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By A. A. Gustafson

The Freeport Sulphur Co. built a portable crusher in 1944 that solved a problem that none of the crusher manufacturing companies contacted were able to do. Two of these crushers have now been in service for 6 years, giving satisfactory service in handling a million tons per year, and having a capacity of over 2000 long tons per 8-hr shift. These machines reduce ton size blocks of sulphur to 12 in. and also feed the conveyor system at the rate of 350 long tons per hr per machine.

Jan 10, 1950

By Raymond Franz

Of the many types of capital equipment found in a surface operation, draglines and mining shovels are probably subjected to the most severe service. Yet, some excavators have seen a generation or more of continuous service-proof, if any is needed, of their ruggedness. To keep these expensive pieces of machinery operating, a continuing maintenance program which includes field weld repairs is essential. During an excavator's working life, minor cracks may appear in parts of the steel structure, caused by fatigue and sometimes material defects-defects so small they could not be detected during manufacture.

Jan 6, 1978

By A. B. Kinzel

SILICON, unfortunately, is not in the same category as some other metals with respect to the absolute value of the highest purity material prepared. Tucker, in England, and Becket, in this country have devel-oped procedures for the purification of silicon, and Becket's process has made industrially available silicon of a purity of 99.8 per cent or better. However, even the term "silicon metal" may be a paradox to some people, although not more so than the term "amorphous" as applied to silicon. These terms come from commerce, and "metal" is used to distinguish industrially high-purity silicon from ferrosilicon, silicon-aluminum, and other high-silicon alloys. Alloys of iron and silicon with 95 per cent Si or less are known as ferrosilicon, with a designation of silicon content where necessary, and the terns "silicon metal" is invariably applied to the grades containing 96 per cent Si and higher. The Becket method of purification was referred to in a monograph on the Alloys of Iron and Silicon, and the Tucker procedure was described in some detail in that publication.1 In order to get silicon of still higher purity, a sample, prepared by the Becket method, analyzing 99.84 per cent Si, 0.020 Fe, 0.016 Al, 0.005 Ca, 0.025 C, 0.033 per cent 02, 0.006 H2, 0.006 N2, and 0.001 per cent Mn, was crushed to pass a 100-mesh sieve said further purified by a modification of Tucker's procedure. This modification differs from Tucker's method in that after treatment the 100-mesh alloy was centrifuged to remove the last traces of acid. Our directly determined analysis of this purified sample shows: Si, 99.952 per cent; Fe, 0.009; Al, 0.012; Ca, 0.003; C, 0.006; or 99.982 per cent. Silicon by difference equals 99.97 per cent. The variation between silicon by difference and silicon as directly determined is important. Although Tucker mentions the amount of insoluble matter in commercial silicon both before and after his treat-ment, he does not mention the existence of carbon in the alloy; neverthe-less, lie reports silicon by difference. Any final figure as to purity obviously results from agreement between direct determination and

Jan 1, 1939

By H. L. Hazen

The uranium mill at Gunnison, Colorado, started crushing ore Dec. 31,1957, and has now been operating four months. The acid leached ore is washed by counter-current decantation through a system of four classifiers and four thickeners and most of the dissolved uranium reports in the overflow from the first washing thickener. This uranium is extracted from the aqueous pregnant solution by solvent extraction using di-2-ethyl hexyl phosphoric acid and tri-butyl phosphate dissolved in a high-flash-point kerosene as the extracting organic. The pregnant organic is then stripped with soda ash solution. The uranium bearing soda ash solution is filtered to remove insoluble carbonates and any sediment reaching that part of the circuit. The clarified carbonate pregnant solution is then acidified to 3 pH, heated to 180°F to drive off the last traces of CO2, and the uranium finally precipitated as yellow cake with MgO.

Jan 11, 1958

By Orville A. Derby

In view of the recent important discussions before this Institute on the genesis of metalliferous deposits, certain features in the occurrence of gold which seem to be more clearly developed in Brazil than elsewhere can hardly fail to be of interest. As the observations here recorded have necessarily been of a somewhat cursory character, they will be presented in the form of brief notes, without any attempt to draw conclusions as to their genetic significance. Gold in Gneiss.—The statement made by me many years ago† that in the districts of Campanha and S?o Gongalo, in southern Minas Geraes, gold occurs in gneiss, can now be reaffirmed in the most positive manner, on the strength of a recent examination of fresh material, confirmed by the testimony of an experienced mining captain from the Morro Velho mine, who, being skeptical on this point, made a prospectingtour in the district. The specimens examined, though so far decomposed as to be readily disaggregated, were clearly of

Jan 1, 1903

By L. S. Castleman, R. Resnick

The self-diffusion coefficient of columbium has been measured over the temperature range 1535o to 2120°C, using the radioactive isotope Nb95 as the tracer. The data for the temperature dependence of the self-diffusion coefficient are best fitted by the equation D = (12.4 ± 0.8) exp [(-105,000 ± 3000)/RT] cm2/sec. THE increasing need for high-temperature structural materials has stimulated considerable interest in the properties of columbium, since it is a strong, ductile metal with a high melting point—in the vicin- ity of 2450oc.l One fundamental property which has not heretofore been measured is the self-diffusion coefficient. The self-diffusion coefficient plays an important role in theories of oxidatioq2 creep,' sintering4 and other phenomena. Accordingly, the investigation reported in this paper was undertaken to determine the value of the self-diffusion coefficient and its temperature dependence by the use of Mb95.

Jan 1, 1961

A. O. GATES, Salt Lake City, Utah (communication to the Secretary*).-The writer is delighted by the results shown in Mr. Bell's paper, which prove in an experimental way different from that followed by the writer' that "the work clone in crushing is proportional to the surface exposed by the operation," per Rittinger's Law. Mr. Bell's work was all clone in commercial types of crushing machines, while my work was clone in a testing machine; his work represents fully one hundred times the expenditure and time that my work represented; a great number of tests were made by his organization to determine single points, while I was obliged to depend on the general trend of a curve for results; we agree absolutely that "Kick's law," for which Mr. Stadler was sponsor, does not apply to rock crushing. While my work indicated the reliability of Rittinger's theory, Mr. Bell's work clearly establishes the reliability and makes it Rittinger's law.

Jan 5, 1917

By W. J. Helfrich, R. A. Dodd

Binary aluminum solid-solution alloys containing various amounts of silver, magnesium, and zinc were prepared by careful directional solidification, and the hydrostatic and X-ray densities were compared. With the exception of the Al(Ag) alloys, the X-ray densities were consistently greater than the hydrostatic measurements, in agreement with earlier observations by Ellwood. In contrast to Ell-wood's interpretation in terms of vacant lattice sites associated with Brillouin zone effects, a tentative explanation based on the existence of solidification microshrinkage was favored. This hypothesis was confirmed by an examination of Al(Zn) alloys prepared by vapor diffusion of zinc into aluminum. The hydrostatic and X-ray densities were now in very close agreement, and it was concluded that the filling of Brillouin zones in aluminum solid-solution alloys does not necessarily result in the formation of defect structures containing an excess of vacant lattice sites. ThE existence of defect structures of the vacancy type in alloys in which the excess vacancies have an electronic rather than a thermal or mechanical, and so forth, origin is well recognized. Examples of incomplete lattices of this type are to be found in the Ni-Al,1-3 Fe-Ni-A1,4 c~-Ni-Al,5 Fe-Cu-Al,= and Co-A17 systems. These defect structures are of a special kind in that the intermediate phases possess an ordered atomic arrangement or superlattice, and in some instances the vacancy concentration may be unusually large, e.g., at 45.25 at. pet Ni in NiA1, approximately 8.8 pet of the lattice sites are unoccupied. Ellwood8-10 has reported similar defect structures in the aluminum solid solution alloys of the Al-Zn and A1-Mg systems and in alloys of the Au-Ni system." In Al(Zn) the (apparent) vacancy concentration rose, somewhat irregularly, to a maximum of about 2 pet vacant sites at 25 at. pet Zn, while in Al(Mg) the (apparent) vacancy concentration increased continuously to 1.7 pet at 15 at. pet Mg. An explanation in terms of Brillouin zone overlap was attempted, although Pearson12 has pointed out the difficulty of reconciling the observations with zone theory. However, the possibility of the effect being caused by the Fermi surface just touching a plane of energy discontinuity inside a prominent Brillouin zone has, in general, been accepted. In fact, Massal-ski13 has interpreted Ellwood's8 observations as confirmation of Leigh's14 theoretically predicted zone overlap occurring at approximately 2.67 electrons per atom. Unfortunately, Massalski was apparently unaware that Ellwood9 had revised his earlier results considerably, and the revised data did not confirm Leigh's analysis. Ellwood's clata were reexamined by the present authors who noted a possible correlation between the percentage defects as a function of alloy composition and the temperature interval of solidification measured from the respective equilibrium diagrams. This suggested an explanation in terms of shrinkage porosity rather than vacant lattice sites, and pointed to the desirability of reexamining appropriate alloy systems using: both Ellwood's method of specimen preparation (casting followed by wrought fabrication) and alternativ'e methods, i.e., diffusion, which might be expected to minimize, or even completely obviate, microporosity. ALLOY PREPARATION 1) Cast Allolys and Aluminum Single Crystals. Al(Ag), Al(Mg;l, and Al(Zn) alloys of various compositions up to 20 at. pet silver, 13.5 at. pet mg, and 30 at. pet Zn were prepared by melting under helium and casting into graphite molds. In the first two systems, the maximum alloying addition was quite close to the limit of solid solubility, but the possibility of transformation to a' during quenching somewhat restricted the suitable Al(Zn) composition range. The alloys were prepared from high-purity aluminum, a lot analysis showing 0.002 wt pet Cu, 0.002 wt pet Fe, and 99.996 wt pet A1 by difference. The silver, magnesium, and zinc were of 99.99+, 99.98+, and 99.998 wt pet respectively. Each composition was analyzed chemically. The as-cast ingots measured 7/16 in. diam and 5 in. length. One in. was removed from the top of the ingot, and the bottom 3 in. was machined to 0.275 in. diam; a point was also machined on the smaller diameter end. The remainder of the original ingot served as a top riser during subsequent remelting and controlled solidification. The machined ingots were now remelted using a Bridgman soft-mold technique to ensure directional solidification and, therefore, a minimum of micro-shrinkage. Alumina powder was used as mold material contained in an alundum thimble, and this crucible was placed in a helium-filled Vycor tube. The assembly was lowered through a suitable temperature gradient at approximately 0.5 in. min-l, and the risered portion of the casting was subsequently removed by sawing.

Jan 1, 1962

By D. J. Weintritt, R. G. Hughes

Statistics show arz increase in the average depth of wells drilled in recent years. As a corollary to this trend, drilling fluids have been improved in an effort to meet the problems inherent at temperatures approaching 500°F. Of importance are (1) deterioration of mud components and (2) the effect of solids on filtration and rheological properties. High-temperature, stable water-base and oil-bare muds are discussed. Those areas in which differences exist are pointed out. Results are based on data taken from the Fann consistotneter, rheometer and shear-strength measurements, static and dynamic filtration tests, methy-lene blue test for bentonite solids and specific heat measLrrenlents of muds. INTRODUCTION Higher well temperatures go along with the fact that the average depth of wells continues to increase. Recent data by Gardner' lists 137 completions deeper than 15,000 ft for the first half of 1964 with a record second-half total of 167 wells drilling or proposed. In addition, there has been an increase in drilling for steam for power production or mineral recovery. In this application the depths are modest, but the mud may approach the critical pressure and temperature of water. Scearce and Magnon' report drilling mud used at temperatures of about 700°F in the Salton Sea area of California. Most deep wells have been drilled with water-base muds. In recent years, however, there has been a substantial increase in the use of oil-base muds because of technological advances in effective additives. The significance of this development was dealt with in considerable detail by Simpson and his co-workers.3 Additiona1 field data have now been obtained to indicate that oil muds are competitive in control, performance and cost with the best types of water muds for use at high temperaturc. This parallel offer of two very different fluid systems, each offering a similar variability in performance, cost and convenience, has created the need to evaluate the merits of these fluids under specified conditions so that the advantages and disadvantages of each can be weighed in relation to the over-all drilling program. This paper is not intended as a review of all the factors. Rather, it attempts to emphasize: (1) important condltions and facts peculiar to high-temperature drilling muds, (2) that more than one imposed test condition or testing method is necessary to describe the quality of a mud at high temperature and (3) that elaborate experimental precautions are necessary whenever laboratory data are used in selection of a mud for field use. WHAT IS A HIGH-TEMPERATURE DRILLING FLUID? For the purpose of this discussion, a high-temperature drilling fluid is any system so formulated or treated to economically minimize the effects of temperature on the properties of the fluid. Our experience in drilling fluids suggests that these effects become obvious for many mud materials at temperatures of 300F or higher. It is understood that hydrolysis of starches, depoly-merization of certain organic thinners, or irreversible chemical reactions (such as that of clay and lime) can affect filtration, viscosity and shear strength at less than 300F. However, the temperature level is not a serious point and in no way affects the precautions and techniques used in this study. An up-to-date review of the literature on high-temperature drilling fluids and the many variations was treated by Rogers'in 1963. EXPERIMENTAL REQUIREMENTS TESTING EQUIPMENT AND PROCEDURES With the advent of deeper drilling and increased demand for temperature-stable drilling fluids, new testing equipment and laboratory techniques were devised for the evaluation of drilling fluids subjected to elevated temperature and pressure. While the equipment has not been standardized, it is in widespread use. Milligan et al. Qescribe a filtration cell for determining the filtration properties of drilling fluids at temperatures in excess of 300F. They showed the effect of variations in temperature and pressure on oil and water muds filtered in the 300 to 400F range. The dynamic filtration apparatus described by Simpson6 permits the study of the filtration properties to temperatures of 350F for drilling fluids circulated over sandstone cores. Watkins et al.' describe the use of pressure bombs for studying the effect of prolonged periods of elevated temperature upon the gelation or solidification of drilling fluids. Chisholm et a1.' describe the use of a modified cement consistometer adapted for use in drilling fluid evaluations. A similar consistometer is used in this study, although the application and data-recording method have been changed. The consistency of a mud sample is measured by timing the movement of a soft iron bob which is magnetically moved up and down in the sample container.* Changer in the time of travel and the temperature of the mud at that moment are plotted with a two-point Brown Elec-tronik Recorder. A 10-in. chart with a speed of 4-in./hr is used. Fia.- 1 is a generalized internretation of the data ob-

Jan 1, 1966

By d&apos, C. Antonio, S. H. Reichman

In the course of our studies of the annealing behavior of vapor-deposited silver films we have determined the electrical resistivity as a function of annealing temperature for films in the thickness range of 630 to 3240A. Fig. 1 shows the resistivity of the silver films vs film thickness in as-deposited and annealed conditions. The films were prepared by depositing 99.999 pct pure silver from molybdenum boats onto Vycor substrates. Deposition was conducted at a residual pressure of 5 x 10"6 Torr at rates of 20 to 408, sec-'. Thicknesses were determined using a multiple-beam interferometer. During annealing, resistance was measured using the four-probe method. Measurements were made every 5°C during two consecutive anneals to 300°C under a continuous vacuum of 2 x X6 Torr. The heating and cooling rates during annealing were approximately l° and 2°C min-', respectively. Typical resistivity vs temperature curves are shown in Figs. 2 through 4. There is an inflection point evident at 120°C on Fig. 2, the first anneal of a 3240A film. This inflection point was found on all films above approximately 1!00A on both first and second anneals. Below 1400A the inflection occurred at approximately 180°C. Figs; 3 and 4 show the first and second anneals of a 1370A film. The inflection point occurs at 180°C on the first anneal and approximately 120°C on the second. Our interpretation of this phenomenon is based on oxygen liberation from the film surface. It is well-documented that the presence of oxygen on silver surfaces causes a reversible increase in resistivity.1"3 The liberation of this oxygen, for example during vacuum annealing, would therefore cause a decrease in resistivity as observed on Figs. 2, 3, and 4 as a change in slope. This is accounted for by the decomposition of Ag20 on the film surface. The free energy of AgzO becomes positive between 125" and 225°C.4 The thickness dependence of the inflection points can be explained as an orientation effect. The films used in this study were preferentially oriented with their (111) planes parallel to the Substrate.''~ In addition it has been sten that the thinner films, below approximately 1500A, possess a decided "hill and valley"

Jan 1, 1969

By Stanley D. Michaelson, Norman Weiss

This was a year of realization. Some years are for planning and development, some for designing and building, others for fulfillment. With greater hopes and plans for the future than ever before, the year 1954, nevertheless, will be remembered principally because of project completion. Among copper mines, for example, there were Silver Bell, Copper Cities, Bisbee, Yerington, and White Pine. In iron, there were the Humboldt, Coleraine, Cerro Bolivar, and Eagle Mountain. In asbestos, Johns-Manville's new mill at Asbestos, Que. In uranium, completion of the ninth mill on the Colorado Plateau-Kerr-McGee's at Shiprock, N. M. In research, 1954 marked the completion of Kennecott's Research Center in Salt Lake City, one of the historic forward strides in the science of minerals beneficiation. The year was fruitful in other directions as well. Investigations of a fundamental nature were on the upswing, and pilot plant projects have also increased in size and number. Progress in new reagents and equipment was greater than normal. It can already be conservatively predicted-from the technological point of view-that 1955 and 1956 will be tremendous years.

Jan 3, 1955

By George W. Riter

OUR mineral-land laws need revising so as to provide definite title at the outset to the mineral deposits within any definite piece of land. The laws as they now stand, especially those applicable to lodes, breed uncertainty as to rights of possession prior to patent; and to my mind this is the worst feature of all, worse even than the apex bugbear. It is now almost impossible for anybody to tell-with certainty what mineral rights exist within any area that is not covered by patent, or whether any valid rights exist at all. Our system is unique in permitting individuals to appropriate and exploit mineral lands of the public domain without notice of any kind to the Federal government, and to relinquish them without any ceremony at all. The result is a clouded record that cannot be cleared up until each claimant is put to some sort of final proof. In order to accomplish this, new Federal legislation will be required. The requirements for a mineral survey and the proceedings for patent have always been cumbersome and expensive; and perhaps out of regard for the poor claim owner, who can ill afford the outlay for that sort of thing, the law does not require him to go. through it unless he chooses to do so. Consequently, every active mining district has become encumbered with tangled groups of doubtful or conflicting locations, whose rights and boundaries, when any valuable ore is found, must usually be determined by lawsuits that are as expensive and as distressing as the stakes are high. So deeply has litigation entered into our mining system that a claim whose rights have never been disputed would probably be set down offhand, by $miner of the old school, as of no value. Think of the litigation over rights of possession on the Com-stock lode—12 leading companies involved 'in an aggregate of 245 suits within a period of less than eight years! Ambiguous local records; the chance of erroneously placed or obliterated monuments; doubt as to the sufficient performance of the statutory annual labor; uncertainty as to prior conflicting or overlapping locations; anxiety as to the changing attitude of the Department of the Interior and the Forest Service—such considerations as these make an unpatented mining claim an unclean thing in the eyes of possible investors. Is it any wonder that they keep themselvesand their money at a safe distance,

Jan 1, 1915

By Walter Renton Ingalls

Metallurgical literature has no record of any ore beneficiated for cadmium alone, and the cadmium of commerce is derived from zinc ore, with which cadmium is generally associated. Zinc ores free from cadmium—e.g., the ores of the Franklin and Stirling mines, New Jersey, and of Broken Hill in Rhodesia—are rare. Blende concentrates of 50 to 60 per cent grade have contained (in production of important tonnage) as much as I per cent Cd, which is unusually high. The concentrates from the Tri-State district average from 0.3 to 0.4 per cent Cd, which is high. The concentrates from mines west of the Rocky Mountains seldom are higher than 0.2 per cent. In the periodic system of the elements, cadmium is in the same group with zinc. Its properties and compounds are similar. Its metallurgy is also similar. Cadmium has a melting point of 320°C. and a boiling point of 778"C., while the melting point of zinc is 415'C. and the boiling point gos°C. These conditions, together with the lower reduction temperature of cadmium oxide, indicate means for. separating cadmium from zinc. Cadmium in spelter is viewed, if not as an impurity, at least as an alloying element that may be objectionable, its special effect being hardening. However, for some purposes, a little cadmium in spelter is desired, and 0.4 per cent may be permissible, even in spelter for rolling. Cadmium in spelter for brassmaking is completely volatilized at the temperature of that process, and in bygone days an immense quantity of cadmium must have been lost in the fumes from these furnaces. Pyrometalltjrgy—Early Cadmium compounds, sulphide and oxide, being more volatile than the corresponding compounds of zinc, loss of cadmium begins to occur from the first furnace operation. In normal roasting, even with Tri-State ore, this loss may not be very high. Raw ore, assaying 0.4 per cent Cd, may be expected to give a roasted product of the same assay, which would imply a cadmium loss of about 15 per cent. Roasted ore, assaying 0.4 per cent Cd when distilled at ordinary furnace temperature, yielded spelter containing about half of that in the ore charged. The first draw of spelter under these conditions may assay 0.8 per cent Cd (accounting for 22 per cent of the cadmium recovery) and after the several draws of spelter have been equalized the cadmium content may average 0.35 per cent. If, therefore, 2000 lb. of blende averaging 0.35 to 0.4 per cent Cd is roasted and distilled, there may be obtained 1000 lb. of spelter, assaying 0.35 per cent Cd or 3.5 lb. content, which entering into Prime Western spelter will be sold at the spelter price. It will be observed from the outline hereinbefore (summarizing conditions prior to the introduction of sintering) that the main loss of cadmium occurred in the distillation process and by failure to condense, which could be ameliorated by attaching a prolong to the condenser, thus collecting

Jan 1, 1944

By N. A. Gjostein

The formal descnption of the decay of an isolated scratch can be written in terms of an appropriate Fourier integral. With the application of certain approximations, this description leads to the second-moment analysis developed by King and Mullins. It is shown that the second-moment analysis does not adequately describe the behavior of a decaying, isolated scratch, and that it is difficult to obtain internally consistent values of the surface self-diffusion coefficient, D,,from this analysis. This inconsistency arises from contributions of higher-order moments to the decay process. Two new analytical methods, based on the Fourier integval representation of a scratch profile, have been developed for determining values of D, from the decay kinetics of isolated scratches. In the profile-matching method, a given initial profile is resolved into its Fourier components, the components are allowed to decay exponentially over an annealing time interval, At, and finally they are synthesized to form a decayed profile. The predicted profile is adjusted to fit the experimental profile by varying only the parameter, D,At; the contribution from volume diffusion is directly taken into account and the integrals involved in the Fourier analysis are evaluated by numerical integration on an electronic computer. In the kinetic method, the widths, W, of a series of predicted profiles are determined for various volume-diffusion contributions, and the results are plotted in the form W vs DSAt. For a fixed ratio of surface to volume diffusivities, R, these plots are linear; the slope of the lines increases as R decreases. A simi-lar analysis can be performed on the depths of the predicted profiles. In this case, plots of (l/df3 vs D,At are found to be nonlinear. The proper value of Ds is found by superimposing the data for the experimental widths and depths on Plots of this kind and adjusting Ds until a fit is obtained with the line having the appropriate value oj R. An analysis of the slopes of these plots for R —= (surface diffusion only) reveals that they do not give the correct value, 2276, for width tf second-moment standard profile. This finding allows one to modify the second-moment analysis in such a way as to obtain internally consistent values of Ds. ThERE are several processes, involving a flow of matter along a surface, due to gradients in curvature of the surface, that may be used to determine the surface self-diffusion coefficient, Ds. These processes are commonly known as 1) thermal grooving, 2) single and 3) multiple scratch decay, 4) blunting of field-emitter tips, and 5) sintering. In this series of papers, the first three of these processes are examined in detail in an attempt to subject the phenomenological theories governing these processes to a critical test and, furthermore, to make a critical comparison of the values of D, obtained from these techniques. Although the thermal grooving technique has been established'' as a reliable method for determining D, , this has not been the case for the process of scratch flattening. Mullins and coworkers374 have proposed phenomenological laws governing the growth of the width and the decay of the amplitude of an isolated scratch, but only in one study5 has the width-growth law been supported by experimental evidence. In paper I of this series detailed experimental evidence is presented that points up the deficiencies of the second-moment analysis; the origins of these deficiencies are also discussed. Following this development, some new analytical procedures, based on representing the scratch profile by Fourier integrals, are presented as a means of obtaining reliable values of D, from the kinetics of the scratch-flattening process. Further applications of the Fourier integral approach are reported in papers 11' and 111,~ where the method has been useful in interpreting the anisotropy of flattening rates of isolated scratches (paper 11) and in describing the multiple scratch decay process (paper 111). THEORY OF SCRATCH DECAY Following ~ullins" approach we consider an arbitrarily shaped scratch profile, Fig. 6, at some time, t. The profile is designated by a function z(x,t) which can be expressed in terms of a Fourier integral as follows:

Jan 1, 1967

By W. M. Peirce, R. K. Waring

Zinc of high purity offers definite advantages in certain fields. A process by which zinc of 99.99 + per cent purity is produced by pyro-metallurgical methods is described in this paper. The process consists of a fractional distillation following the primary reduction; this fractional distillation employs the principles of rectification for the separation of lead and other high-boiling impurities and cadmium and other low-boiling impurities. Theoretical Considerations Involved in Production of High-purity Zinc by Distillation Fractional distillation, fractional condensation, and rectification are recognized methods of separating mixtures of liquids. In the field of organic liquids these methods are widely used but not commonly to effect as complete a separation of liquids as is done in the problem under consideration. Zinc boils at 905" C., cadmium at 778" C. and lead at about 1620" C. Zinc may contain from several hundredths of one per cent to over one per cent each of cadmium and lead, and the problem is to reduce these impurities to a few thousandths of one per cent. For lead and zinc, the spread in boiling points is substantial, 715° C., while for zinc and cadmium it is only 127" C. The basic limitation of any separation by distillation may be found from the relation between the equilibrium composition of the vapor and the liquid for all mixtures of the two substances involved. If a mixture of constant boiling point is found, or if a stable compound that vaporizes without dissociation occurs, there is a definite theoretical limit to the degree of separation that is possible when operating at atmospheric pressure with respect to that mixture. Otherwise, any degree of separation is theoretically possible. The equilibrium composition of vapor in contact with liquid mixtures of zinc and cadmiurn at the boiling point has been determined experi-

Jan 1, 1937

By R. B. Woodworth

In the sinking of bore holes, there are but two fundamental operations —drilling and hoisting—which determine in the main the character of drilling mechanism and structures. There are endless ramifications, however, in the execution of these fundamental operations, according to the purposes for which the bore holes are drilled, their maintenance after completion, the protection and convenience of workmen, etc. The three main lines of use for bore holes are in mineral exploration, the sinking of water and salt wells, and the exploitation of pqtroleum and natural gas. This paper has to do more especially with the last. Here again there are many divergences. Wells may be drilled by either the percussive, the hydraulic, or the abrasive method. Finally, each of these methods, as applied by drillers of diverse nationalities, has followed somewhat different lines of development. The American system of cable-tool drilling has perhaps had the widest application; the hydraulic rotary is also in extensive use; but the Canadian system, the Galician system, and the Russian free-fall system all have their points of recognized merit and are preferred by operators accustomed to their use. These differences in drilling procedure, which rest ultimately on essential variations in geological conditions, are reflected in the drilling structures as well as in the drilling mechanism. The purpose of the present paper is to record those stages in the development of the application of steel to the construction of drilling mechanism and structures with which the writer has been intimately associated, and to contribute to the history of the art of drilling other data acquired in the course of his personal investigations. It is necessarily limited by reason of space to American practice, with especial reference, therefore, to the cable-tool system and the hydraulic rotary method of drilling wells for oil and gas.

Jan 1, 1916

By W. M. Brown

SEQUACHEE Valley includes portions of the counties of Marion, Sequachee, Bledsoe and Cumberland. It extends in a general direction parallel with the Great Valley of East Tennessee, some 75 miles northward from the Alabama state line. It is separated from the Valley of East Tennessee by a mountain arm about a dozen miles wide, known as Wallen's or Walden's Ridge. The genesis of the valley, geologically speaking, is simple. It is an erosion-valley along the axis of an anticlinal. The point of the wedge remains in a row of low "saw-tooth" hills, running up the center of the valley. These hills are of Lower Silurian age, and consist of Trenton limestone, covered and protected in some measure by chert. Walls of Carboniferous age form the inclosing mountains on either side; whilst a magnificent arch of Hudson River, Niagara, Hamilton and Subcarboniferous strata closes the valley at the

Jan 1, 1886

By J. Campbell

Various models are discussed for the evaluation of the negative pressures which may occur in solidifying materials which exhibit various deformation modes: elastic-plastic, Bingham, viscous, or creep flow. The inadequacy of the previously proposed elastic-plastic solution for solidifying metals is revealed by comparison with the more reliable creep results which are given graphically for aluminum, copper, nickel, and iron. The maximum tensions experienced in the liquid phase of solidifying spheres ranging in size from large castings to submicron powders are in the range from —10' to —105 atm for these metals. THERE has been much recent interest in the negative pressures associated with the volume change on solidification and in the possibility of the occurrence of cavitation. Considering the freezing of a highly supercooled liquid, an attempt to evaluate the stresses in the liquid ahead of the rapidly moving solidification front has been made by Horvay1 on a microscale and by Glicksman2 on a macroscale. In a casting of a wide freezing range alloy, the pressure differential due to viscous flow of residual liquid through the pasty zone has been discussed by Piwonka and Flemings,3 In a previous publication4 the author has attempted to estimate the negative pressure occurring in the residual liquid of a spherical casting, employing an elastic-plastic model to describe the collapse of the solidified shell under the internal tension. An earlier model assuming a rigid shell was shown to be inaccurate by many orders of magnitude. The elastic-plastic model is critically reviewed here, and other models are developed which are thought to be more closely related to metals and other materials near their melting points. The spherical geometry (Fig. 1) is chosen because the highest shrinkage pressures would be developed, although the analyses are readily adaptable to cylindrical geometry. A parallel sided casting experiences little internal tension because of the relatively easy dishing inward of the sides. (This commonly observed phenomenon has previously been attributed solely to atmospheric pressure.) Furthermore, small regions of confined liquid in a large solidified volume of a casting approximate reasonably well to spherical geometry. ELASTIC-PLASTIC MODEL The author has shown4 that as solidification proceeds the internal hydrostatic tension builds up until the elastic limit of the shell is exceeded. At this point the internal pressure is closely -2Y/3. Subsequently a plastic zone spreads from the inner surface toward the outer surface of the shell. When the whole casting is deforming plastically a rather more generalized analysis taking account of the externally applied pressure PA + 2y/b gives the internal pressure as: P = Pa + 2y/a + 2ys/b - 2 Y In(b/a) [1] The 2y/a and 2ys/b terms result from the tendency of the liquid-solid and solid-vapor interfaces to shrink, reducing their energy, and thereby helping to collapse the solid phase and compress the liquid phase. The 2y/b term would be important only for powders. The last term arises because of the plastic restraint of the solid, resisting collapse and so effectively expanding the residual liquid. From Eq. [I] it is easily shown that there is a minimum in the pressure at the radius amia= y/Y [2] which is of the order of 103K for the metals aluminum, copper, and iron, and corresponds to the minimum pressure Pmin = 2 Y[l-ln(bY/y [3] The results of a fully worked out elastic-plastic solution are given in a previous reporL4 The main criticism which may be leveled at this analysis when applied to metals at their melting points is the strong dependence of the yield stress on the strain rate. The strain rate varies with both solidification conditions (e.g., whether chill-cast or slowly cooled) and during solidification, as is indicated in the following section. Thus an appropriate choice of Y is very arbitrary. Before proceeding to a discussion of models which are strain-rate-dependent, it is necessary to evaluate the strain rate as a function of the rate of solidification. SOLIDIFICATION RATE Various empirical relations have been deduced5 for the rate of thickening of the solid shell by pour- out tests on partially solidified spheres. These, however, are unsatisfactory for our purposes since they become very inaccurate when the liquid core is very small. A theoretical approach is therefore necessary, and some solutions are set out below. Making the assumptions of constant surface temperature of the casting during freezing, no superheat, and a material freezing at a single temperature, Adams8 deduces the approximate solution: which becomes when b » a: Employing a semiempirical approach vallet6 finds:

Jan 1, 1969

By I. R. Kramer

A delay time for yielding in cold-worked face-centered-cubic metals was found. Slip on (123) planes was observed. Glide on these planes occurred during the delay-time period before slip starts on the (111) planes. AN important approach to the study of the anchoring and blocking of dislocations is available through the delayed-yield phenomenon which has been observed in body-centered and hexagonal close-packed metal by several investigators. Clark and his associate1-5 showed that a delay time for yielding is present in mild steels and fine-grain molybdenum. Type 302 stainless, SAE 4130 normalized, SAE 4130 quenched and tempered, and 24s-T aluminum aid not have a delay time. Kramer and Maddin6 studied the delay-yield effect. in metal single crystals. While they found a delay time in body-centered-cubic metals none could be found in the face-centered-cubic metals. Later7 a delay time was found in hexagonal close-packed metals. cottrell8 has proposed an explanation for the difference in the yield phenomena of b.c.c. and f.c.c. metals based upon the anchoring of edge dislocations by the proper types of impurity atoms (C and N). In the body-centered-cubic lattice the interstitial atoms are near a cube edge and can interact with an edge dislocation, while in a face-centered-cubic lattice the distortion around an interstitial atom is of spherical symmetry and cannot anchor a screw dislocation which has practically no hydrostatic component. Cottrell's theory seems to account rather well for the behavior of body-centered-cubic . metals. EXPERIMENTAL PROCEDURE The apparatus used in these experiments is essentially of the same design as described previously.' Single crystals 1 in. long and having a diameter of % in. were placed in a pendulum which consisted of a bar 8 ft long designed with a crystal holder to accommodate the specimen at low temperatures. This portion of the apparatus was supported on fine molybdenum wires. A bar of the same diameter and length comprised the other portion of the apparatus. This bar was supported on a set of roller bearings arranged around the periphery of the bar to allow accurate alignment. This bar was propelled by means of a spring-loaded gun and allowed to strike the lead bar in front of the single-crystal specimen. SR-4 type A-8 resistance strain gages were cemented to the specimen and the strain measurements were obtained by amplifying the strain-gage output by means of a high-gain preamplifier. A tektronix 545 oscilloscope was used together with a polaroid camera to record the strain and time sweep. An Ellis Associate Bridge was used to calibrate the strain gages and calibration readings were obtained before each test. The sweep of the time signal was initiated by means of a miniature thyraton which was fired when the two bars came into contact. The single-crystal specimens were cut from single-crystal bars about 12 in. long, grown by a modified Bridgman technique. The aluminum crystals were made with material of 99.99 pct purity while the purity of the copper was 99.999 pct. A cut-off wheel was used to prepare the specimens which were then machined to the desired length. The two opposite faces of the specimen were parallel to each other and perpendicular to the axis of the specimen. The specimens were compressed 1 pct. No machining followed thereafter. In some cases prestraining was carried out in liquid nitrogen by impacting the specimens directly in the apparatus so that subsequent observations could be made without allowing the specimen to warm up to room temperature. The single crystals were compressed 1 pct at room temperature in a hand press without much control of the rate of deformation. In some cases specimens were recompressed to obtain the desired length change. As far as could be determined in these experiments this factor did not seem to influence the results. The SR-4 strain gages were glued with a cellulose type cement onto the specimen surface and baked at 45°C for 12 hr. As a check on the baking treatment gages were allowed to dry at room temperature. All delay time tests in this paper were conducted in a liquid nitrogen bath at -195°C. A schematic delay time oscilloscope trace is shown in Fig. 1. At point B the elastic stress wave caused by the impact reaches the strain gage on the specimen. The portion BC is the elastic strain. In this investigation the strain at point C was used to calculate the critical resolved shear stress by multiplying by the proper modulus depending upon the orientation of the single-crystal specimen. The time between C and D is the delay time portion of the curve. This portion of the curve is fairly flat but does have a definite microstrain associated with it. After the point D is reached the specimen deforms rapidly and the strain reaches a maximum at E. Following this, depending upon the length of the bar behind the specimen, the strain remains constant for a period and then decreases when the reflected elastic wave returns from the end of the pendulum bar. A permanent plastic strain is recorded on the oscilloscope trace and also measured by a strain-measuring bridge. The strain, E p,

Jan 1, 1960

By C. S. Giggins, F. S. Pettit

The oxidation of Ni-Cr alloys in 0.1 atm of oxygen has been studied at temperatures between 800" and 1200°C. For alloys with 30 wt pct or more Cr, continuous layers of Cr2O3 are formed during oxidation. In the case of alloys with chromium concentrations between approximately 5 to 30 wt pct, external scales of Cr203 are formed over grain boundaries whereas internal precipitates of Cr2O3 and external layers of NiO are formed at other areas on the alloy surface. When such conditions are present on the alloy surface, chromium diffuses laterally from those areas covered with a continuous layer of Cr2O3 to areas where a Cr2O3 sub scale exists and it is possible for the sub-scale zone to become separated from the alloy by a continuous layer of Cr2O3. Whether such a state will be attained depends upon the initial grain size of the alloy and the oxidation time. When the concentration of chromium in the alloy is less than 5 pct, Cr2O3 is formed internally both at grain boundaries and within the interior of grains and the alloy is covered with an external layer of NiO. MECHANISMS which describe the growth of oxide scales on nickel-base superalloys are complex and the effects produced by the various elements in these alloys on the oxidation behavior of superalloys are not clearly understood. In order to determine the influence of the different elements on the oxidation behavior of superalloys, it is first necessary to examine the oxidation properties of binary nickel-base systems which contain the principal elements present in the superalloys and then progressively more complex systems until compositions typical of the superalloys are attained. Chromium is present in virtually all nickel-base superalloys and the purpose of the present studies was to examine the selective oxidation of chromium in Ni-Cr alloys. The oxidation characteristics of Ni-Cr alloys have been extensively studied1-" to date principally as a result of the high oxidation resistance exhibited by some of these alloys. Ni-20Cr* has long been known *All compositions are given as wcight percent unless specified otherwise. to be oxidation resistant and is commonly used as resistance heating elements for service temperatures up to 1100°C. This alloy cannot be used for extended periods of time at higher temperatures because of the apparent reaction of the external scale with oxygen to form gaseous CrO3. In spite of the considerable work cited above some important aspects of Ni-Cr oxidation still remain unresolved. Virtually all of the previous studies agree that small additions of chromium to nickel, e.g., <10 wt pct Cr, result in increased oxidation rates as compared to that of pure nickel, whereas larger additions, e.g., 20 to 30 wt pct Cr, form alloys with substantially lower oxidation rates. The controversial aspects of the oxidation mechanisms for these alloys that still remain unresolved are as follows: 1) A description of the oxidation mechanism for the low chromium alloys. 2) A description of the oxidation mechanism for the high chromium alloys, particularly with respect to the composition of the external scale which results in the lower oxidation rates. 3) The specific alloy compositions at which the oxidation mechanism changes from that obtained for low chromium contents to that of the high chromium alloys and the reason for this transition. EXPERIMENTAL The Ni-Cr alloys listed in Table I were prepared from high purity metals by nonconsumably arc melting and casting as buttons. These alloys were then given a preliminary annealing treatment in argon at 815°C for 100 hr to promote homogeneity. Each button was cut into 0.250 in. thick sections that were subsequently cold-rolled to 0.050 in. thicknesses and annealed in argon at 815°C for 48 hr to provide a twinned, equi-axed grain structure. The grain size for these alloys was not uniform and the limits, within which the average grain size lies, are given in Table I for the single-phase alloys. All the alloys were single phase with the exception of the Ni4OCr alloy in agreement with the Ni-Cr phase diagram.&apos;&apos; Rectangular specimens were cut from the sheet to provide surface areas of approximately 2.5 sq cm. Exact areas were determined with a micrometer after surface preparation was completed. All of the specimens except the Ni-40Cr alloy and pure chromium were polished through 600-grit Sic abrasive paper, ultrasonically agitated in ethylene trichloride, rinsed with ethyl alcohol, and electro-polished. The specimens were electropolished in a 10 vol pct H2SO4 (conc), 6 vol pct lactic acid, methyl alcohol solution at 70" to 80°C for 2 min at a current density of 0.8 to 1.2 amp per sq cm. This electro-polishing procedure did not produce acceptable surfaces on the Ni-40Cr alloy nor on pure chromium and the oxidation properties of these materials were obtained for specimens polished through 600-grit Sic

Jan 1, 1970