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By Sidney Snook

FLUORSPAR production is the most important industry in a compact area in southern Illinois and western Kentucky bordering the Ohio River. Producers' activities do not usually figure much in the mining news of the country, so that few know that the last year or so has been an unusually active one. Mine shipments more than doubled in 1939 compared with the poor year 1938. The average price changed but little, though it is now about one-sixth higher than at the beginning of last year. The outbreak of war in Europe a year ago lent an immediate stimulus to the industry, though only about 15 per cent of the domestic consumption is normally imported, thanks to a tariff of $8.40 per ton, equivalent to about 30 per cent ad valorem. Be- cause of the increased production and many expansions and improvements in the mines and plants, the period since the beginning of 1939 has been the most important one for the industry in the last 15 years.

Jan 1, 1940

By R. W. Heckel

A method is described whereby the relationship of both the "at-pressure" powder compact density and the "zero-pressure" compact density to the applied pressure may be obtained from continuous measurements of punch movement during a single compaction operation. The rate of density increase with applied pressure for the metal powders is found to be proportional to the volume fraction of pores for pressures exceeding a lower limit which varies from 15,000 to 30,000 psi, depending on the powder. 1 HE compaction of powdered materials is carried out primarily to increase the density of the material. If the ultimate goal of the over-all process is the attainment of minimum porosity, compaction is responsible for most of the densification. For example, loose powdered metals have porosities of about 65 to 75 pct. Axial loading in a die or hydrostatic pressure may effectively reduce the porosity of most powders to 20 pct or lower with pressures of 50,000 psi and greater. The relationship between the density of a powder compact and the pressure needed to achieve that density is most commonly obtained by pressing several compacts, each at a different pressure. Measurement of the densities of the individual compacts when they are removed from the die then provides the density-pressure relationship. However, this method suffers from several disadvantages. Because a large number of compacts and pressing operations are required, it is inherently slow. Furthermore, since density measurements are made after the specimens are removed from the die, data obtained refer only to pressures greater than those necessary to form a coherent compact. The third disadvantage is the inability of this method to provide information about the compact density at the applied pressure in the die. Because the determination of density-pressure relationships has been a slow, tedious process, investigators have sought to express the compaction behavior of powders by other means. The general terms "comparability" and L'compressibility" have been used to rank powders qualitatively according to their compaction characteristics. To restore a quantitative nature to the subject and to prevent confusion, Schwarzkopf1 has proposed that compac-tibility be defined as the minimum pressure needed to produce a given green strength, while compressibility should be used to indicate the extent to which the density of a powder is increased by a given pressure. Probably the most widely used of the compaction parameters is the "compression ratio,'' which is generally defined as the ratio of the compact density obtained by pressing at a given pressure to the apparent density of the loose powder.2 However, the description of the compaction behavior of a powder by these parameters provides only limited information about the process because of their applicability to just one specific condition such as a given green strength or a given pressure. The method of obtaining density-pressure relationships which will be described in the present paper was designed to eliminate the shortcomings of the previous techniques while maintaining equivalent accuracy and precision. EXPERIMENTAL TECHNIQUES The general principle employed makes use of the fact that the linear movement of the punch during a

Jan 1, 1962

By S. W. Kennedy, M. Cohen, L. D. Calvert

A high-temperature X-ray diffraction method has been used to study the composition and the kinetics of formation of oxide scales at 800 °C on iron and pure iron-nickel alloys containing 25.6, 75, and 84 pct Ni. This technique has been combined with chemical analysis, and metallographic examination, and determination of weight-gain time curves. The 75 and 84 pct Ni alloys form a three-layer scale consisting of porous NiO next to the metal, a spinel layer, and a -Fe203 on the outside. The 25 pct Ni alloy produces a scale of spinel and Fe,O,, in which, however, traces of FeO and NiO are observed near to the metal. On all the nickel alloys the Fe20, is orieqted with the (107) plane parallel to the surfaces. The exposed surface of the Fe20, is in the form of needles whose axis is perpendicular to the specimen surface. Although the alloys show nonuniform oxidation rates as determined from weight-gain measurements, the X-ray data indicate that the total scale and individml scale layers grow uniformly and parabolically. Deep subscale formation is observed in the 25 pct Ni alloy only. This appeared to be associated with cracking of the scale and penetration of the oxygen along the grain boundaries. ALTHOUGH film formation has been investigated by high-temperature electron-diffraction techniques, for example by Gulbransenl and Hickman,' there have apparently been no investigations of scaling by methods permitting study of the scale during formation at the reaction temperature. Methods involving quenching of scales are based on the working assumption that no significant changes take place on cooling. In general, however, compounds may disproportionate, and the different thermal expansions of constituents may cause disruption of the scale on cooling. In particular, some scales cannot be quenched without spalling. These difficulties are avoided by X-ray diffraction examination at the temperature of formation. High-temperature diffraction procedures also provide a method of determining the kinetics of formation of each phase separately in a multicom-ponent scale. The scaling of binary iron-nickel alloys Containing up to 30 pct Ni at a temperature of 800°C has been studied by Benard and Moreau using cooled specimen~,~ whilst Foley, Druck, and Fryxel14 made an electron-diffraction study of cooled oxide films formed on an iron 42 pci Ni alloy. In the present work the scaling of three iron-nickel alloys containing 25.6, 75, and 84 pct by weight of nickel, at 800°C in oxygen at atmospheric pressure was investigated by X-ray diffraction techniques using a Norelco Geiger-counter diffrac-tometer. The oxidation of iron was investigated for comparison. In addition normal metallographic examinations and chemical and X-ray analyses were made, and weight-gain time curves obtained. EXPERIMENTAL Materials Used—The analyses of the alloys were as follows: Percent by Weight Nickel 25.6 pct 75.4 pct 83.2 pct Aluminum 0.004 None found 0.002 Cobalt — 0.05 0.05 Chromium — — — Silicon — 0.01 None found Carbon All less than 0.05 pct The chemical analysis of the iron was: Al— 0.002 i 0.001 pct, C—0.007 pct, Cr less than 0.001 pct, Cu—0.002 ± 0.001 pct, Mn—0.003 ± 0.001 pct, N—0.0002 pct, 0-0.013 pct, P—less than 0.0002 pct, Pb—not detected, S—0.0017 pct, Si—0.0095 pct, Sn—none detected. This iron was the same as that used to make the alloys and was obtained from the same source-Vacuum Metals Corp. One specimen of pure iron from The British Iron and Steel Research Association was used for preliminary investigation. Specimens were machined to shape from cast rod, polished (the final polish being with 600 Sic paper), degreased in trichlorethylene, washed, and etched. The etching and neutralizing procedure adopted by

Jan 1, 1960

By K. P. Gupta, P. C. Panigrahy

The stabilization of the R, a-Mn, and 0-Mn phases have been studied in the Mn-Ti-Fe and Mn-Ti-Co systems. Iron and cobalt both appear to stabilize the (Mn-Ti) R phase to almost the sarne extent. The R-phase region was found to extend from the lowest e/a to slightly beyond the maximunz e/a limit known for this phase. But, while iron appears to stabilize the a-Mn phase, cobalt tends to stabilize the p-Mn phase. In the two systems manganese appears to get replaced by iron and cobalt in each of the mentioned phases. The instability of the a-Mn phase in the Mn-Ti-Co system and the /3 -Mn phase in the Mn-Ti-Fe system cannot be explained on the basis of adverse size effects because atomic diameters for both iron and cobalt (C.N. 12 at. diam) are ziery similnr and not much different from manganese which they replace. Qualitatively, the reason for the stability of the a-Mn and the p-Mn phases can be traced to the more favorable e/a ratio prevailing in the respective systems and to a competing tendency between the two phases. In transition metal alloy systems the o, p,P, R, a- Mn,' and p-Mn2 phases have been claimed as electron compounds. A large volume of work has been done to establish the criterion for the formation of the o phase but until very recently practically no systematic work was done on the a-Mn and the /3-Mn phases. A recent investigation on the P-Mn phase3 indicates the e/a criterion for p-Mn phase stabilization. Since the R phase was first known to appear only in certain ternary systems1 no detailed work was then possible for this phase. The R phase has been recently discovered as a binary intermetallic compound in the Mn-Ti~ and Mn-si~-' binary systems. The existence of binary R phases opens up the possibilities of studying the effect of alloying elements on the stabilization of the R phase. Of the two binary systems possessing an R phase, the Mn-Ti system appears to be more interesting because at a suitable high temperature it is possible to find the three electron compounds, the a-Mn, p-Mn, and R phases, side by side and it is possible to study the effect of a third transition element on these three electron compounds. For the present investigation iron and cobalt, so called B elements for the formation of electron compounds, have been used as the third element to study the stabilization of the a-Mn, P-Mn, and R phases. EXPERIMENTAL PROCEDURE The alloys were prepared by using 99.9 pct pure electrolytic Fe and Mn, 99.5 pct Co, and crystal bar titanium, supplied by Semi Elements Inc., New York and Gallard Schelsinger Mfg. Co., New York. Weighed amounts of the components were melted in recrystal-lized alumina crucibles in an inert atmosphere (argon) high-frequency induction melting unit. Titanium was made into fine chips for easy dissolution and a special charging procedure was adopted to avoid contacts of titanium chips with the alumina crucibles. Up to 20 at. pct Ti, the maximum titanium content in the investigated alloys, there was no visible sign of reaction of titanium with the alumina crucibles. With a careful control of melting time and temperature the losses were minimized and were always found to be below 0.1 pct. Because of such small and almost constant weight losses, the alloys were not finally analyzed. The alloys were wrapped in molybdenum foil and annealed in evacuated and sealed silica capsules at 1000" * 2°C for 72 hr and subsequently quenched in cold tap water. Annealed samples were examined metallographically and by X-ray diffraction. For all high manganese alloys oxalic acid solutions of various concentrations and 1.0 pct HN03 solution were found suitable as etching reagents. Best contrast between the a-Mn and the R phases could be obtained by using freshly prepared 60 pct glycerine + 20 pct HN03 + 20 pct HF solution. For high iron and cobalt containing alloys, especially for alloys containing the a-Fe, y-Fe, and P-Co phases, 15 cc HNOJ + 60 cc HC1 + 15 cc acetic acid + 15 cc water solution was found to be the best etching reagent. All X-ray diffraction work was carried out (using specimens prepared from annealed powders) with a 114.6 mm diam Debye-Scherrer camera using unfiltered FeK radiation at 25 kv and 10 ma. All calculations for X-ray diffraction work were carried out using an IBM 7044 digital computer RESULTS AND DISCUSSION The two ternary systems, MnTiFe and MnTiCo, were investigated near the manganese rich end, Figs. 1 and 2, and show some common features. In both alloy systems large extensions of narrow R phase regions occur at almost constant titanium contents. At titanium contents higher than that of the single phase R-phase alloys, the same unidentified X phase was found in both ternary systems. The extensions of the X phase close to the Mn-Ti binary indicate that this phase could be the TiMns phase. Too few X phase diffraction lines were present in the diffraction patterns to make positive identification of the X phase. In contrast to this similarity the two systems show opposite behavior in the extensions of the a-Mn and 8-Mn phase regions; while iron tends to stabilize the a-Mn phase, cobalt

Jan 1, 1970

By B. Lustman

IT has been known for a number of years that the addition of certain alkaline-earth and rare-earth metals to nickel-chromium base electric resistance alloys causes marked increase in their oxidation resistance as measured in an intermittent oxidation test similar to the ASTM—B 76-39 test. However, the mechanism whereby such additions confer protection is still unknown. On the basis of the experimental observation that the increase in life in intermittent tests of nickel-base alloys is proportional to the atomic radius of the added element, Hessen-bruchl has proposed that the added metal ions occupy holes in the oxide lattice which prevent diffusion of nickel ions in the oxide. Horn2 has postulated that the effect of such additions is to accelerate the rate of diffusion of chromium atoms in the metal and thus to favor the formation of Cr2O3 scales. Hickman and Gulbransen3 concluded from electron diffraction observation that the addition of the elements in question results in the formation of a barrier to the diffusion of nickel ions to the surface. In connection with some experiments conducted to develop a test for the resistance to oxidation of alloys in massive form under conditions of intermittent heating and cooling, some features of the oxidation of nickel-chromium base alloys were revealed which may serve to elucidate the mechanism of protection conferred by rare-earth and alkaline-earth elements. Specimens of cylindrical shape 0.360 in. diam x 0.37 in. long were placed in alumina thimbles and inserted into and withdrawn from a Globar-heated furnace operating at 2150°F at 7.5-min intervals. The weight of oxygen absorbed as well as the weight of oxide spalled were measured at intervals. With the particular experimental conditions used, the specimens in a 7.5-min cycle were at temperature for 2 min which corresponds to the heating time of the ASTM test. The weight changes of similar specimens under conditions of continuous heating in air at 2150°F were also measured. The specimens after oxidation were examined metal- lographically and samples of the spalled oxide collected for X-ray diffraction identification of the phases. The specimens used were from the same lot of material used by Hickman and Gulbransen3 and had the compositions shown in table 1. Included in table I are results of ASTM life tests on the materials in the form of wires. These materials, their composition and the ASTM life test data thereon were all supplied by F. E. Bash of the Driver-Harris Co. It may be noted that alloy 13246 of 80 pct nickel, 20 pct chromium nominal composition showed the shortest life in the ASTM test; alloy 12246 with the addition of small amounts of the elements zirconium, calcium, and aluminum, intermediate life; and alloy 12046 with the further addition of silicon, the longest life. In fig. 1 are shown the results of intermittent oxidation tests made on bulk specimens at 2150°F as well as continuous tests conducted at the same temperature. Duplicate tests were made on each specimen. The ordinate scale, inches of metal oxidized, was derived from the experimentally observed weight gain of oxygen by assuming the scale to be entirely Cr2O3. It may be noted that the metal-loss curves during intermittent oxidation show a constant or continuously increasing rate of weight

Jan 1, 1951

By Michel Elle, John Chipman

The equilibrium of gaseous H20-H2 mixtures with liquid iron-columbium alloys in the range 0.2 to 2.4 pct Cb shows that the activity coefficient of oxygen is strongly diminished by Cb. The oxide in equilibvium with the melt is identified as CbO2. The equi-librium constant at 1600 deg C is [%Cb][fo. % 0]2 = 2.9 x 10-4 where log fo= —0.14 [%Cb]. The deoxidizing power is comparable to that of vanadium, COLUMBIUM (niobium) is finding increasing use as an alloying element in steel. It forms several stable oxides and is removed from the steel bath by oxidizing slags. The specific oxide formed in steel-making is not known although Sazanov snd Shvarts-man,' in their study of its partition between slag and metal, have assumed this to be Cb2O5 It is the purpose of this study to determine its deoxidation equilibrium at 1600°c, the nature of the oxide formed and the interaction between columbium and oxygen in the melt. The investigation was based on the reaction H2 + O=H2O; Kl=ph2o/(pH2[%O]) [1] in which 0 signifies oxygen dissolved in the liquid Fe-Cb alloy. The method and equipment of recent studies2,3 were utilized. In brief, the molten alloy, contained in a small crucible, is held in a controlled mixture of steam, hydrogen, and argon until equilibrium is reached. It is then cooled quickly in a stream of helium and analyzed for columbium and oxygen, the latter by vacuum fusion.4 The solubility of the oxide in liquid iron is determined by visual observation of scum formation on the surface of the melt. Crucibles of MgO proved unsatisfactory because of partial reduction at the metal interface. Pure A12O3 crucibles were heavily blackened by the melt and could not be used at high concentrations of columbium. Silica crucibles were more satisfactory but these introduced some silicon into the melt thus necessitating an uncertain but small correction for its effect on the activities of the other solutes. In silica it was possible to observe the scum formation when the melt became saturated and there was no apparent reaction between scum and crucible. The procedure for saturated melts was as follows. The alloy charge composed of electrolytic iron and columbium grain was melted and held at constant temperature. The gas ratio H2O:H2 was progressively increased by raising the saturator temperature until a point was reached at which a bright film appeared on the surface and covered it completely. This film could be dissolved by raising the temperature of the melt and it reappeared when the temperature was lowered. Under a partial film covering, utilizing bare areas for temperature measurement, the melt was brought to equilibrium with the atmosphere by holding at temperature for about 1 hr as suggested by Dastur.5 INTERACTION IN THE MELT Several experiments were made without columbium to establish a base in silica crucibles. The results are shown in Table I. Except for one run, they agreed well with Floridis1 comparable results in other crucibles. The value of log K1 is taken from Table I as 0.58. This is slightly larger than Floridis' result, probably because of less elaborate safeguards against thermal diffusion. Results obtained in the Fe-Cb-0 series in which no scum formed are shown in Table 11. The equilibrium ratio Kl is defined as ph2o/(ph2[%O]). It is related to the equilibrium constant K1 as follows:

Jan 1, 1962

By C. M. Schwartz, A. E. Austin, W. B. Wilson

High-temperature X-ray diffraction studies were conducted with Th-U alloys with up to 10 wt pet U. The solid solubility of uranium in thorium as a function of temperature was determined by the method of lattice parameters. Thorium will dissolve up to 2.5 wt pet U at 950°, 4.5 wt pet U at 1150°, and 7.5 wt pet U at 1250°C. Determinations were made of the temperature of the transition of thorium and of the effect of uranium upon the transition. The a to ß transition for thorium was observed to occur at 1330' ±20°C. Mean coefficients of expansion were calculated for thorium and two alloys, and for ThO2 in contact with the thorium, using X-ray lattice-parameter data. Values obtained at 950° C for thorium and Tho2 were 12.1 and 9.40 X 10-6 per OC, respectively. Impurities obtained during the X-ray exposure were identified by diffraction and were essentially Tho2 and ThC, with two additional unknown phases being detected. The effect of the impurities upon the results is discussed. DIRECT investigation (i.e., high-temperature X-ray diffraction studies) of the phase diagram of thorium-rich uranium alloys has been shown to be necessary since recent work1 - has disclosed the presence of an allotropic transformation near 1400°C in pure thorium with the room temperature face-centered-cubic phase transforming to a body-cen-tered-cubic structure at the elevated temperature. The effect upon the transition of the addition of uranium to thorium and of the solubility of uranium in thorium at high temperatures remained unknown, yet was of interest in understanding fabrication procedures and elevated temperature use. The present work was undertaken to provide information in this area by determining the transition temperature, the effect of uranium on the transition temperature, and the solubility of uranium in thorium as a function of temperature. Experimental Work The high-temperature diffraction data were obtained using a camera especially designed for the purpose3 and capable of reaching temperatures in excess of 2000°C at pressures as low as 1 x 10." mm Hg. Temperature regulation was provided by regulating the power input to ±0.1 pet variation, and by regulating the water flow through the camera jacket to provide a constant thermal load. The X-ray sample was a rod nominally 80 mil diam, which was further turned down to 20 mil and then etched to 18 mil over 1/2 in. of one end. This was placed in the sample holder and mounted on the camera so that the smaller part was surrounded by a cylindrical tantalum-sheet radiation-type heating element. Diffraction from the sample was recorded on film after passing through a slot in the heating element and radiation-baffle shield and through beryllium vacuum windows. The X-ray film mounting was of the Straumanis type4 with a camera diameter of 114.59 mm. Since previous work of Chiotti' indicated that impurities considerably alter the transition temperature, chemical analysis of the arc melted iodide crystal-bar thorium samples was obtained prior to testing. The analysis disclosed the material to contain as low as 0.001 ±0,0002 wt pet H and 0.007 ±0.001 wt pet 0. Carbon was 0.003 wt pet and nitrogen less than 0.002 wt pet. This material was sealed in mild steel in an inert atmosphere and subsequently hot rolled to 3/8-in. diam rods at a temperature of 732°C. Following removal of the jacket, the material was pickled and cold swaged to 1/8-in. rods, from which the diffraction samples were prepared. The alloys were similarly prepared, with the uranium being added during arc melting. The uranium analyses of the alloys prepared appear in Table I. The experimental procedure for diffraction examination of the three samples of high-purity thorium differed from those of the Th-U alloys. The original practice, later modified, consisted of pumping down the camera with the diffusion pump on and then admitting liquid nitrogen to the cold trap of the system. This was modified for the Th-U alloys by maintaining liquid nitrogen in the cold trap at all times before and while the diffusion pump was heated. This minor change produced a reduction in the amount of carbon pickup by the sample during exposure to the diffusion-pump vapors. The sample was brought to the desired test temperature and exposed for 21/2 hr at pressures which were usually 2 x 10-6 mm Hg, or lower. Exposures were made at

Jan 1, 1959

By V. B. Tare, H. Schmalzried

The use of solid electrolytes for determining kinetic paraneters at elevated tevnperatures is pointed out. The reaction rate constant k1 of the phase-boundary reaction during oxidution of iron to wiistite by CO2-CO gas mixtures has been deternined between 850 nnd 975C, using ZrOz(+CaO) as an electrolyte. Values are between 1.4 x 10-a and 5.2 x 10 ole per sq ctn atm. The tzain difficulty is due to mixed potentials arising from side reactions at the electrolyte inteyface. In a number of papers the calcium-doped zirconia electrolyte has been used for the determination of thermodynamic data from measured differences in oxygen activities (or potentials) between two electrodes. The purpose of this note is to suggest the use of this solid electrolyte for kinetic measurements as well. The principle can be seen from Fig. 1. A thin and compact phase II (electron conductor) is fixed on a plate of gas-tight, polished ZrO2(+CaO) (I), which separates two compartments with different oxygen potential. p, is a constant reference pressure of oxygen (1 atm). The electromotive force of this galvanic cell is given by E = RT5 In pep, and pe is the oxygen partial pressure at the interface electrolytephase 11. If phase I1 is in equilibrium with the surrounding gas phase, p, = DR. If pg changes sud- denly to a value pi, p, and therefore the electromotive force, E, change as a function of time according to the phase-boundary reaction rate at the gas phase I1 interface and the transport processes inside phase 11. It is assumed that local equilibrium is established at the boundary electrolytephase 11, that the gas phase shows no concentration gradients, and that the con-

Jan 1, 1967

By Donald H. McLaughlin

ZEST in the search for new supplies of metallic ores and petroleum is difficult to maintain with stocks of raw materials accumulating and with over- production rightly or wrongly blamed for most of our industrial troubles. Enthusiasm over new methods of prospecting has consequently diminished and exploration programs in many fields have been drastically cur- tailed. Very naturally the effects have been felt with particular keeness in highly specialized phases of the work, such as geophysical prospecting, for the feverish scramble for new areas in which to drill beneath magnetic or electrical anomalies has abated, and there is even a lull in the firing in the battle over salt domes on the Gulf Coast. It is unquestionably an unhappy time for many of the organizations dependent on this work, but in certain respects the situation may be beneficial in correcting unsound practices that .have grown up through the necessity for haste and for quick decisions. With the restriction of the field to the more competent workers by the harsh rule of survival of the fittest, a general improvement, not only in technique but in business methods, can be expected which may go far in restoring public confidence. Geophysical prospecting in the short period that it has been utilized in North America, has suffered severely both from over-popularity and from excessive abuse. The former evil now

Jan 1, 1931

By John V. Beall

Never having done it before, it took us all day and until 11 at night to select and pack for a four-day back- pack trip up Lake Chelan last month. When we were through, we couldn't lift our own pack and Sylvia's, OUT spouse's, we barely managed to budge. Nevertheless, the next morning we were at the dock to board the Laldy of the Lake for the 3 ½ -hr boat trip to Lucerne. Our dress and accouterments creating the appearance of a veritable expedition into the wilderness made a sharp contrast with our fellow passengers, a senior citizens tour group from Spokane. We had come out to Seattle for the SME Fall Meeting and were taking advantage of the occasion for a vacation trip back to Lucerne and Holden where we had lived briefly 25-years ago, and a backpack trip up Railroad Creek from Holden to the Glacier Peak country, weather permitting. No matter what you say, weather is important, and this is one of the ingredients that went into making the SME Fall Meeting and Exhibit in Seattle, September 22-24, a thoroughly delightful experience for the 700 plus persons who attended. Seattle is a beautiful city, but with late September sunshine, which we experienced, it is the best. The second ingredient, is a swinging host committee. Under the leadership of Don Anderson and Tom Van Zandt, co-chairmen, and Mrs. Cecilia Reed, Ladies Program, superb hospitality and fine arrangements were blended. Earl Beistline, from Fairbanks, organized a two-day short course on arctic operations which preceded the meeting and drew an attendance of 44. Dick Robbins, in charge of arrangements, provided Masters-at- arms for technical sessions and a presentation of the colors by the U.S. Coast Guard at the Welcoming Luncheon. Eric Cheney's field trips ranged far and wide with events both before and after the meeting. David (Jeff) Kroft, capably managed audio-visual operations with a group of students from the University of Washington. Charles Hochmuth worked long, hard and effectively before and during the meet- ing on finances. Hank Reed, managed an authentic three-ring circus as Entertainment Chairman. His activities covered two cocktail receptions for all registrants and a dinner-dance. Dolph Campbell and Joe Hackbarth provided publicity by press and TV (see p. 37-40). SME's meetings have certain characteristics and possibly not all of these are known to everyone. The first of these is the deliberate involvement of the AIME Section in the area of the meeting. Most trade shows and conventions are run 100% by a professional staff and although SME staff could also do this, it has been our experience that a more friendly and better meeting results when the local members apply their talents. Actually SME only considers a site for a meeting after it has received an invitation from a Section. The knowledge of local conditions which Section committeemen bring to a meeting is of great value.

Jan 1, 1971

By George J. Young

(San Francisco meeting, October, 1911.) THE nature of slimes handled in the treatment of gold- and silver-ores has been discussed in technical literature to a considerable extent. The subject of slime-filtration from the practical worker's stand-point has also received much comment, and scattered through the literature of the subject are descriptions of many slime-filtration installations. Articles of this nature serve a valuable purpose and assist materially in the design of new and the improvement of old plants. The subject of the physics of slime-filtration has been touched upon to only a slight extent. The underlying principles are worthy of more intensive study and experimentation than they have received, and the main purpose of this paper is to present the results of such study and experimental work as will serve to make clear in part at least many of the principles which control the filtration of slime. Nature of Slime. Much has bean written concerning an accurate definition of the term ? slime," but no comprehensive definition seems to be generally accepted. The reason for this is clear. A slime consists of at least three different substances, each, when separated, possessing distinctly different physical and to a certain extent chemical properties. These substances are extremely fine sand, a colloidal material which may be and generally is in a coagulated condition, and a colloidal material which is in a non-coagulated condition. Suspending a slime in a relatively large volume of water by shaking and allowing sedimentation to take place, results in the fine sand settling out with comparative rapidity, followed by the coagulated material, which settles much more slowly and finally a certain portion remains

Nov 1, 1911

By D. K. Deardorff, H. Kato

THE transformation temperature of hafnium from hcp to bcc is 1750° + 20 °C in contrast to previously published values by Duwez and fast2 which are believed inaccurate. The Bureau of Mines determined this value by measuring the temperatures at which a sudden decrease was observed in the electrical resistance of hafnium alloys containing up to 18 at. pct Zr, and then extrapolating the temperatures to 0 pct Zr. Duwez1 previously reported a transformation temperature of 1310°C, obtained by use of a rapid-cooling thermal-analysis technique. Later, Fast2 published a much higher value of 1950° 100°C based upon: a) his own determination of 1690°C for the beginning of the transformation range for hafnium containing 5.7 at. pct Zr, and b) his belief that lattice parameters reported3 for Duwez' hafnium indicated i contained 19 at. pct Zr and that the 1310°C value should be associated with that composition. Russell4 subsequently stated that Duwez and Fast probably were reporting their lattice parameters in different units and reassigned a value of 6.0 at. pct Zr to Duwez' hafnium. If this assumption were true, Duwez' hafnium was of approximately the same purity as Fast's, but his transformation value was considerably lower. The reason for this divergence is not known. Fast's value for hafnium containing 5.7 at. pct Zr agrees well with our data. McGeary5 determined a transformation value of 1660°C by metallographic examination of heat-treated specimens, but the zirconium content of his hafnium was not definitely established. The specimens used in this investigation were 1/8-in.-diam rods 6 1/2 in. long, fabricated by hot-swaging bars cut from arc-melted buttons. These buttons were melted from crystal bar hafnium and crystal bar zirconium. The chief impurity in the hafnium

Jan 1, 1960

By E. R. Johnson

THE copper concentrator of the Braden Copper Co. is at Sewell, Chile, on the western flank of the main Cordillera of the Andes, at an air distance of approximately 50 miles southeast of Santiago, the capital of Chile. The region is mountainous and space is at a premium because of the rough terrain and the danger of snowslides. The ore, a porphyry copper, is mined by a block-caving method in the El Teniente mine. It is hauled to the crushing plant, a distance of 2.6 miles, through a tunnel because of the severe climatic conditions. The usual large, coarsely set, primary reduction machines found in many ore-treating plants are not required because of the mining method employed and the limiting 12-in. spacing of the grizzlies at the head of each ore pass in the mine. It is the purpose of this paper to describe the numerous improvements made in the crushing section of this large flotation concentrator during the past 15 years to increase the efficiency of the plant and to raise the daily output from around 20,000 to 30,000 tons. The reader should keep in mind that all changes were made within the existing building because of the limited space and the high cost of the heavy mill construction required to withstand the snow loads. The present plant, as well as the former, operates on a 24-hr, 7 days a week basis. FORMER PLANT The crushing plant commenced operations at its present site in 1921, the main equipment being No. 7 1/2 gyratories, followed by 48-in. horizontal Symons disk crushers. Fines were removed by 1-in. stationary grizzlies ahead of each unit. In 1924 a third stage of crushing was provided by the addition of 55 1/2-in. rolls in open circuit. During 1925, the Symons disks were replaced by 73 1/2-in. rolls. All the rolls were changed to closed circuit, with elevators and screens to give a final product of 9 pct plus 3-mesh. The flowsheet of a typical crushing section of this period is shown in Fig I. The ore was withdrawn from a common bin serving the five crushing sections in the plant by means of any number up to six 36-in. wide-apron feeders, which discharged onto a common conveyor belt. This conveyor was equipped with a magnetic head pulley and the crusher attendant was stationed near the discharge end to pick out pieces of mine timber that might be in the ore. The ore was discharged over a 1 3/4-in. spaced bar grizzly and the oversize of this grizzly was crushed by a No. 7 1/2 McCully gyratory crusher set at 1 3/4-in. opening on the closed side. The grizzly undersize joined the gyratory discharge and was conveyed to a set of 73 1/2 by 20-in. Garfield rolls set at I in. These rolls operated in closed circuit with a bucket elevator and two vibrating screens placed in parallel.

Jan 1, 1947

By G. R. Belton, Y. K. Rao

A galvanic cell, using liquid MgCl2 or MgC12-CaC12 mixtures as the electrolyte, has been used to determine activities in Mg-A1 liquid alloys between 700' and 880°C. The incovporation of a chlorine electrode in the cell also allowed measurements to be made of the standard free energy of formation of MgCl2(l). The results are shown to be in good agreement with thermo-chetrlical values from the literature, and this is taken as evidence that the small, known solubility of magnesium in iMgCl2 introduces no significant error in galcanic cell measurements. Within experimental error, the activity coefficients and relative partial molar enthalpies at 800°C are shown to be represented by the following "subregular" solution equations: logy~~ =-0.68(1 -xMgj3 log yAL =-1.02(1 - XMf + 0.68(1 - XMf H.M = -4400(1 - %)3 / cal Mg 7Ag' HZ =-6600(1 - xA1)' + 4400(1 - XMf cal SCHNEIDER and toll' have used a transpiration technique to measure the vapor pressures of magnesium over Mg-A1 alloys between 544" and 594°C. amsstad,' however, has since suggested that the extrapolation to zero flow rate, used by these authors in interpreting their apparent pressure vs flow rate data, gives unreliable results. Rogers, Tomlinson, and Richardson,3 in interpreting the results of solution equilibria between Mg-A1 alloys and liquid MgC12, also considered the measurements of Schneider and Stoll to be unreliable and preferred to derive activities for the alloys from the earlier boiling point determinations of ~eit~ebel~ and the partial molar heats recommended by Kubaschewski and ~atterall.~ These latter heats were based substantially on the early calorimetric work of Kawa-kami but, unfortunately, his work on other systems has sometimes been found to be inaccurate.7 Rogers et al., in the above-mentioned paper,3 tentatively concluded that the most likely species responsible for the limited solubility (0.3 mole pct at 800°C) of magnesium in MgC12 were Mg° (neutral) and Mg2++. Two more recent studies8,9 have supported Mg2++ as the soluble species. In the present study, activities in Mg-A1 alloys have been determined by means of a galvanic cell involving liquid MgCl2 or MgC12CaCl, mixtures as the electrolyte. Since the reactive nature of magnesium precluded simple Faraday yield experiments, a chlorine electrode was incorporated in the cell in order that the performance of the cell could be checked by measurements of the heat and free energy of formation of MgC12. This procedure was considered necessary since it has been suggested1' that the solubility of a metal in a molten salt might introduce electronic conductivity; also, previous determinations of the standard electrode potential for MgC12 differed by as much as 70 mv11-13 EXPERIMENTAL Materials. Analyses of the materials used in preparing the alloys and the electrolyte mixtures are presented in Table I. The alloys were prepared by induction melting weighed amounts of the metals in a graphite crucible held under an argon atmosphere. Pure anhydrous magnesium chloride was prepared by heating the mixture MgCl, . 6H20 +NH4C1(1:1) to 650°C, followed by melting under dry argon. The melting point of the dry MgC12 was found by differential thermal analysis to be 714.8oC, which compares well with the accepted value of 714C.14 This agreement was taken to be an indication of the high purity of the dried salt. Table I. Compositions of Materials, wt pn Impurity Mg Al MgCI2 CaCI, Ba - - 0.005 Ca - - 0.010 Cu 0.02 0.02 Fe - 0.10 0.001 0.010 Pb 0.01 - 0.001 0.005 Mn 0.15 0.001 Si - 0.10 Sr - - 0.005 MBSO* - 0.040 ARGON TUNGSTEN CHLORINE LEAD—411 11 II ALUMINA 'A I / ave GRAPHITE on irA~_ ( ^"l ROD MAGNESIUM S>ILICA~^ /, OR ALLOY-. I /A] ___________ -«^- _ ELECTROLYTE I y FRITTED DISCS Fig. l—Arrangement of chlorine and metal electrodes in electrolytic cell.

Jan 1, 1970

By J. D. Edwards, C. S. Taylor, A. S. Russell

Solubilities and densities are reported for alumina hydrates in NaOH solutions under the conditions of the Bayer process employed to purify alumina for aluminum production. The equilibrium constants for reactions to form A102- accurately correlate the effects of NaOH concentration on the solubilities; the temperature coefficients of the equilibria lead to heats of solution of 7.34, 4.76, and 5.24 kcal for the a trihydrate, a monohydrate, and ß trihydrate, respectively. Moderate calcination does not change the solubility of the a trihydrate but increases that of the a monohydrate. At solution temperatures above 100°C, the trihydrates transform rapidly to a monohydrate. Hydro-thermally produced a monohydrate is the stable phase above 20°C. CORNERSTONE of the aluminum industry, the Bayer process for alumina production is based on the difference in solubility of hydrated alumina in NaOH solutions between 170" and 40°C. Solubilities and densities in this system were determined thirty years ago by M. Tosterudl under the direction of J. D. Edwards and C. S. Taylor. The solubility data, which still appear more concordant than those in the literature, are employed to sort out the complex equilibria in this system. The nomenclature for the alumina hydrates is that presented in The Aluminum Industry' and more recently summarized in Alumina Properties.3 a trihydrate is the purified phase analogous to gibbsite, a monohydrate is similarly akin to boehmite, and ß trihydrate is sometimes known as bayerite. Literature Goudriaan4 reviewed the early literature on alumina in NaOH solutions and presented data on the solubility at 30°C of several forms. The gel precipitated from aluminum sulphate or chloride with ammonia and dried at 130" to 140°C had the highest solubility but was unstable, its solubility being cut to one-tenth on standing in NaOH. The solubility of the gel was decreased one-third on calcination at 300" to 400°C, while that of the gel transformed in NaOH at room temperature to a crystalline trihydrate was unchanged on calcination. The preparation produced by slow hydrolysis of sodium aluminate solution with CO, in the air gave solubilities in rough agreement with later values for a trihydrate. The solubility of this form was increased slightly by the calcination. Fricke and Jucaitis5 extended the work to 30" and 60°C with a trihydrate. They also gave solubilities for ß trihydrate (bayerite b), although the residue belonging to the left branch of the solubility curve corresponded to a trihydrate. The residues at high NaOH concentrations were mono and trisodium aluminates, the latter being 3Na2O . AL2O3 • 6H2O. Solubilities of a trihydrate at 95°C and of a monohydrate at 150" and 200 °C come from the work of Magarchak.6 a trihydrate transformed to a monohydrate above 95°C. A few measurements on the solubility at 25°C of an alumina trihydrate prepared by slow hydrolysis of NaAIO, solutions were presented by Sprauer and pearce.? Their analyses showed the monosodium aluminate to have the composition Na2O.Al2O3-2.5H2O.

Jan 1, 1956

By Kenneth R. Hancock

Iron oxides are unique in that they are the only significant colored mineral found in a natural state suitable for use as a pigment after it has been pulverized to pigmentary size. The current world production of iron oxide pig¬ments is estimated by the author to be between 450,000 and 550,000 tons based on 1969 data. The fact that highly colored natural deposits of iron ore are found throughout the world ac¬counts for its use in prehistoric man's artistic cave paintings. These early artists did not realize that they had established man's first paint test fence which now has some 20,000 years of exposure. In addition to abundance, constituting about 7 % of the earth's crust, iron oxides have the advantages of low cost, permanency, and are not toxic. Through the centuries, succeeding civilizations have utilized iron oxides as a major source for decoration and protection when coloring was desired. In the last century the chemical industry has improved on nature by developing a complete range of synthetic iron oxide pigments which surpass the pigments pro¬duced from natural iron ores in uniformity, color quality, and chemical purity. In the United States alone, the combined production of natural and synthetic iron oxides produced sales of over $28,000,000 in 1970 (Stipp, 1970). Nomenclature With the increasing importance of the syn¬thetic iron oxides it is necessary to make a distinction between the natural or mineral pig¬ments and the synthetic pigments. Natural pigments are those products which are derived from selected ores and should not be confused with iron ores mined for steel production. Iron ores that are mined for steel must be capable of being mined and reduced to iron on a com¬mercial basis. These ores are selected on the basis of iron content and processing economics. It is therefore unusual when iron ores for steel production are suitable for use as mineral pig¬ments. Natural pigment ore sources are se¬lected for their special physical-chemical prop¬erties and can command a premium price. Synthetic pigments, and in this instance iron oxides, are those pigments produced from basic chemicals. Through chemical synthesis pig¬mentary sized particles are produced as opposed to comminution, the major procedure common to all natural iron oxide pigments.

Jan 1, 1975

By AIME AIME

WITH the example of the steel open-hearth men and their round table conference before the copper men, the query naturally arose "Why cannot we do likewise?" The advantage of pooling and comparing knowledge on smelting in the copper reverberatory furnace seems particularly pertinent at this time when all metallurgical economies possible must be rigorously enforced. A great deal of data had also been obtained and filed during the period of litigation over the Carson patent, and it would naturally be available with the cessation of further suits. With these ideas in mind, H. Foster Bain took up the advisability of holding such a conference directly with the heads of all the companies in the United States operating copper reverberatories, and found a nearly unanimous response. The mining companies appointed representatives directly, or indicated to the heads of various metallurgical operations what members of their staffs should be sent to such a conference.

Jan 1, 1930

By HORACE H. EJIRICH

(New York Meeting, February, 1912.) PREFATORY NOTE.-The first part of this paper was sent to me by Mr. Emrich nearly nine months ago ; and. I held it, waiting for the second part, which he had promised to forward soon, so that I might submit the whole to some of his former professional associates, and advise him of their criticisms and suggestions before offering his work to the Institute. But, five days before the second part reached me, I received by telegraph the news of Mr. Emrich's sudden death. The paper has therefore not had the benefit of such a revision by the author as might have made it in some respects clearer and more complete. Nevertheless, I believe that experts in the branch of metallurgy with which it deals will find it both original and suggestive.-A. EILERS. I. PARTIAL REFINING IN THE ANODE-FURNACE. During my connection with one of the large New Jersey copper-refineries, and probably before that period, from 15 to 20 per cent. of the copper-bullion received was the very foul, leady blister-copper produced from lead blast-furnace matte. It had been customary to mix a small part of this blister with each charge of purer pig-copper, in the effort to dilute it as much as possible before casting into anodes; but tank-house conditions were such that I was led to try making entire furnace-charges of this blister, and refining it as much as possible in the furnace-afterwards casting to anodes and refining electrolytically, in tanks and solution separate from the main bulk of the purer copper. In making this experiment, notes were made, for several furnace-charges, of everything thought to have a bearing on the question, and some interesting facts were brought out, both in the furnace-working and afterwards in the tanks.

Jun 1, 1912

By A. G. Guy

IN the course of a research on steady-state diffusion it became necessary to make diffusion calculations for a finite solid. This problem was found to be sufficiently different from the corresponding problem for the semi-infinite solid for an entirely new approach to be necessary in obtaining a useful solution. The assumption of an exponential variation of the diffusion coefficient with concentration' was no longer a practical necessity, so that the new solution offered the possibility of handling diffusion in semi-infinite solids for arbitrary variations of the diffusion coefficient with concentration. In discussing the principle on which this method of calculation is based, it is convenient to consider the relatively simple problem of one dimensional diffusion into a matrix that initially contains none of the diffusing substance. The solution of the set- ond Fick Law,?C/?t=D0?2C/?x2, for diffusion into a semi-infinite solid is3 C/C=1-F(x/2vD0t [1] where C is the concentration of the diffusing substance at a depth x cm below the surface after dif- A. G. GUY, Member AIME, and M. GOLOMB are Professor of Metollurgicol Engineering and Professor of Mathematics, respectively, Purdue University, Lafayette, Ind., A. S. YUE, formerly with Purdue University, is now with the Research Laboratory, Dow Chemical Co., Midland, Mich. TP 4505E. Manuscript, July 18,1956. fusion has occurred for t seconds; C, is the concentration of the diffusing substance at the surface of the matrix; Do is the diffusion constant, expressed in sq cm per sec; and + represents the Gauss error function. The corresponding solution for diffusion into a finite solid of thickness, 1, is conveniently written for the change in concentration, C+, at a point midway through the matrix and for times, t, great enough for the following equation to be used4 c1/2/C1=(1/2-2/?e-?2D0t/l2) [2] In Eqs. 1 and 2 the diffusion coefficient is represented by the symbol Do (rather than by D) to emphasize that these equations are valid only for constant values of D. To understand how these equations can be modified to take account of actual variations of D, such as that shown in Fig. 1, first consider the fact that for a given time of diffusion theconcentration at a given point is determined, not by the D value alone, but by the ratio x/vD0 in Eq. 1 and by a similar ratio, l2/D0 in Eq. 2. Even though in fact D varies, it is possible to keep this ratio constant by using a special coordinate system, x,, that varies with D in the appropriate manner. The necessary character of this special coordinate system can be easily visualized by imagining that

Jan 1, 1958

By B. L. Averbach, M. F. Comerford, M. B. Rough

The volume fraction of ß phase was determined in a Ti-6Al-4V alloy by measurements of integrated diffraction intensities. The (0002), and (100)ß diffraction lines were chosen because this combination minimizes the errors resulting from preferred orientation. The difficulties arising from fluorescence radiation were eliminated by use of a diffracted beam monochromator. A specimen quenched from 1475OF (800°C) contained approximately 5 pct ß, but in specimens quenched from higher temperatures no ß was found. The ß phase formed during aging, and in specimens solution treated at 1570oF (855oC) approximately 10 pct ß was present after aging at 1000°F (540°C) for 24 hr. This ß appears to form by decomposition of martensitic a'. ThE kinetics of the reactions which occur during the heat treatment of titanium alloys are complex ' and not completely understood. It has been proposed that hardening occurs in some alloys' on aging by the precipitation of a transition phase w followed by the formation of the stable a and ß phases. It has been proposed for other alloys2 that the a' marten-site decomposes by precipitating finely dispersed a particles. Most investigations have been hampered by the difficulties of determining quantitatively the amounts of the various phases present. This paper is concerned with the measurement of the amount of ß phase by an X-ray method, similar to one developed for the determination of retained austenite. The principal new feature was the use of a mono-chromator in the diffracted beam in order to reduce the fluorescence arising from the sample. EXPERIMENTAL PROCEDURE The experiments were carried out on an alloy of nominal composition Ti-6Al-4V (actual weight percentages: 6.2 Al, 4.1 V, 0.02 Mn, 0.17 Fe, 0.005 H, 0.03 C, and 0.02 N). The material was received as 5/8-in.-diam centerless ground rods in the annealed condition. The heat treatments were carried out in a vacuum of approximately 0.03µHg. The X-ray intensity measurements were made on 3/8-in. thick discs. The surface was prepared by grinding off about 0.060 in. and electropolishing in a solution af 60 ml (70 to 72 pct) perchloric acid in 1000 ml glacial acetic acid with a current density of 0.5 amp per sq cm.q The X-ray determination is based on the proportionality of the diffracted intensity of each line to the volume fraction of the corresponding phase. In calculating the intensities for a powder sample it is assumed that a large number of grains con- tributes to the diffracted intensity and that the grains are oriented at random. The presence of preferred orientation introduces serious errors in the relative intensities. The material used in this investigation exhibited a strong preferred orientation, which could not be removed by heat treatment. Other investigators have also found that preferred orientation may be retained after phase transformations. Glen and pugh5 performed a detailed analysis of the randomness expected after several allotropic transformations, but stated that this is not observed. Burgers,6 and Burgers and Ploos van Amstel,7 found that, in zirconium, the original orientation is retained after two phase transformations. Newkirk and Geisler8 observed similar behavior in titanium. On the basis of this evidence, it appears that, in the absence of plastic deformation, textures present in annealed titanium alloys are retained. Heating an a-ß alloy to the all-ß region and subsequent cooling to room temperature do not make the orientation of the mar-tensite different from that of the original a phase. In the present investigation it was possible to take advantage of the crystallographic relationships involved in the martensitic transformation to minimize the errors associated with preferred orientation. The relative orientation for titaniu-m marten-site9 takes the form (0001), 11 (110)ß; [1120], 11 [lll]ß. The same relationship has been proposed for zirconium' and certain titanium-base alloys.10-12 Additional sets of approximately parallel planes have been determined for titanium-nickel alloys." The influence of preferred orientation can be minimized by comparing intensities from parallel planes in the two related phases. If it is assumed that each family of planes in a given phase is equally well populated, the effect of preferred orientation can be eliminated by using the normal multiplicity for the family of planes since each set of parallel planes is equally preferred for any orientation of the sample relative to the X-ray beam. The most suitable combination of reflections in the Ti-6A1-4V alloy appeared to be (0002), and (110)ß It must be recognized that the ß formed during aging of the Ti-6A1-4V alloy is a precipitate rather

Jan 1, 1960