prevents further oxidation until the temperature is raised. Columbium is reported not to become brittle on heating in air for short periods like tantalum because the oxide film prevents further reaction. The columbium oxides dissolve into the metal when heated in a vacuum at temperatures between red heat and 1200°C. Above 1200°C the oxides are reported to evaporate. Columbium, in the oxide free state, is an active getter in vacuum tubes. 2. Preparation and Structure: G. Grube, O. Kuba-schewski and K. Zwiauer15 have studied the decomposition of Cb2O5 in argon. They find that CbO2 is formed slowly at 1150° and rapidly at 1300°C. Cb2O5 can be reduced to CbO2 by moist H2. The reduction of this dioxide to the lower oxides is rapid. By varying conditions CbO2, Cb2O3, CbO and Cb2O can be formed. CbO2, CbO and Cb2O have independent lattices while Cb2O3 is a stoichiometric mixture of CbO and CbO2. In a later paper O. Kuba-schewski" has shown that CbO is cubic and that CbO2 has a rutile type of lattice. The most exhaustive work on the oxides of columbium is that of G. Brauer.8 The number and constitution of the solid phases in the binary system Cb-O were investigated by the preparative, analytical and X ray methods. He indicates that only the oxides Cb2O5, CbO2 and CbO exist with limited regions of homogeneity. The solid oxide Cb,O, exists

Jan 1, 1951

By C. E. Shoenfelt

Wildcat drilling in the Rocky Mountain region did not suffer as large a decline in 1942 as was anticipated. The drilling program laid out by the Government at the beginning of the year stressed wild-catting operations and called for reduction of drilling in proved fields. The increased wildcatting campaign did not yield a great many new discoveries, nor important extensions to old fields. Several interesting wildcat wells were drilled in Colorado in 1942 but no new fields were discovered. The Wilson Creek field was extended and about 400 acres added to its reserves. In Montana two new oil fields and two small gas fields were discovered. The developments in the marketing situation had improved, however, making the prospects especially bright for 1943, as will be shown presently in the section on Montana in this report. In New Mexico eight wells were completed, which constituted discoveries ol either oil or gas but none of these was of major proportions. In Wyoming one new oil field and one new gas field were discovered, and one old oil field and one old gas field were extended. Most important was the disco-very of prolific oil producers in deeper sands in three old oil fields, of which one at least, Elk Basin, probably is of major proportions. Government Action On Dec. 26, 1942, President Roosevelt signed the O'Mahoney bill, calling for a flat 12.5 per cent royalty on lands in the public domain. It is expected that the enactment of this bill will encourage wildcatting in the public land states. Opportunity for a full discussion of the problems of reserves and production was afforded at the hearings conducted on the O'Mahoney bill by the minerals subcommittee of the Senate Committee on Public Lands and the statements submitted at these hearings last fall placed the situation, its causes and the logical remedy, clearly on record. It was established at the hearings that for several years the volume of oil discovered per wildcat well drilled has steadily declined; new fields discovered have not been of major proportions; drilling costs have advanced rapidly; a sharp decline in exploratory drilling took place in 1942, while the proportion of dry holes increased; the inescapable conclusion is that to find new reserves the search for oil must be intensified and much more wildcat drilling ' must be done. To ensure an adequate drilling campaign, the Petroleum Industry War Council, the Interstate Compact Commission and other representative oil organizations have voiced by resolution their opinion that an upward revision of crude prices is necessary to provide an incentive to the prospector to undertake the hazards of wildcat drilling, since statistics prove that only ope in five or six wells drilled results in actual production. Former Price Administrator Henderson rejected the recommendations for price increases and declared himself unalterably opposed to a general price advance, On the ground that such advances would contribute to inflation. Now that Mr. Hender-

Jan 1, 1943

By C. E. Shoenfelt

Wildcat drilling in the Rocky Mountain region did not suffer as large a decline in 1942 as was anticipated. The drilling program laid out by the Government at the beginning of the year stressed wild-catting operations and called for reduction of drilling in proved fields. The increased wildcatting campaign did not yield a great many new discoveries, nor important extensions to old fields. Several interesting wildcat wells were drilled in Colorado in 1942 but no new fields were discovered. The Wilson Creek field was extended and about 400 acres added to its reserves. In Montana two new oil fields and two small gas fields were discovered. The developments in the marketing situation had improved, however, making the prospects especially bright for 1943, as will be shown presently in the section on Montana in this report. In New Mexico eight wells were completed, which constituted discoveries ol either oil or gas but none of these was of major proportions. In Wyoming one new oil field and one new gas field were discovered, and one old oil field and one old gas field were extended. Most important was the disco-very of prolific oil producers in deeper sands in three old oil fields, of which one at least, Elk Basin, probably is of major proportions. Government Action On Dec. 26, 1942, President Roosevelt signed the O'Mahoney bill, calling for a flat 12.5 per cent royalty on lands in the public domain. It is expected that the enactment of this bill will encourage wildcatting in the public land states. Opportunity for a full discussion of the problems of reserves and production was afforded at the hearings conducted on the O'Mahoney bill by the minerals subcommittee of the Senate Committee on Public Lands and the statements submitted at these hearings last fall placed the situation, its causes and the logical remedy, clearly on record. It was established at the hearings that for several years the volume of oil discovered per wildcat well drilled has steadily declined; new fields discovered have not been of major proportions; drilling costs have advanced rapidly; a sharp decline in exploratory drilling took place in 1942, while the proportion of dry holes increased; the inescapable conclusion is that to find new reserves the search for oil must be intensified and much more wildcat drilling ' must be done. To ensure an adequate drilling campaign, the Petroleum Industry War Council, the Interstate Compact Commission and other representative oil organizations have voiced by resolution their opinion that an upward revision of crude prices is necessary to provide an incentive to the prospector to undertake the hazards of wildcat drilling, since statistics prove that only ope in five or six wells drilled results in actual production. Former Price Administrator Henderson rejected the recommendations for price increases and declared himself unalterably opposed to a general price advance, On the ground that such advances would contribute to inflation. Now that Mr. Hender-

Jan 1, 1943

Joseph W. RichaRds, South Bethlehem, Pa. (communication to the Secretary*): The hold experiment of Mr. James Gayley in drying the blast used in the Isabella furnace has attracted the attention of the whole metallurgical world, and has given rise to a wide discussion of the reasons for its great success. Mr. Gayley and the capitalists who backed him in his work deserve congratulations on the success of the venture, not only because it succeeded, but because they have been rewarded far beyond the maximum that could be expected from theory or probability. To state the case in its simplest terms, all that could have been predicted was: (1) that the removal of the moisture from the blaet would result in the saving of the heat required for its decomposition, representing from 3 to 5 per cent. of the heat-value of the coke used; hence about that quantity of fuel might be saved; (2) that the furnace would be somewhat more independent of variations in the weather; (3) that the campaign would be a little hotter; and (4) that the speed of the blowing-eugines would be decreased, at least in amount proportionate to the reduction in temperature of the air led to them. I do not think anyone anticipated a much larger output per day. The results actually attained were: (1) the furnace made an increase of 24.86 per cent. in the output of pig-iron per day; (2) it consumed 19.6 per cent. less coke per ton of pig-iron made; (3) the blowing-engines were run 15.8 per cent. slower; and (4) the saving in power made up for the power required to run the refrigerating-plant. In addition, the blast was hotter; the waste-gases cooler, because of their smaller volume; and there was a greater proportion of carbon dioxide to carbon

Jan 1, 1906

By E. C. Truesdale

A FEW years ago H. M. Cyr, working in the Research Laboratories of The New Jersey Zinc Co., produced a few pounds of zinc1 of such purity that no other elements were detected in it by spectrographic analysis, using the facilities then available. This zinc contained less than one ten-thousandth of one per cent of metallic impurities.2 During the decade that followed upon the laboratory production of this "spectro-graphically pure" zinc, commercial developments brought about the production of large tonnages of zinc of purity exceeding 99.99 per cent, and today zinc of 99.999 per cent purity is produced and marketed as "chemically pure" zinc. Typical analyses of present supplies of high-purity zinc are given in Table 1. TABLE 1.-Typical Analyses Percentage by Weight Sum of Zinc Pb, Fe, Pb Fe Cd Al Cd Special High Grades 0.007b 0.005b 0.0056 none 0.0106 C.P. (chemically pure) <0.0002 0.0005° 0.000052 S.P. (spectrographically pure).. <0.0002d <0.00005d a A.S.T.M. Standard Specification for Special High Grade Slab Zinc (A.S.T.M. Designation: B 6-37). b Maximum. c Fe chemically determined. Pb and Cd are spectrographically determined. d Differences between composition of C.P. and S.P. zinc are discussed later in this paper. The availability of commercial tonnages of special high-grade zinc has been the basis for the development of the zinc-base die-casting alloy industry which, in the year 1936, consumed one-eighth of the zinc used in the United States for all purposes. This and the C.P. and S.P. grades have given impetus to scientific investigations into the properties of pure

Jan 1, 1939

&apos;T. C. MERRIMAN, New Haven, Conn. (written discussion *).-This most interesting paper gives much carefully obtained and valuable data. However, there are two points in connection with the commercial application of such data that might possibly be a source of trouble and mis-understanding. In the first place, the examination of thin sections of annealed brass, subjected to standard Brinell test.(500 kg. on a 10-mm. diameter ball) at thicknesses from 0.075 to 0.150 in. (1.9 to 3.8 mm.) indicates that cold work has been performed on the specimen during the application of the load sufficient to extend way through the section, and have the hardness of the metal affected by the backing. If the usual steel support is used, this effect is very evident. If a piece of soft brass is used as a support, there is an indentation in the surface of the support accompanied by a bulge on the under side of the tested specimen opposite the impression made by the 10-mm. ball. The result is that Brinell specifications (governmental or otherwise) on stock for a certain purpose may not be fair in all cases, since manufacturers, owing to differences in equipment, etc., may not all use precisely the thickness and conditions of stock on which the Brinell specifications were based. This would mean that the government Brinell specification might not give them the temper of stock best suited for their manufacturing methods. The concluding paragraph of this paper, stating that "the hardness of cartridge brass may be determined with greater accuracy by the Brinell hardness measurement than by attempting to judge it from the grain size" appears to be in line with the movement of the last year or so among brass manufacturers toward substitution of the Brinell test for microscopic examination as an acceptance test on cartridge brass. The statement may he strictly true that the Brinell test is the best test for hardness, but it is not, as the statement might readily be construed, a sufficient test of suitable condition. For instance, some cartridge brass might accidentally have been overheated to a point where it would be distinctly unsafe to use for the manufacture of small arms cases and then be so rolled (reduction 3 to 5 per cent.) as to pass perfectly proper Brinell specifications. Under such conditions the microscope would reveal its unsuitability where the Brinell test had failed so to do.

Jan 4, 1919

By B. W. Dyer

IN 1924, the Crescent Eagle Oil Co., while drilling the salt section of the Paradox formation in Grand County, Utah, encountered a salt that did not appear to be sodium chloride. This salt was analyzed and showed the presence of potash minerals, both sylvite (KC1) and carnallite (KMgC12.6H20). Because of the high potash content of the sample, there was considerable speculation: (I) as to whether the hole had been salted, and (2), if not, the extent, richness, and the depth at which the deposit occurred. The discovery caused a large amount of activity in the area. During the next few years, 68 potash prospecting permits were issued by the Government, 24 under the Act of 1917 and 44 under the Act of Feb. 7, 1927, each including about four sections of land. Several holes, all shallow, were drilled for potash. A number of holes were drilled for oil into the salt horizon and the cuttings collected at the oil wells were examined petrographically and chemically. The shallow test holes were not sufficiently deep to reach the potash horizon and revealed nothing of value, but several of the oil test holes gave some indication of where potash might be found. LOCATION AND GEOLOGY OF DEPOSITS The potassium and magnesium salts have been found in various places from the Denver and Rio Grande Western Railroad tracks about seven miles west of Thompsons, in eastern Utah, to Cane Creek, a tributary of the Colorado Rivera distance north and south of about 35 miles. In this locality, there appear to be five separate deposits: the Crescent Eagle area, which is in T. 22 S., R. 19 E.; the Salt Valley area, in the vicinity of the north-south line of T. 23 S., between R. 20 E. and R. 21 E.; the Seven Mile area, in the eastern part of T. 25 S., R. 2o E.; the Cane Creek area, on the Colorado River, in T. 26 S. and T. 27 S., R. 2o E. and R. 21 E.; and the Salt Wash area, in T. 22 S. and T. 23 S., R. 16 E. and R. 17 E. (Fig. I.) The Crescent Eagle and Salt Valley areas are in the Salt Valley anticline, some of the wells being in the fault graben and others outside. Structurally, the Salt Valley anticline is very complex, and can be described in general terms as a northwesterly plunging collapsed anticline about 15 miles long. In the Crescent Eagle area, the valley graben is about 1 mile wide and the salt probably forms a plug, the apex of which is in the vicinity of the Crescent Eagle well. Owing to the complex structure, there has been every opportunity for flowage in the salt to cause local thinning or thickening of beds. The regular succession of formations in the general area* is: [Cretaceous Mancos Dakota Jurassic Morrison Summerville Entrada Carmel]

Jan 1, 1945

Jan 1, 1970

By G. Derge, Lo Ching Chang

The chemical and physical propertties of slag systems are of special interest to metallurgists, for nearly all metals are in contact with molten slags during the primary reduction from their ores and then during the subsequent refining and alloying processes that determine their ultimate use. These processes are carried out at high temperatures and involve such complex chemical systems that funda-mental scientific knowledge of the Properties and behavior of these slags is inadequate. Various hypotheses have been Proposed to explain known slag characteristics. The commonest of these regard the molten slag as constituted of compounds that are dissociated in varying degrees into their constituent oxides, as illustrated by Schenckl and the recent Papers of Chipman and co-authors. Another proposal is that these compounds dissociate by com-plete6 or partial ionization, the evidence for which has been reviewed by Martin and Derge.? whatever hypothesis is favored, the exact formulation of these compounds is incomplete. It is based on three principal types of information: 1. Studies of solidified 51% samples by X ray diffraction, petrography, and similar methods that can be used at room temperature. The correlation of this information with the high-temperature properties of the molten slag is uncertain. 2. Studies of slag-metal equilibria, which have the advantage of providing observations on the molten slag at high temperature. However, even these data present problems of interpretation because they require a complete knowledge of the metal phase. 3. Direct measurements of properties of molten slag at the temperature of greatest metallurgical interest. Viscosity, electrical conductivity, specific heats, and similar properties have been measured, but the data of this type are widely scattered and frequently difficult to interpret. Additional direct measurements of properties of molten slag that can be interpreted in terms of chemical behavior are required, and this paper shows that the standard physical-chemical measurement of reversible electrode potentials, which measure the activity of specific constituents, is a fruitful source of such information. The purpose of this investigation, therefore, was to find an electrode combination that would yield reversible electromotive force measurements when dipped into the molten slag to be studied. Slags of the systems cao-sio2 and cao-120,-SiO2 were chosen for study because graphite containers could be used and the data could be correlated with those for viscosity, conductivity, and other proper-

Jan 1, 1948

By G. Derge

The chemical and physical propertties of slag systems are of special interest to metallurgists, for nearly all metals are in contact with molten slags during the primary reduction from their ores and then during the subsequent refining and alloying processes that determine their ultimate use. These processes are carried out at high temperatures and involve such complex chemical systems that funda-mental scientific knowledge of the Properties and behavior of these slags is inadequate. Various hypotheses have been Proposed to explain known slag characteristics. The commonest of these regard the molten slag as constituted of compounds that are dissociated in varying degrees into their constituent oxides, as illustrated by Schenckl and the recent Papers of Chipman and co-authors. Another proposal is that these compounds dissociate by com-plete6 or partial ionization, the evidence for which has been reviewed by Martin and Derge.? whatever hypothesis is favored, the exact formulation of these compounds is incomplete. It is based on three principal types of information: 1. Studies of solidified 51% samples by X ray diffraction, petrography, and similar methods that can be used at room temperature. The correlation of this information with the high-temperature properties of the molten slag is uncertain. 2. Studies of slag-metal equilibria, which have the advantage of providing observations on the molten slag at high temperature. However, even these data present problems of interpretation because they require a complete knowledge of the metal phase. 3. Direct measurements of properties of molten slag at the temperature of greatest metallurgical interest. Viscosity, electrical conductivity, specific heats, and similar properties have been measured, but the data of this type are widely scattered and frequently difficult to interpret. Additional direct measurements of properties of molten slag that can be interpreted in terms of chemical behavior are required, and this paper shows that the standard physical-chemical measurement of reversible electrode potentials, which measure the activity of specific constituents, is a fruitful source of such information. The purpose of this investigation, therefore, was to find an electrode combination that would yield reversible electromotive force measurements when dipped into the molten slag to be studied. Slags of the systems cao-sio2 and cao-120,-SiO2 were chosen for study because graphite containers could be used and the data could be correlated with those for viscosity, conductivity, and other proper-

Jan 1, 1948

By Milton E. Wadsworth, R. Ted Wimber

Cobalt sulfate solutions containing ammonium acetate and chloroplatinic acid were reduced by hydrogen in a pyrex-glass lined autoclave in the temperature range of 170o to 232°C and hydrogen partial pressure range of 115 to 830 psia. The reduction rate was directly proportional to the hydrogen partial pressure and surface area of the pyrex glass and was independent of the quantity of chloroplatinic acid added initially. Experiments involving the variation of the relative concentration of ammonium acetate indicated that the reducible cobalt complex was probably the diacetate complex of cobalt, Co(AC)4H20, or a new mononcetate complex Co Ac, which was in solubility equilibrium with a pink precipitate of CO(AC)-4HzO. THE reaction in which a metal is dissolved by an acid to produce gaseous hydrogen and a salt solution was discovered early in the history of chemistry. In 1859 Beketoff found experimentally that this reaction could be reversed; i.e., a salt solution could be reduced by gaseous hydrogen to produce a metal and an acid. A review of work done on this phenomenon since that time may be found elsewhere., The hydrogen reduction of a cobalt salt solution is facilitated by complexing the cobalt ion. An ammonia complex of cobalt has been reduced commercially in the recovery of cobalt metal. A new reducible complex of cobalt was discovered5 when it was found that a co-baltous sulfate solution containing ammonium acetate could be reduced by hydrogen at temperatures in the region of 200°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature below its normal boiling point, a violet color became apparent, indicating complex formation. The nature of this complex was investigated5 by the addition of NH4Ac to a CoSO4 solution maintained at 85o. During the first additions of NH, Ac, the pH of the solution remained fairly constant at about 5.85. However, as the ratio of NH,Ac to CoSO, approached two, the pH rose and then leveled off at about 6.05. The absorption spectra of a Co(Ac), solution and a CoSO,, NH Ac solution were obtained at 85°C and were compared and found to be the same. These findings suggested that the diacetate complex of cobalt, Co(Ac),.4H20, was formed at 85°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature above about 165o, a finely divided pink precipitate appeared. The X-ray diffraction pattern of this precipitate indicated that it was Co(Ac), - 4H,O. In addition, it was discovered that when chloroplatinic acid, H,PtCl;, was added initially to the cobalt sulfate-ammonium acetate solution, a faster reduction was obtained. The roles of the solution complex, pink precipitate and chloroplatinic acid in the reduction process were then investigated. APPARATUS The experimental work was carried out in a two-liter stainless-steel autoclave. Adetailed description of the autoclave and the auxiliary equipment used in maintaining constant temperature and pressure may be found elsewhere.= Because the stainless steel was corroded, and also because it acted as a hydrogena-tion catalyst, an all-glass liner was fabricated such that the solution came only into contact with flame-polished pyrex glass. EXPERIMENTAL PROCEDURE The solutions used in the experimental work were prepared by dissolving reagent grade chemicals in distilled water. Although variation of the brand of ammonium acetate appeared to have no effect on the experimental results, CoSO, 7H O from the J. T. Baker Chemical Co. of Phillipsburg, N. J.,was found to give faster reductions than that prepared by Allied Chemical and Dye Corp., N. Y. The former was used throughout the course of the experimental work and was weighed up at the outset of each experiment. The ammonium acetate was dissolved to form a 6M stock solution, which was stored under refrigeration. A 10 pct solution of chloroplatinic acid (J. T. Baker Chemical Co.) was diluted to a 1.15 x 1Q2 M stock solution, which was standardized by precipitation of K,PtCl, as outlined by Scott. The appropriate volume of the chloroplatinic acid, H,PtCl,, solution was pipetted into the clean, dry glass liner. The cobalt sulfate-ammonium acetate solution, which had previously been saturated with

Jan 1, 1962

By George Sachs, S. M. Clark, George Espey

he tendency of a commercially drawn cartridge case to crack in the mercury test and the relation of cracking tendency to residual stress retained after drawing were studied. The fourth drawpiece (next to the final) of caliber 0.30 cartridge cases produced by Frankford Arsenal were selected as test pieces. These exhibited an exceptionally high cracking tendency, making a detailed study possible. To obtain fast cracking in the mercury test, about 0.0015 to 0.003 in. must be removed from the wall thickness of the drawpiece by pickling, and it must be subjected to the mercury test immediately after washing. Removal of the adhering mercury by annealing and subsequent squeezing of the case in a vise was used to reveal definitely the presence or absence of cracks. Various lots of apparently identically fabricated cases were shown to possess a different cracking tendency. Machining off or boring a hole in the base gradually reduced and eventually eliminated the cracking tendency. On the contrary, shortening of the wall (body) reduced the cracking tendency only if the wall became so short that the cracking zone was directly affected. By boring out the base and pickling from the outside and then splitting the resulting rings, it was possible to determine the approximate stress distribution in the base and in the adjacent part of the wall. Small compression stresses were present in the core and the major part of the base, while the surface of the base and the adjacent wall contained high circumferential tensile stresses. On the contrary, the wall when parted from the base contained only insignificant residual stress. The conception is advanced, that the stress distribution in a drawn cartridge case corresponds fundamentally to that of a tube (wall) shrunk on a disk (base). Such a stress distribution results from the tendency of the base to recover elastically by an increase in diameter from the biaxial compression during drawing while the wall exhibits little tendency to change its diameter after progressing through the die. This is confirmed by measurements which show the base diameter to be slightly larger than the wall diameter.

Jan 1, 1945