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By E. T. Turkdogan, Klaus Schwerdtfeger

OelSEN and Maetz1 detected some 20 years ago the existence of a miscibility gap in iron oxide-CaO-P2O5 slags melted in iron crucibles at about 1400°C. Because of the importance of this system for the dephos-phorization of steel in the basic Bessemer process, equilibria between liquid iron and selected iron oxide-CaO-P2Q slags have been measured since by numerous investigators.2-5 When in equilibrium with metallic iron, the iron oxide of the slag is present mainly as FeO. In connection with oxygen-blowing steelmaking processes, it is useful to know the phase relations in the slag system at higher oxygen pressure, when major parts of the iron oxide are present as Fe2O3. This problem was investigated by Turkdogan and Bills7 by equilibrating the oxide mixtures contained in platinum crucibles with CO2-CO mixtures at 1550°C. It was found that increasing the Fe2O3 content decreases the composition range of the miscibility gap strongly so that the miscibility gap has almost disappeared at pco2/pco = 75. This result was refuted by the careful work of Olette et a1.,''' who equilibrated their slags with controlled Ha-H2-Ar gas mixtures. Their equilibrium measurements, at 1600°C and at oxygen pressures of 5 x 10"* and 10"5 atm, showed that the oxidation state of the iron has almost no influence on the formation of the miscibility gap. The present experiments were undertaken to check the previous results of Turkdogan and Bills. The experiments were performed at 1625°C in the strongly oxidizing atmosphere of air (PO2 = 0.20 atm) for which no experimental data are available. About 10 g of slag were melted in platinum crucibles and held at constant temperature for 1 hr. After equilibration, the crucible was rapidly pulled out of the furnace and cooled in air. The platinum crucible was removed from the sample. The two slag layers were carefully separated with a small diamond disc, and the surface of the top layer, which may have changed its oxidation state during cooling, was removed. The slags were crushed and analyzed chemically for CaO, P2O5, Fe2+, and Fetotal. The starting mixtures were prepared by sintering the desired amounts of reagent-grade 2CaO . P2O5 - H2O, CaCO3, and Fe2O3. Sintering and subsequent crushing were done three times to ensure homogenization. Molybdenum wire resistance heating was used. The furnace was provided with a recrystallized alumina reaction tube which was left open to air at the top. The temperature was controlled electronically. The reported temperature was measured with a Pt/Pt-10 pct Rh thermocouple and is estimated to be accurate within +5°C. The composition of the equilibrated melts is given in Table I. For the graphical illustration of these quaternary slags the type of projection suggested by Trömel and Fritze10 was used. In this representation, Fig. 1, the composition point of a mixture within the tetrahedron Fe2O3-CaO-P2O5-FeO is projected into the Fe2O3-CaO-P2O5, triangle (triangle I) so that the direction of projection is parallel to the side FeO-Fe2O3, and into the triangle Fe2O3-P2O,-Fe0 (triangle 11) so that the direction of projection is parallel to the side CaO-P2O5, of the tetrahedron. The projected point has the coordinates wt pct CaO, wt pct P205, and wt pct (FeO + Fe2O3) in triangle I and wt pct FeO, wt pct Fe2O3, and wt pct (CaO + PzO5) in triangle 11. Both triangles are turned into the same plane around the Fe203-P20, side of the tetrahedron. An illustration of the projection of a quaternary point in the present system is shown in Fig. 1. The advantage of this type of projection is that all four components for an equilibrium curve can be read directly from the diagram. The present results are shown graphically in Fig. 2. The curves depicting the miscibility gap are dashed in parts where no experimental points were obtained. The composition range covered by the miscibility gap

Jan 1, 1968

By William H. Breeding

The remarks that follow are based substantially on experience covering 45 years, 80% of which has been in placer work, rather than on a review of available literature. Most commercial placers have been deposited by the action of water. The richer and more- difficult-to-mine placers are those in the headwater areas where gradients are steepest. The most lucrative placers are generally in inter- mediate areas where volumes are greater, fewer boulders are present, and gradients are from 3% to 1-1/2%. The higher volume, lower grade placers are in the lower reaches of river systems where gradients are lower. Where gold-bearing rivers have discharged into the sea, wave action can concentrate values on beaches, past and present. Most of the rich, readily accessible placers were mined by our forefathers. Current opportunities exist: (1) in remote areas where infrastructure has been absent in the past, or development has been prohibited by adverse ownership - political or commercial; (2) in deposits that could not be mined by equipment available to our forefathers; (3) in deposits unidentified by our forefathers; (4) where the-price-of-product/cost ratio is substantially better than in earlier years; or (5) a combination of those factors. When I entered the placer business in the late 1930s, and subsequently, a prevailing opinion believed that glacial deposits should be avoided as irregular in mineral content and composition, and unrewarding to explore and develop; yet an operator has been mining a fluvio-glacial deposit profitably for the past 17 years. Rich buried placer channels, of ten called paleo-channels were worked in the last century, generally by hand methods, and under conditions that would be unacceptable today. Exploration and mining equipment now available make some of these channels attractive targets. Well-known examples are in California and Australia. The formation of a commercial placer requires a source of valuable minerals. Above primary deposits, there may be eluvial deposits formed by the erosion of gangue minerals and the concentration "in situ" of valuable minerals. Down slope from these deposits are the hillside or colluvial deposits, and below them are the alluvial deposits of redeposited material. Most of the great placer fields of the world are the result of several generations of erosion and deposition. Well-known examples are in California and Colombia. Gold is a very resistant and malleable material, and gold placers may extend for 64 or 80 km (40 or 50 miles) along a river system. Platinum is less malleable, but is very resistant to disintegration. Diamonds are extremely hard, and (especially gem diamonds) may be found over great lengths of a river system. Cassiterite is less resistant to disintegration, and tin placers seldom extend over two miles without resupply from an additional source or sources of mineralizaton. Tungsten minerals are generally more friable, and within a few hundred yards of the source disintegrate to the point that they are uneconomical to recover. Rutile, ilmenite and zircon placers generally result from the weathering of massive deposits, and may be encountered over extensive areas; most are fine grained and durable. What does a geologist or mining engineer look for in placer exploration? The old adage to look for a mine near an existing mine is still valid. You need a source of valuable mineral. Then you require conditions for concentration, which means a satisfactory gradient and/or other conditions that will permit heavy minerals to settle. Nicely riffled gravel, often called a shingling of the bars, is conducive to placer formation. Coarser gravel is logically associated with coarser gold. Excessive clay and/or high stream velocities in narrow channels can carry gold far downstream and distribute it uncommercially over a large area. When material is extremely fine, in situ weathering and concentration become more important. Placers frequently occur distant from lode mines, and one must remember that in a larger watershed the exceptional floods that occur once in a hundred or a thousand years can move great quantities of material long distances. The carrying power of water is said to vary with the fifth or sixth power of its velocity. I am not ready to disagree with Waldemar Lindgren and accept that many commercial placers are substantially enriched by the chemical deposition of gold from solutions; however, I have seen crystalline gold in clayey material quite distant from known sources of primary gold that is dif-

Jan 1, 1985

By U. K. Custred, E. W. Long, V. R. Degner

In 1973, the United States production of marketable phosphate rock set a record in excess of 42 million tons. This production rate is expected to continue to increase, due to the growing international requirement for fertilizer, at a rate exceeding 5% per year well into 1977. One approach towards increasing plant production capacity to meet the growing demand is through large-capacity flotation cells, provided they achieve metallurgical performance comparable to existing smaller cells. A 9-month evaluation test program recently completed at the Haynsworth mine at Bradley, Fla., demonstrated the feasibility of achieving economically acceptable concentrate grade and recovery levels using large, high-capacity flotation cells. The composition of the feed to the Haynsworth beneficiation plant is a typical Florida pebble phosphate matrix composed of phosphorite pebbles ranging in size from approximately 1-1/2 in. down to 150 mesh and intimately associated with a mixture of clay and sand (essentially silica). The feed contains approximately 22 to 28% phosphate reporting as tricalcium phosphate, Ca3 (PO,) 2, or "bone phosphate of lime" (BPL). The flotation section utilizes the double-float procedure typical of Florida plants. The phosphate is first floated away from the silica in the rougher circuit, using crude fatty acid, ammonia, and fuel oil or kerosene. Rougher conditioning is accomplished at 60 to 70% pulp solids with sufficient ammonia added to raise the pH to 9 to 9.5. Following coarse and fine rougher flotation, the concentrate (overflow) streams are joined and conditioned (sulfuric acid cleaned and washed) prior to entering the cleaner circuit where an amine float (cationic reagent and kerosene added in the feed box; pH 7.3 to 7.8) is employed to float the silica. The feed to the coarse rougher circuit averages 29% +35 mesh while the fine rougher feed averages 10%+35 mesh. Primary attention was directed toward the large rougher cell performance (recovery and grade) on coarse feed during the Haynsworth evaluation program. Flotation Cell Test Program A row of three No. 120 size (300 cu ft) WEMCO flotation cells was installed in parallel with an existing air-cell row. The total installed volume of the large cell circuit was 900 cu ft and required a floor space of 306 sq ft. This compared to the air-cell total volume of 200 cu ft and 152 sq ft floor space. (Both floor areas include feed and tails hoppers but exclude walkways.) Fig. 1 is a schematic cross section of the large flotation cell showing the relative location of key mechanism elements. In operation, the rotor generates a fluid vortex extending up along the walls of the standpipe and creating a sufficient vacuum within its core to ingest air into the standpipe/rotor cavity through the air inlet duct. The ingested air mixes with the pulp, which has been recirculated through the false bottom and draft tube, in the rotor. Further mixing occurs as the air and pulp move radially outward from the rotor, finally passing through the disperser into the flotation cell. Flotation is accomplished outside the disperser, where phosphorite laden air bubbles rise and the remaining pulp recirculates down along the cell wall to the false bottom and draft tube. Large-flotation-cell performance is influenced by the ability of the mechanism to (1) circulate, or suspend, the solids in the pulp; (2) ingest air into the rotor cavity; and (3) mix the air and pulp effectively. The proper balance between pulp circulation and air ingestion is a key consideration in achieving good recovery in a course feed application. Large-flotation-cell pulp circulation and air transfer characteristics are significantly influenced by rotor speed and rotor submergence; therefore, these two operational parameters can be used to "optimize" a particular mill application. Fig. 2 maps the hydraulic performance of the WEMCO No. 120 size flotation cell. This map can be used to relate the cell operational parameters which influence metallurgical performance. At a given rotor speed, power intensity (i.e., pulp circulation) is seen to increase, and airflow decrease, as rotor submergence is increased. The inverse relation between power and airflow is due to the two-phase air-liquid mixture density reduction accompanying the increased airflow rate. For any fixed rotor submergence, the power intensity (i.e., fluid circulation) and airflow both increase as rotor speed is increased. The selection of these two mutually related operating conditions (i.e., rotor speed and submergence) was a key consideration in the Haynsworth evaluation program.

Jan 1, 1976

By R. W. Stormont, F. Wald

The phase diagram of the Pseudobinary section PbTe-Fe was determined. It was found to contain a monotectic and a eutectic reaction, the latter one taking place at 14 at. pct Fe and 875° * 5°C. The solid solubility of iron in PbTe was found to be 0.3 at. pct by electronmicroProbe analysis. No solubility of PbTe was detected in iron. Slight deviations from true pseudobinary behavior were found to occur in the range of - 5 to 10 at. pct Fe. In the course of a general investigation of reactions of various metals with lead and tin telluride,' the lead telluride-iron system was reinvestigated. It had been established much earlier than iron does not chemically react with lead telluride but forms a eutectic with a melting point of 879" The eutectic composition or other related information has never been reported, but for a number of years iron has been in general use for contacting of lead telluride and lead telluride alloys for thermoelectric applications. It seems therefore desirable to clarify the exact constitution of the system to furnish a base for the long-term evaluation of bonds made between lead telluride and iron either by pressure contacting or by brazing methods. I) EXPERIMENTAL METHODS Lead telluride-iron alloys were prepared in 10-g charges, using premelted lead telluride. This material was prepared from high-purity, semiconductor-grade lead and tellurium obtained from the American Smelting and Refining Co. and described as 99.999 pct pure. The iron used was "Armco" iron; the major impurities found here were 0.02 pct C, 0.018 pct Si, and 0.015 pct Cr. All remaining impurities were less than 0.01, the total of all impurities not exceeding 0.15 pct. Charges were prepared in closed quartz arnpoules which were evacuated and in some cases backfilled with high-purity argon to retard excessive lead telluride evaporation and deposition in slightly cooler parts of the ampoule. For high iron concentrations, this can lead to total separation of the constituents, since the vapor pressure and the sublimation rate of PbTe are quite high.4 Nevertheless, since the ampoules are closed, no change in overall composition was expected and the nominal composition of all alloys was assumed to be retained. X-ray diffraction analysis, thermal analysis, and microsections were used in the evaluation of the alloys. The nature of the system was such that X-ray diffraction was not particularly helpful. It merely served to establish that at all concentrations PbTe and a! iron were in equilibrium at room temperature. Thermal analysis was carried out by taking direct temperature vs time curves on a Sargent recorder where a width of 10 in. was kept as 1 or 0.5 mv by use of an automatic bucking voltage network. Quartz ampoules with minimized dead space, coated with boron nitride and fitted with a thermocouple reentrant, were used as containers for the charge. At high temperatures and over long periods of time, boron nitride reacts with iron. For the thermal analysis runs, however, this was not significant. More significant was the fact that the vapor pressure of PbTe at some of the meas -uring temperatures apparently exceeded I atrn quite considerably. This, in some cases, caused the slightly softened quartz tubes to blow out if great care was not taken to contain them and minimize time and temperatures used. As containers pure nickel tubes were used which also served to avoid temperature gradients in the quartz ampoule. Nevertheless, the experimental difficulties at high temperatures were severe and the monotectic temperature could therefore not be determined accurately. In general, the accuracy reached by the thermal analysis setup in this case is *4"C as determined with gold, silver, and tin, under the conditions of analysis here. Inherently, the apparatus is capable of reaching accuracies better than i 1°C. Also, difficulties were encountered in microsection-ing. They were related to polishing, since it is rather difficult to avoid pulling the iron out of the weak and brittle lead telluride matrix. It proved best to follow a procedure where, after grinding to 600 grit on carborundum paper, a polish with 6 p diamond was used on nylon cloth. Finally, #3 "Buehler" alumina and an automatic polisher were used for -5 min only, to avoid relief. The best etching results were achieved with

Jan 1, 1969

By P. Greenfield, C. C. Smith, A. M. Taylor

J. E. Harris (Berkeley Nucclear Laboratories, England)—Greenfield et al.11 attribute abrupt changes in slope of their log o/log i curves for heat-treated Mg/0.5 pet Zr alloy (zA) to &apos;atmosphere&apos; locking. It is proposed here that a more reasonable explanation of the apparent strengthening at low rates of strain can be based on precipitation either during the preanneal or during the creep tests. All the tests were carried out above 0.5 Tm where solute atmospheres are likely to be largely evaporated2 and can migrate sufficiently rapidly so as not to impose any &apos;drag&apos; on the moving dislocations. McLean3 has derived an expression for determining the temperature Tc above which, due to the high-migration rate of the atmospheres, Cottrell or Suzuki locking can play no part in determining creep strength. This expression, which holds for an applied shear stress of not greater than 5 X 107 dynes per sq cm is: Tc/Tm= 7/6.8 - log10? where i = secondary creep rate The values for T, corresponding to the maximum and minimum reported creep rates at each temperature have been calculated from the data of Greenfield et al. These are given in Table VII. All the test temperatures were above T,, the margin being greater for the higher temperatures and for the lower strain rates where the breaks in the log s/log ? curves occurred. Dorn and his collaborators14, 17 have studied systematically the effect of solute hardening on the creep properties of an A1/3.2 at. pet Mg alloy. In the temperature range where strain aging occurred in tensile tests, abnormally high-activation energies for secondary creep were obtained but at temperatures above 0.43 Tm, solute alloying did not have any effect on the creep parameters. Moreover, there have been no reports of any strain aging phenomenon during elevated temperature tensile tests with ZA material.18 Instead of the observed strengthening being due to atmosphere locking, it is now proposed that precipitates play an important role in enhancing the creep strength of the material. There are two possibilities—precipitation of zirconium hydride during the high-temperature preanneal and/or precipitation of the hydride or a-zirconium during creep. On the basis of the former the results can be interpreted in terms of a critical stress being necessary to force the dislocations through or over preexisting precipitates. From the latter, if the strengthening is due to pre- cipitation during the test then hardening should be associated with a critical strain rate. At low rates of strain, time is available during the tests for precipitation to occur either directly onto dislocations (thus pinning them) or generally throughout the matrix (which would impede dislocation movements). Examination of the data of Greenfield et al. suggests that both mechanisms may be operative since they observed precipitation during creep and also found that their alloys exhibited high-creep strength in the early stages of the low-stress tests, i.e., before creep-induced precipitation had time to occur. It is not easy to understand why they considered that precipitation of zirconium hydride is unlikely to occur at 600°C while it can take place in tests in air at as low a temperature as 200°C. Precipitation of the hydride during the preanneal cannot be ruled out merely on the basis of metallographic examination. Hydride precipitates in ZA type alloys are very small and can only be accurately resolved in the electron microscope.9 For example, in this laboratory20 hydride platelets with major dimensions <(1/10) µ have been observed by electron transmission through thin film specimens of hy-drogenated ZA material. Complex interactions between dislocations and such particles are illustrated in Fig. 12. Additional evidence for precipitation during pre-annealing is provided by the data presented in Greenfield&apos;s Fig. 1 and Table IT. These show that the creep strength at 200o and 400°C increases with the time of preanneal at 600°C. Such increases cannot be explained on the basis of increases in grain size alone for further improvements in strength were observed when the material was annealed for longer times than that required to stabilize the grains. Although the main discussion is confined to ZA material, similar arguments can be used against the strain aging hypothesis proposed to explain the binary Mg/Mn alloy data. In this case no precipitation is possible during the preanneal, but precipitation-hardening during creep can occur.

Jan 1, 1962

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

In a recent communication14 we have reported on the kinetics of the reactions of zirconium with O2, N2 and H2 as a function of the time, temperature and pressure variables. A systematic study was made and the results correlated with fundamental theories of gas-metal reactions. This paper will present a similar study for titanium. Titanium and zirconium are members of the IV group of the periodic table and possess many similar physical and chemical properties as a result of their similar electronic configuration for the outer electrons. The two metals are relatively inert to both gas and liquid phase corrosion at room temperature. However, at moderate temperatures the metals become active and react readily with the common gases including O2, N2 and H2 which are of interest in this study. A study of the kinetics of these gas-metal reactions is of interest for three reasons: (1) to understand the rate of reaction of titanium and its role in the behavior of high temperature alloys; (2) to understand the practical difficulties of the reduction, refining and working of titanium; and (3) to correlate the data with fundamental theories of gas-metal reactions and crystal structure predictions. Literature Survey Several review papers8 and books4243 exist on the preparation and properties of titanium and its alloys. THE METAL Titanium has, at room temperature, a hexagonal lattice of the zinc type. Hagg19 gives a value of 2.953A for the (a) axis, a value of 4.729 for the (c) axis and a density of 4.427 at 20°C. Burgers and Jacobs6 have observed the transformation of the hexagonal to the body-centered cubic structure at 880°C and have established a value of 3.31 for the cube edge and a density of 4.31. TITANIUM-OXYGEN Carpenter and Reavell6 using a pressure change method have studied the reaction at temperatures of 742° and 1000°C and for a pressure of one-fifth of an atmosphere. The probabilities for reaction are calculated from kinetic theory and they report a value of 10-5 for O2 at 1000°C and 10-6 at 740°C. The titanium-oxygen system has been investigated by Ehrlich.10,11 Five phases are observed. Between (TiO2 and TiO1.90) an alpha-phase, consisting ofarutile lattice, is found. A beta-phase is observed between (TiO1.80 and TiO1.70). A gamma-phase is homogeneous between (TiO1.56 and TiO1.46) and has a structure of the corundum type. The delta-phase exists between TiO1.25 and TiO0.6 and has a sodium chloride structure. From TiO0.42 to Ti the metal structure is observed. The surface oxide films have been studied by Hickman and Gulbransen.20 The rutile structure is observed in the temperature range studied, 300 to 700°C. Three crystalline modifications of TiO2 exist: rutile and anatase which are tetragonal and brookite which has an orthorhombic structure. Anatase is reported36 to exist in two forms: I and II. Anatase II changes to anatase I at 642°C. Anatase I is stable up to 915°C where rutile becomes the stable modification. At 1300°C rutile transforms to brookite which melts at 1900°C. The monoxide, TiO, may be prepared from the dioxide by high temperature reduction with carbon or magnesium. Its melting point is 1750°C. TITANIUM-NITROGEN Carpenter and Reavell6 report that at 1000°C a linear rate law is observed. The probability of reaction is given as 10-8 at 1000°C. Fast12 has studied the solubility of nitrogen and its effect on the mechanical properties of the metal. The crystal structure of TiN has been shown by several workers2&apos;21&apos;44 to follow the sodium chloride structure. However, the calculated density is found to differ from the pycnometric value. This is studied by Brager3,4 in detail. He has suggested that the titanium sites in the lattice are only partially filled at low temperatures. As the temperature of preparation is raised the vacant sites become occupied which expands the lattice and increases the hardness and density. An (a) value of 4.22Å is given for room temperature. TITANIUM-HYDROGEN The solubility and the crystal structures observed in this system have been reviewed in a recent book by Smith.40

Jan 1, 1950

By C. E. Sims, F. W. Boulger, H. A. Saller

Most of the data on equilibrium constant and the deoxidations potentialities of those elements, considered to be stronger deoxidizers for steel than is silicon, have been calculated from thermodynamic data. The reason for this is, primarily, the obvious difficulty of obtaining direct experimental evidence of equivalent accuracy. This is an excellent use of the principles of thermodynamics and has given valuable data not otherwise available. Such results, of course, can be no more accurate than the physical constants used in the calculations, and one can never be sure that the basic data are either complete or accurate. In fact, as in the case with silicon,1 there are not only discrepancies among the calculated theoretical values of the equilibrium constant for deoxidation of steel but also between the theoretical and experimental values. It is highly desirable, therefore, to obtain experimental values for checks on calculated results whenever possible. If they disagree, both cannot be right, but if there is good agreement, their value is enhanced. The present work was done in an effort to obtain experimental evidence in regard to some of the common alloying additions but more particularly the so-called "strong" deoxidizers for steel. The method used was to determine the minimum concentration of the deoxidizer that would effect a certain definite degree of deoxidation in steel. The criterion of deoxidation was the change from the large globular Type I sulphide to the eutectic Type II as described by Sims and Dahle.2 This change is sharp and definite, and inasmuch as it can be produced with equal facility by aluminum, zirconium, and titanium, it is considered a manifestation of a certain degree of deoxidation and not an alloying effect. Ostensibly such a procedure could give only a comparison of deoxidizing powers and no absolute values. Nevertheless, repeated observations have shown that, when increasing increments of aluminum are added to a steel, the residual aluminum content begins to increase simultaneously with the appearance of Type II inclusions. Thus it seems warranted to postulate that the Type II inclusions appear coincident with the virtual elimination of FeO as an active constituent of the steel. Experimental Procedure The data obtained were primarily from the microexamination of polished and unetched specimens and from chemical analysis. Experimental heats weighing 200 to 250 lb were made in a basic-lined high-frequency induction furnace. The base composition was nominally that of a medium-carbon casting steel to which the appropriate additions were made. Specimens were poured into sand-cast ingots 3 in. in diam as shown in Fig 1. Sand-cast ingots were used to prevent chilling and to allow sufficient time in freezing for normal inclusions to form of a size large enough to be studied readily. In the first few heats, the tapered wall ingot was used, but in the majority, the extra large riser was used to prevent piping in heavily deoxidized steels. Specimens for microexamination were taken from the location shown in Fig 1, and drillings for chemical analysis were taken from a similar location. The procedure was to melt the base composition and deoxidize with the usual manganese and silicon additions and then to pour an ingot. The furnace was then tilted back, and the first increment of strong deoxidizer or special alloy was added and allowed to disseminate through the melt, with enough power on to hold the temperature constant, for 45 sec. Then a second ingot was poured. After this, another increment was added, and after the same holding time another ingot was poured. In this way from 9 to 12 ingots were poured from each heat, each successive ingot having progressively larger total additions of alloy. Eighteen heats were made altogether, and the range of alloys used and additions made are outlined in Table 1. The three principal types of sulphide inclusions found are illustrated in Fig 2. The globular Type I sulphides are characteristic of silicon-killed steels, the eutectic Type II are characteristic of steels deoxidized with a small amount of aluminum, while the larger, angular Type III are usually found in steels with a residual aluminum content above about 0.02 pct. In all specimens studied, the transition from Type I to II either did not occur at all or was very abrupt and clear cut. There never was any doubt as to just which increment produced the change, although the individual additions were small, in the order of 0.01 pct. The change from Type II to Type III was considerably less sharp, and, in some cases, both types were found together. Inasmuch as the formation of Type III sulphides is apparently not a deoxidation phenomenon, they will not be discussed here.

Jan 1, 1950

By R. F. Shurtz

R. Duval (Mining Engineer, Ancien eleve de PEcole Polytechnique, Paris, France) I do not agree with the Eq. 3, reading: m =1/100- [(0.214x30.4) + (0.7B6 x0.00)] =6.5pct CaO If 0.214 and0.786 were proportions by weight, the equation would represent the well known mixtures law of the conventional arithmetics and 6. 5 pct CaO would be the correct average content. But it is not the case as the author states: "In samples consisting of single grains of mineral, those grains must, as already mentioned, be either of dolomite or magnesite. Since 78.6 pct of the deposit consists of magnesite and 21.4 pct of dolomite (excluding for present purpose the presence of other minerals), for any single grains picked at random the probability will be 0.214 that is it dolomite and0.786 that is it magnesite. In 1000 such samples the expected numbers of dolomite and mapesite grains will be 214 and 786 respectively." 0.214 and 0.786 would be proportions by weigbt under the necessary condition that all grains of dole mite and magnesite should have an identical weight. Obviously it is not the case, as the specific gravities are not the same for mapesite and dolomite and the volumes of the grains are different. Furthermore, because of these differences the conditions for a random sampling are not fulfilled and we are not authorized to state that the probabilities are, respectively, 0.214 and 0.786. The author however makes a simple application of Eq. 1: M = 1/n— ? fi x i . n Should we deduce that this relation is wrohg? Not at all, but when applying Eq. 1 you must not overlook what it actually. means. Eq. 1 gives a definition of the arithmetic mean of a total of n observed values Xi and nothing else. But the average conteht of a deposit has not the same significance. It is the ratio between the weight of concerned mineral in the deposit and the total weight of the deposit. As from 1000 particles the 214 of dolomite and the 786 of magnesite have not the same weight, the two definitions do not concur, and when applying Eq. 1 the result is an arithmetic mean of figures which has no connection with what is named average contentof a deposit. The situation is similar to the calculation of an average velocity. If a car travels a first mile over at 30 miles per hr and a second mile over at 60 miles per hr, when applying formula 1 you find as average velocity for the 2 miles: 30+60 ------- - 45 miles per hour. Many people calculate in this way and they do not realize that a mistake is involved. In fact the definition of he average velocity for the 2 miles is the quotient of the distance of 2 miles by the time (in hours) necessary for 2 miles travel, i.e.: 2 ---------- = 40 miles per hr. 1 + 1 30 60 In other words, the average volocity wanted is not the arithmetic but the harmonic average of the two velocities. The above mentioned bias in the calculation of the average contents of deposits is frequent, even in the assessments made by experienced engineers and is independant of what is named the sampling error. In order to supress the bias and to be able to use Eq. 1, you must apply a correction. An example on the subject can be found in an article by Duval et al. in the January 1955 issue of the &apos;&apos;Annales des Mines" (French), page 19. R. F. Schurtz (Author&apos;s Reply) Mr. Duval&apos;s position is quite correct. The proportions shown for dolomite and magnesite., respectively, of 0.214 and 0.786 are, in fact, proportions by weight uncorrected for specific gravity. In our day to day operation of producing magnesite from these mines at a very substantial rate, we do not normally make corrections for the difference between the specific gravity of dolomite and that of magnesite. If these corrections are made in Eq. 3 as shown in my article, then the numbers of grains turn out to be in proportions of 0.226 dolomite and 0.774 mapesite instead of the values actually shown in the equation. For the purposes of our work, and in view of the inherently low accuracy of the data, this correction was not deemed worthwhile making.

Jan 1, 1961

By R. F. Hehemann, Darrell W. Smith

The kinetics of alloying- in W-5 rot pct Re powder compacts were investigated at temperature about the upper limit for the formation of the x phase, such that a single intermediate phase was involved in the process. The rates and directions of motion of the a-o and o-b interface were assessed as functions of tinze at the sintering teri7peraticve by quantitative izetallog-ralhic techtziques. The iiotion 01 these interjuces could be specified approxitnate1.y by u Parabolic )-ate law and deviations from this ,rate law were attribuled to a complex interaction between surface dif&apos;fusion and volume diffusion during the initial stages of sintering. WHEN binary or more complex alloys are produced by sintering compacted blends of elemental powders, a complication is encountered which does not arise in the sintering of pure metals. In addition to concern for grain size and densification, the rate of inter diffusion of the component elements must be considered. The general problem of alloying during sintering has been treated by numerous investigators.&apos;-7 These investigations have been concerned only with systems that form continuous series of solid solutions and a concentric-sphere diffusion model4 provides a useful description of homogenization in these stems.&apos; Some controversy remains, however, over the contribution of surface and grain boundary diffusion to the homogenization process. Heckel% ePorts that homogenization can be described by volume diffusion at all temperatures, whereas other invetiators&apos;&apos; recognize the importance of surface and grain boundary diffusion, particularly at lower temperatures. Analysis of the homogenization process in partially miscible systems is complicated by the motion of the interfaces separating the individual phases. A simple analytical solution does not exist for such finite systems with spherical symmetry. It was the purpose of this work to examine the kinetics of the formation and dissolution of an intermediate phase in a binary system through an assessment of the motion of the interfaces separating this phase from the terminal solid solutions. PROCEDURE The W-Re system is an example of a partially miscible binary system and was selected for study because of its current importance in refractory-metal technology. The equilibrium phase diagram, Fig. 1, shows that the o phase will be formed by interdiffu-sion between tungsten and rhenium. At temperatures between approximately 2125" and 282O°C, the o phase will appear as the only intermediate phase in the diffusion system. In this work, a mixture of elemental powders containing 5 pct Re was employed. In such a mixture, the rhenium particles will be distributed randomly in a tungsten matrix. During sintering, a o-phase layer will form at the W-Re interface. The development and subsequent disappearance of the o phase are controlled by the relative rates and directions of motion of the 0-0 and a-p interfaces. The motion of these interfaces can be inferred from quantitative metallographic measurements of the average radii of the o shells surrounding rhenium particles. Elemental tungsten and rhenium powders of commercial purity were employed in these investigations. The rhenium powder was spheroidized from +200 mesh agglomerates by plasma-arc spraying and was then classified to yield a powder composed of essentially

Jan 1, 1967

By R. E. Carter, F. D. Richardson

Self-diffusion coefficients have been measured for iron in wustite (700° to 1000°C) and for cobalt in cobaltous oxide (800&apos; to 1350°C) by means of radio-isotopes. Both sectioning and decrease of surface-activity methods have been used and a particular shortcoming of the latter method has been disclosed for wustite. The effects of oxygen pressure on the composition of cobaltous oxide and on the diffusion coefficient of cobalt in the oxide have been established. The effect of the preparation conditions of the cobalt-oxide specimens on the diffusion measurements has been determined. It has been concluded that diffusion of cobalt occurs via vacant cation sites and that a cobaltous-oxide disk reaches equilibrium with its environment in a time which is very short compared with that needed for diffusion of the radio-isotope. THE availability of radioactive isotopes in recent years has permitted the measurement of many self-diffusion coefficients which were hitherto impossible to determine. With the advent of radioactivity, the method of measuring diffusion coefficients has also changed. The earlier sectioning method by which the concentration profile of the diffusing species was determined in the diffusion specimen has often been rejected in favor of the decrease of surface-activity method first developed by Von Hevesy,&apos; and extended by Steigman, Shockley, and Nix,&apos; and Raynor, Thomassen, and Rouse." With the experimental arrangement where an infinitely thin deposit of tracer is diffused into a semi-infinite cylinder, the decrease in activity of the active face due to diffusion of the tracer into the specimen is measured by counting the active face before and after diffusion. Under these conditions, the appropriate solution of the diffusion equation is R = e*(l-<K/Z) [1] where R is the ratio of the counting rates after-to-before diffusion, $& is the Gaussian error integral of \/Z, and Z is defined as Z = p2Dt, p being the linear-absorption coefficient of the detected radiation in the diffusion specimen, D the self-diffusion coefficient, and t the diffusion time. In the older sectioning method the concentration distribution of the tracer is found after diffusion by analysing thin parallel sections cut from the active face of the diffusion specimen. As seen from the solution of Fick&apos;s second law for the distribution of an infinitely thin source after diffusion into a semi-infinite cylinder the log of the concentration plotted against x&apos; will be a straight line of slope log e/4 Dt. The diffusion coefficient thus can be calculated directly. The units of the tracer concentration are completely arbitrary, since any change in units does not change the slope of the log c vs x2 lot. Although both of the above methods have been widely used, a thorough experimental comparison does not appear to have been made. Birchenall and Mehl,&apos; during an investigation of the self-diffusion rate of a and r iron by the surface method using Fe" tracer, diffused and sectioned one welded couple. The diffusion coefficient from this run agreed with those by the surface method. Buffington, Bakalar, and Cohen," during an investigation on a and y iron

Jan 1, 1955

By K. Barron

The glass insert stressmeter, or photoelastic stressmeter, is an instrument designed to determine stress changes occurring in rocks. It has several potential advantages over other such devices in that it is a biaxial device, it is simple and it is cheap to make. The object of this study was to assess the behaviour of the meter under biaxial loads and to examine some of the problems associated with measurement and interpretation of the fringe pattern. This assessment has been carried out by comparing theoretical and laboratory behaviour of the meter. It has been shown that: a) There are certain optimum measuring points in the meter at which measurements should be made for best accuracy. The position of the points depends on the ratio, n, of the biaxial stresses. b) The meter&apos;s sensitivity can be assumed to be independent of the rock modulus E provided that the rock modulus is < 2.5 x 106 psi and not, as previous workers have assumed, if E < 5 x 106 psi. c) There are several methods of separating the principal stresses; some of these are unsatisfactory. A new method is proposed and discussed. d) The meter sensitivity decreases as the ratio of the biaxial stresses approaches unity; the accuracy thus also decreases. e) The axes of symmetry of the fringe pattern give an excellent indication of applied stress direction. f) Laboratory calibrations are in good agreement with theory. The glass insert or photoelastic stressmeter is an instrument designed to determine stress changes occurring in rocks. It has several potential advantages over other such devices in that it is a biaxial device, it is simple and it is cheap to make. This stressmeter has been described in detail.l,2 Basically it is a hollow glass cylinder that has at one end a light source and filters producing circularly polarized light. The glass cylinder and source are grouted into a borehole in rock and the face of the cylinder is viewed through a quarter wave plate and an analyser. If, after installation, a stress change occurs in the rock, then a distinct colored isochro-matic fringe pattern is seen in the meter. The fringe order at any point in the meter can be determined by counting the fringes and measuring the fractional fringe orders by the Tardy compensation method. The relation between the fringe order at any point and the applied stress change can be determined either by calculation or by calibration. The object of this study was to assess the behavior of this stressmeter under biaxial loading conditions and to examine some of the problems of interpretation of the fringe pattern. THEORY Hiramatsu et a14 have determined the stress distribution in a hollow cylindrical inclusion in an elastic host material when subject to uniaxial stress. Using this solution, the biaxial case of stress p in the x direction and stress q in the y direction (Fig. 1) can be solved by superposition. This has been done in Appendix 1. It is shown that the principal stress difference (s1 -s2) at any point (r,?) in the cylinder is given by:

Jan 1, 1965

By I. S. Servi, N. W. Marr

TIN markedly increases the softening temperature of pure copper with only a moderate effect on conductivity. Smart and smith&apos; indicated a substantial increase in softening temperature upon addition of different levels of tin up to 0.05 pct in oxygen-free copper. However, after finding no effect of tin in copper containing about 0.025 pct O, they concluded that "the presence of oxygen completely nullifies these changes in properties by precipitation of SnO2.&apos;&apos; Since preliminary tests on Cu-Sn-0 alloys indicated that this conclusion is not valid outside the extremely limited tin range investigated by Smart and Smith, research was primarily directed toward the partition of tin between the copper-base matrix and the oxide phases. Experimental. Material was prepared by sealing an 80 to 100-g charge consisting of oxygen-free copper, tin, and copper oxide into a y-in.-ID quartz capsule which was evacuated and back-filled with tank-grade argon to 3 atm. The sealed vials were heated to 1125ºC, kept at temperature for 30 min, occasionally agitated, and then allowed to air-cool outside the furnace ("as-cast"). The castings were cold-swaged to 0.370 in., annealed 1 hr at 600°C ("as-annealed"), and cold-swaged 16.5 pct ("as-swaged"). Cross sectional wafers were annealed for 1 hr at various temperatures and Rockwell F hardness measured. The "softening temperature" was defined as the interpolated temperature at which the hardness was 50 Rockwell F. Electrical resistance was measured by an ac poten-tiometric method on 0.040-in.-diam wires after a 1 hr anneal at 600°C. Relative accuracy was of the order of 1 pct. Chemical analyses for tin were performed by two methods, identified as "Acid flux" and "HN03 dissolution". The first consisted of fusing the sample with potassium pyrosulfate and leaching the resulting melt with 10 pct sulfuric acid. The spectrophotometric procedure which followed is described in Ref. 2. Oxygen analyses were performed by the vacuum-fusion method with a bath temperature of 1650°C. Tin content of oxides and copper phases was measured with the X-ray microprobe, using a calibration curve based on a series of oxygen-free Cu-Sn alloys. Results. In Fig. 1, the nominal tin composition for alloys containing nominally 400 ppm O was plotted vs the analyzed or the computed tin content—the latter derived from one of the following: 1) "acid flux" chemical analysis; 2) "HN03 dissolution" chemical analysis; 3) X-ray microprobe analysis of the copper matrix; 4) equivalent tin content, based on the measured increase in electrical resistivity (an increase in resistivity of 1.6 microhm-cm is approximately equivalent to 1 wt pct of sn1,3). It is evident from Fig. 1 that the results of the acid flux analysis are consistent with the nominal composition while the HNO3 dissolution method generally yields lower values, consistent with those obtained from electrical resistivity measurements and somewhat higher than those obtained by microprobe analysis. Microprobe and resistivity values are affected only by the tin in solid solution; hence the HN03 method

Jan 1, 1970

By Oscar Weiss

An aerial magnetometer survey was carried out by the author&apos;s geophysical organization over the Vrede-fort dome, where Witwatersrand beds are wrapped around a granite plug 25 to 30 miles in diameter. The well-known magnetic shales of the Lower Witwatersrand system (to be referred to as LWW) give strong negative anomalies over the out-cropping portion of the dome. This is unusual as these same shales cause positive anomalies over large areas near Johannesburg and along a strike of 130 miles between the East Rand and Klerksdorp. It is suggested that the negative polarization is caused by heat and stresses connected with the doming. This negative polarization of sedimentary beds, which usually cause positive anomalies, is a good example of how "magnetic lows" can be caused by "structural highs." Significant magnetic anomalies should be tested by gravity and seismic methods irrespective of the sign of the anomalies. South of the line X — Y (see Fig 2 and 5) the gravity anomalies are smaller over the LWW beds and magnetic anomalies suddenly become weaker and even change signs by becoming positive. This peculiar phe- nomenon is explained by faulting which truncated the nearly vertical LWW shales at depth. In this manner the mass of the LWW beds has been reduced together with the weakening of the negative magnetic anomalies by positive poles which occupy the truncated end. Furthermore, by uplifting the beds between f1 and f2 (Fig 2) positive polarization becomes predominant, thus causing positive magnetic anomalies. General The Vredefort dome is one of the internationally known geological structures, which, among others, has attracted the attention of numerous American geologists. It was for this latter reason that our aerial magnetic results over this structure were selected by us for publication in the United States of America. A full description of the exposed geology has been published by Nell and readers are referred to this paper, which is subject to only slight modifications inasmuch as the subdivision of the Witwatersrand system (to be referred to as WW system) is concerned. The Vredefort dome is about 60 miles southwest of Johannesburg. The WW system, after being exposed in the vicinity of Johannesburg, plunges with southerly dips beneath the Vent-ersdorp and Transvaal systems. Along a section southwest from Johannesburg, as shown diagrammatically in Fig 4, we see no outcrops of the WW system until the Vredefort dome, where the Upper and Lower WW system are wrapped around an almost circular arc of a granite mass. Here the whole WW system is overturned around the perimeter of a huge granite plug 25 to 30 miles in diameter. Less than half of the circumference of this dome is exposed; the rest is covered by Karroo dolerites and sediments. The determination of the exact shape of the concealed part of the dome has been a matter of considerable interest and obviously geophysical methods were eminently suited for obtaining this information. A good start was made with a gravimeter survey carried out by the Geological Survey of the Union of South Africa.2 Our own

Jan 1, 1950

By W. M. Lehrer

RECENT development of high-temperature brazing alloys has required information regarding the eutec-tic temperature and composition of the Pd-rich section of the Pd-B system.. Literature on this subject was found to be scanty with no complete system yet determined. Buddery and welch1 report an inter-metallic compound occurring in the Pd-B system at 6.33 wt pct B (PdsBz). Another source, Sieverts and Bruning,2 indicates that after annealing at 700°C, a 1.6 and a 2.0 wt pct B alloy were two phase whereas a 0.75 pct B alloy was single phase. Recent work3 using a hot-stage microscope has proposed a eutectic temperature of 743OC. This method utilized the observation of the onset of incipient melting at grain boundaries. The eutectic composition, however, was not determined. METHODS AND PR0CEDURES Five alloys were prepared by triple inert arc-melting high-purity palladium (95.98 pct) with additions of 2 to 6 pct purified amorphous boron. The alloys were crushed within a hardened steel mortar with a steel pestle. The 2 pct alloy, however, was too tough to be crushed in the above manner so was crushed by successive reductions through a rolling mill. Approximately 17 to 18 g of the crushed alloy was used in the thermal analysis. The alloys were melted in pure quartz crucibles. The thermocouple protection tubes were also of quartz and fused along the inside wall of crucibles to prevent floating of the thermocouple. This was an expediency as centering of the thermocouple in the melt would have been preferable. Melting was done in a tube furnace with a slow flow of tank helium maintained as a protective atmosphere. Heating and cooling rates were maintained at 3.5OC per min through the critical temperature ranges by means of a synchronous motor hook-up to a furnace controller. All specimens were heated to 100°C over the indicated liquidus on heating prior to reversing to the cooling cycle. Specimens emerged from the furnace with mirrorlike brightness attesting to the protective quality of the helium atmosphere. Thermal arrests were detected by the differential thermocouple technique using chrome l-alumel couples and nickel as the reference specimen. Arrests were recorded on a Leeds-Northrup automatic X-Y recorder. The specimen temperature and temperature difference were read to + 7.5OC and ± 1.5OC, respectively. These readings were well within the sensitivity of the instrument amplifier. Chromel-alumel couples were used in lieu of Pt-Rh as very few arrests were contemplated in excess of 1200" to 1300°C, the approach of instability. No standardization was performed on these thermocouples subsequent to their use. RESULTS The thermal arrest temperatures obtained are plotted in Fig. 1 as a function of wt pct B. The composition function was obtained by chemical analysis of portions of the specimens after the thermal analysis was completed. The 2 to 6 pct nominal alloys were found to have 1.80, 2.35, 3.65, 4.18 and 5.90

Jan 1, 1960

By D. H. Polonis, M. B. Kasen

AN unusual thermal etching phenomenon has been observed on the surface of a Cu-Si alloy. The observations were made during studies of vacancy condensation pit formation which were reported in previous papers.1,2 Figs. 1 and 2 are photomicrographs of the surface of a Cu-4.8 pct Si alloy after heating in vacuo (3 x X mm Hg) to 525°C and subsequently holding at that temperature for 16 hr in an impure (air-contaminated) argon atmosphere. Under these conditions preferential removal of silicon from the matrix by oxidation results in a surface which is entirely a phase overlying an a plus y structure. The light areas of Fig. 1 are regions in which very little thermal etching has occurred, while the majority of the surface has experienced severe etching. Similar regions in Fig. 2 are seen as plateaus above contours produced by net transfer of material from the specimen surface. Twin boundaries are also visible in Fig. 2. The difference in matrix mi-crostructure between Figs. l and 2 reflects the par- ticular orientation of low-index planes with respect to the surface of observation. Thermal etching contours of this type have been studied in detail by Hondros and Moore Both of the photomicrographs show that one or more dark spots are located approximately at the center of every protected area; where two spots are in close proximity, the protected areas have merged. The microstructures indicate that the anomalous resistance to thermal etching is related to the presence of these spots. Williams and Hayfield have shown that local regions of unusually high oxidation resistance can be caused by a surface monolayer of atoms with a work function higher than that of the base material. The result is an inhibition of the rate of electron removal from the base material and a decrease in the oxidation rate. The source of the protected layer may be either surface diffusion from contaminants on the specimen surface or pipe diffusion of solute atoms followed by migration across the surface. In the latter case the driving force is a difference in chemical potential resulting in a Gibbs adsorption phenomenon. In the present case, chemical polishing of the specimen surface precluded contaminants of a strictly surface nature. Consequently, diffusion of impurity atoms from within the lattice appears to be the most tenable explanation of the observed phenomena. The authors propose that the structures of Figs. 1 and 2 reflect the diffusion of impurity atoms along extended dislocations within the individual a phase grains prior to surface oxidation. The central spots within the protected regions are seen as sites of dislocation emergence which have become locally decorated with oxide in the manner discussed in Ref. 1. Williams and Hayfield observed protected regions adjacent to the grain boundaries of iron-contaminated copper which they attributed to the segregation of iron to the grain boundaries coupled with high dif-fusivity along the complex dislocation array at such boundaries. No evidence of such grain boundary protection was observed in the Cu-Si alloy; this

Jan 1, 1964

By J. M. Oblak, R. F. Hehemann, R. H. Goodenow

STUDIES of surface relief and growth kinetics have lead to the concept that widmanstatten ferrite along with upper and lower bainite constitute a continuous series of decomposition products.1-4 Current models4 propose that these products form as plates with a coherent or semicoherent leading edge which propagates at a rate controlled by diffusion of carbon into the surrounding austenite. There are, however, important crystallographic and morphological differences between these products—particularly between upper and lower bainite. For example, upper bainite appears to exhibit a (11lIy orientation habit, whereas lower bainite develops with a more irrational habit near {2251y.5-7 Many of the morphological features of these decomposition products are not yet well-documented. Recent studiess have demonstrated that low-carbon martensites form as sheets of closely spaced needles on {lllly planes while higher-carbon martensites form as plates with {225}? or other orientation habits. The similarity in the crystallography of these two modifications of martensite with upper and lower bainite is striking. Therefore, a study of the morphology of bainite in a series of hypoeutec-toid alloy steels has been initiated to explore these relationships further. The question of immediate interest is whether upper and lower bainite form as plates or needles. A two-surface (approximately perpendicular) metallographic method was employed to study the morphology of bainite in a variety of low and medium alloy steels. Compositions of these steels have been reported elewhere. The behavior of 4340 and 4370 was typical and will be described here. Austenitizing treatments involved 20 min at 2350°F for 4340 and at 2000°F for 4370. Isothermal transformation was conducted in molten-salt baths. Upper bainite was produced at 925°F in the 4340 steel and lower bainite at 575°F in 4370 with transformation times adjusted to produce 10 to 15 pct of the decomposition product. Many of the morphological features of upper bainite have been catalogued in the recent literature.&apos;&apos; The two principal variants observed in the present investigation are illustrated in Fig. l(a). One form appears as long, thin plates or needles and the other as small, frequently irregularly shaped particles. Both variants may occur as isolated forms but more frequently appear in groups as demonstrated in Fig. l(a). Two-surface analysis reveals that these two variants constitute different sections through a single morphological form. To demonstrate this, a number of sections perpendicular to the plane of Fig. l(a) were prepared at various positions along the length of the elongated particles. A section taken at position 1 in Fig. l(a) is presented in Fig. l(b). Here, the dark line represents the edge of the sample and the left-hand portion of this photomicrograph is that from the surface perpendicular to the original plane of polish. Since it was necessary to repolish the original surface after each sectioning, the shape of the bainite particles on this surface, right hand side of Fig. l(b), changes with each sectioning. The disappearance of plate A, Fig. l(a), in Fig. l(b) emphasizes the small cross section of these structures. The group of particles in the lower left-hand

Jan 1, 1964

By Norman P. Goss

What would appear to be a very simple process on paper has proved to be overrun with a multitude of unseen difficulties. For more than 70 years attempts have been made to cast metals in a continuous manner, but it has been only within the last Io years that some degree of success has been achieved.1 Historical Development Bessemer&apos;s Experiments—Method I Bessemer was the first to try to cast molten metal in a continuous manner. His method is fully described in U. S. Patent No. 49053, issued in 1865. The patent drawing is shown in Fig. I. In this method the molten metal was poured between a pair of rolls of large diameter, which were cooled by water sprays. Means were provided to prevent moisture from coming into direct coptact with the molten metal. The width of the strip was controlled by the flanges. On paper this should work to perfection, but it is beset with many difficulties still awaiting solution. Bessemer failed to reduce his invention to commercial practice. About 1890 Bessemer&apos;s method was revived by Norton and associates (U. S. Patent No. 441375). They formed the Fluid Metal Rolling Co. at Maywood, Ill., and spent $250,000 in endeavoring to develop the technique for this simple method. Finally they had to abandon it. Naturally, they did carry the technical development far beyond anything Bessemer had done, but even so it was far from being a useful commercial success. In recent years it has undergone further development by C. W. Hazelett (U. S. Patent No. 2058447), who has succeeded in obtaining long lengths of copper, brass, aluminum, and even stainless steel. He introduced many&apos; ingenious devices but the greatest obstacle still remained—the disintegration of the roll surface when the surface is heated and chilled in rapid succession. Difficulty is also experienced in maintaining a uniform supply of molten metal to the rolls. The patents pertaining to this method would indicate these to be the major obstacles. Experimental work by Mellen—Method 2 A departure from the method introduced by Bessemer, was tried by Grenville Mellen, of East Orange, K. J., sometime between 1914 and 1920, who obtained a number of patents.2 His method is illustrated in Fig. 2. This method failed to make an impression upon the art; however, it is of value in pointing out the difficulties the inventor ran into and the way in which he tried to meet them. The split mold sections form two endless chains. When going through the center of the apparatus, these sections engage each other to form a complete mold. As the engaged mold section moves downward at a constant speed, molten metal is teemed into it. As this is going on, another set of cooperating mold sections move into position on top of the one being filled. The molten metal is teemed into the mold through a silica tube. According to the teachings of this patent, the level of molten

Jan 1, 1945

By D. N. Collins, J. R. Stevens

New expressions in the technical assessment of mineral concentration processes have been defined as Concentration Efficiency: Concentration Index: where h is the percentage of head grade; c, percentage of concentrate grade; maximum percentage of concentrate grade obtainable at 100 pct recovery; and R, percentage of recovery. In developing these expressions, the basic requirements for the technical assessment of concentration operations have been defined and the various expressions suggested by others for asses-sing the results of such operations reviewed and criticized. The derived expression for E, depends on a simple combination of recovery (R) and a new term selectivity (s), where S is (c-h)/(c,,, -h), by definition. Limitations of the new expressions are discussed and examples given of applications to concentration operations. It is also shown that the formulae for E, and I, can be applied to scatter diagrams, multi-component systems, size-assay analyses, and classification data. Many methods of quantifying concentrating operations have been proposed. These include direct presentation of weights and assays together with the derived data for other items such as ratio of concentration, recovery, rejection losses, and enrichment ratio. These terms are now accepted mineral dressing nomenclature, and in the assessment of the results of concentration processes, concentrate grade and recovery are together the most widely accepted measures of concentration efficiency. For practical purposes when the concentrate grade is equal to or greater than a predetermined acceptable value, test or operation results may be assessed by the recovery figures alone. Similarly when recovery is within specification, the operation can be assessed by concentrate grade. The ultimate assessment and selection of a concentration operation is—admittedly with a few ex-ceptions—a matter of economics. There is however an intermediate stage in laboratory and pilot plant testing when evaluations must be made without the assistance of an economic yardstick. Numerous techniques are employed to facilitate such evaluations among which may be mentioned graphical plots of grade vs recovery, cumulative weight vs cumulative recovery, scatter diagrams, etc. The desirability of combining metallurgical results and product weights and assays into a single value has been recognized and discussed by many workers1-" with the resultant suggestion and use of such terms as Metallurgical Efficiency ,&apos; Summation Index,&apos; Selectivity Index,&apos;- and Absolute Efficiency B None of these expressions completely satisfies all the requirements of a selectivity or efficiency formula and it is proposed in this report to define the terms, relating to the technical efficiency of a concentrating operation, concentration index and concentration efficiency. Examples are given of their application and a comparison is made of their use in relation to other formulae. All product grades in this paper will be referred to in terms of mineral percentages and a list of symbols is given in Table I. CONSIDERATION OF EXISTING FORMULAE A number of the existing efficiency and index terms used in quantifying concentrating operations are considered below. Metallurgical Efficiency:

Jan 1, 1961

By B. M. Larsen

ATTEMPTING to review the fundamental aspects of segregation in steel ingots of all types in a paper of reasonable length, we encounter two difficulties: (I) the fact that a large number of different physical and chemical effects are involved, and (2) rather incomplete and confusing evidence on certain aspects of detail and mechanism in the freezing process in which the segregation effect is involved. The best solution seemed to be to link together most of the underlying factors into a simplified theoretical picture that appears to the writer to explain most of the observed data, in the hope that this will serve as a reasonably good target for discussion and criticism. Segregation effects, especially in steel ingots or castings, are often divided into " microscopic " and " macroscopic," depending on whether the variations in concentration of solutes? or dissolved elements in the iron occur as: (I) a periodic variation over the small distances between the nuclei and the surfaces of the primary grains, or (2) as a larger scale effect involving concentration gradients over distances of the order of several inches, more or less. The reason for this somewhat artificial division is, of course, that it is only the macroscopic scale effect that has much practical importance. About the only effect of practical importance that results from microscopic segregation is the banded structure often left in rolled sections, and even this is relatively harmless in most cases. However, the causes of microscopic segregation also underly the larger scale effect, so we must first consider matters such as the formation and growth of crystal nuclei, selective freezing and diffusion, and others that are fundamental to all segregation effects. UNDERCOOLING AND NUCLEI FORMATION It is probable that although the degree of undercooling is small in iron, as in metals in general, a certain amount of it takes place, and also that the number of crystal nuclei increases very rapidly with increased undercooling below the liquidus tempera¬ture. In practical terms this means that the nuclei number increases very rapidly with increased cooling or freezing rate, thus being dependent on the rate of heat flow out from the zone of crystallization. TEMPERATURE GRADIENTS AND HEAT DISSIPATION DURING FREEZING Each pound of steel evolves about 100 B.t.u. when freezing. In addition to this, the temperature gradient in the solidified portion (required to dissipate the heat as freezing progresses into the axis) necessitates a loss of heat required to cool the solid metal below its freezing range, which is equivalent to an amount of not so much less in magnitude. In a 5-ton ingot, the total would include about one million B.t.u. for freezing alone and about 0.4 to 0.5 million B.t.u. for the gradient, up to the end of the freezing period: Thus the rate of freezing depends primarily on the rate of heat dissipation. In the ordinary ingot shapes, the axial rate of growth of the solid

Jan 1, 1944

By W. J. Babyak

The habit planes for hydride precipitation in large grains of alpha zirconium and Zircaloy-4 were determined in specimens containing 161 and 136 ppm hydrogen, respectively. In zirconium, the hydride platelets precipitated on various pyramidal planes inclined to the basal plane at angles ranging from 10 to 50 deg and 75 to 90 deg. Hydrides were most frequent at inclinations of about 20 deg and 90 deg. In Zircaloy-4, hydride plates were inclined to the basal plane at angles vanging from 5 to 25 deg with the predominant inclinatioiz equal to 12 deg; no platelets were found near the prism plane position. In both zircoinium and Zir-caloy-4, hydrides were principally, but not exclusively, parallel to (1011) type planes. When the Zircaloy-4 gmins were subjected to tension stresses of 12,100 psi and 19,400 psi during hydride precipitation, the hydride habit was unchanged except that precipitation favored those habit planes which were inore nearly perpendicular to the stress direction. The stress-orientatioiz effect increased with the magnitude of the stress. THE hydride habit plane in a zirconium has been determined by several investigators. Langeron and Lehr1 in 1956 found platelets parallel to (1010) slip planes. In 1962, Westlake and Fisher2 confirmed these findings and showed that hydride precipitation on twin planes, as reported by Kunz and Bibb,3 was probably due to incomplete removal of worked metal from specimen surfaces. Secondary habit planes, ( 1011) and (1015), were also found by Westlake and Fisher under particular charging conditions where a hydride layer may have existed at the hydrogenation temperature. Most recently, walters4 and westlake5 again observed the (1010) habit exclusively in zirconium. Louthan and hgermans have reported that hydrides precipitate on various ( 101l ) and (112l) planes positioned 31.5 to 90 deg to the basal plane in Zircaloy-2. The present investigation was concerned with the hydride habit in Zircaloy-4 in relation to that in zirconium and the possible change in habit when precipitation occurs under stress. The latter consideration was prompted by the stress-orientation phenomenon originally reported by Marshall and Louthan.7, 8 I) EXPERIMENTAL Materials and Specimens. Chemical analyses of all materials are given in Table I. The zirconium specimen was a 1 by 4 in. section cut from wrought crystal bar that was hot-rolled at 790°C to 0.300 in. and cold-rolled to a final thickness of 0.095 in. All surfaces were mechanically polished and then chemically polished with a solution of H2O, HNO3, and HF (10:10:l by volume) prior to annealing. Grains as long as 0.25 in. were grown by thermally cycling the specimen three times (in 10-5 mm Hg vacuum) between 825" and 1000°C at approximately 125°C per hr. The specimen was isothermally annealed at 825°C for 24, 40, and 120 hr after each cy-

Jan 1, 1968