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By T. D. Tiemann

Extraction of silica from the taconites of the Wisconsin Gogebic range by high temperature digestion in caustic solutions has been described.1,2 The ores consist essentially of hematite, goethite, and microcrystalline quartz, detailed descriptions of which appear in the literature.1,3 It is the purpose of this communication to describe some results obtained from a laboratory investigation of an alternative method, that of sintering the ore with sodium carbonate followed by water extraction of the sodium silicate produced. This is analogous to the Deville-Péchiney4,5 soda ash sinter process for the production of alumina from bauxites in which soluble sodium aluminates are formed. Raw mixes of the desired composition were prepared from 10.0 g minus 200 mesh samples of taconite and sintered in nickel crucibles in a muffle furnace controlled to within ±10°F of the operating temperatures. The resulting sinters were pulverized and then leached in distilled water with continuous agitation for 30 minutes at 95°C. The suspensions were vacuum filtered and the residues dried, ignited and weighed. Iron assays on the ignited samples were made by the standard dichromate procedure after dissolution in hydrochloric acid. The percentage of extraction was calculated from the iron assays by the relation:

Jan 1, 1964

By R. A. Stauffer

The chief ore of lithium is spodumene, a lithium-aluminum silicate containing up to 3 pct lithium. The preparation of lithium salts from spodumene is costly because of the low concentration of the metal and the difficulty of separating it from the other alkali metals present. Dr. Kroll's and Dr. Schlecten's recent paper1 has reviewed various methods proposed for preparation of lithium. It will be seen from this paper that the methods proposed to date have required one or another of the lithium salts as a raw material. The high cost of these salts has been the chief item of expense in the lithium metal produced. This situation has made it interesting to investigate the possibility of producing the metal directly from spodumene. When spodumene is calcined at 1000ºC in the presence of lime, lithium oxide is replaced in the ore as is evidenced by the fact that it may be leached from the reaction mixture with water.2 Free energy calculations suggested that lithium oxide might be reduced with aluminum or silicon and the lithium produced distilled from the reaction mixture by heating-to about 1000ºC in a vacuum. These facts taken together suggested that it might be possible to prepare lithium metal directly from spodumene by heating a mixture of the ore, lime, and a suitable reducing agent in vacuum and distilling off the lithium metal as formed. The Replacement of Li2O in Spodumene A series of experiments were undertaken to determine the ratio of lime to spodumene necessary to free substantially all the lithium oxide Present in the Ore. The spodumene used in these experiments was supplied by Foote Mineral Co. in the form of powder of about 200 mesh' Analysis of the spodumene was as follows: PCT SiO2......................... 62.7 Al2O3........................ 29.9 Li2o......................... 4.9 Na2O........................ 0.89 CaO......................... 0.75 MgO........................ 0.49 K2O......................... 0.44 Lime (cp —200 mesh) was added in various ratios to spodumene and thoroughly mixed in a ball mill. Two hundred gram samples of spodumene-lime mixtures were charged loosely in fireclay crucibles and held at 1000ºC in a gas-fired furnace for 5 hrs. The product in each case was ground to pass 140 mesh and then placed in a thimble in a soxhlet extractor. Extraction with water was carried on for 6 hrs. After this period the extract was reduced in volume by evaporation in order to precipitate dissolved lime and was then filtered and titrated with 1/4 normal hydrochloric acid. After correcting for residual calcium oxide in solution, the alkali present was calculated as lithium oxide. The results of these experiments are shown in Table I and Fig I. At lime-spodumene ratios less than 1.5, the products were invariably fused. At the ratio of 1.5 and above, the product was loosely sintered with little evidence of fusion. When the ratio of lime to spodumene was three, replacement of alkali oxides in the

Jan 1, 1949

By Arnulf Muan, Klaus Schwerdtfeger

Equilibrium ratios C02/C0 of a gas phase coexisting with selected phase assemblages of the system Fe-Mn-0 have been determined in the temperature range 1000" to 1300°C. The oxygen pressure for the "hfnO" +hfn30, equilibrium and for the "(Fe,hTn)O" + (Fe,Mnh 0* equilibrium at high manganese contents has been determined by electromotive force measurements using stabilized zirconia as a solid electrolyte. The notstoichometry 01' "hTnO" and of "(Fe, iM1z)O" solid solutions has been determined by ther-mog-/avi?netry and by wet-chemical analysis. The data obtained are used to derive activity-composition relations in "(Fe,hfn)O" and (Fe,Mn),O4 solid solutions. WUSTITE "FeO" and manganosite "MnO" form a continuous series of solid solution at high temperatures,' and so do magnetite Fe304 and the high-temperature, cubic modification of Mn304 (Ref. 2) (high hausmannite, -1170). The oxides "FeO" and "MnO" are cation-deficient phases.495 The nonstoi-chiometry of "(Fe,Mn)O" solid solutions has been studied by Engell and ~ohl' at two selected C02/C0 ratios at 1250°C. The two oxide end members of the spinel solid solution, FesO4 and Mn,04, however, are known to be close to stoichiometric under the experimental conditions used in the present investigation.''' The oxygen pressures of "(Fe,Mn)07' solid solutions in equilibrium with iron have been determined by Schenck and coworkers,8 by Foster and welch," and by ~n~e1l.l' The two former groups equilibrated the condensed phases in C02-CO atmospheres of lmown compositions, whereas Engell" used a galvanic cell with stabilized zirconia as a solid electrolyte. The results of these investigators are not in good agreement. Activities of FeO in manganowiistite as calculated from the results of Foster and Welch show ideal behavior, those of Engell yield a pronounced positive deviation, and those of Schenck et 01. show a moderate positive deviation from ideality. In the present work oxygen pressures for the iron + manganowiistite and manganowustite + spinel equilibria and the nonstoichiometry of manganowiistites have been measured. The data were used to calculate activities in the manganowiistite and spinel solid solutions. EXPERIMENTAL METHODS The COz/CO ratios at which manganowustite and iron are in equilibrium were determined by thermo-gravimetric and quenching methods. Experimental details are described in a previous publication.'2 In the thermogravimetric technique, incipient reduction of manganowiistite pellets to metallic iron was observed as a break in the weight vs log COZ/CO curve. In the quenching technique, manganowiistite samples were partially reduced to metallic iron, or the metallic iron of manganowustite + metallic iron mixtures was partially oxidized to manganowustite, in atmospheres of constant C02/CO ratios. After quenching the composition of the oxide phase was determined by X-ray lattice parameter measurements and comparison with a standard curve obtained from oxide solid solutions of known compositions. The nonstoichiometry of "MnO" and "(Fe,Mn)07' solid solutions was determined by chemical analysis of samples equilibrated in C02-CO atmospheres and quenched to room temperature, as well as thermo-gravimetrically by reducing (Fe,Mn),04 or Mn304 to manganowiistite or manganosite. The equilibrium between manganowiistite and (Fe,Mn),04 was measured thermogravimetrically by reducing (Fe,Mn),04 solid solutions having composition in the range of %„ l(NFe +NM) from 0 to 0.63. No experiments could be performed with this technique at higher manganese contents, because the equilibrium C02/C0 ratios are too large for accurate control. An additional difficulty arises at the higher manganese contents due to the strong increase in oxygen content of the manganowustite phase with increasing log Py near the manganowiistite-spinel boundary. Consequently a sharp break in the weight loss vs log C02/CO curve cannot be observed at the phase boundary. At high manganese contents of the manganowiistite, e.g., (NMn/(NF~ + NMn) > 0.9, electromotive force measurements with stabilized zirconia as a solid electrolyte were made to determine the equilibrium oxygen partial pressure. Experimental details are described in a previous paper.* Mixtures of "(Fe,Mn)O" and (Fe,Mn),04 were pressed to pellets, and the oxygen pressure of the equilibrated samples was compared to that of Ni + NiO mixtures in the cell The composition of the manganowiistite in the equilibrated two-phase mixture was determined by lattice parameter measurements and comparison with known standards. The oxygen pressure for the Ni + NiO equilibrium was taken from available data.l3~l4 No reliable results were obtained with the electromotive force technique on iron-rich oxides. The electromotive force drifted strongly with time in this composition range. An additional difficulty arises from the partial de-

Jan 1, 1968

By P. G. Winchell, A. J. Heckler

An experimentally simple method for determining the effect of alloying elements on the activity of carbon is validated in Fe-Ni-C austenite. The technique consists of the equilibration of carbon between specimens of different nickel contents within a sealed silica capsule. The attainment of carbon equilibrium within each capsule is evidenced by: 1) in each capsule specimens of the same nickel content attained the same final carbon content regardless of their initial carbon contents, 2) in every capsule the final carbon content was reached for most nickel contents by carburizing and by decarburizing. The activity of carbon attained within each capsule was calculated from the carbon content of a binary Fe-C alloy placed within the capsule, and from the activity coefficient of carbon in the Fe-C system as found by Smith for CO/CO2/C equilibrium. The activity of carbon in Fe-Ni-C austenite determined by this method at 1000°C agrees with prior work by Smith, who used mother method. The measurements are extended to 800°and 1200°C. The activity coefficient of carbon 7c, in Fe-Ni-C austenite is given by: where xC is the ratio of carbon to metal atoms and XNi is the ratio of nickel to metal atoms and where the standard state is chosen such that yC = 1 as xc approaches zero in Fe-C alloys. This equation appears to be valid for xni < 0.3, and 1073° < T<1473°K. ThE activity of carbon in Fe-C austenite has been measured by smithL at 800°, 1000°, and 1200°C. Smith has also studied the effect of nickel on the activity A. J, HECKLER and P. G. WINCHELL are Graduate Student and Associate Professor of Metallurgical Engineering, respectively, School of Metallurgical Engineering, Purdue University, Lafayette, Ind. This paper is based on a thesis submitted ty,to Purdue University, in partial fulfillment of the requirements for the degree of M.S. in Metallurgical Engineering which A. J. HECKLER received from Purdue in January 1962. Manuscript submitted August 13, 1962. IMD of carbon in austenite at 1000°C. In both these studies the activity of carbon was fixed by a flowing CO-C02* *Gas mixtures of hydrogen and methane were also used in Ref. 1 but these results are not incorporated in Ref. 2 or in the present study. gas mixture. In the present work, Smith&apos;s results for Fe-Ni-C austenite are confirmed and extended to 800" and 1200°C by a different experimental technique. EXPERIMENTAL PROCEDURE In essence the experimental technique consisted of enclosing specimens of various nickel contents in an initially evacuated silica capsule and annealing the capsule until carbon equilibrium was attained among the enclosed specimens. The carbon activity obtained within the capsule was determined from the final carbon content of the binary Fe-C alloy included in each capsule and the results of smith.&apos; In order to evaluate this method the absence of nickel transfer between specimens must be established and the attainment of carbon equilibrium between samples must be assured. The absence of nickel transfer was demonstrated in the case of an originally pure iron sample which was annealed at 1200°C in a capsule with a 27.3 at. pct Ni alloy. The final nickel content of the iron specimen was less than 0.1 at. pct, a change which has a negligible effect on carbon activity. The attainment of carbon equilibrium was demonstrated within every capsule and in over half the results by achieving the same final carbon content in a sample which carburized during equilibration and in a sample of the same nickel content which decarburized during equilibration. The base Fe-Ni alloys were vacuum melted from Ferrovac E or electrolytic iron and Mond or electrolytic nickel. The samples were rolled and/or swaged and their carbon content adjusted to the desired pre-equilibration level either by methane-hydrogen carburization or by direct carbon transfer from a graphite source in a sealed silica capsule. As mentioned previously, high-carbon and low-carbon samples were prepared for most nickel levels in each capsule. The specimens were cleaned and

Jan 1, 1963

By M. J. Duggin

Evidence is produced below to show that the carbide "Mn,C," reported by Kw,and ersson&apos; is really a mixture of two carbides. One is an Fe-Mn carbide which is probably isomorphous with hexagonal Mn15C4, reported by Bouchand and Pruchart.&apos; The othev is a tetragonul Fe-Mn carbide with cell dzmensions close to those reported previously by the author3 for an Fe0.1Mno. carbide. IN a recent investigation several Fe-Mn carbide specimens, each weighing about 5 g, were prepared in a manner previously reported.3 Debye-Scherrer X-ray photographs were taken of at least two samples from different parts of each specimen using a 114.6-mm-diam camera. The exposure time was 2 hr using filtered chromium radiation, a tube voltage of 35 kv and a tube current of 10 ma. In the case of one specimen, which contained nominal weight percentages of iron, manganese, and carbon of 9.40, 84. 6,, and 6.0, respectively, duplicate chemical analyses indicated f1.2 and 5.5 wt pct C to be present in the two samples taken of the specimen: no graphitic carbon was detected. One powder-diffraction pattern of this specimen indicated the presence of the tetragons: carbide reported earlier,3 (a = 6.772A, c = 9.427A), plus cementite (O), plus an unknown structure. The second powder-

Jan 1, 1970

By P. Beardmore, A. H. Holtzman, M. B. Bever

Specimens of the alloy CU3AU in the ordered and disordered states were subjected to explosive loading at shock pressures in the range from 160 to 475 kbars. The resulting changes in the resistivity, stored energy, microhardness, and microstructure were determined. By comparing the effects of explosive loading on ordered and disordered specimens a separation of structura1 and configurational changes has been made. In the pressure range from 290 to 370 kbars, representing a small increment of strain, the degree of long-range order in the ordered alloy decreased sharply. This change is attributed to the generation of shear stresses in excess of the theoretical shear strength of the alloy. Disordered CU3AU under explosive loading behaves in a manner considered to be characteristic of fee solid-solution alloys generally. The response of metals to high-velocity deformation and, in particular, to explosive loading has attracted much interest in recent years.&apos; In general, metals are substantially strengthened by the passage of shock waves although the permanent strains are small. Explosive loading induces this strengthening by causing the metal to undergo rapidly a transient strain in a narrow region, first in the shock front and then in the rarefaction wave, which releases the pressure. The transient strain is given by e = 4/3 In V/Vo, where Vo and v are the specific volumes in the uncompressed and compressed states.2 The process produces many defects, which account for the strengthening. For the investigation reported here, an ordered alloy was chosen because it was expected to give sensitive indications of the near-neighbor effects produced by shock waves. The ordered alloy CU3AU was of special interest because of past work on the effects of conventional deformation on this alloy.314 The disordered alloy was included as a standard for comparison and as an alloy typical of a solid solution containing short-range order. The effects of explosive loading were followed by measurements of the resistivity, stored energy, and microhardness, and by metallographic examination. EXPERIMENTAL PROCEDURES Preparation of Specimens. Part of an ingot of the alloy Cu3Au prepared previously4 was cold-rolled with several intermediate anneals in vacuum to a final thickness of 0.042 in. Specimens of dimensions 2.0 by 1.0 by 0.042 in. were machined from this strip. After a recrystallization treatment of 1 hr at 565oC, half of the specimens were disordered by heating in evacuated Pyrex capsules for 1 hr at 460°C and quenching into water. Although they contained short-range order, they will be referred to as &apos;disordered" to indicate the absence of long-range order. The rest of the specimens were cooled slowly from 380°C to induce long-range order. The grain size of the ordered and disordered specimens was 0.012 mm. Explosive Loading. This was carried out at the Eastern Laboratory, Explosives Department, E. I. du Pont de Nemours & Co., by a driver-plate procedure described elsewhere.2 Two ordered specimens were stacked alongside two disordered speci-

Jan 1, 1964

By T. L. MacKay

Oxidation rates of single-crystal and poly crystalline zirconium in oxygen at temperatures from 307° to 815°C obey the parabolic rate law for short ex-posure time, 4 to 6 hr. The activation energy for the oxidation of single-crystal zirconium between 420° and 790°C is 42.6 ± 0.7 kcal per mole, and in the temperature range 307" to 600°C the activation energy for oxidation of poly crystalline zirconium is approximately the same. The high-activation energy is indicative that diffusion through the bulk oxide film is the primary mode of mass transport for both types of metal. The higher oxidation rates for poly -crystalline zirconium in this temperature range were attributed to differences in the orientation of the grains in the metal with respect to the oxidizing surfaces. Above 600°C, vain growth was observed in polycrystalline zirconium, and the oxidation rates approached those of single-crystal zirconium. ThE kinetic data of previous oxidation studies1-&apos; of zirconium in oxygen have been interpreted by both parabolic and cubic rate laws. There is some evidence that there is a transition from the parabolic to the cubic rate law at prolonged exposures, but the question is still controversial. For the parabolic rate law activation energies are reported in the range 18.6 to 35 kcal per mole, and for the cubic rate law in the range 38 to 47 kcal per mole. So far as the mechanism of zirconium oxidation is concerned, inert marker studies10,11 have indicated that the oxidation proceeds by oxygen (anion) diffusion through the oxide film toward the metal-metal oxide interface. Pemslerl2 observed that the orientation of the grains in the zirconium metal substrate affected the rate of formation of the oxide film on the surfaces of the grains and that the orientation dependence of the corrosion rate persisted beyond the initial stages of reaction. The rate of oxidation was a minimum when the c axis of the grain was parallel to the surface of the sample, and rose to a maximum when the c axis was inclined at about 20 deg to the plane of sample surface, and decreased again at higher inclinations. cox13 observed that in 300°C steam a thin oxide film was formed initially on zirconium and that this oxide film, which exhibited interference colors, became dark first along the grain boundaries and then over the whole surface in an inhomogeneous manner as the film thickened. Cox proposed a mechanism in which oxygen diffused along preferred paths created by grain boundaries in the metal and formed a much thicker film at or near the grain boundary than on the central zone of the grain. In the present study, the oxidation rates of single crystals of zirconium were measured in oxygen and compared with the oxidation rates of polycrystalline zirconium of the same bar stock. It was felt that such a comparison would elucidate the role of grain boundaries in the metal substrate. SAMPLE PREPARATION Single crystals of zirconium were prepared by following the procedure of I3apperport,14 starting with 1/4-in. rod purchased as crystal-bar zirconium. Zirconium rods 2 in. long were wrapped in tungsten foil and sealed in quartz tubes at pressures of less than 10-6 mm of mercury. Large single crystals were grown by thermal cycling above and below the a-/3 transformation temperature, 862°C. Several specimens were simultaneously subjected to the same cycling procedure, heating to 1200°C, holding for 4 hr, then cooling in the furnace and holding at a temperature of 840°C for 5 to 10 days. This cycle was repeated five or six times for each set of specimens. The grain size of the crystal-bar zirconium before thermal cycling was between 10 and 30 p. Fig. 1 shows the microstructure of an end section of as-received crystal-bar zirconium. A longitudinal section of each zirconium rod after thermal cycling was polished and examined under polarized light, see Fig. 2, and the largest single crystals were selected for this study. Zirconium rods 1/8 in. in diameter and 1/2 in. long with spherical ends were machined from the single crystals and from the as-received bar stock. An X-ray examination showed that the c axis of the single crystals made either a 34-deg or an 89-deg angle with the rod axis. The specimens were chemically etched for 2 min in solution consisting of 15 parts hydrofluoric acid (48 pct), 80 parts nitric acid, and 80 parts water. The chemical polish removed 1 to 2 mils from the surface. EXPERIMENTAL The Sartorius vacuum microbalance used in this study has a sensitivity of 0.5 pg and a capacity of

Jan 1, 1963

By John Henry Harden

WITH imperfect instruments it is impossible to make accurate surveys; the results are inaccurate maps, with their attendant consequences. The design of the writer is to describe an improved form of tripod head, and certain defects in an English transit and a miners&apos; dial, with the method taken to remedy the defects of the transit. When the present transit superseded the surveyor&apos;s compass, there was one special objection brought against it, and with some show of reason ; namely, that the tripod of the compass with its ball and socket motion, allowed a quicker levelling-up (and, consequently, more work) than was possible with the transit. To this objection it was replied, that the ball and socket would not allow the instrument to be levelled with the same degree of precision that could be attained with the levelling screws, and that if time was sacrificed greater accuracy was attained. Nevertheless, it is a well-known fact that in this country, and especially in England, the compass or miners&apos; dial holds its ground solely from its rapid adjustment. Ever since the introduction of the transit, efforts have been made to give to this instrument the same facility of levelling possessed by the compass or dial, and the same means have been tried, i. e., a . ball and socket motion, since a modification of this in some form was the only method that would answer. The upper part of a transit is, however, much heavier than the corresponding parts of a compass, and, therefore, requires more binding power, which cannot be ob¬tained with an ordinary ball and socket joint. It has been a study with instrument-makers to combine the facility of these two tripods -the quickness of the ball and socket with the steadiness and accuracy of the screws; but in all attempts in this direction the ball and socket of the compass has been literally followed, the entire stability of the instrument depending upon the friction of the ball in its socket. There is great need for a tripod that can be more easily manipulated than the present form, for it rarely happens that an engineer has a level surface on which to set his instrument, and very often

Jan 1, 1879

By W. J. Tait, A. E. Craig, E. P. McCurdy

C. M. Marquard—The problem of the automatic control of a grinding-classification circuit is not nearly as simple as has been indicated and it cannot be universally solved through the application of this device. The sound emanating from a ball mill such as the metallic clink of the balls against the liners can at times be misleading. The fact that the sound level due to the balls hitting the liners may be at a minimum does not necessarily mean that the mill is properly loaded. I have in mind an ore we treat that has a soft talcy gangue. The soft fluffy nature of this material makes the sound from the ball mill a most misleading parameter that is worthless as a means for controlling the amount of ore fed to the mill. In every milling plant there are transportation lags due to the time it takes the ore to travel from the mill bins to the ball mill. In many plants there may be several different transportation lags due to varying distances of bins from ball mill. These transportation lags can most seriously affect the operation of a controller. It has been found that under many circumstances the transportation lags can be so bad as to cause the controller to hunt seriously. Hunting can and in many cases does become so serious as to render automatic control impossible because of the surges it causes. While it is possible to compensate for this type of lag, this apparatus does not lend itself readily to accomplish the required compensation. Further, if there are groups of bins at various distances from the ball mill, compensation for one may not be sufficient or may be too great for another. Each milling plant presents a separate problem. The apparatus as presently described does not appear sufficiently flexible to accomplish this. It should be noted that the load on the classifier rakes is determined by measuring the current input to the rake drive motor. Variations in line voltage will

Jan 1, 1951

By E. P. McCurdy, W. J. Tait, A. E. Craig

C. M. Marquard—The problem of the automatic control of a grinding-classification circuit is not nearly as simple as has been indicated and it cannot be universally solved through the application of this device. The sound emanating from a ball mill such as the metallic clink of the balls against the liners can at times be misleading. The fact that the sound level due to the balls hitting the liners may be at a minimum does not necessarily mean that the mill is properly loaded. I have in mind an ore we treat that has a soft talcy gangue. The soft fluffy nature of this material makes the sound from the ball mill a most misleading parameter that is worthless as a means for controlling the amount of ore fed to the mill. In every milling plant there are transportation lags due to the time it takes the ore to travel from the mill bins to the ball mill. In many plants there may be several different transportation lags due to varying distances of bins from ball mill. These transportation lags can most seriously affect the operation of a controller. It has been found that under many circumstances the transportation lags can be so bad as to cause the controller to hunt seriously. Hunting can and in many cases does become so serious as to render automatic control impossible because of the surges it causes. While it is possible to compensate for this type of lag, this apparatus does not lend itself readily to accomplish the required compensation. Further, if there are groups of bins at various distances from the ball mill, compensation for one may not be sufficient or may be too great for another. Each milling plant presents a separate problem. The apparatus as presently described does not appear sufficiently flexible to accomplish this. It should be noted that the load on the classifier rakes is determined by measuring the current input to the rake drive motor. Variations in line voltage will

Jan 1, 1951

By H. Scott

Since Bohler discovered, in 1903, on cooling certain alloy steels, the phenomenon of a new and lower temperature transformation than the usual Ar 3-2-1 obtained by increasing the maximum temperature to which the material was heated, much has been published1 connecting this phenomenon with a large number of dissimilar steels of high alloy content. From the fact that the transformation divides itself, taking place at two widely separated temperatures, it has been called a "split transformation." The significant facts established by recent investigators2 are: that when the transformation occurs at the higher temperature Ar1, troostite or a decomposition product is formed, and that when the transformation occurs at the lower temperature Ar", the resulting structure is martensite. The terminology Ar&apos; and Ar" adopted here is that of Portevin. Previous Investigations Reviewing the work on this subject published in a recent issue of Revue de Metallurgie and referring in particular to his statement that martensite is a solution of carbide in alpha iron, Le Chatelier says :4 "How then can a theory already 20 years old demand new investigations? The reason for it is that we have not succeeded in proving directly the real presence of the transformation of iron during the very short duration of the quenching. The fall of temperature takes place at the rate of several hundred degrees per second and the observation of

Jan 1, 1920

By Hannon, J. W. G.

Silicosis is today&apos;s most important industrial disease and probably dates back to the Stone Age. Since the industrial revolution, increasing attention has been paid to those occupations where mineral dust is present in the air breathed by the workers. For many years it was assumed that the inhalation of all mineral dusts was hazardous. but investigations conducted in several countries pointed the statistical finger of guilt at free silica in any of its numerous physical forms as a dust of outstanding toxicity. Recognition of silica as the chief hazard has resulted in widespread use of the term "silicosis." Depending upon the concentration of finely divided silica dust to which the individual is exposed and the duration of exposure, silicosis may become a disabling condition in from one to thirty years. The structure of the lung and respiratory passages is such that only minute particles of silica can gain entry to the air cells in the lung (5 microns or under are most toxic). When these minute particles gain entry to the lung tissues they stimulate certain protective cells in the lung to multiply at an excessive rate. The cell&apos;s undergo inflammatory changes which result in nodular scars and a low-grade inflammation of the lung tissue. These progressive changes in the lung structure gradually encroach

Jan 1, 1949

By M. C. Fuerstenau, D. W. Fuerstenau

Studies of the collection of alkali and ammonium halides utilizing vacuum flotation techniques and contact angle measurements show that ionic size controls the flotation of techniquesthese halides with amine salts measurementsas collector. Contact angles of air bubbles on sylvite in saturated brines were withaminemeasured salts asascollector.a function of such variables as collector addition, length of collector chain, and pH of the brine. No contact occurs between halite and an air bubble in brines containing dodecylammonium acetate as collector. LONG-CHAINED aliphatic amine salts have been used for the separation of sylvite (KCl) from halite (NaCl) by flotation.1,2 It is puzzling how these two minerals, which are so similar chemically and crystallographically, can be separated by this method. Gaudin" has postulated that the difference in floatability of halite and sylvite with salts of primary amines depends on ionic size: In the case of amine flotation, the cation would attach itself to the chloride. I have a speculation there, which I cannot prove, that the ammonium group, that is the —NH3 group in the amine, floats potassium chloride because the dimensions of this grour, as it has been measured in other compounds is almost identically the dimensions of the potassium ion, quite different from the sodium ion, and so it fits where potassium had been, in place of it and not attached to it. Apparently, because an aminium ion (RNH3+) is much larger than a sodium ion, it cannot fit into the lattice of halite. Taggart also has speculated that ionic size may control the floatability of sylvite.4 The object of this experimental investigation has been to test this hypothesis and to study what controls the adsorption of cationic collectors at the surface of sylvite. Since collection is to be approached from the viewpoint of ionic size, the ionic radii that are of interest in this work are presented in Table I. The values of the ionic radii of the ions listed in Table I, except NH4+, are those given by Pauling." Several different values for the radius of the ammonium ion have been given, but that of Goldschmidt6 seems to be preferred. The radius of the charged head of a dodecylammonium ion is assumed to be the same as that for the ammonium ion. Little experimental work has been reported in the technical literature concerning the separation of sylvite from halite by flotation. Guyer and Perren studied the separation by flotation of 50 pct binary mixtures of NaCl, KC1, NH,Cl, NaNO3, KNO3, K2SO4, and Na,SO, using either oleic acid or a sodium sul-fonate as collector.&apos; It is possible to measure floatability under actual flotation conditions where all three phases, air- water-mineral, are present by vacuum flotation tests and contact angle measurements.9 Both of these techniques were used in the experimental approach in this paper. Experimental Method and Materials The vacuum flotation tests were run with glass-stoppered pyrex graduated cylinders. Twenty-five ml graduates were used to test the floatability of all salts studied except rubidium and cesium salts. For each test distilled water containing the desired collector concentration was saturated with the salt to be floated. Sufficient salt (—48 mesh) was added to leave about 2 ml of solids in the bottom of the graduate. After the graduate had been agitated several minutes to saturate the solution with air, a vacuum was applied. If the salt were floatable in the collector solution, the gas bubbles attached themselves to the particles, and the particles floated to the surface. In determining the floatability of the expensive Rb and Cs halides, the experiments were run in 10 ml graduates with about 11/2 ml of collector solution initially. Contact angles were measured in the usual manner except that the solutions had to be previously saturated with the mineral to avoid dissolution of the crystal. Solutions for studying contact angles were made by adding the desired amount of collector to a saturated brine, giving the collector concentration in molarity. The mixture was agitated until dissolution of the collector was complete, with the exception of those concentrations greater than about millimolar. At these high concentrations complete dissolution of the collector was impossible. The face of the mineral to be tested was a freshly cleaved crystal of halite or sylvite. The mineral was placed in the brine and conditioned with collector for at least 15 min, which was found to be long enough to obtain a maximum value for the contact angle. The temperature remained constant during each experiment. The experiments were run at 24°C ±2°C. For contact angle measurements, a crystal of halite from Carlsbad, N. M., was used. Several samples of sylvite were used in this work: a crystal of sylvite from Stassfurt, Germany; a crystal from Carlsbad, N. M.; and a crystal of chemically pure potassium chloride. Saturated brines were made from reagent grade chemicals and distilled water.

Jan 1, 1957

By Wheeler P. Davey

When metals are subjected to mechanical working, such as rolling, one of the phenomena that take place is a movement of the crystals of the metal into a system or systems of orientation which bear an angular relation to the direction of working. In rolled metal the crystals may orient themselves with respect to the rolling plane or the rolling direction, or both. Direct evidence of the existence of preferred orientations in rolled metal has been obtained by numerous investigators from X-ray patterns of the rolled metal. Most of these workers used a monochromatic pinhole method. Where the degree of preference for a single orientation is high the monochromatic pinhole pattern may be interpreted by a geometrical calculation based on the angular relationships of the planes in the crystal and the diffraction arcs on the X-ray pattern. This process may be aided by the geometrical construction of the locus sphere (Lagenkugel), and reflection circles of Polanyi,l Polanyi and Weissenberg,2 and Mark and Weissenberg,3 and of the plane polar figures (flachenpolfigur) of Franz Wever.4 R. M. Bozorth5 solves X-ray patterns from metals having a single preferred orientation by means of a series of charts which when placed over the X-ray pattern give directly certain angular relationships, between the crystal planes and the surface of the specimen.

Jan 1, 1930

By Wheeler Davey

WHEN metals are subjected to mechanical working, such as rolling, one of the phenomena that take place is a movement of the crystals of the metal into a system or systems of orientation which bear an angular relation to the direction of working. In rolled metal the crystals may orient themselves with respect to the rolling plane or the rolling direction, or both. Direct evidence of the existence of preferred orientations in rolled metal has been obtained by numerous investigators from X-ray patterns of the rolled metal. Most of these workers used a monochromatic pinhole method. Where the degree of preference for a single orientation is high the monochromatic pinhole pattern may be interpreted by a geometrical calculation based on the angular relationships of the planes in the crystal and the diffraction arcs on the X-ray pattern. This process may be aided by the geometrical construction of the locus sphere (Langenkugel), and reflection circles of Polanyi,1 Polanyi and Weissenberg,2 and Mark and Weissenberg,3 and of the plane polar figures (flachenpolfigur) of Franz Wever.4 R. M. Bozorth5 solves X-ray patterns from metals having a single preferred orientation by means of a series of charts which when placed over the X-ray pattern give directly certain angular relationships, between the crystal planes and the surface of the specimen.

Jan 1, 1929

By A. J. Shaler

The subject of the mechanism of sintering has received much attention in the past few years, particularly since the beginning of the series of AIME seminars in powder metallurgy of which this paper introduces the fourth. In the first of these, F. N. Rhines1 brought together and discussed the available experimental data on the sintering of pure metallic powder, and succeeded in bringing to a sharp focus the attention of workers in this field on the established observations which a satisfactory theory must explain. Several other authors3,5,6 have, in the last few years, studied the phenomena that occur when cold metallic powders, loose or in the form of compacts, are first brought to elevated temperatures. Some workers&apos; in the field of friction have recently studied the adhesion of solid metal surfaces when they are brought into close contact. These researches have indicated that several separate mechanisms operate simultaneously, at least during the first part of the sintering process. Some of them have been called transient mechanisms4 because they are in general not absolutely necessary to sintering. Powders may be so prepared and so treated that these transient phenomena do not take place during subsequent sintering. This does not mean, of course, that their industrial and scientific importance is any less than that of the steady-state phenomena. The latter are changes that go on during sintering no matter how the powders are made or treated; they cannot be divorced from sintering. One way to analyze the process of sintering into its component parts is perhaps to distinguish between these transient and steady-state phenomena. Some of the transient phenomena have been studied in the past few years. Huttig3 has shown that, when the temperature of metallic powder is slowly raised, the following events generally occur in order: (1) physically adsorbed gases are desorbed; (2) there is an atomic rearrangement of the surface, a sort of two-dimensional "surface-reciystallization"; (3) there is a breakdown of chemically adsorbed surface compounds; (4) there is a recrystalliza-tion in the volume of the metal. All these changes are shown by Huttig and his coworkers to be completed fairly rapidly at lower temperatures than those generally used in sintering and are therefore not a part of the mechanism whereby the density of a mass of powder continues to change after long heating at an elevated temperature. But the first and third of these changes release gases in quantities which may or may not help to control the steady-state mechanisms, depending on when the voids become isolated from the outside of the compact. Among the phenomena studied by Steinberg and Wulff,8 there is the effect on sintering of residual stresses arising from the pressing operation. They found that the lateral surfaces of a green compact of iron are under a longitudinal residual tension-stress of the order of magnitude of half the yield-point for solid iron. If the outside surface is in tension, the core must be under longitudinal compression. When the compact is heated, the surface residual stress is thermally relieved first, and the compact therefore initially expands in the direction of its axis. This is a transient phenomenon, if for no other reason than the possibility of sintering unpressed powders, as demonstrated by Delisle,9 Libsch, Volterra and Wulff10 and others.1 The subject of recrystallization is dealt with further in a separate section, in view of its prominent place in sintering literature. It, too. is one of these transient phenomena. Among the steady-state parts there may be distinguished the attraction between particles and its consequences, the spheroidization of voids in the compacts, and the densification or swelling of the compact. There is considerable evidence4,7 showing that cold metallic surfaces, when brought to within a few interatomic distances of one another, are attracted to each other by forces of the order of many thousands of pounds per square inch. A calculation, discussed in greater detail in another section, shows that this force changes but slightly when the temperature of the surfaces approaches the melting point. Actual measurements of forces of adhesion of this magnitude have been made by Bradley12 on some nonmetals, but none has yet been made on cold or hot metals. This force is of sufficient magnitude to cause some plastic deformation in powder compacts, as will be shown below. A second force of steady-state nature is due to the surface tension, which probably has the same origin as the force of attraction between surfaces.164 A paper by Udin, Shaler, and Wulff1,3 gives the results of precise direct measurements of its value for solid copper. The demonstration of the tendency for the surface tension to shrink a pore was long ago given by Gibbs.17 He showed that its effect on a curved surface between two phases is equivalent to a pressure perpendicular to that

Jan 1, 1950

By Irving Cadoff, Richard Nolder

An analysis oj a series of samples of single -crystal silicon grown on sapphire shows that ,four distinct orientation relations exist. There are at least thirteen crystallographic planes which serve as substrates ,for epitaxial growth The model which assumes that silicon substitutes for aluminium and bonds with the oxygen atoms of the sapphire to form the first later for subsequent growth can account for the epitaxial geometry in all four cases. Multiplici-ties 01 specific orientations are found which are explained by the symmetry of both the sapphire and silicon crystal structures. It was reported in the previous paper&apos; that single-crystal silicon films can be deposited on single-crystal a A1,03 (sapphire) with a wide variety of orientations. The silicon films, however, were found to deposit in only four different orientation relationships with respect to the sapphire substrate. The X-ray data have been analyzed to determine the plane and direction of atomic fit and an atomic model to account for the epitaxial relationships at the silicon-sapphire interface has been developed. These results are described in the present paper. EXPERIMENTAL The Laue X-ray data described in the previous paper were reduced to stereographic projections in a standard manner. These data were supplemented with X-ray reflection data obtained with -& E and A Full-Circle Goniometer (Electronics and Alloys, Inc.) mounted on a Phillips diffractometer unit. The silicon films were thin enough to result in characteristic reflections from the substrate as well as the silicon. The superimposed stereographic projections were analyzed to determine the orientation relationships. Ambiguities were resolved by referring to constructed models of various lattice planes for both silicon and sapphire. These lattice models were also used to develop the model for atom fit at the interface. DATA AND ANALYSIS 1) Crystal Structures. The crystallography of silico-n, which is of the diamond cubic class with a. = 5.4~, is straightforward. The sapphire structure is more complex and generally difficult to represent in pictorial form. It is of the rhombohedra1 class but usually referred to hexagonal axes. The transformation of indices between these two systems can lead to ambiguities which will have bearing on the analysis presented herein. Therefore, the basis used in this paper is described in the appendix. Referred to the hexagonal system, the parameters of sapphire are co = 12.95.&, a, = 4.75~, c/a = 2.73. All parameters are for room temperature. Figs. 1 and 2 illustrate schematically the hexagonal unit cell model of sapphire used for this analysis. The oxygen atoms are assumed to occupy positions in an idealized hexagonal array on basal planes. Their actual positions are in a slightly distorted hexagonal array. The aluminum-atom positions are scaled to their actual positions in the lattice with respect to the basal layers of oxygen atoms. It was found that an idealized model where the aluminum atoms are assumed to lie exactly at the octahedral interstices of the oxygen lattice, similar to that used by ~ronberg,&apos; was not adequate for this study.

Jan 1, 1965

By R. I. Jaffee, J. G. Dunleavy, W. Hodge, H. R. Ogden

IN a search for an improved conductor for use in field wire for the L. S. Army Signal Corps, an alloy of copper and silver was developed from which it was possible to obtain 29 B & S ga. strands with tensile strengths in excess of 160,000 psi combined with an electrical conductivity of over 70 pct IACS. Such a favorable combination of strength and electrical conductivity has not been reported previously in the rather extensive literature covering this subject. The properties obtained from various binary alloys of copper and silver, together with the method of fabrication of these alloys which has been developed to obtain the properties desired in fine wire strands, are discussed in this paper. LITERATURE The effect on the electrical conductivity of copper of the various elements in solid solution is shown in Fig I, taken from published data by J. O. Linde and others.&apos; It will be noted that silver in solid solution depresses the electrical conductivity to a lesser extent than any other element for which data are given, and is followed rather closely by cadmium, and then by chromium. Zinc, which lies between cadmium and chromium, has so high a solid solubility in copper that the data for zinc are scarcely comparable to the data for the other two in the range covered. Not many data are available on the strain hardening of copper-rich Cu-Ag alloys. Corson2 reports a 3 pct Ag alloy properly cold worked and annealed to have 100,000 psi tensile strength and 90 pct IACS conductivity. On straight cold working, Hessenbruch3 reports 101.000 psi for a 5 pct Ag, 0.3 pct Be alloy, and 129,000 psi for a 30 pct Ag, 0.5 pct Be alloy. Here it would he expected that much of the strain hardening came from the silver content of the alloys. The copper-rich side of the Cu-Ag diagram, according to Stockdale,4 is shown in the upper part of Fig 2. The electrical conductivities for copper-silver alloys annealed at 750 and 350°C, taken from the work of Johansson and Linde,5 are shown in the lower part of Fig 2. The sloping line corresponds to the conductivity of solid solutions of silver in copper, and the horizontal offshoots correspond to the conductivity of the two-phase alloys in equilibrium at the two temperatures shown. The electrical conductivities are very high, even for the 750°C anneal. The potentiality for age hardening from supersaturated alpha copper solutions appears to be excellent from the solubility line, but Smith and Lindlief6 have shown that the response to age hardening of solution-annealed alpha alloys is not good. They found that the tensile strength of a 5 pct Ag alloy aged at various temperatures was not as great as in the quenched condition, even though, anomalously, the hardness increased from RB68 to RB78 by annealing for 4 hr at 400°C after a 750°C quench. Weist7 also found that the alloys increased in hardness

Jan 1, 1948

By S. F. Reiter, W. R. Hibbard

A survey of the effect of heat treatment on the room temperature hardness of Fe-Mo alloys has been made. Constant strain rate tensile tests were performed between room temperature and 1800°F. These data were analyzed to determine the effect of temperature and composition on the strain hardening coefficient and strain rate sensitivity. Constant load creep-rupture tests were made on these alloys and the results related to composition and structure. A relation between the high temperature strength of the precipitation hardened alloys and the volume of precipitate has been observed. IN view of the extensive use of ferritic materials at elevated temperatures, it is surprising to note the limited amount of information relating the variables of plastic deformation, i.e., composition, structure, temperature, stress, strain, and strain rate. Hollomon and Lubahn&apos; showed how the several variables of plastic flow might be treated analytically. No data were available on carbon-free iron and its alloys in a form suitable for this analysis. Several German investigations2-" constitute most of the experimental work relating high temperature properties to the constitution of these types of materials. In order to obtain new data, the iron-rich alloys of the Fe-Mo system were selected for detailed investigation for the following reasons: 1—Some of the important effects of molybdenum on the mechanical properties of iron have already been studied.&apos; , 821 2—By suitable heat treatment of selected alloys, it is possible to study strengthening effects of four types: AT -a transformation, B—substitutional, C—precipitation, and D—dispersion of hard inter-metallic compound. Materials and Treatment Four-pound ingots were vacuum cast, employing the same melting schedule previously used.? The raw materials were electrolytic iron and lamp-grade molybdenum. The ingots were forged to l/z in. sq. rod and one portion swaged to 0.350 in. diam rod for the production of 1 15/16 in. long button-head specimens. The button-head specimen blanks were solution treated for 16 hr at 2100°F in hydrogen of —70°C dewpoint and then water quenched. They were subsequently plunge ground to the standard 0.160 in. diam test bar. Micrographs of the solution treated alloys are given in Figs. la through Id. The higher molybdenum alloys contained large equiaxed ferrite crystals similar to those in Fig. Id. A portion of the % in. rod was hot rolled to 0.100 in., sandblasted, and cold rolled to 0.020 in. Strip tensile specimens having a 0.020x0.200 in. cross-section and a 2.25 in. gage length were machined from the sheet. The alloys containing molybdenum were subsequently annealed 1 hr at 1560°F. The iron strip was annealed 4 hr at 1300°F in wet hydrogen. The resultant structures are shown in Fig. 2a through h. The ASTM grain sizes were 1 to 3 as solution heat treated or 3 to 4 as annealed. The chemical analyses of the alloys are given in Table I. Carbon contents were obtained after the heat treatments in hydrogen. Alloy 15.9 pct Mo was tested as a cast alloy.&apos;

Jan 1, 1956

By D. W. Gillmore, C. C. Wright

DEWATERING is a major problem in the preparation and utilization of fine-sized coals now being recovered in increasing amounts from colliery effluents, refuse banks, and silt ponds. Of the various methods which have been proposed for dewatering fine coal, gravity drainage is probably the oldest and most widely used, and yet little information on this subject has been published. Consequently a laboratory investigation of gravity drainage phenomena was undertaken not only to provide basic data for predicting the drainage behavior of fine coals in cars, bunkers, basins, and silos, but also to obtain some understanding of the moisture retention properties of fine coal. Because of practical interest in the problem, a reproducible laboratory technique, which simulated plant conditions as closely as possible, was developed for the evaluation of drainage variables. The apparatus selected consisted of vertically-mounted lucite columns, nominally 4 to 8 ft in length and 2, 3 or 6 in. in diam; the bottom of the column was provided with a rubber stopper through which was inserted a ½ -in. diam drainage tube; a wad of glass wool was placed on the upper part of this outlet tube to retain the coal and a plug was temporarily located at the lower end to prevent drainage during charging of the column, see Fig. 1. The most satisfactory testing procedure is as follows: 1-The fine coal, which has been thoroughly

Jan 1, 1952