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By G. Derge, R. E. Grace

A S detailed studies of mass transport in hetero- geneous systems are made, a knowledge of the chemical diffusion coefficients in various liquid and solid phases is necessary to understand the kinetics of any total reaction. For example, in zone refining some information must be available about the diffusion coefficients of various species in the liquid and solid regions near the moving interface. In liquid-liquid reactions, of which slag-metal reactions are of particular interest to metallurgists, the diffusion coefficient of a transferring species must be known accurately in both phases in order to predict a transfer coefficient for the over-all process. Diffusion data for various elements in liquid iron and iron-carbon alloys have been roughly deter-

Jan 1, 1959

By T. E. Scott, D. H. Sherman, C. V. Owen

Mechanical properties and optical metallographic characteristics of vanadium containing 53 ppm (wt) H were investigated from, 77° to 298°K. A sharp ductile to brittle transition induced by the presence of hydrogen was observed between 238° and 223°K and a mar-tensitically formed hydride appeared at 200°K. While there appears to be a subtle relationship between the hydride formation and the ductile-brittle transition, it was concluded that the hydride per se was not sufficietzt to cause the severe em brittletnent. On the basis of the metallographic experiments and the results of a Petch analysis it is suggested that the mechanism of the embrittlement involves a reduction of the true surface energy, or cohesion, of the uanadiunz. THAT hydrogen can severely embrittle vanadium is well-documented;'-5 however, the mechanism by which hydrogen induces the observed embrittlement has not been established. It is not known whether the embrittlement of vanadium is caused by the formation of vanadium hydride or by a more subtle role of hydrogen. Until very recently6>' the solid solubility of hydrogen in vanadium at temperatures in the,range of the embrittlement was not known to a useful accuracy. In general, a severe embrittlement of the type produced by the presence of hydrogen in vanadium can be caused by changes in either of two properties of a metal. Either the yield stress of the metal is raised to the extent that plastic deformation at the tip of a crack cannot occur or the cohesive properties of the metal are reduced, at least locally, to the point at which cleavage is the natural response to applied loads. Of course a combination of these is possible. It is not known which of these properties of vanadium is influenced most by the addition of hydrogen. The purpose of this investigation was to determine the role of hydrogen in the embrittlement of vanadium. Accordingly, the solubility of hydrogen in vanadium in the temperature range where embrittlement is most severe was determined, the appearance of vanadium hydride was examined in relation to the initial ductile to brittle transition temperature, and an attempt was made to evaluate the effect of hydrogen on the yield stress and cohesive properties of vanadium. MATERIAL AND PROCEDURES Sample Preparation. The vanadium used in this investigation was prepared by the iodide refining process described by Carlson and owen.' Three ingots, 3 in. diam by 6 in. long, were cold-swaged to 0.096 in. diam, cut into short lengths, and then arc-melted under purified argon into one ingot. This process was repeated to insure a uniform composition in the final ingot. Chemical analysis of the metal is given in Table I. On the basis of work of Loria et a/ .' the following sequence of treatments was performed in order to obtain a uniform equiaxed ultimate grain structure: a) cold swage q-in.-diam ingot to 0.230 in. diam; b) anneal 6 hr at 1000°C in vacuum; c) by cold swaging reduce 81 pct in area in three steps: 0.230 to 0.187 in. diam, 0.187 to 0.150 in. diam, 0.150 to 0.096 in. diam. This sequence provided the desired grain structure after subsequent annealing treatments. Because annealing in evacuated quartz capsules resulted in contamination by oxygen, all anneals in this investigation were performed in a 304 stainless-steel chamber under a dynamic vacuum of 10- I Torr with the vanadium wrapped in tantalum foil. Prior to all annealing treatments the wires were electropolished for 1 min at 16°C in an 80 pct methanol-20 pct sul-furic acid electrolyte at 12.5 v. Following the final reduction the 0.096-in.-diam wire was cut into 2-in. lengths. A 1-in. gage section was reduced to 0.090 in. diam by electropolishing as above. Five different grain sizes were obtained by annealing the 2-in. samples at different temperatures for 8 hr to insure uniform grain size and residual hydrogen removal. The annealing temperatures used and the resulting grain sizes are given in Table 11. The final step in sample preparation was to charge half of the specimens of each grain size with hydro-

Jan 1, 1969

By K. Tangri, B. Swaroop

Simultaneous measurements of lattice (elastic) strain by X-ray line shift method and total strain with an electrical strain gage have been carried out on polycrystalli,ne nickel with the help of a specially designed tensometer attachment for the X-ray dif-fractometer. During the initial stages of deformation, the rate of increase in lattice strain closely follows the total strain until the plastic strain sets in. From then onwards, the two strains deviate from each other and with further increase in afiplied stress the rate of increase of lattice strain eventually decreases. Depending upon the mode of unloading, both compressive and tensile strains have been observed in nickel deformed up to 0.29 pct strain. These results have been explained on the basis of the effects of clustering of dislocations and also the production and behavior of point defects during loading and unloading, respectively. POLYCRYSTALS deformed plastically in a uniaxial tension test show residual lattice strains (hereafter referred to as RLS), which broaden the X-ray line profiles and shift their peak positions.''4 It is known that uniform straining of a crystal lattice (macrostrain) produced movement of ddfraction line peaks, whereas nonuniform straining (microstrain) causes line broadening.= Though the nature and origin of RLS in deformed metals is not yet clearly understood, these are believed to be due to the presence of some form of a locked-up stress system. Several possible detailed interpretations6'" of the stress system have been proposed by various workers and common to all these interpretations is the assumption that different parts of the aggregate have different tensile yield stresses; e.g., that a part A yields under a lower applied stress than a part B. Therefore, during the deformation process, the elastic strain in A will be less than that in B, and, after completion of deformation, B will tend to contract further than A but will be prevented from doing so by the restraining influence of A. Thus, when equilibrium is reached, A will be in compression while B is in tension. Although there is general agreement on the correctness of this argument, controversy still exists as to the exact nature of the parts A and B in a deformed metal. In an alternative approach to the creation of parts A and B, many other investigators have assumed that the RLS observed in unloaded specimens are in some way connected with the lack of proportionality between lattice strain and applied stress in the region above the yield stress." cullity13 has prepared a schematic summary of the results of previous workers, mainly Smith and Wood,2'11 which suggests that, above the elastic limit, the lattice strain may increase less rapidly with respect to strain, or may even decrease with increase in applied stress. If the applied stress is then decreased, the lattice strain would decrease along a line parallel to the loading line in the elastic region and thus produce a compressive residual lattice strain after unloading. At equilibrium, to balance these compressive stresses? there would have to be regions under tensile stress which may well be the grain boundaries or the substructure walls formed during deformation. The present investigation was undertaken to gain a better understanding of the nature and origin of RLS and also to experimentally verify the salient features of this hypothesis. EXPERIMENTAL Stress and strain determinations were made with a specially constructed tensometer attachment for the X-ray diffractometer, Fig. 1: which permits the following measurements simultaneously on a sheet specimen under uniaxial tension at various stress levels during loading and unloading: a) lattice strains, E=. in a direction perpendicular to the direction of pulling (x direction) from shifts in X-ray line peak positions; b) the total strain, ex, in the direction of pulling. with the help of an electrical strain gage affixed to the back of the specimen directly below the area irradiated by X-rays: and c) the applied stress, with the help of a load cell which consisted of a calibrated stainless-steel sample of dimensions identical to those of the specimen under investigation, and to which it was coupled. Because of its high stacking fault energy.I4 nickel

Jan 1, 1970

By A. F. Henderson, C. F. Cornell, A. F. Dunyon, D. A. Dahlstrom

Ossi E. Palasvirta (Development Engineer, Oliver Iron Mining Diu., U. S. Steel Gorp.)—The authors are to be congratulated for their interesting article, which thoroughly illustrates the variables inherent in filtration of taconite concentrate. The work and the conclusions based thereon largely parallel the test work done by the writer at the Pilotac plant" and the experience gained with a commercial size agitating disk filter in the same plant. At Pilotac, however, a thorough study was also made of the effect of depolarizing (demagnetizing) the filter feed, and it is the purpose of this discussion to comment on the merits of depolarization of the magnetite concentrate prior to filtering. The work at Pilotac was done in three phases: 1) preliminary laboratory testing with a circular filter leaf of 0.047 sq ft, followed by 2) plant testing using a 4-ft diam, single-disk agitating filter that was purchased on the basis of the pilot tests on the 4-ft model. In the laboratory tests depolarization was achieved by slowly withdrawing' batches of thickened concentrate from a coil producing an alternating field of about 300 oersteds. In plant tests the standard Pilotac procedure' was employed, wherein the pulp falls freely through the depolarizing coil. The preliminary tests in the laboratory at first seemed to indicate that although depolarization of the filter feed decreases the cake moisture, it also tends to decrease the thickness of the cake, thus decreasing filtering rate. The tests with the 4-ft disk filter soon showed, however, that the compactness of the cake, attained during the form period because of depolarization, permitted a considerable decrease in drying time without any sacrifice in final moisture content. Thus, the filter could be operated at a much higher speed, and the overall capacity was higher than with magnetized feed. Because of the great compactness of the cake there was little shrinkage during the drying period, which prevented cracking and subsequent loss in vacuum. This in turn permitted operation with as thick a feed pulp as the diaphragm pumps could handle, eliminating the necessity of pulp density control. On the basis of these findings, the 6-ft agitating disk filter has been operated at 2 rpm, using feed pulps varying from 65 to 73 pct solids. Initially Saran 601 was used as medium, but it was later replaced with a relatively open, tight-twist nylon cloth. Filtering rates up to 750 lb per ft- er hr can be attained with feeds averaging about 70 pct- 270 mesh, and there is no trouble because of cracking. The cake moistures vary between 8.5 and 9.5 pct. To recapitulate, the merits of depolarizing the filter feed may be summed up as follows: 1) The well dispersed pulp shows less tendency to settle in the filter tank. 2) The homogeneous filter pool results in more even cake formation. 3) Because of absence of flocs, great compactness of cake is attained during the form period. 4) The cake does not tend to crack during the drying period. 5) A drier cake is produced. 6) A shorter drying period is necessary, permitting higher operating speed, which in turn results in increased capacity. 7) Density of the feed pulp can be kept as high as the equipment can handle. This increases capacity, since it is directly proportional to the percentage of solids in the pool. A few tests were also made to study the effect of chemical flocculants on filtration efficiency. Results showed that the effects of chemical and magnetic floc-culation were quite similar. Thus the use of a floccu-lant would impair rather than improve the filtering of magnetite concentrate. A. F. Henderson, C. F. Cornell, A. F. Dunyon and D. A. Dahlstrom (authors' reply)—We want to thank O. E. Palasvirta for his comments, particularly in view of the encouraging results obtained with demagnetized taconite concentrate. In our studies an attempt was made to evaluate the effects of depolarizing the feed to the plant filters by passing the slurry through a coil, similar to the method described by Palasvirta. Unfortunately, in our experiments there were no startling improvements in performance level, neither cake rate increase nor cake moisture reduction. However, when slow filter cycle speeds were employed, the filter cake tended to crack and the vacuum level dropped, resulting in an increase in cake moisture content. When demagnetized feed was used during slow speeds, no cake cracking was evidenced and the vacuum level remained constant. Thus the depolarizing coil was found necessary only in cases of cracking. It should be noted that most of our test work concerned a feed of 85 to 90 pct —335 mesh and about 60 pct by weight solids concentration. This contrasts with 70 pct —270 mesh and 65 to 73 pct by weight solids as noted by Palasvirta. Reviewing both sets of results, it might be concluded that depolarizing may be successfully employed to alleviate cake cracking tendencies and may markedly improve cake rates and moistures on the coarser taconite concentrates. Further investigations may disclose the exact relationship of grind and pulp density to the depolarizing action.

Jan 1, 1959

By M. R. Annis, P. H. Monaghan

The control of mud properties affords two practical means of tnitigating pipe sticking caused by differential pressure: (I) teducing weight and, therefore, differential pressure; and (2) reducing the friction berween the pipe and mud cake. This paper describes investigation of the second of these—the friction between the pipe and the mud cake. Friction between a steel plate and a mud cake, held in contact by a differential pressure, was measured in the laboratory while maintaining a constant area of contact. Experiments were performed to determine how this friction varied with changes in mud composition and with changes in experimental conditions such as the differential pressure, time of contact of plate and mud cake, and filter-cake thickness. It was found that the apparent coefficient of friction, or the "sticking" coeficient, was not a constant; instead, it increased with increased time of contact between plate and mud cake, and with increased barite content of the Mud. The sticking coeficient varied from about 0.05 to 0.2 afer 20 , and eventually reached values of 0.1 to 0.3 after two Hours. Quehracho or ferrochrome lignosulfonate reduced the sticking coefficient at short .set times but did not reduce the maximum value. Carboxy-~t~etlz~lcellulose had no effect on the sticking coeficient. Emulsification of oil in the mud reduced the sticking coefficient. Some oils reduced the sticking coefficient to about one-third of its Value in the oil- free base mud, while other oils reduced it only slightly. Addition of certain surfactants with the oils further reduced the sticking coefficient. Spotting a clean fluid over the stuck plate caused a reduction in sticking coefficient only if the differential presslrrr was reduced, either temporarily or- permanently. INTRODUCTION Often during drilling operations the drill string becomes stuck and cannot be raised, lowered, or rotated. This condition can be brought about by a number of causes, such as sloughing of the hole wall, settling of large particles carried by the mud, accumulation of mud filter cake during long stoppage of circulation and, finally, sticking by pressure of the mud column holding the pipe against the filter cake on the hole wall. This paper is concerned with the last-mentioned phenomenon. Helmick 2nd Longley' in 1957 suggested that a pressure differential from the wellbore to a permeable formation covered with mud cake could hold the drill pipe against the borehole wall with great force. This situation occurs when a portion of the drill string rests against the wall of the borehole, imbedding itself in the filter cake. The area of the drill pipe in contact with filter cake is then sealed from the full hydrostatic pressure of the mud column. The pressure difference between the mud-column pressure and the formation pressure acts on the area of drill pipe in contact with the filter cake to hold the drill pipe against the wall of the borehole. Helmick and Longley also presented laboratory cxperiments which showed that the force required to move steel across a mud cake increased with increasing differential pressure and with the time the stcel and mud cake had been In cuntact. Their data indicated that replacing the bulk mud with oil reduced the force required for movement. Field evidence was rcported that spotting oil over the stuck interval sometimes freed the pipe. Outmans- in 1958 presented a theoretical paper which described the sticking mechanism and explained the increase of sticking force with time with equations derived from consolidation theory. Since publication of these papers, there has been interest in the differential pressure sticking of drill strings, and several mud additives to reduce sticking or special equipment to free stuck pipe have been proposed."" Haden and Welch" have recently reported laboratory evidence showing that the composition of the filter cake influences the force necessary to move steel on the filter cake. There seems no doubt that differential pressure sticking is a real phenomenon and that its severity depends on the magnitude of the pressure differential across the mud cake, the area of contact and the friction between pipe and mud cake. The mud weight required to control a well is determined by the highest formation pressure in the well: hence, the magnitude of the differential pressure opposite normal or subnormal pressure formations cannot bc reduced. The area of contact may be minimized in several ways (control of filter-cake thickness, use of stabilizers and spirally grooved drill collars), but there arc practical limitations which prevent reduction of contact area from becoming a complete solution of the problem. However. the mud composition might bc altered to reduce the friction between pipe and mud cake. This paper presents quantitative measurements of the friction between steel and mud filter cake and shows how the friction varies with mud composition for given experimental conditions.

By C. Chu

An investigation has been made of the radial heat-wave process using a mathematical model in two-dimensional cylindrical coordinates. This model considers combustion, convection and conduction inside the reservoir, but only conduction in the bounding formations. From a study of the general features of the process, an important phenomenon has been revealed, namely, the feedback of heat into the reservoir on the trailing edge of the heat wave. The effects of various process variables on the performance characteristics of the process have also been investigated. It was found that up to the time when the combustion front reaches a given point, the per cent heat loss, provided it is not higher than 40 per cent, is approximately directly proportional to the square root of thermal conductivity arid fuel content, but inversely proportional to the square root of gas-injection rate and oxygen concentration. The effecr of reservoir thickness is more pronounced, since halving the thickness doubles the per cent heat loss. The most decisive factor in determining the center-plane peak temperature is the fuel content of the reservoir. Within the temperature range investigated, doubling the fuel content doubles the peak temperature in the early stage, but the rate of decline of the peak temperature is high. Reservoir thickness is also a very influential factor. The peak temperature is lowered when the thickness is reduced; however, the effect of thickness becomes less pronounced when the thickness is high. Reduction of oxygen concentration increases the peak temperature in the early stage but lowers it afterwards because of the higher rate of decline of the peak temperature. Increase in gas injection rate or decredse in thermal conductivity geives a higher peak temperature which stays high for a longer period. The propagation range of the heat wave is chiefly governed by the fuel content of the reservoir. An increase of 0.2 1b/cu ft in the fuel content increases the propagation range by 100 per cent. The propagation range is more than doubled by doubling the gas injection rate, or reservoir thickness, or by reducing the thermal conductivity by 50 per cent. Comparatively, oxygen concentration has less effect on the propagation range. INTRODUCTION Several investigators have conducted theoretical studies of a radial heat wave. Vogel and Krueger1 studied a system with a moving cylindrical heat source of constant temper- ature, considering conduction in the radial direction only. Ramey2 included conduction in the vertical direction in his studies. Bailey and Larkin2 attacked a more general problem where initial well heating, vertical heat losses and arbitrary frontal velocities were included. In all these studies, however, conduction was considered to be the only means of heat transfer. Bailey and Larkin in a later paper included the effects of convection in a study involving both linear and radial geometries. Vertical heat losses were neglected in the radial case. Katz5 studied a similar problem in a one-dimensional radial model, using a heat-loss coefficient to account for vertical heat losses. Selig and Couch6 mployed a cylindrical model and investigated two limiting cases. In one case they considered no heat loss from the reservoir whereas in the other they assumed a constant temperature at the interface between the reservoir and its bounding formations. Thomas' studied a more general case but assumed a permeable bounding formation so that the convection effect is not confined to the reservoir. In the present work a more realistic and more generalized model is used. It involves a two-dimensional cylindrical system with combustion, convection and conduction inside the reservoir, but only conduction in the bounding formations. The purpose is to establish the temperature distribution both inside and outside the reservoir, to study the general features of the radial heat wave process, and to investigate the effects of various process variables on the performance characteristics of the process. THEORY We fist consider a circular porous reservoir of thickness H extending vertically from y = — H/2 to y = + H/2. The reservoir extends from a well bore radius r, to an external radius re. A stream of oxygen-containing gas is introduced into the reservoir through the wellbore. The oxygen-containing gas reacts with the fuel contained in the reservoir and forms a combustion front wherever the prevailing temperature can support the combustion. It is here assumed that this combustion front constitutes a cylindrical surface source of heat having an infinitesimal thickness in the radial direction and extending vertically throughout the whole thickness H. This is designated as Region I. We next consider a Region II corresponding to the upper and lower formations bounding the reservoir, extending from y = — - to y = — H/2 and from y = + H/2 to y = + m. Since r, is very small, we may assume that the two bounding formations have the same dimensions, symmetric with respect to the center plane of the reservoir. In this way, we may take the upper half of the system alone into consideration. In contrast with

By D. B. Hunter, H. W. Rosenberg

The titanium-rich portion of the Ti-Pd system was investigated from 0 to 75 wt pct Pd by metallo-graphic and X-ray techniques. A 0 eutectoid occurs at 24 wt pct Pd and 1190°F. Two compoutzds are indicated in the region below 75 wt pct Pd, Ti,Pd and Ti2Pd3. The solubility of palladium its a titanium is low, probably less than 1 pct. In 1960 Rudnitskii and Birunl published a complete version of the Ti-Pd phase diagram. However, their work was in disagreement with the earlier literature in that they reported only one inter metallic compound, whereas three had been reported earlier. In view of these discrepancies, it was therefore necessary to redetermine those portions of the diagram of immediate interest. The following account describes our work on the system over the range of 0 to 75 wt pct Pd. MATERIALS AND METHODS Distilled titanium sponge and elemental palladium were used in the formulation of the alloys; the chemistry of these materials is detailed in Table I. The alloys were prepared as 10 to 50 g blended compacts that were melted into buttons by arc melting under gettered argon on a water-cooled copper hearth. Weighing of the ingredients before and after melting showed that negligible weight changes occurred. Therefore, no analyses were undertaken and the compositions of all alloys are nominal. All alloys were fabricated by hot rolling at 1700°F to 0.070-in.-thick sheet. Scale was removed by sandblasting and pickling in a 5 pct HF-35 pct HNO,, balance H20 solution. For metallographic examination, specimens were mounted after heat treatment transverse to the rolling direction, ground on silicon carbide papers of increasing fineness to 600 grit, and then electro-polished using a solution containing 600 ml me-thanol, 60 ml perchloric acid, 360 ml butyl cello-solve, and 2 ml "Solvent X". Unless otherwise specified, etching of alloys containing up to 42 pct Pd was carried out by swabbing with a 12 pct HN03-1 pct HF aqueous etch where a bright etch was required, or by a 1 pct hydrofluoric in saturated oxalic acid solution where contrast between phases was required. The Ti-52.8 Pd alloy was etched with a solution of 25 ml HF, 40 ml glycerine, 35 ml methanol, and 18 g benzalkonium chloride. For X-ray examination, 1/2-in.-square speci- mens of sheet were mounted flat in a standard 1-in. metallographic mount and ground and polished as above. X-ray diffraction was performed using a Norelco type 12045 Diffractometer, employing CuKa radiation with a nickel filter at 40 kv and 20 ma. Specimens were rotated about the sheet normal during exposure. Although this procedure did not remove the effects of sheet texture from the relative intensities, it had the advantage that oxidation or contaminants entering during preparation of powder samples could not confuse the patterns obtained. RESULTS AND DISCUSSION Fig. 1 illustrates the Ti-Pd phase diagram according to Rudnitskii and Birunl with the work of the present authors superimposed. Both interpretations agree that the system is of the 0 -eutectoid type with an extensive 0-phase field, and that the eutectoid temperature is just below 1200°F. There is also agreement that the solubility of palladium in a titanium is restricted. Our work would indicate that the a solubility of palladium is low, probably less than 1 pct. However, whereas Rudnitskii and Birunl place the eutectoid composition at 41 wt pct Pd, this investigation shows it to be at about 24 wt pct Pd. Moreover, this investigation confirms the existence of compounds at Ti2Pd and Ti2Pd3, whereas Rudnitskii and Birun report only a single Berthol-lide phase covering the TiPd to TiPd, range. Laves et a1.' and Wallbaum, whose work was summarized by Maykuth , reported the existence of Ti2Pd3 and TiPd, in addition to Ti2Pd. More recently, Nevitt and Downe~' have reported the structure of

Jan 1, 1965

By J. B. Mitchell

The intelligent selection of comminution systems for industrial minerals requires a broad background of comminution experience. At the same time a thorough knowledge of the specific mineral occurrence, the applicable process and the product end use is required. To illustrate the different ways to process potash ores three flow sheets have been selected for presentation.

Jan 1, 1970

REPORT OF PRESIDENT C. F. RAND FOR THE YEAR 1917 The noteworthy occurrences during 1917 were the creation of Engineering Council; the completion of the addition to the Engineering Societies Building. and the occupation by the American Society of Civil engineers of the space thus provided for it; the addition of 67,000 vol-

Jan 3, 1918

By M. J. Miller

In modern mill design, a stockpile storage system for raw and/or semiprocessed ore has become almost indispensable. This paper discusses the benefits of such stockpile storage as well as the available types of belt conveyor stockpiling units. Alternative reclaiming arrangements for stockpiles are reviewed, and the advantages and disadvantages of each arrangement are discussed.

Jan 1, 1982

The ten-year "supply-demand relationship" tables in this chapter for various mineral and metal commodities have been adapted from Minerals in the U.S. Economy, compiled by the Bureau of Mines, U.S. Department of the Interior, published in 1975. Acknowledgment is made to the Bureau of Mines for compilation of the tables. [ ]

Jan 1, 1976

By W. M. Baldwin, C. R. Johns

Cobalt is reported1,2 to scale in accordance with the Pilling and Bed-worth3 parabolic law: where w = weight increase per unit surface area K = constant l = time The reported values of the parabolic oxidation constant, K, in the temperature range 600 to 1100°C follow an Arrhenius type of equation as inspection of Fig 1 shows. According to Valensi's theory5 on the scaling of metals where multiple-layered scales (for example, MeX, MeX2, and others) are possible, this fact could be construed as indicating that a single oxide only is formed on cobalt in this temperature range. Since the single straight line extends above 920°C where only CoO is stable in air (see Fig 2) it might be inferred that this is the only oxide formed on scaling. Arkharov and Voroshilova10 have studied the scales formed when cobalt is heated in air in the temperature range 385 to 800°C and report that CoO is indeed found in the scale but that CoO4 is also found as an overlay and in increasing amounts in the lower temperature ranges. No quantitative data regarding the relative proportions of the two oxides were reported. Again in the light of Valensi's theory this would indicate that the straight line in Fig 1 would be expected to undergo an inflection at some point in the temperature range 385 to 800°C. Chauvenet2 has studied the oxidation rates of CoO to Co3O4 and has found this reaction to proceed parabolically with time but reports parabolic scaling rates which are considerably (about ten times) larger than the scaling rates of cobalt metal itself. This is difficult to explain in terms of Valensi's theory although a full discussion of the possible discrepancy cannot be made in view of the lack of sufficient data. These points made an investigation of the scaling behavior of cobalt in air an attractive study. Discussion of Results Relatively large (approximately 95 sq cm of surface area) samples of 0.020 in. thick electrolytic cobalt strip,* sanded with 2/0 paper, were heated in air in a cyclone type furnace. The samples were weighed before and after the scaling treatment. The weight increases so observed obeyed the Pilling and Bedworth parabolic law at all temperatures studied. The parabolic scaling constants when plotted on a logarithmic scale as a function of absolute temperature are reproduced

Jan 1, 1950

By Geoffrey Gilbert

THE Montana Phosphate Products Co., subsidiary of the Consolidated Mining and Smelting Company of Canada, operates three phosphate properties north and northeast of Garrison, Powell County, Mont. Production of all three is from the same phosphate bed, a 3 to 4-ft. member of the Phosphoria formation, whose outcrop is traceable across the mountains of the Garnet Range in a series of southeasterly pitching folds. Because of topographical differences and of variations in the attitude of the bed, each property has its own mining methods and problems. Most of the phosphate rock produced since I930 has been shipped to the plant of the Consolidated Mining and Smelting Co. at Trail, B.C., where it is treated with sulphuric acid for conversion to phosphoric acid, which in turn is used to produce various fertilizers. HISTORY The occurrence of rock phosphate in Montana has been known. since 1910, and the Garrison area was mapped by the United States Geological Survey in 1913In the nineteen twenties William Anderson, owner of a ranch 8 miles north of Garrison, discovered phosphate on his land, and the Montana Phosphate Co., which later became the Montana Phosphate Products Co., was formed to work the deposit. Montana Phosphate Products Co. later obtained United States leases on two adjoining parcels of ground, and this combined property, known as the Anderson mine, has been the main source of Consolidated's phosphate rock. The mine now includes an adjoining parcel leased from Anaconda and mined from the Anderson workings. In 1940, the Graveley mine, a small privately owned property 6 miles east of the Anderson, was leased from the owner by Montana Phosphate Products Co., and a U. S. lease held by Graveley on some adjoining ground was subleased. In 1943 the Luke mine, on the Mineral Hill property, 1 ¾ miles south-southwest of the Graveley, a U. S. lease, which previously had produced a few thousand tons, was optioned from the lessees by Montana Phosphate Products Co., and is now being developed. At both these mines the rock is appreciably higher grade than at the Anderson mine. GEOLOGY The Phosphoria formation is the Permian member of an extensive sequence of Paleozoic and Mesozoic rocks. It is underlain by Pennsylvanian (Quadrant) quartzite and Mississippian limestone, and overlain without any marked unconformity by Jurassic (Ellis) shale and Cretaceous shale and sandstone. In the Garrison area, the Phosphoria itself consists mainly of about 50 ft. Of gray to yellow chert. Immediately below the chert is the phosphate, usually 3 to 4 ft. thick. Below the phosphate occur a few

Jan 1, 1945

By A. S. Joy

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

Jan 1, 1964

By J. H. Frye, R. M. Treco

One of the chief hindrances to an understanding of the hardness of solid solutions is the sparsity of suitable hardness data. There is great need of a large body of hardness data obtained from many different alloys of high purity by identical testing methods and corrected to correspond to a single grain size. A considerable amount of such data has been obtained by means of the Meyer analysis on copper-rich and silver-rich solid solutions. There are enough of these data to permit comparison of numerous alloys at equal solute concentration in these two solvents, but only in a few cases is it possible to construct hardness-concentration curves for any given alloy. Therefore additional hardness work on most of these alloys is desirable. The primary solid solutions of silver with cadmium, indium, tin, or antimony as solute are of special interest, since all elements are from the same period of the periodic table and since, as shown previously,l the hardening effect of equal percentages of these solutes is proportional to the lattice expansion produced by them. This paper presents the relation between hardness and concentration in the silver-antimony system from very dilute to nearly saturated solutions of antimony in silver. Experimental Procedure Alloys were made from silver, 99.99 per cent pure, and antimony, 99.975 per cent pure. Silver and antimony were placed in graphite crucibles that had an ash content of less than 0.7 5 per cent. These metals were melted and allowed to solidify in a vacuum, which, after melting was corn- . plete, was usually equivalent to 3 mm. of mercury. A high-frequency furnace was used. The ingots so obtained were worked and annealed to lessen segregation and to control grain size. Annealing was done in evacuated and sealed glass tubes. Hardness measuremeuts on specimens from these ingots were by means of the Meyer analysis.394 Using a 4-mm. ball, impressions were made under seven loads from 25 to 400 kg. The diameter of impression made under each load was measured. This enabled calculation of the constants in the well-known formula of Meyer. L = adn where L = load, d = diameter of impression, a = a constant, n = a constant The Meyer hardness is defined as P = L/i(1/4pd2) or P = 4adn-2/p Meyer hardnesses corresponding to d = I and to d = 4 are of especial interest, since the first corresponds to comparatively slight 'plastic deformation and the second to the maximum plastic deformation producible by penetration of the ball. These

Jan 1, 1945

By Geoffrey Gilbert

The Montana Phosphate Products Co., subsidiary of the Consolidated Mining and Smelting Company of Canada, operates three phosphate properties north and northeast of Garrison, Powell County, Mont. Production of all three is from the same phosphate bed, a 3 to 4-ft. member of the Phosphoria formation, whose outcrop is traceable across the mountains of the Garnet Range in a series of southeasterly pitching folds. Because of topographical differences and of variations in the attitude of the bed, each property has its own mining methods and problems. Most of the phosphate rock produced since 1930 has been shipped to the plant of the Consolidated Mining and Smelting Co. at Trail, B.C., where it is treated with sulphuric acid for conversion to phosphoric acid, which in turn is used to produce various fertilizers. History The occurrence of rock phosphate in Montana has been known since 1910, and the Garrison area was mapped by the United States Geological Survey in 1913. In the nineteen twenties William Anderson, owner of a ranch 8 miles north of Garrison, discovered phosphate on his land, and the Montana Phosphate Co., which later became the Montana Phosphate Products Co., was formed to work the deposit. Montana Phosphate Products Co. later obtained United States leases on two adjoining parcels of ground, and this combined property, known as the Anderson mine, has been the main source of Con-solidated's phosphate rock. The mine now includes an adjoining parcel leased from Anaconda and mined from the Anderson workings. In 1940, the Graveley mine, a small privately owned property 6 miles east of the Anderson, was leased from the owner by Montana Phosphate Products Co., and a U. S. lease held by Graveley on some adjoining ground was subleased. In 1943 the Luke mine, on the Mineral Hill property, 1 3/4 miles south-southwest of the Graveley, a U. S. lease, which previously had produced a few thousand tons, was optioned from the lessees by Montana Phosphate Products Co., and is now being developed. At both these mines the rock is appreciably higher grade than at the Anderson mine. Geology The Phosphoria formation is the Permian member of an extensive sequence of Paleozoic and Mesozoic rocks. It is underlain by Pennsylvanian (Quadrant) quartzite and Mississippian limestone, and overlain without any marked unconformity by Jurassic (Ellis) shale and Cretaceous shale and sandstone. In the Garrison area, the Phosphoria itself consists mainly of about 50 ft. of gray to yellow chert. Immediately below the chert is the phosphate, usually 3 to 4 ft. thick. Below the phosphate occur a few

Jan 1, 1948

By Geoffrey Gilbert

The Montana Phosphate Products Co., subsidiary of the Consolidated Mining and Smelting Company of Canada, operates three phosphate properties north and northeast of Garrison, Powell County, Mont. Production of all three is from the same phosphate bed, a 3 to 4-ft. member of the Phosphoria formation, whose outcrop is traceable across the mountains of the Garnet Range in a series of southeasterly pitching folds. Because of topographical differences and of variations in the attitude of the bed, each property has its own mining methods and problems. Most of the phosphate rock produced since 1930 has been shipped to the plant of the Consolidated Mining and Smelting Co. at Trail, B.C., where it is treated with sulphuric acid for conversion to phosphoric acid, which in turn is used to produce various fertilizers. History The occurrence of rock phosphate in Montana has been known since 1910, and the Garrison area was mapped by the United States Geological Survey in 1913. In the nineteen twenties William Anderson, owner of a ranch 8 miles north of Garrison, discovered phosphate on his land, and the Montana Phosphate Co., which later became the Montana Phosphate Products Co., was formed to work the deposit. Montana Phosphate Products Co. later obtained United States leases on two adjoining parcels of ground, and this combined property, known as the Anderson mine, has been the main source of Con-solidated's phosphate rock. The mine now includes an adjoining parcel leased from Anaconda and mined from the Anderson workings. In 1940, the Graveley mine, a small privately owned property 6 miles east of the Anderson, was leased from the owner by Montana Phosphate Products Co., and a U. S. lease held by Graveley on some adjoining ground was subleased. In 1943 the Luke mine, on the Mineral Hill property, 1 3/4 miles south-southwest of the Graveley, a U. S. lease, which previously had produced a few thousand tons, was optioned from the lessees by Montana Phosphate Products Co., and is now being developed. At both these mines the rock is appreciably higher grade than at the Anderson mine. Geology The Phosphoria formation is the Permian member of an extensive sequence of Paleozoic and Mesozoic rocks. It is underlain by Pennsylvanian (Quadrant) quartzite and Mississippian limestone, and overlain without any marked unconformity by Jurassic (Ellis) shale and Cretaceous shale and sandstone. In the Garrison area, the Phosphoria itself consists mainly of about 50 ft. of gray to yellow chert. Immediately below the chert is the phosphate, usually 3 to 4 ft. thick. Below the phosphate occur a few

Jan 1, 1948

By J. H. Frye, R. M. Treco

ONE of the chief hindrances to an understanding of the hardness of solid solutions is the sparsity of suitable hardness data. There is great need of a large body of hardness data obtained from many different alloys of high purity by identical testing methods and corrected to correspond to a single grain size. A considerable amount of such data has been obtained by means of the Meyer analysis on copper-rich and silver-rich solid solutions. There are enough of these data to permit comparison of numerous alloys at equal solute concentration in these two solvents, but only in a few cases is it possible to construct hardness-concentration curves for any given alloy. Therefore additional hardness work on most of these alloys is desirable. The primary solid solutions of silver with cadmium, indium, tin, or antimony as solute are of special interest, since all elements are from the same period of the periodic table and since, as shown previously,1 the hardening effect of equal percentages of these solutes is proportional to the lattice expansion produced by them. This paper presents the relation between hardness and concentration in the silver-antimony system from very dilute to nearly saturated solutions of antimony in silver. EXPERIMENTAL PROCEDURE Alloys were made from silver, 99.99 per cent pure, and antimony, 99.975 per cent pure. Silver and antimony were placed in graphite crucibles that had an ash content of less than 0.75 per cent. These metals were melted and allowed to solidify in a vacuum, which, after melting was complete, was usually equivalent to 3 mm. Of mercury. A high-frequency furnace was used. The ingots so obtained were worked and annealed to lessen segregation and to control grain size. Annealing was done in evacuated and sealed glass tubes. Hardness measurements on specimens from these ingots were by means of the Meyer analysis.3,4 Using a 4-mm.. ball, impressions were made under seven loads from 25 to 400 kg. The diameter of impression made under each load was measured. This enabled calculation of the constants in the well-known formula of Meyer. L=ad¬n where L = load, d = diameter of impression, a = a constant, n = a constant The Meyer hardness is defined as P = L/(1/4pd2) or P = 4adn-2/p Meyer hardnesses corresponding to d = 1 and to d = 4 are of especial interest, since the first corresponds to comparatively slight plastic deformation and the second to the maximum plastic deformation producible by penetration of the ball. These

Jan 1, 1944

By William J. McCaughey, Richard L. Barrett

For sixty years—in fact, ever since the inception of the basic steelmaking process —basic slags have been the subject of study by chemists, metallurgists and petrog-raphers! with the purpose of providing a better understanding of the reactions between the slag and the metal during the refining process. The result of this work and of the researches of mineralogists and physical chemists into the chemistry of oxide systems is a considerable body of literature dealing not only with slags themselves but with equilibrium relationships in systems synthesized from pure components. Since any actual slag is a multicom-ponent system more complex than any yet worked out in the laboratory, a complete solution to the problem is still far away. The writers have recently published a paper1 which they believe sheds light on the role of the slag in the elimination of phosphorus and it is the purpose of the present paper to discuss the metallurgical applications of that work. Since the pioneer investigations on the constitution of basic slags carried on by Stead and Risdale, Carnot and Richards, Hilgenstock and others in the I88o's, a considerable body of literature on this subject has appeared. Many of the more important of these papers were summarized in the previous paper,l therefore they will not be reviewed here. PetRographic Study The present writers have had occasion, over a period of years, to examine petro-graphically a great number of basic steel-making slags having a very wide range of chemical compositions and made under various conditions of operating practice. Although certain of these slags exhibit some unusual features, it is a remarkable fact that the great majority of mature slags show certain typical characteristics, which persist throughout the wide range of chemical compositions. The typical mature slag usually appears under the microscope to consist of two phases. The phase of primary crystallization is light colored and doubly refracting. If separated mechanically and subjected to chemical analysis, it is found to consist essentially of SiO2, CaO, and P2O6. Sometimes, although not usually, two such silicate-phosphate phases are found. The other conspicuous phase is dark in color and optically isotropic, and occurs as the interstitial material between the grains of the light colored phase. This dark colored interstitial phase when analyzed is found to consist essentially of FeO, Fe2O3, MnO, and MgO. In some 'lags high in iron oxide, particularly those from low-carbon heats, dicalcium ferrite is found. This phase is dark reddish brown in color and anisotropic.

Jan 1, 1944

By B. M. Larsen, T. E. Brower

THIS discussion is based on statistical manipulation and evaluation of operating data from several commercial blast furnaces which include rather wide variations in practice. We are concerned here mainly with the effect of manganese on sulphur elimination under operating conditions in commercial blast furnaces, but this effect can be outlined more clearly by including certain other variables such as silicon in iron and slag basicity, which are all in part interrelated. Real progress in understanding all of the smelting-zone reactions in this process requires more laboratory studies of slag-metal melts similar to those in the blast furnace, with careful control of oxygen pressure. Such experimental work is very difficult, however, and in the meantime, with the present scarcity of more fundamental data, such statistical trends and correlations as can be obtained from commercial furnace operating records may help in choosing laboratory test conditions as well as adding to our knowledge of operating procedures. We do not know just why the furnace data are apparently so irregular that statistical treatment of large numbers is needed to obtain accurate trends. It is partly caused, no doubt, by the many simultaneous variables present, but there are perhaps also such factors as: (I) the con- tinual swings up and down so characteristic of the process; (2) difficulty of accurate sampling of co-existing phases, as well as (3) the presence of both equilibrium and rate factors as a result of the fast driving of the process. In desulphurization, for example, the flow of thin layers of slag and metal over solid coke surfaces, plus the contact between droplets of iron falling through the slag layer in the hearth, would lead one to expect a close approach to equilibrium. On the other hand, most of the critical part of sulphur removal may occur in a short time and distance below the tuyeres with perhaps an accompanying decrease in oxygen pressure and the concurrent reduction of much of the silicon and manganese, so its degree of approach to equilibrium may be quite variable. Probable Chemistry of Desulphurization Since there is little evidence that sulphur atoms in the iron solution are aasociated to any appreciable extent in molecules such as MnS, the transfer from slag to metal and back again can be written:* (FeS) ? [FeS], [I] hence the following reactions seem most probable in the slag phase, (FeS) + (CaO) ? (CaS) + (FeO), [2] and, (FeS) + (MnO) ? (MnS) + (FeO). 131

Jan 1, 1949