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By Ravindra M. Nadkarni, Milton E. Wadsworth

The kinetics of cetnentation of copper with iron were observed to follow first-order kinetics and increase with speed of agitation to a limiting value. Maximum rates agree closely with theoretical values based upon a model of aqueous solution diffusion through a litniting boundary film. Back reaction kinetics are shown both theoretically and experimentally to be independent of ferrous iron concentration in solution. The inlportance of attnospheres of air, oxygen, nitrogen, and hydrogen was studied and the results have been correlated with several impovtant oxidation processes involving metallic iron and copper. The kinetics of the reaction of ferric ion with metallic iron were found to be slow in the absence of metallic copper and essentially proportional to the surface area of metallic copper present in the system. THE precipitation of copper on iron is classic as an example of a relatively ancient art applied successfully for centuries with little fundamental understanding of the important parameters involved. There is some indication that the process has been a commercial means to produce copper since the sixteenth century.' The amount of fundamental work on the cementation of copper with iron is not great. Wartman and Roberson2 carried out a series of detailed copper cementation experiments using natural and synthetic mine water. The following were presented as the three principal reactions: Reaction [I] is the desired cementation reaction and accordingly 0.88 lb of iron would produce 1 lb of copper. In actual practice iron consumption would more normally fall in the range of 1.5 to 2.5 lb per lb of copper. Wartman and Roberson attributed the excess consumption of iron to Reactions [2] and [3]. They found that Reactions [I] and [2] proceeded at approximately the same velocity while Reaction [3] was much slower and would be diminished by controlling the contact time. It was also pointed out that increased agitation is beneficial in removing hydrogen bubbles and barren layers of solution at the iron surface as well as removing contaminants resulting from the hydrolysis of iron. Episkoposyan3 and Episkoposyan and Kakovskii4 studied copper and silver cementation on rotating iron disks in chloride solutions. The kinetics based upon a diffusion model were first order and varied linearly with surface area and with angular velocity raised to the one-half power according to the Levich equation. The experimental activation energy for both copper and silver was approximately 3 kcal per per mole. Excess iron consumption was found to increase with temperature. The rate of cementation first increased with increasing acidity and then diminished at high acid concentrations. sutolov5 has presented an excellent review of the Leach-Precipitation-Flotation (LPF) process including a discussion of copper cementation from an electrochemical point of view although few experimental results were presented. From voltage considerations he predicted that cementation should not be influenced by the concentration of ferrous iron in solution. He considered several secondary reactions including Reactions [2] and [3] and pointed out the importance of oxidation of ferrous iron to ferric with oxygen. In addition it was suggested that Reaction [2] was enhanced by the dissolution of metallic copper by ferric iron which in turn consumed excess iron by the cementation reaction, Eq.[1]. Cementation of copper on metals other than iron has been studied by several investigators but, as in the case of iron, the amount of fundamental work is not extensive. Bashkova and kovalenko6 and Bashkova7 studied the cementation of copper on indium from copper and indium sulfate solutions. The rate was found to be first order and to increase with acidity. This was associated with a decrease in potential (EIn — ECu) and the simultaneous reduction of hydrogen ions at low pH. The rate of cementation also decreased with increasing indium concentrations which was postulated to be due to the decrease in the rate of diffusion of the ions in solution. Below 97°C the experimental activation energy was found to have the unusually low value of 2 kcal per mole and was attributed to diffusional control. Above 97°C the rate increased suddenly and was explained as a change in the rate-controlling step to a chemical reaction. In Part I of this study Nadkarni et a1 .1 have reported on preliminary results obtained in a laboratory study of the kinetics of the cementation process. The rate was found to be first order, proportional to the surface area of the iron, and to increase with speed of stirring until a maximum rate was observed. At low stirring speeds the deposit was spongy and adherent. At medium speeds the copper peeled off in bright strips and at high speeds finely divided copper was produced and continually removed from the surface. The amount of excess iron consumed increased with speed of stirring and with temperature. The average experimental activation energy combining results from several types of iron was 5.8 + 1.6 kcal per mole suggesting diffusional control through a limiting boundary film. Traditionally copper cementation has been carried out over the centuries in gravity-fed launders of various design containing scrap iron. More recently rotating drum precipitators and activated launders8'10 have been used. In the latter, copper-bearing solutions are

Jan 1, 1968

By B. A. Wilcox, A. H. Clauer

The steady-state creep of TD Nickel NL + 2 001 pct TltOz) has been studied orer the telirperatve range 325&apos; to 1100O and the stress range 15,000 to 36,000 psi. At high temperatures (aboue 0.5 T& gran-boundary slzding is the )nost znportant )node of creep deformation, and the steady-state creep rate, is, can be related to stress and temperature by: where Q = 190 kcal pev mole and n has an unusually high value of 40. A creep mechanism based on cross slip of dislocations around The O2 particles can satisfactovily explain the low-temperature (T < 0.5 T,) cveep behavior, and the follo wing relation is applicable: Q, (a) is found to decrease from 57 to 46 kcal per mole as the stress is increased from 32,000 to 36,000 psi. THERE have been a variety of theories proposed to explain the influence of dispersed second-phase particles on the yield strength and flow stress of metals, and these have been reviewed recently by Kelly and icholson.&apos; However, only several attempts2"4 have been made to develop mechanistic treatments which characterize the creep behavior of dispersion-strengthened metals, and to date these have not been fully evaluated experimentally. weertman2 and Ansell and weertman3 proposed a quantitative creep theory for coarse-grairzed dispersion-strengthened metals, based on the concept that the rate-controlling process for steady-state creep was the climb of dislocations over second-phase particles, as suggested by choeck. The theory predicted that the steady-state creep rate, <,, was proportional to the applied stress, a, for low stresses and that is a4 o for high stresses. The activation energy for creep, Q,, was equivalent to that for self-diffusion, Qs.d., in the matrix. Some limited experimental evidence in support of this theory was obtained on a recrystallized Al-Alz03 S.A.P.-type alloy by Ansell and Lenel.6 Ansell and weertman3 also developed a semiquanti-tative theory for high-temperature creep of lineg-rained dispersion-strengthened metals in order to explain their results on an extruded S:A.P.-type alloy, which had a fine-grained fibrous structure. They suggested that the rate of dislocation generation from grain boundaries was the rate-controlling process, and fitted their results to the equation: where Q, was found to be 150 kcal per mole, i.e., QC- 4Q,.d. in aluminum. Similar high activation energies for creep7-&apos;&apos; and tensile deformation" of dispersion-strengthened alloys have been observed by other investigators for S.A.P.,&apos;" indium-glass bead omosites, and Ni + A1203 alls.&apos; There is no general agreement regarding the mechanisms involved in the creep of dispersion-strengthened metals, and this is due in part to the lack of detailed studies relating the structures of crept specimens to the mechanical behavior. The present investigation on thoriated nickel was undertaken with the aim of studying the structural changes which occur during creep of a dispersion-strengthened alloy and rationalizing the observed mechanical behavior in terms of the creep structures. EXPERIMENTAL METHODS The material used in this investigation was 1/2-in.-diam TD Nickel bar, which contained 2.3 vol pct Tho,. Obtained from E. I. duPont de Nemours & Co., Inc. The final fabrication treatment by DuPont consisted of -95 pct reduction by swaging followed by a 1-hr anneal at 1000°C. Transmission and replica electron microscopy revealed that the material had a fine-grained fibered structure with an average transverse grain size of -1 p and a longitudinal grain size of 10 to 15 p. Selected-area diffraction indicated that the fiber axis was parallel to (OOl), in agreement with the results of Inman eta1." All creep specimens were vacuum-annealed at 1300°C for 3 hr prior to testing. Transmission electron microscopy showed that the only structural change due to annealing was a slight decrease in dislocation density, confirming the reported high degree of structural stability.13 Furthermore, recrys-tallization or grain growth during creep was never observed. The structure typical of uncrept material (after the 1300 C, 3-hr anneal) is shown in Fig. 1. The grain boundaries are predominantly high angle and. although some areas show a tangled cell structure, the grain interiors are relatively dislocation-free. Individual dislocations are strongly pinned by the Tho2 particles; i.e., very rarely did dislocations move within a thin foil. The grey "halos" around some of the larger particles which protrude out of the foil surface arise from contamination in the electron microscoge. The Tho, particle size ranged from -100 to IOOOA, and the distribution is shown in Fig. 2. The technique used to obtain the data in Fig. 2 consisted of dissolving the nickel matrix in acid, collecting the Tho2 particles on cellulose acetate, and measuring about 1000 particle diameters in the electron microscope. Similar results were obtained by measuring about 600 particles in thin foils, an; the average particle size was found to be 2r, = 370A. Using the data in Fig. 2 (annealed structure), the mean planar center-to-center particle

Jan 1, 1967

By W. F. Hosford, E. W. Kelley

By testing polycrystalline specimens from textured plates which had Previously been used to provide materials for growing single crystals, it has been possible to relate the plastic anisotropy of textured materials to the deformation behavior of single crystals. The deformation studies have been conducted at room temperature on textured polycrystalline magnesium and binary Mg-Th and Mg-Li alloys. Variously oriented specimens of the textured materials were deformed in plane-strain compression and in uniaxial tension and compression. The stress-strain curves are similar in their general jorm of anisotropy and stress levels to those obtained on single crystals of the same alloys. The degree of anisotropy is lower, however, in the polycrystalline materials and correlates with the intensity of the basal texture. Yield loci for the textured materials appear reasonable in terms of the deformation mechanisms, and deviate sharply from the form predicted by the Hill analysis for aniso-tropic material. A N earlier study1 of single crystals has shown that magnesium and magnesium alloys with thorium and with lithium deform at room temperature primarily by basal slip, {10i2) twinning, and (1011) banding. The (10i1) banding mode is a combination of {10ll) twinning followed by (1012) twinning and basal slip within the doubly twinned material.2, 3 Magnesium with lithium can also deform by {1010)(1210) prism slip.1&apos;4&apos;5 Still other deformation modes have been reported for magnesium6-11 but these are considered to play a minor role in room-temperature deformation. In a polycrystalline material, plastic deformation must occur in the individual grains through the operation of one or more of the various deformation modes. Because the critical shear stress for basal slip is very low compared to the activation stresses for the other deformation modes,&apos; basal slip accounts for much of the deformation in the polycrystalline aggregate. However, since there are only two mutually independent basal slip systems, and because five independent systems must be active for an arbitrary shape change in any material,&apos;&apos; modes other than basal slip must account for some of the strain. The deformation of textured magnesium, like that of other hcp metals, must be controlled by the same mechanisms observed in single crystals. In strongly textured material, the form of the anisotropy should be similar to that of single crystals, and the degree of anisotropy should depend on the intensity of the texture. EXPERIMENTAL PROCEDURE The anisotropy of deformation was investigated through the use of plane-strain compression tests, as well as uniaxial tension and compression tests. Materials. Test specimens were cut from the three textured plates of magnesium which had previously been used to provide material for single crystals.&apos; These plates, furnished by Dow Chemical Co., had been reduced about 80 pct during the process of being hot-rolled to their final 1/4-in. thicknesses. The plates had the three respective compositions, pure magnesium, Mg-0.5 wt pct Th (0.49 pct Th by spectro-graphic analysis), and Mg-4 wt pct Li (3.84 pct Li by chemical analysis). Impurities other than iron were less than 0.0005 pct Al, 0.01 pct Ca, 0.001 pct Cu, 0.0006 pct Mn, 0.001 pct Ni, 0.003 pct Pb, 0.001 pct Si, 0.001 pct Sn, and 0.01 pct Zn. Iron was 0.001 pct in the pure magnesium, 0.002 pct in the Mg-0.5 pct Th, and 0.014 pct in the Mg-4 pct Li. The textures of the three plates were determined by X-ray diffraction utilizing only the reflection technique out to an angle of 50 deg from the sheet normal. The resulting basal pole figures are presented in Figs. 1, 3, and 5. Grain sizes in the plates were ASTM number 4 in the pure magnesium and number 7 in each of the alloys. Plane-Strain Compression Tests. Plane-strain compression specimens approximately $ in. thick by 4 in. wide by $ in. long were prepared for each of the three compositions. These specimens were prepared in a manner similar to that used for the single-crystal specimens of the earlier study.&apos; All polycrystalline specimens were stress-relieved at 500°F for hr as the final step in their preparation for testing. The testing procedure was identical to that used for the single crystals, involving compression in a channel and using 2-mil Teflon film as a lubricant. The specimens were tested in six orientations of interest, these being the six combinations of the rolling, transverse, and thickness directions of the material serving as loading, extension, and constraint directions in the plane-strain compression test. Each of the six orientations was assigned a two-letter identifying code. These are combinations of the letters (thickness direction), R (rolling direction), and T (transverse direction) with the first letter signifying the loading direction and the second letter the extension direction. For example, ZR specimens were compressed in the thickness direction while extension was permitted to operate in the rolling direction of the textured material. To facilitate comparison of the present work with that of the single-crystal study1 the orientations used for single crystals are given in Table I along with the polycrystalline orientations that most nearly correspond. To insure reproducibility, at least three duplicate

Jan 1, 1969

By W. J. Slatosky

W. 0. Philbrook (Cairiegie Institute of Technologyogv—Mr. Slatosky has presented an interesting and constructive paper that represents another step along the way of converting steelmaking from an art to a science. I am confident that his computer will be practical and successful and that with a very few months of experience it will provide a significantly better degree of control than his record of 65 pct of heats within range obtained with the slide-rule calculator . A paper such as this, with a lot of symbols and condensed mathematics, is difficult to comprehend quickly. Since I have had an opportunity to study it carefully, perhaps my evaluation of its validity and accomplishments will save time for others. Mr. Slatosky has correctly used standard principles of stoichiometry and heat balances, which are available to anybody, but he has also brought to them two original contributions: 1) He has developed from operating data some empirical relations for predicting the final FeO content of the slag (at 0.5 pct C end-point) as a function of slag basicity, lance height, and scrap, ore, and scale in the charge. This improves the accuracy of prediction of temperature or scrap requirement compared with assuming an arbitrary, constant FeO content at the end of each heat. There is no assurance yet that exactly the same relations will hold for other furnaces or practices, but similar correlations can be expected. 2) He has combined calculations that are ordinarily carried out laboriously as a number of individual steps into a single, simple linear equation that can readily be fed into a machine. This involved a tremendous amount of painstaking detail work as well as the imagination to see the possibility and work out the steps. While his particular Eqs. [3] and [6] are valid only for the furnace design, charge weight, and blowing time used at Aliquippa Works, only a few numerical values have to be changed to adapt it for other conditions. In order to arrive at a useable solution, Mr. Slatosky had to make some basic assumptions about the process that are similar to those used by others. He neglected variation in some process variables and assumed an arbitrary average value for waste gas analysis and temperature for want of more exact information at the present time. All of these judgments are clearly stated. In addition, some thermody-namic data presently available are not adequate for the job, notably in relation to heats of formation and sensible heat in slag, and some expedient has to be adopted to get around the difficulty. Other people might prefer slightly different judgments about these details and hence obtain somewhat different numerical solutions. This is not of serious importance, however, because the errors accumulate in the "heat loss" term and are largely self-compensating for a constant heat time. Although the extended Eq. l(a) in Appendix I was set up as a rate equation originally, for convenience in using an analogue computer as stated in the paper, the time dependence was removed by later mathematical manipulations and assumptions about the process. The final result is an integration of element and energy balances from initial to final states; this procedure is as legitimate here as in any other form of heat-balance calculation. The formal handling of stoichiometry and thermochemistry appears to be correct, and it is assumed that any arithmetical errors would have come to light in applying the calculations to furnace practice. Mr. Slatosky&apos;s approach is not necessarily unique, in that other people might start with apparently different equations or prefer another form of final equation for another type of computer. However, he has presented an accomplished result that appears to be a theoretically sound and practically useful way of applying scientific principles and rapid computation for better control of steelmaking. His success will undoubtedly encourage himself and others to improve on the mathematical model and its use as better informatioq becomes available. John F. Elliott (Massachusetts Institute of Teck-t2ology)-The last comment by Mr. Richards that a calculator is quite unnecessary for an L-D operation ?-equi??es a rebuttal. The L-D furnace is a very high capacity process which places a premium on close control. When one is making steel at rates between 100 and 200 tons per hr, one cannot afford the luxury of an extra 5 or 10 min at the end of a heat correcting for an error that should never have been made in the first place. Mr. Slatosky&apos;s paper is a very sound application of the simple principles of stoichiometry and the energy balance. It is a satisfactory and valuable start, but only the start of the development of methods of control for this process. An analysis of the process shows that it should be very suitable to control by a computer. This is especially the case when various grades of steel are to be made. In fact, it would seem that the organizations who are planning new and bigger installations of L-D vessels should consider carefully the advantages that would stem from computer control of a vessel with the operator present to do little more

Jan 1, 1962

By J. J. Frawley, W. J. Childs

The dynamic nucleation of supercooled bismuth and Bi-Sn alloys has been studied over a frequency range of 15 to 20,000 cps. For low-frequency vibration, a minimum vibrational energy was required for enhancement of nucleation. Above this critical energy, the dynamic supercooling was less than static supercooling showing that vibration promoted nucleation. The amount of dynamic supercooling continued to decrease with increasing vibrational energy until a minimum or threshold value was reached. This minimum value of supercooling for nucleation remained constant joy all further increases in vibrational energy. For higher frequencies, similar results were observed. This behavior has been related to the necessity of cavitation for dynamic nucleation. When a liquid is cooled to a temperature below its equilibrium melting point, the solid phase is more thermodynamically stable. However, for solidification to occur, a two-step process, nucleation and subsequent growth of the solid phase, must occur. When a liquid is supercooled, that is cooled below the equilibrium melting point, the controlling process for solidification to begin is the rate of nucleation. Once nucleation has occurred, the solidification process is controlled by the rate of growth. Nucleation can be induced by two factors: either by a catalyst or by the use of mechanical shock. Numerous investigators1-4 have studied the effect of nucleation catalysis but much less systematic study has been made of nucleation by mechanical shock waves. The influence of vibrations on grain size in castings and ingots has been studied by many authors but no clear understanding of the mechanism or accurate prediction of the effect has been presented.5 It would be intuitively expected that the further the departure from equilibrium (i.e., the greater the supercooling), the easier it would be to induce nucleation. This has been quantitatively demonstrated both by walker6 and later by Stuhr,7 that the greater the degree of supercooling the easier it is to nucleate by a shock wave. Stuhr also attempted to obtain the mechanical energy required for nucleation of bismuth as a function of supercooling. He vibrated a crucible containing supercooled metal at low frequencies and various amplitudes and noted the corresponding dynamic supercooling obtained. The amount of supercooling was inversely proportional to the mechanical energy applied. Limitation of his experiment was the problem of the confinement of the liquid in the crucible without splashing and minimizing other unwanted modes of vibration. Tiller et al.8,9 did similar work on tin and Sn-Pb alloys using an electromagnetic stirring device. Their conclusions were that the magnitude of the magnetic field strength did not affect the amount of undercooling at which nucleation was initiated. While conclusive experimental results have been lacking to explain this effect of mechanical vibration on inducing nucleation, a number of theories have been proposed. Two of these theories are discussed below. 1) The Change in Melting:- Point Locally Due to the Change in Pressure (Clapeyron Equation). According to Vonnegut10 the most plausible explanation for the nucleation of a supercooled melt by cavitation is the effect of changing the melting point by a change in pressure. For materials where the volume decreases on solidification, an increase in pressure raises the melting point; for materials which expand on solidification, the melting point is raised for a decrease in pressure, i.e., rarefaction. Using the Clapeyron equation, the melting point of a metal can be calculated as a function of pressure. If it is assumed that the equation can also be used to calculate the temperature of nucleation of a supercooled melt as a function of pressure (i.e., the temperature of heterogeneous nucleation will increase with pressure at the same rate as the melting point), the amount of supercooling required for nucleation will be constant at all pressures as shown in Fig. 1. It is obvious that an isothermal change which results in an increase in melting point results in an equal increase in supercooling. This increase in supercooling may now be sufficient for nucleation. A pressure of 80,000 atm was calculated, using the Clapeyron equation, as the pressure required to increase the temperature of nucleation of nickel by 200°C. According to Lord Rayleigh,11 this very large pressure could be generated for a very brief period of time by the collapse of a cavity. This pressure wave is radiated in all directions from the collapsed cavity. If the temperature of the melt is slightly below its equilibrium melting temperature at atmospheric pressure, stable growth can follow; that is, once nucleation occurs, growth becomes the main driving force of the solidification process. This proposal has been extended to water which expands on freezing by assuming that nucleation occurs during rarefaction following the pressure pulse. This negative pressure pulse should follow immediately after the positive pressure pulse with its magnitude approaching the critical tensile strength of the liquid. The negative pressure developed during this period would raise the melting point of water and thus promote nucleation. Hunt and jackson12 have suggested this for water. Similarly, it could be postulated that bismuth which also expands on freezing could be nucleated during the negative pressure pulse. 2) Nucleation by a High-pressure Phase. An extension of the Clapeyron equation to systems where density decreased on freezing at atmosphere pressure has been proposed by Hickling.13 The phase diagram for water initially shows the well-known decrease in

Jan 1, 1969

By AIME AIME

[The American Institute of -Mining Engineers does not assume responsibility for any statement of fact or opinion advanced in its papers or discussions.] A detailed list of the&apos; papers contained in this section is given in the Table of Contents, pages i. and ii. Comments or criticisms upon all papers given in this section whether private corrections of typographical or other errors or communications for publication as "Discussions," or independent papers on the same or a related subject, are earnestly invited. ERRATA. The following corrections and. additions to papers contained in Bi-Monthly Bulletin No. 7, January, 1906,-were received too late for incorporation in the text of said papers ; but will be introduced in their: proper places: in the volume of the Transactions: These corrections are here published in order to bring them -promptly to the notice of the Institute. Page Line Cover, title-page and at the top of pages in the preliminary section "No. 1 " should be "No. 7 ". 1. Bottom For :" Dr. P. H. Shimer" read "Dr. P. W. Shinier " 69. Fig. 3. "N" of compass-record should be ?S". A new block for this illustration has been made as shown on p. xxxviii of this Bulletin. 78. 3 from bottom. For " slope " read " stope." 89. Fig. 2, small diagram in upper left-hand corner. Omit use 50 ft. to 1" scale ". For "Thro&apos; 250 " read " Thro&apos; 200 ". Add dotted line extend¬ing from upper right-hand corner of the square

Mar 1, 1906

By Francis M. Walters, Irwin R. Kramer

The substitution of cobalt for part of the nickel in Invar was found by P. H. Brace1 to lower the coefficient 01 expansion. Scott1 extended the use of cobalt to alloys of higher inflection temperatures. Such alloys have a larger temperature range of low expansion than those without cobalt, and their use up to 400&apos; or 500°C. offers decided advantages in certain applications. However, it has been found that the iron-nickel-cobalt alloys are not stable in this temperature range. Experimental Methods Two methods were used in studying the stability of the low-expansion iron -nickel-cobalt alloys. Dilatometer specimens were held at 480°C. for 9 months and the change in expansion characteristics was dctcr- mined. Filings were held for about 2 months at various temperatures and the change in structure was determined by X-ray diffraction. As shown by Table I, the alloys studied covered a wide range in nickel plus cobalt content (which determines the inflection temperature) as well as some variation in the ratio of nickel to iron (which controls the temperature of the gamma to alpha transformation). Included also are alloys containing carbon and vanadium, carbon and titanium and three with various amounts of copper. The alloys were melted in a high-frequency induction furnace with a magnesia crucible, using ingot iron, electrolytic nickel and commercial cobalt. Fifteen-pound heats were cast into iron molds after deoxidizing with silicon, or

Jan 1, 1942

By W. B. Devereux

I have observed three deposits of iron ore in Pitkin County, which present unusnal characteristics, and wliich seem to throw some light upon the genesis of iron ores under certain conditions. They occur in the precipitons mountain ranges, forming spurs on the Pacific slope of the main continental backbone. The first is a body of limonite, lying upon the side of a high mountain, which forms part of the base of Hayden&apos;s Peak. This limonite forms a sheet of considerable area, and is thin at the edges, and about 3 feet in thickness in the central portions. It is conformable with the slope of the mountain side, and rests upou the eroded rocks, but is not comformable to them. The ore is laminated and shaly in texture, and has the physical characteristics of the hard limonites, such as are found in the Marquette District, Lake Superior. It is covered with loose earth and rocks, from 1 to 2 feet in thickness. Much of the ore is filled with impressions of&apos; spruce leaves, such as are found in the forests now covering the slope of the mountain. In the rocks forming the mountain, iron pyrites occurs in bodies, and this limonite probably owes its origin to such a body not far distant. Not far up the mountain large masses of conglomerate are now forming, the cementing material being a similar hydrated oxide of iron. The iron is

Jan 1, 1884

By Francis M. Walters, Irwin R. Kramer

The substitution of cobalt for part of the nickel in Invar was found by P. H. Brace1 to lower the coefficient 01 expansion. Scott1 extended the use of cobalt to alloys of higher inflection temperatures. Such alloys have a larger temperature range of low expansion than those without cobalt, and their use up to 400&apos; or 500°C. offers decided advantages in certain applications. However, it has been found that the iron-nickel-cobalt alloys are not stable in this temperature range. Experimental Methods Two methods were used in studying the stability of the low-expansion iron -nickel-cobalt alloys. Dilatometer specimens were held at 480°C. for 9 months and the change in expansion characteristics was dctcr- mined. Filings were held for about 2 months at various temperatures and the change in structure was determined by X-ray diffraction. As shown by Table I, the alloys studied covered a wide range in nickel plus cobalt content (which determines the inflection temperature) as well as some variation in the ratio of nickel to iron (which controls the temperature of the gamma to alpha transformation). Included also are alloys containing carbon and vanadium, carbon and titanium and three with various amounts of copper. The alloys were melted in a high-frequency induction furnace with a magnesia crucible, using ingot iron, electrolytic nickel and commercial cobalt. Fifteen-pound heats were cast into iron molds after deoxidizing with silicon, or

Jan 1, 1942

By Francis M. Walters, Irvin R. Kramer

THE substitution of cobalt for part of the nickel in Invar was found by P. H. Brace1 to lower the coefficient of expansion. Scott1 extended the use of cobalt to alloys of higher inflection temperatures. Such alloys have a larger temperature range of low expansion than those without cobalt, and [ ] their use up to 400° or 500°C. offers decided advantages in certain applications. However, it has been found that the iron-nickel-cobalt alloys are not stable in this temperature range. EXPERIMENTAL METHODS Two methods were used in studying the stability of the low-expansion iron-nickel-cobalt alloys. Dilatometer specimens were held at 480°C, for 9 months and the change in expansion characteristics was determined. Filings were held for about 2 months at various temperatures and the change in structure was determined by X-ray diffraction. As shown by Table I, the alloys studied covered a wide range in nickel plus cobalt content (which determines the inflection [ ] temperature) as well as some variation in the ratio of nickel to iron (which controls the temperature of the gamma to alpha transformation). Included also are alloys containing carbon and vanadium, carbon and titanium and three with various amounts of copper. The alloys were melted in a high-frequency induction furnace with a magnesia crucible, using ingot iron, electrolytic nickel and commercial cobalt. Fifteen-pound heats were cast into iron molds after deoxidizing with silicon, or

Jan 1, 1941

By R. W. Smith, M. E. Brookes

The temperature at which th: quenched 0&apos; (ordered bcc) phase transfo.rms to the ( (complex hexagonal) phase on heating has been examined for certain Ag-Zn and Ag-Au-Zn alloys using an electrical resistivity method. The transition temperature decreases by approxinzately 7°C as the zinc content is reduced by 1 at. pct. The critical temperature, Tc, for long-range order has also been measured for a number of Ag-Au-Zn alloys. Extrapolation to zero gold content suggests that Tc decreases by approximately 5°C per 1 at. pct reduction in zinc content. The 0 phase of the Ag-Zn system exists over a narrow range near the composition Ag zn,&apos; Fig. 1, and has a bcc structure which is disordered above 272°C. Slow cooling to temperatures below the range 274"/258"C allows the complex hexagonal phase, r° to form.2 This is the stable structure at room temperature.3 Upon quenching 0 -phase alloys from high temperatures, it is found that the 0 — (&apos; transformation is suppressed; but ordering takes place (i.e., 0 -0&apos;). This ordered structure can also be obtained by the room-temperature aging of cold-worked (0.4 Deformation of the 0&apos; phase gives rise to a fur- ther hexagonal phase ( (of nearly ideal axial ratio) which reverts to b&apos; within a few hours.= In view of this, it has been suggested that the equilibrium struc-

Jan 1, 1969

By Frank C. Greene

The year 1941 was uneventful in oil and gas development in Missouri. No new pools were opened and several areas with promising structures, in the northwestern part of the state, were disappointing when drilled. In looking for an explanation of these failures, it is suggested that it will be necessary to find areas in which the lower beds of the Mississippian are upfolded, in order to obtain production in northwestern Missouri. To do this, geophysical exploration or test drilling far enough into the Mississippian beds to get cores or cuttings of definitely established age appear to be the best methods. Although not leading to new production, drilling in Missouri established two new state records, one for depth and another for the amount of rotary drilling. An important well† in sec. 24, T. 19 N., R. 11 E., Pemiscot County, in the southeastern corner of the state, was drilled with a rotary to 4740 ft., several hundred feet deeper than any previous hole. The total footage drilled by rotary rigs of various types was 31,135 ft. and that by cable tools, 29,166 feet. The total number of completions was 85, of which 18 were gas wells with an initial open-flow capacity of 12,528,000 cu. ft., and 67 were dry holes. Of the latter, 19 were drilled into Mississippian or older formations. Table I gives a summary of activities by counties.

Jan 1, 1942

By Frank C. Greene

The year 1941 was uneventful in oil and gas development in Missouri. No new pools were opened and several areas with promising structures, in the northwestern part of the state, were disappointing when drilled. In looking for an explanation of these failures, it is suggested that it will be necessary to find areas in which the lower beds of the Mississippian are upfolded, in order to obtain production in northwestern Missouri. To do this, geophysical exploration or test drilling far enough into the Mississippian beds to get cores or cuttings of definitely established age appear to be the best methods. Although not leading to new production, drilling in Missouri established two new state records, one for depth and another for the amount of rotary drilling. An important well† in sec. 24, T. 19 N., R. 11 E., Pemiscot County, in the southeastern corner of the state, was drilled with a rotary to 4740 ft., several hundred feet deeper than any previous hole. The total footage drilled by rotary rigs of various types was 31,135 ft. and that by cable tools, 29,166 feet. The total number of completions was 85, of which 18 were gas wells with an initial open-flow capacity of 12,528,000 cu. ft., and 67 were dry holes. Of the latter, 19 were drilled into Mississippian or older formations. Table I gives a summary of activities by counties.

Jan 1, 1942

By F. C. Blake

The best method for the estimation of copper in ores and secondary products is that proposed by Dr. Steinbeck* for the award offered by the Mansfeld&apos;schen Ober-Berg-und Hutten-Direction. It is based upon the decolorization of the blue ammonia solution of copper by potassic cyanide.7 It is necessary for the accurate estimation of copper in arsenides that the arsenic be separated from the copper before the ammonia solution is made. The presence of a notable amount of arsenic renders the titration by potassic cyanide inaccurate, the end reaction being obscured by the appearance of a yellowish-green tint towards the end of the titration. The change of the color of the ammonia solution from blue to the tint caused by the presence of arsenic cannot be used for an end reaction, for the intensity and quick appearance of the latter color depend upon the amount of arsenic present in the solution. In the analysis of speise, the method of separating the copper by an oxidizing and reducing treatment in the muffle, to volatilize the arsenic, gives poor results, and there may easily be some loss of the weighed sample. The separation of the precipitated sulphides of arsenic and copper by treating with sodic sulphide, gives good results, but the process is tedious. I have used the two following methods, which are simpler and more expeditious than those mentioned, with good results

Jan 1, 1881

By Charles E. Wait

In the use of the apparatus purchased for the new chemical laboratories of the university, no piece has given us more satisfaction, or has been a greater success, than a new still which is the subject of this paper. In the designing of this still I had two definite objects in view ; one, the utilizing of steam from the large 60 horse-power boiler used in heating the building, and the other, a provision for making distilled water with gas, when steam from the heating-plant was not available. The still is encased in wrought-iron, with a lining of asbestos, and is provided with a float which automatically regulates the flow of water from the supply-pipe. It was made for me by G. J. M?rrle, Pforzheim, Germany, and was imported by Messrs. Eimer & Amend, of New York City. It is a beautiful piece of apparatus, and the workmanship is excellent in every detail. The essential parts of this apparatus will be understood by consulting the accompanying figures, but a few words of explanation may be appropriate. The still has a capacity of seven gallons, and is made of heavy copper, tin-lined. It has a water-gauge showing the height of the water in the still, also an exit for steam, and safetyvalve, V; inlet for steam through a coiled perforated block-tin pipe; also an outlet, 0, for cleaning out the still; and there is also a heavy

Jan 1, 1895

Professor Somasundaran has given an excellent presentation of the numerous problems which remain to be solved before the selective aggregation of fine particulates is likely to see broad commercial application in the beneficiation of mineral fines. However it is useful, I think, to reiterate some of the major problem areas. The over-riding factor which has limited the development of selective aggregation techniques is that processes such as coagulation and flocculation tend to be inherently non-selective. Conditions which favor the aggregation of one kind of fine particles usually favor the aggregation of all kinds of particles. As Professor Somasundaran has pointed out, the state of aggregation of a fine-particle dispersion is primarily determined by the forces of interaction between the individual particles. In most systems, the dominant forces are: 1. van der Waals - London Dispersion forces between the particles themselves 2. electrical double layer forces 3. steric forces between adsorbed layers on the surfaces of the particles. The London Dispersion forces between like particles are always attractive, but for dissimilar particles dispersed in a fluid medium can, in some cases, lead to a net repulsion. Electrical double layer forces always lead to repulsion between like particles but can, again, cause either attraction or repulsion for dissimilar materials. The steric forces, which are by far the least understood of the three types, can also lead to attraction or repulsion depending on condi-

Jan 1, 1979

PUGET SOUND SECTION SIMON H. ASH, Chairman, I. F. LAUCKS, Vice Chairman, CHARLES SIMENSTAD, Sec.-Treas., 425 Lyon Building, Seattle, Wash. GLENVILLE A. COLLINS, JOHN N. POTT. The Puget Sound Section met at the Arctic Club, Seattle, Wash., on Jan. 20, 1917. Sixteen members and five guests were present. Dinner having been served, the meeting was called to order. A letter from secretary of Associated Engineering Societies was read, requesting payment of this section&apos;s assessment to the quarterly budget, and upon motion it was voted that the Secretary-Treasurer be instructed to pay this assessment. It was moved and carried that this section join with the Chemical Society in a meeting. At the, close of the business meeting, Mr. Asa C. Baldwin gave an illustrated lecture on the "Alaska Boundary Survey." On Feb. 24, the Puget Sound Section again held a meeting at the Arctic Club, 16 members and three guests being present. Chester F. Lee, as member of a committee representing this section in the joint council of the Associated Engineering Societies, reported that by lots it had been decided that the term of service of said committee would be as follows: Chester F. Lee, two years; George. Watkin Evans, one year. Following adjournment of the business meeting, Prof. Joseph Daniels, of the University of Washington, delivered a very interesting lecture on "Milling Practice of The Alaska-Castineau Mining Company." CHAS. SIMENSTAD, Secretary.

Jan 5, 1917

By J. K. Abraham

In recent years there has been interest displayed in the precipitation phenomena occurring in austenitic alloys based on the binary Fe-Ni system.1&apos;2 Previous communications have been extended covering the kinetics of clustering in the Fe-Ni-Ti system and the effect of cluster size on subsequent mechanical properties.3&apos;4 To a great extent the question of coherency, which has a dominant role in determining the mechanical properties, is dictated by the degree of misfit between the precipitate and matrix. Thus, the change in lattice parameter of the matrix with composition is an important variable that should be examined. The lattice parameter, ao, of austenite was determined for Fe-29.75 Ni-1 to 6 Ti and Fe-27 Ni-1 to 10 Ti alloys in this study. The alloys used in this investigation were melted in a vacuum induction furnace from a starting stock of plast iron (99.95), electrolytic nickel (99.9), and ti- tanium sheet (99.5) in a MgO crucible. The alloy compositions in atomic percent are given in Table I and their relative position in the Fe-Ni-Ti ternary is indicated in Fig. 1. The chemical analyses were taken from the homogenized bulk materials treated in a manner related earlier.3 A diamond file was used to obtain powder from the bulk. To remove the stresses induced by filing, the powders were austenitized at 1875°F for

Jan 1, 1969

By Hugh Rose

JAY A. CARPENTER, Tonopah, Nev: (communication to the Secretary*).-This description of the Santa Gertrudis mill is of great interest to the operators of similar silver mills in Nevada. At the San Francisco meeting last September there were two excellent papers presented on Nevada silver mills; one by A. H. Jones on The Tonopah Plant of the Belmont Milling Co., and the other by E. E. Carpenter on Cyaniding Practice of the Churchill Milling Co., Wonder, Nev. At the same meeting, I presented a paper on-Slime Agitation and Solution Replacement Methods at the West End Mill, Tonopah, Nev., covering this .particular feature of our milling practice. A comparison of the data presented in these four papers is interesting in that, while the general design and practice is much the same in all cases, there is a wide difference in the design and practice in the various departments of &apos;the mills. It is to be regretted that Mr. Rose did not round out. this excellent article by following Mr. Jones&apos;s and Mr. Carpenter&apos;s&apos; lead in giving the average gold and silver content of the ore milled and the resulting tailing, with the consumption of chemicals and the? cost of milling. The practice of the Santa Gertrudis mill in the use of ?cyanide and zinc offers an interesting comparison with that of the Nevada mills, and a discussion of this point may bring out the reasons for the differences that exist.

Jan 12, 1916

By J. P. Manning

UNQUESTIONABLY, the outstanding feature of the piping for the sulphide plant is the large amount which had to be done in almost every size from instrument tubing to 84 in. OD pipe. In this article the piping will be considered under the main headings of Yard Piping and Building Piping. Tables I and II give data concerning the individual systems. In the case of yard piping the figures pertaining to lengths and weights are approximately correct; those for building piping are given only for the concentrator and smelter buildings where the amounts were the most extensive. Yard Piping The installation specifications for yard piping called for all sizes larger than 12 in. to have welded joints made with outside welding rings. This type of joint was selected over butt-welded joints because less time would be needed for lining up, damaged pipe ends would be less of a problem, and deflections up to 6° per joint could be made when necessary. These advantages were thought to outweigh the disadvantage of the greater amount of welding required. Yard piping in sizes of 3 to 12 in. was specified to have butt-welded joints made with inside welding rings which were intended to facilitate lining up and keep welding material out of the lines. Screwed connections were specified for sizes under 3 in. No protective coatings or wrappings were required on pipe to be buried because of the dry climate at Chuquicamata.

Jan 1, 1952