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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

By A. A. Smith, J. S. Smart

THe elements silver, cadmium, tin, antimony and tellurium either are found as impurities in commercial coppers or are intentionally added to produce coppers for special uses. When present in small quantities, each of these metals exerts a significant effect on the properties of copper, but despite considerable experience and investigation much remains to be learned about their specific behavior. The presence of extraneous elements, particularly oxygen, complicates the study of individual additions of impurities in the range o to 0.05 per cent, and the use of high-purity copper has been found extremely helpful in circumventing these difficulties. It has also been found that individual behavior can be satisfactorilv determined from measurements of two commercially important properties, conductivity and softening temperature, according to methods that have been described previously.1,2 Data of this type, obtained in the course of a general investigation of the effects of impurities on the properties of both oxygen-bearing 2nd oxygen-free copper are presented herewith. All samples except those containing cadmium were prepared as 3/8-in. continuously cast oxygen-free rod from pure copper and weighed amounts of a similarly synthesized master alloy. Composition was checked by chemical methods, which in every case verified the calculated analyses. Test wires were cold-drawn one B, and S. number per pass on a string-up machine using four 30-min. 600°C. anneals at 0.3125, 0.257, 0.204 and 0.162 in. and a final cold reduction of 75 per cent to 0.081 in. Some oxygen-bearing samples were produced directly from the 3/8-in. oxygen-free rods by diffusion from a surface scale at 850°C. and drawn to size as listed above, but most of the alloys were remelted in pure graphite and cast through air into a I-in. round mold. The slugs were then hot-rolled to 5/16 in., drawn to 0.162 in., annealed as listed above, and drawn to 0.081 inch. Conductivity wires were annealed for I hr. at 100°C. intervals between 300' and 800°F., using a hydrogen atmosphere for oxygen-free samples and purified nitrogen for the oxygen-bearing type. All samples were quenched from the annealing temperature in 10 per cent H²S04 and conductivity was measured on a Hoopes bridge that had been checked against a Kelvin bridge. The softening temperatures represent the half-hard stage of the annealing curve as determined by a standard procedure.' Effect of Silver Numerous excellent studies of the argentiferous coppers are found in the literature, and these have been adequately

Jan 1, 1943

By A. A. Smith, J. S. Smart

THe elements silver, cadmium, tin, antimony and tellurium either are found as impurities in commercial coppers or are intentionally added to produce coppers for special uses. When present in small quantities, each of these metals exerts a significant effect on the properties of copper, but despite considerable experience and investigation much remains to be learned about their specific behavior. The presence of extraneous elements, particularly oxygen, complicates the study of individual additions of impurities in the range o to 0.05 per cent, and the use of high-purity copper has been found extremely helpful in circumventing these difficulties. It has also been found that individual behavior can be satisfactorilv determined from measurements of two commercially important properties, conductivity and softening temperature, according to methods that have been described previously.1,2 Data of this type, obtained in the course of a general investigation of the effects of impurities on the properties of both oxygen-bearing 2nd oxygen-free copper are presented herewith. All samples except those containing cadmium were prepared as 3/8-in. continuously cast oxygen-free rod from pure copper and weighed amounts of a similarly synthesized master alloy. Composition was checked by chemical methods, which in every case verified the calculated analyses. Test wires were cold-drawn one B, and S. number per pass on a string-up machine using four 30-min. 600°C. anneals at 0.3125, 0.257, 0.204 and 0.162 in. and a final cold reduction of 75 per cent to 0.081 in. Some oxygen-bearing samples were produced directly from the 3/8-in. oxygen-free rods by diffusion from a surface scale at 850°C. and drawn to size as listed above, but most of the alloys were remelted in pure graphite and cast through air into a I-in. round mold. The slugs were then hot-rolled to 5/16 in., drawn to 0.162 in., annealed as listed above, and drawn to 0.081 inch. Conductivity wires were annealed for I hr. at 100°C. intervals between 300' and 800°F., using a hydrogen atmosphere for oxygen-free samples and purified nitrogen for the oxygen-bearing type. All samples were quenched from the annealing temperature in 10 per cent H²S04 and conductivity was measured on a Hoopes bridge that had been checked against a Kelvin bridge. The softening temperatures represent the half-hard stage of the annealing curve as determined by a standard procedure.' Effect of Silver Numerous excellent studies of the argentiferous coppers are found in the literature, and these have been adequately

Jan 1, 1943

By W. L. Austin

At the Steptoe metallurgical plant, where ore of the Nevada Consolidated Copper Co. is beneficiated, a small copper-leaching annex has been in operation treating flue dust from roasting-furnace dust chambers, together with a siliceous oxidized ore. This leaching plant was designed to obviate smelting low-grade siliceous flue dust, which interfered with the operation of the reverberatories by forming a blanket on the charge. The major portion of the copper content of the flue dust accumulating in the upper chambers of the roaster flue, and at the stack, is water soluble, and also contains much free sulphuric acid and soluble sulphates. It was found that sufficient acid could be obtained by mixing this material with water to provide a lixiviant for leaching the siliceous copper ore mentioned. This was the sole source of the lixiviant used in the operation to be described. An analysis of the flue dust showed it to be composed as follows : Per Cent. Copper.............................................. 3.00 siO2................................................. 23.41 Fe................................................... 4.08 CaO + MgO......................................... 2.72 Al203................................................ 0.07 Free H2S04........................................... 19.94 SO3 combined as sulphate.............................. 25.10 H2O combined with the sulphates....................... 10.67 0................................................... 2.50 Total................................... 97.49 Copper soluble in dilute H2SO4.......................... 2.56 The oxidized ore, locally known as carbonate, has the following composition:

Jan 1, 1915

By Walter R. Hibbard, Ming-Kao Yen

VARIOUS rationalizations of preferred orientations in cold worked polycrystalline metals have been based on the operation of at least two,1 three,2 five,4 an indefinite number,5 and all,6 slip systems of the type occurring in single crystals. Pickus and Mathewson3 suggested that the cold rolling texture in face-centered cubic metals could be rationalized on the basis of two or more operating slip directions symmetrically disposed about the direction of flow in such a manner that the resolved shear stress factor is equal for all operating slip systems and lattice rotations cancel each other. The importance of the direction of flow, † the necessity for the operation of slip systems capable of producing the required, changes in external dimensions, the maintenance of a common surface between adjacent grains and a symmetrical arrangement of the operating slip systems in order to produce an end orientation which is stable under additional deformation lead to the following rationalization of textures based on the type of slip systems operative in single crystals. The rationalization is intended to explain why certain orientations are suitable for deformational flow without a change in orientation and thus are stable end orientations or ideal texture orientations. It does not attempt to explain how the grains of a randomly oriented polycrystalline aggregate will reach this orientation. The rationalization is based on the following four postulates: I. The ideal textures for polycrystalline aggregates are the result of reorientations of individual crystals toward the same stable end orientation at which no further reorientation will occur even during additional deformation. Since, in simple slip, - the relative orientations of the stress axis and the active slip system determine the change in orientation during slip, it is considered that the orientation of the stress axis with respect to the ideal texture determines what slip systems must be active to retain the stable end orientation. Therefore the stable end orientation should be a symmetrical one around the stress axis with respect to the active slip systems such that lattice rotations resulting from slip will cancel each other and prevent a resultant change in orientation. (Rotational symmetry only-not translation, inversion, nor others-is considered here.) Thus a metal under a pure stress should develop a texture consisting of one or more of the crystallographically symmetrical directions, <100>, <110> or <111> for cubic metals or <0001>, <1010> or <1120> for hexagonal dose-packed metals, parallel to the stress axis. 2. Since the active slip direction is the direction of glide during simple slip and thus the direction of maximum shear movement, in the ideal texture the active slip

Jan 1, 1948

By G. J. Wilson

Review of difficulties experienced in drilling directional wells in the offshore Grand Isle Block 43 field showed most failures of drill pipe, drill collars and casing to have been associated with excessive dog-legs. Alleviation of difficulties was approached by synthesizing theoretical and practical concepts in a planned dog-leg control program. Preventive measures necessary to control dog-leg severity and corrective measures used to reduce unacceptable doglegs are discussed. When other measures fail, deliberative measures as outlined can be employed after the probable cumulative fatigue damage to be sustained by the drill pipe has been determined. Results of a program successful in virtually eliminating problems stemming from excessive dog-legs indicate that control of dog-leg severity in directional wells is feasible and will cause no decrease in the over-all drilling rate. INTRODUCTION Prompted by an increasing frequency of drill pipe, drill collar and casing failures, a study of 50 directional wells representing 592,000 ft of hole, including 444,000 ft of deviated hole, drilled in the offshore Grand Isle Block 43 field was conducted in early 1965. A number of drill pipe washouts and six keyseating problems were recorded and a detailed review was made of 16 failures which had required fishing effort in 10 of the 50 directional wells drilled prior to June, 1965. These problem wells are exemplified by Wells G and F for which pertinent data are shown in Figs. 1 and 2. Data pertaining to all of the 16 failures are summarized in Table 1. Inspection of these data shows most of the problems to have been associated with dog-legs in excess of theoretical limits suggested by Lubinski&apos; and excessive dog-legging is indicated to have been concomitant with whipstocking in several of the problem wells. Results of the investigation agreed with those reported by Schenck2 who had concluded that problems could be expected when dog-leg severity exceeded limits proposed by Lubinski. Since Schenck had demonstrated the desirability and feasibility of drilling directional wells without excessive dog-legging, a dog-leg control program was established in June, 1965 for wells drilled in the Grand Isle Block 43 field. This paper reviews the methods by which theoretical and practical concepts were synthesized to develop a program of preventive, corrective and deliberative measures which virtually eliminated problems stemming from excessive dog-legs in directional wells. Dog-legs of a magnitude causing no damage are referred to as permissible +1CONTINENTAL OIL CO. HARVEY, LA.

By Clarence Zener

The internal friction of nonferrous metals vibrating at low stress amplitudes has so far always been successfully interpreted in terms of inhomogeneities of one sort or another. Examples are the fluctuation of stress across a specimen vibrating transversely,1,2,3 the stress inhomogeneities due to the elastic anisotropy and partial random orientation of the individual crystallites, localized weak regions introduced by cold-working,6&apos;7 grain boundaries and possibly twinning planes.8&apos;9 Perfect single crystals are, by definition, homogeneous. Actual single crystals usually, perhaps always, contains some imperfections. The present investigation was undertaken to determine whether the internal friction of single crystals may likewise be attributed to inhomogeneities. This study was made possible through the gift of a large single crystal of 70-30 alpha brass by H. L. Burghoff, of the Chase Brass and Copper Co. The specimen, 3.i in. in diameter and 10 in. long, was similar to samples previously described by Mr. Burghoff. Experimental Method The experimental method used has previously been described in institute papers.5&apos;6&apos;9 The measure of internal friction adopted here, I/Q, is X the logarithmic decre- ment, a measure used by some writers, and is also X the specific damping capacity, a measure used by other writers. In all measurements the stress level was kept so low that the measurements were independent of stress level. In all measurements in which the temperature was varied, observations were made as the specimen slowly cooled from its highest temperature. The specimen was vibrated transversely. Observations were made at the fundamental frequency and at the first overtone, of about 620 and 1710 cycles per second, respectively. No attempt was made to avoid acoustical losses. Experimental Results The specimen was annealed for several hours at 450°C. The temperature dependence of the internal friction was then determined from room temperature to 400°C. As shown in Fig. I, the internal friction increased by only a factor of 2 from room temperature to 300°C., then by a factor of 100 during the next Ioo° interval. These measurements are consistent with the view that the observed internal friction is the superposition of two distinct parts. One, dominant at room temperature, is nearly independent of temperature. This part may be accounted for by acoustical losses and by transverse thermal currents. It was not further investigated. The second part, when plotted in the manner of Fig. I, lies upon a straight line. Therefore it has a heat of activation H; i.e., it varies with temperature as Internal friction e-H/RT [I]

Jan 1, 1943

By Clarence Zener

The internal friction of nonferrous metals vibrating at low stress amplitudes has so far always been successfully interpreted in terms of inhomogeneities of one sort or another. Examples are the fluctuation of stress across a specimen vibrating transversely,1,2,3 the stress inhomogeneities due to the elastic anisotropy and partial random orientation of the individual crystallites, localized weak regions introduced by cold-working,6&apos;7 grain boundaries and possibly twinning planes.8&apos;9 Perfect single crystals are, by definition, homogeneous. Actual single crystals usually, perhaps always, contains some imperfections. The present investigation was undertaken to determine whether the internal friction of single crystals may likewise be attributed to inhomogeneities. This study was made possible through the gift of a large single crystal of 70-30 alpha brass by H. L. Burghoff, of the Chase Brass and Copper Co. The specimen, 3.i in. in diameter and 10 in. long, was similar to samples previously described by Mr. Burghoff. Experimental Method The experimental method used has previously been described in institute papers.5&apos;6&apos;9 The measure of internal friction adopted here, I/Q, is X the logarithmic decre- ment, a measure used by some writers, and is also X the specific damping capacity, a measure used by other writers. In all measurements the stress level was kept so low that the measurements were independent of stress level. In all measurements in which the temperature was varied, observations were made as the specimen slowly cooled from its highest temperature. The specimen was vibrated transversely. Observations were made at the fundamental frequency and at the first overtone, of about 620 and 1710 cycles per second, respectively. No attempt was made to avoid acoustical losses. Experimental Results The specimen was annealed for several hours at 450°C. The temperature dependence of the internal friction was then determined from room temperature to 400°C. As shown in Fig. I, the internal friction increased by only a factor of 2 from room temperature to 300°C., then by a factor of 100 during the next Ioo° interval. These measurements are consistent with the view that the observed internal friction is the superposition of two distinct parts. One, dominant at room temperature, is nearly independent of temperature. This part may be accounted for by acoustical losses and by transverse thermal currents. It was not further investigated. The second part, when plotted in the manner of Fig. I, lies upon a straight line. Therefore it has a heat of activation H; i.e., it varies with temperature as Internal friction e-H/RT [I]

Jan 1, 1943

By A. A. Collins

OF widespread interest to all lead metal¬lurgists is a dross smelting process that will consistently give mattes and speiss of low lead and high copper contents. It is -a problem that has intrigued operators through the years. In the past few years, with increased amounts of copper and overcrowded metallurgical furnaces, it has been almost imperative to evolve some method. Experience at El Paso has shown that high copper-to-lead ratios can be consistently attained by use of the new soda process.* OLDER METHODS Three older methods; i.e., I. Dross plus siliceous ore and limestone, 2. Dross plus one fourth blast-furnace speiss and siliceous ore, 3. Dross plus sulphides and siliceous ore and scrap iron, do not give consistent results and the products are higher in lead and lower in copper than those produced with the soda process. Any radical changes in the blast-furnace drosses will throw any of these older methods into a tailspin. For almost ten years, El Paso used the third method, with varying results. It was noted that as the arsenic and antimony contents of the dross increased, the speiss and matte steadily increased in lead and decreased in copper. A dross containing four parts of copper to one part of arsenic was considered to be ideal. At times this balance of copper to arsenic was almost impossible to obtain, especially when handling copper Cottrell dusts, which vary so greatly in copper and arsenic. Custom smelters like El Paso, handling a great variety of dusts, concentrates and ores, are apt to have anywhere from 1 to 15 pct copper on charge, with a variable in arsenic of from 0.5 to 2 pct. With such conditions, and drosses varying from 12 to 40 pct copper, an operator using the older dross reverberatory practices would find it just about im¬possible to control the reverberatory operations and to produce a good product low in lead and high in copper. These conditions prevailed at El Paso from the year 1940 to the present. In May 1942 it, was decided to experiment with the soda process. THE SODA PROCESS After considerable work the soda method was finally evolved to the present state. It has never failed to produce a good product even under the most adverse conditions. It might be well to remember that many men of thought in the smelting industry have at one time or other suggested the removal of all copper, arsenic and antimony from the lead blast-furnace charge as an aid to better metallurgy.

Jan 1, 1947

Without having asked for it, the writer has apparently been drawn into the discussion regarding relative hoisting capacities which was started by Woodward Iron, egged on by Joe Haller of Cleveland-Cliffs [Mining Engineering, August p. 642] and Axel Kjelgaard [November p. 919], who took exception to Mr. Haller&apos;s remarks of tonnage hoisted and avers that they do better in Sweden. It does not appear to the writer that Mr. Haller was inclined to refer to the tonnage hoisted at Cleveland-Cliffs in a manner to imply that they claimed any hoisting record, but rather as a statement that they had hoisted a certain amount of ore during the year 1950. Mr. Haller has been in the mining game long enough to appreciate what Mr. Kjelgaard did not apparently take into consideration, that length of haul, shifts hoisted, nature of ore, method of loading and the many other factors which influence the hoisting cycle make a comparison of tonnages hoisted of two given mines almost an impossibility. Mr. Cheyette sent you .a copy of his letter to Bob Manegold relative to the capacities of the Orient #2 mine. There are several mines around the Country which constantly set up records about which little or nothing at all is ever heard. We cite the Snow Hill Coal Co. mine at Terre Haute, Ind., which has an automatic Nordberg hoist and which hoists 12 tons per trip or 700 tons per hr from 700 ft. This is a counter-weighted installation and a complete cycle is made every 62 seconds or 58 trips per hr. Another mine, The Potash Company of America mine at Carlsbad, N. Mex., has a Nordberg automatic hoist, hoisting eight tons per trip from 1150 ft on a one minute cycle. The materials hoisted in these two mines are ideal for automatic hoisting-they are free flowing so that no hang up is anticipated and hoisting is continuous. Multiplying out the above figures you will find that it is possible to hoist 11,000 tons in two shifts at Snow Hill or over 3 million tons in 300 days per year and over 2 million tons at Potash. Other mines have records which can be pointed to with pride. When a record for one year is established, it doesn&apos;t stand too long as here in America the ambition of all the men connected with the operation forces them on to larger tonnages. T. C. WIEDENHOEFER MANAGER MINE HOIST DEPARTMENT NORDBERG MANUFACTNRING CO. MILWAUKEE, WIS.

Jan 1, 1952

By John Philip Zannaras

John Philip Zannaras (Registered Professional Engineer, Congress, Ariz.)- The authors show in their [Fig. 4] the cumulative results of grinding with two sizes of bails, one 30 mm and the other 20 mm. The Gaudin-Meloy probability for breakage for a single fall used by the authors in their paper is given by their [Eq. 6]. Another form of [Eq. 6] is given by Gaudin-Meloy in their paper as follows: [ ] From the definition of A given by Gaudin-Meloy it is obvious that A30 is greater than A., it therefore follows from the foregoing equation that according to the Gaudin-Meloy formula the probability of breakage for a single fall of all the balls in the 20-mm experiment was more than 2.25 times the probability of breakage in a single fall of all the 30-mm balls which is contradicted by the authors&apos; experimental evidence in [Fig. 4] in which is shown that much more grinding took place with the 30-mm balls. In fact the authors present convincing evidence that the Gaudin-Meloy work is erroneous because their work is based only on a geometric configuration and on ambiguous and uncertain definition of A and disregards the fact that the distribution of fracture depends on other important and indispensable factors including the intensity of stress caused on the feed grain by the balls. That there is an immense and chaotic variation of stresses caused on the feed grains by the balls is shown by a formula, derived by this writer and published in 1955. The derivation of this formula is given in the Appendix of this discussion; it contains the variables in the operation of ball mills and is based on the science of mechanics-not on probabilities. [ ] where T is the unit stress in pounds per square inch produced by the moving load, h is the height in feet through which P has fallen, E is the modulus of elasticity of the rock, P is weight of one ball, and L is the size of the grain (assumed to be a cube of side L). It will be shown by this writer&apos;s formula that when a 30-mm ball strikes any size of feed grain it will cause 1.837 times higher stress than the 20-mm ball when striking the same size grain. It will be shown that when the 30-mm ball or the 20-mm ball strikes a feed grain of 0.1 mm it will cause 90 times more stress on the grain than when it strikes a 2-mm grain.

Jan 1, 1974

By T. M. Gurr

The United States is the world&apos;s leading producer of phosphate rock. In 1975 according to the US Bureau of Mines&apos; statistics, 44.3 million tonnes (48.8 million st) of phosphate rock were produced in the United States, 1 which is 40.6% of the world&apos;s production.2 The major phosphate producing areas of the United States are located in Fig. 1 and the production for 1975 is listed as follows:

Jan 6, 1979

By R. W. Heckel

The densification of molybdenum powder by hot pressing has been studied as a function of time (up to about 3 x 104 sec) at pressures of 5000, 15,000, and 30,000 psi in the temperature range from 3700o to 1200°C. Excluding results below 2 to 5 x 10 sec, the density (D) - pressure (P) - time (t) data followed the general form:

Jan 1, 1965

By R. F. Mehl, B. Lustman

The formation of intermediate phase layers in cementation processes has been subjected to extensive qualitative investigation though to relatively little quantitative study; this work has recently been fully summarized by F. N. Rhines.&apos; It is necessary here only to cnumerate the general conclusions drawn concerning the kinetic laws governing the growth of intermediate layers and to state what is known concerning the structural changes accompanying the generation of phase layers. I. When the intermediate phase is protective in type—i.e., when its density is less than that of the base metal, so that a continuous coating is formed and maintained—the isothermal growth of the phase follows a simple parabolic equation: X2 = kt [i] where X is the thickness of the alloy layer, k thc reaction rate constant, and t the time. The applicability of this equation to diffusion processes is tested by plotting the square of the thickness versus time, or by plotting the thickness versus the square root of time; the resultant achievement of a straight line in such a plot has been considered sufficient proof of the validity of this equation. Exceptions have been found where liquid phases are involved in the reaction, where the diffusion layer is cracked,2 and where thin semimetallic oxide and sulphide coatings are formed on metals.$ In the first two cases the thickness increases linearly with time, and in the latter it is a logarithmic function of time. 2. The rate of thickening varics with temperature according to the Arrhenius equation: k = Ae-Q/RT [2] where k is the parabolic rate constant of Eq. I, or some other rate-descriptive function, A is the action constant, e the base of natural logarithms, Q the heat of activation, R the gas constant, and T absolute temperature. This equation has been found to be generally valid except when transformations occur during reaction in either the base metal or in the reaction layer; in such instances Eq. 2 is still applicable with different values for the constants A and Q above and below the transformation temperature. 3. Ali phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two components. In some cases certain of the phases may be too thin to be observed and identified easily. Nonequilibrium phases have never been noted in thick reaction layers; i.e., layers of a thickness that may be discerned microscopically. The relative thickness of each phase in a diffusion layer is proportional to the concentration gradient and to the rate of diffusion in that phase.4 The reaction layers tend to have a

Jan 1, 1942

By R. F. Mehl, B. Lustman

The formation of intermediate phase layers in cementation processes has been subjected to extensive qualitative investigation though to relatively little quantitative study; this work has recently been fully summarized by F. N. Rhines.&apos; It is necessary here only to cnumerate the general conclusions drawn concerning the kinetic laws governing the growth of intermediate layers and to state what is known concerning the structural changes accompanying the generation of phase layers. I. When the intermediate phase is protective in type—i.e., when its density is less than that of the base metal, so that a continuous coating is formed and maintained—the isothermal growth of the phase follows a simple parabolic equation: X2 = kt [i] where X is the thickness of the alloy layer, k thc reaction rate constant, and t the time. The applicability of this equation to diffusion processes is tested by plotting the square of the thickness versus time, or by plotting the thickness versus the square root of time; the resultant achievement of a straight line in such a plot has been considered sufficient proof of the validity of this equation. Exceptions have been found where liquid phases are involved in the reaction, where the diffusion layer is cracked,2 and where thin semimetallic oxide and sulphide coatings are formed on metals.$ In the first two cases the thickness increases linearly with time, and in the latter it is a logarithmic function of time. 2. The rate of thickening varics with temperature according to the Arrhenius equation: k = Ae-Q/RT [2] where k is the parabolic rate constant of Eq. I, or some other rate-descriptive function, A is the action constant, e the base of natural logarithms, Q the heat of activation, R the gas constant, and T absolute temperature. This equation has been found to be generally valid except when transformations occur during reaction in either the base metal or in the reaction layer; in such instances Eq. 2 is still applicable with different values for the constants A and Q above and below the transformation temperature. 3. Ali phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two components. In some cases certain of the phases may be too thin to be observed and identified easily. Nonequilibrium phases have never been noted in thick reaction layers; i.e., layers of a thickness that may be discerned microscopically. The relative thickness of each phase in a diffusion layer is proportional to the concentration gradient and to the rate of diffusion in that phase.4 The reaction layers tend to have a

Jan 1, 1942

By Arnlf Muan, Bert Phillips

The quenching technique has been used for- a study of phase velntiorzs within the composition triangle 2CaO.Fe2O3-FeO.Fe2O3 Fe2O3 of the system Ca-Fe-O. Desired total compositions of sanzples were attained by weighing of starting materials in required proportions and keeping them in sealed 80 pct Pt 20 pct Rh tubes during equilibration .runs. The liquidus surface has been delineated. the existence of two ternary compounds has been established, and seven ternary inwariant situations have been determined. ONE unit within the research program on refractory oxides in progress in our laboratories is the study of phase relations in the system Ca-Fe-Si-O. The present paper deals with the ternary system 2CaOFe2O3-FeO.Fe2O3-Fe2O3, which is only a small part of the enormously complex quaternary system. Many of the phases occurring in iron ore sinter products have compositions which can be closely approximated within this ternary system, and a knowledge of stability relations existing among these phases may be expected to be a useful guide for improving sintering operations. Two fundamentally different experimental approach es are commonly used in studies of systems containing iron oxides, both permitting control of the oxidation state of Fe. One method consists in keeping constant the oxygen partial pressure of the gas phase in equilibrium with condensed phases (liquid and crystalline). In the other method, which is the one used in the present investigation, the total composition of condensed phases is kept essentially constant by keeping the samples in a gas-tight container. The details of this experimental procedure will be described in a later section. PREVIOUS WORK Extensive studies of phase relations in the bounding binary system FeOFe2O3-Fe2O3 have been reported by Greig, Posnjak, Merwin, and Sosman,&apos; by Darken and Gurry,2, 3 and recently by Phillips and Muan.4 A diagram summarizing the results of these studies is shown in Fig. 1. Particular attention is

Jan 1, 1961

By M. D. Scott

A second generation tailings system, consisting of 8 km (5 mile) of large diameter 914- mm (36-in.) po1yethylene pipeline, the bulk of which was laid on a 0.2% grade, has been successfully operated by Lornex Mining Corp. for the past 2 yr. The system was designed to operate as a partial flow pipeline during average flows with the ability to pressurize itself and operate as a pressure pipeline under high flows, or clean itself out under sanding conditions. The system has exceeded design capacity and has had very little downtime. Polyethylene pipe was easily and inexpensively installed and has exhibited superior abrasion resistance characteristics.

Jan 1, 1978

By B. Amero, W. Petruk, D. R. Owens, D. R. Morris

Samples taken at different heights in the lead blast furnace of Brunswick Mining and Smelting corporation were studied to determine the phases present in order to interpret the reactions In the furnace. The main phases in the blast furnace feed are Pb3Ca2S13011, Zn ferrite (ZnFe204), and hardystonite (Ca2ZnSi207); rninor ones include lead and a Pb silicate. The temperature in the furnace varies from about 300°C at 4.2 m above the tuyeres to 1150°C at 1.1 m. There is no evidence of reactions in samples from points cooler than 800°C. Some reaction occurs between 950° and llOO°C and the lead sinter is nearly decomposed at about 1150°C. The first evidence of reaction was the decomposition of Pb silicate to lead and S102. At higher temperatures the Pb Ca2Si3011 decomposed to form lead and hardystonite (Ca2ZnS120rf. The Zn required for hardystonite was derived from the Zn ferrite which apparently re-equilibrated to a new Zn ferrite with less Zn. The decomposed sinter consists essentially of lead, hardystonite, wustite and a Zn ferrite with a low Zn content.

Jan 1, 1984

By R. A. Sharma, F. D. Richardson

Manganese oxide acitivities and sulfide capacities have been measured at 1650°C in mixtures of MnO + A1203 and MnO + SiO2 - Al2O3. Sulfide capacities have also been measured at 165O0C for melts of MnO + SiO2, MgO + SiO2, MgO + SiO2 + Al2O3, MgO + MnO + SiO2, and SiO2 + Al2O3 and for crystalline CaO. The activity coefficients of the sulfides of manganese and magnesium have been derived where possible. It looks as though the activity coefficients of sulfides are greatest at compositions where the free energies of formation of the silicate mixtures have their maximum negative values. The amphoteric nature of alumina is reflected in the results for the binaries and ternaries in which it is present with silica. The limiting solubility of CaS in CaO at 1650°C is 6.3 x 10-4 mole fraction. THE activities of manganese oxide have been measured in a variety of silicate and aluminate melts by use of the equilibrium (MnO)slag = [Mn]pt .½O2 [l] and the experimental techniques described previously.&apos; Sulfide capacities (CS = wt pct S (PO2/PS2)½) have also been determined in a series of melts, by use of an established method2 which exploits the equilibrium (O°) + ½S2 = (S") . ½O2 [2] If CS and the activity of a metal oxide are known in a melt, the activity coefficient of the metal sulfide can be calculated by use of the equilibrium constant K, for the pure phase reaction MO i ½S2 = MS + ½O2 [3] The activity coefficient of the sulfide is then given by the equation

Jan 1, 1965

E. A. Peretti (University of Notre Dame, Notre Dame, Ind.)—Mr. Deitz and Professor Halpern are to be congratulated on a fine piece of work which adds to our knowledge of precious metal—cyanide-solution reactions. I should like to offer the following comments: The authors state, "the rate plots were always linear, indicating a zero order reaction rate." This appears to conflict with the data of Fig. 6 which clearly show the rate to vary with the NaCN concentration. It seems to me that the rate curves are linear because of the experimental setup. The volume of solution is so large that over a three-hour period the change in NaCN concentration is very small. A rough calculation for the experiments of Table I where the initial NaCN strength was 0.0096 mol per liter show a change of NaCN concentration of about 0.0009 mol per liter at the end of three hours. In short, over the period of time that the experiment was in progress, the NaCN strength was practically constant; hence the rate of dissolution remained practically constant. Eq. 10, as written, specifies that 1 mol of H202 and 2 mol of hydroxyl ion are formed when 2 mol of silver react. Is this true? The effect of H,O2 on the rate was made in solutions having an oxygen pressure of 4.8 atm. Were any tests made in solutions containing hydrogen peroxide, but no oxygen? G. M. Willis (University of Melbourne, Melbourne, Australia)—The authors have shown that, under their experimental conditions of high O2 concentrations, the rate of solution of silver in aqueous cyanide solutions is controlled by diffusion of O2 or CN- to the metal surface. With diffusion control, it is generally not possible to obtain further information about the mechanism of a process.

Jan 1, 1955