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By J. J. Bowman, E. H. Dix

A LACK of experimental data illustrating the effect of composition, particularly in respect to impurities, on the mechanical properties and corrosion resistance of aluminum-alloy die castings induced the authors and their associates to undertake a limited study of these relations. A number of commercial alloys and several experimental variations of a commercial alloy were used for the investigation. Mechanical property, growth, steam, paraffin, salt spray and atmospheric exposure tests were employed. This paper deals with the more accelerated tests and the results they have produced. It is concluded that a high-silicon alloy with all impurities except iron strictly limited to small amounts will develop an excellent resistance to corrosion and retain satisfactory mechanical properties and casting characteristics. As a direct result of this investigation an alloy of this character with superior corrosion resistance is now available commercially. In general, copper increases the strength and decreases the elongation and corrosion resistance. Tin reduces the mechanical properties and the resistance to corrosion. Iron reduces the elongation and, if excessively high, may adversely affect the tensile strength. Even excessively high iron contents do not affect the corrosion resistance, which is fortunate for the die caster as it is this element that is the most difficult to control. Nickel and zinc in limited amounts do not seem to affect the properties or corrosion resistance of at least the high-silicon alloy. Growth tests have confirmed the previous common belief that dimensional changes under either dry or wet conditions at 100° C. are too small to be of practical importance.

Jan 1, 1935

By Pradeep K. Rohatgi, Clyde M. Adams

Structures obtained on freezing of several hypo-and hypereutectic Al-Cu alloys over a range of solidification rates have been examined. Dendrite spacing, L, increases linearly with solute concentration and with the square root of the inverse freezing rate. The relationship for hypoeutectic alloys is: where rate of change of fraction solid with time, is freezing rate, C is solute concentration, (pct Cu)=1. Mass transport in inter dendritic liquid during solidification is analyzed; the experimental observations suggest maximum concentration differences and constitutional supercooling in the inter dendritic liquid increase with an increase in the solute concentration. The dendrite morphology changes with freezing rate and alloy composition. The dendrites of the a phase are parallel, uniformly spaced plates with slow freezing and rods with rapid freezing. Nonor-thogonal side branching has been observed in phases with cubic and tetragonal structures. Side branches in a dendrites are orthogonal with slow freezing and at 60 deg with rapid freezing. Formation of second-phase envelopes around the Primary phase is also discussed. DENDRITIC structure is characteristic of many types of phase transformation. The most extensively studied so far has been solidification of liquid solutions. chalmersl and coworkers have interpreted the formation of dendrites in terms of the breakdown of a planar interface. Most of the work done concerns itself with the development of an instability at the interface. Little theoretical work has been done quantitatively to relate the parameters of dendritic structure to mass transport in the liquid phase. A few empirical relations based on the experimental2'3 observations exist in the literature. Several workers2 including Brown and Adams1 have studied dendrite spacing in A1-Cu system as a function of solidification variables. In most cases, dendrite spacing has been found to increase linearly with the square root of some parameter proportional to the freezing time. The effect of solute concentration is not clear; some workers report the dendrite spacing increases with solute concentration4 whereas others report vice versa.''' ~ohatgi' has observed an increase in the spacing between ice dendrites with an increase in solute concentration in water. Tiller has also suggested that dendrite spacing should increase with solute concentration. In the present work dendrite spacing and morphology have been examined as a function of solute concentration and freezing rate. The freezing rate is defined as the fraction of liquid solidified per unit time, dfs/dß?, where f, is the fraction solid and 8 the time. The fastest freezing rate studied was 4550 times the slowest freezing rate. THEORETICAL CONSIDERATIONS It is of interest to analyze the concentration distribution in the liquid phase between growing dendrites during solidification, Fig. 1. Since this distribution is a direct consequence of the rejection of solute by the growing solid, a diffusional process, the concentration gradients increase with the freezing rate. However, when solidification rate is the only variable in a series of experiments, the interdendritic liquid regions become smaller (i.e., the dendrites become more closely spaced) with an increase in freezing rate. The main purpose of the analytical treatment of interdendritic liquid diffusion will be to reveal a tendency for dendrite spacing to decrease with increasing solidification rate in just such a way that the maximum concentration differences developed in the liquid phase are remarkably independent of freezing rate. Two rather different analyses are set forth, one pertaining to the one-dimensional diffusion which obtains in the interdendritic liquid between parallel plate-shaped dendrites, and the other to the cylindrically symmetrical diffusion around rod-shaped dendrites during early stages of solidification. The results of the two analyses are quantitatively similar, correlating dendrite spacing, maximum concentration difference, and freezing rate. First consider the simpler one-dimensional case. Two parallel plate-shaped dendrites are separated by a distance, L, between centers, Fig. 1. Solidification takes place by the thickening of these plates, with solute being rejected into the liquid. It is assumed there is no diffusion in the solid. This thickening process is slow enough and the dendrite spacing small enough that the concentration differences which develop, although interesting and important, are very small (an important assumption which is verified ex-

Jan 1, 1968

By W. R. Hibbard Jr., R. W. Guard, N. G. Ainslie

Evidence is presented that copper-base solid solutions of different solutes having equal grain sizes, no preferred crystal-lographic orientation, equal electron-atom ratios, and, within experimental scatter, identical initial yield strengths, need not have identical stress-strain curves at strains larger than about 0.04. The stress-strain behavior is rationalized in terms of the proposed Suzuki chemical interaction between solute atoms and extended dislocations using what is thought to be a somewhat different means of representing stress-strain data. ALTHOUGH the effect: of alloying element upon the strength characteristics of sold solutions is a subject which has received considerable attention in the past, the exact relationships between the common deformation parameters and certain common variables are not really known in some cases. As a result some of the experiments reported in the literature in which these variables are inadequately controlled lose some of their persuasion regarding underlying principles. Nonetheless, facts are known which bear pointing up: When the true stress, a, and true plastic strain, E, of tensile deformatic~n are plotted on a double logarithmic coordinate system, one may observe a straight-line relationship at strains greater than 0.02. The form of the curve in the linear region is given by a = Ken! where a represents true stress, E, true strain, and K and tn, constants. If the relationship holds, K and m define the flow characteristics of the material being tested. m and K, however, may vary with other parameters. Hollomon found that in a-brass, m is influenced by grain size. French and HibbardZ found in alloys of copper that inverse relationships existed between m and 1) the solute concentration for a given solute, 2) the 0.01 yield strength, and 3) the constantK. Lacy and Gensamer3 observed (du/d~) (= U/Em) to increase with increasing values of K in systems of alloyed ferrites (although with considerable scatter of data which may be attributed to uncontrolled grain size). Brick, Martin, and Angier* deduced in copper-base alloys a straight-line relationship (with some scatter) between the change in the Dph number due to solid-solution strengthening and the change in the Dph number due to work hardening which suggested that copper-base alloys having equal yield strengths might have identical stress-strain curves in the plastic flow regions. French and HibbardZ concluded that the yield strength of copper-base solid solutions is the proper basis for comparing the effects of solute elements. Also, Allen, Schofield, and ate' showed that, within their experimental variation, copper-base alloys of zinc, gallium, germanium, and arsenic having the same electron-atom ratios have the same true-stress true-plastic strain curves. Dorn, Pietrokowsky, and ~ietz' also found that with aluminum-base alloys the stress-strain curves in the flow regions are approximately the same if "equivalent" concentrations of alloying elements are used. Solute valence and lattice parameter distortion were the parameters used to determine equivalency. The present report describes an investigation in which an attempt was made to obtain copper-base solid-solution alloys of four solute elements having within close tolerances equal grain sizes and yield strengths, and to see if the level of yield strength does indeed define the flow curve regardless of solute type. During analysis of the data certain unexpected features of the stress-strain curves became apparent which gave rise to some speculation and are discussed at length in the paragraphs that follow. EXPERIMENTAL PROCEDURES Alloy Preparation—Using the data of French and HibbardZ as a first approximation, four different binary copper-base alioys were designed so as to have the same yield strength. In addition, other alloys were prepared in which the solute aoncentrations varied slightly from those calculated above so as to span a range of yield strengths, see Table L The yield strengths of all alloys prepared except the copper-tin alloys were subsequently found to Lie fairly close to one another. The copper used in the alloys was produced by the American Smelting and Refining Co. and was of very high purity (99.999 pct). The alloy additions and their initial purities are as follows:

Jan 1, 1960

By J. J. Scott

During 1967 wage settlements and strikes ran at a high rate and it has been estimated that union gains of 4 ½ % to 5% per year have been attained in many instances. When these events are coupled with the need to operate on lower grade and deeper deposits the need for technological advances in underground mining becomes obvious. Emphasis has been on ways to reduce the number of manshifts required per ton of product. Most significant advances have been made in rapid advance of primary mine openings, development of mobile, rubber-tired, front-end loaders and hauling units, high-speed drilling with rotary and rotary percussive units and a serious look at nuclear devices to break large volumes of ore cheaply. Boring Developments in bit manufacture and metallurgy have allowed continuous boring-type machines to be used on harder formations than was deemed feasible in the past. Hecla Mining Co. has been using raise boring equipment for drilling 9 7/8 in. diam pilot holes in raises which are later reamed in an upward direction to 48 in. diam. The machine used is a J. S. Robbins model 42R raise borer which has been used successfully to drill two relatively long 48-in. diam holes. The first was 520 ft in length at a dip of 76º, and the second was a 785-ft vertical hole.

Jan 2, 1968

By A. R. Gregory, M. R. J. Wyllie

The literature reveals that scant attention has been paid to the systematic experimental determination of the formation factors of unconsolidated porous media. No experiments appear to have been made on the effect of increasing cementation on the formation factor of an initially unconsolidated porous medium. Measurements have accordingly been made of formation factors as a function of porosity for aggregates of spheres in the porobity range 12-56 per cent and of cubes, cylinders, discs and triangular prisms in the porosity range 30-45 per cent. The results are examined in the light of the theoretical equations of Clerk Maxwell. Fricke and Slawinski. Aggregates of unconsolidated spheres and beach sands have been artificially cemented with silica and the formation factor-porosity relationships determined. A theory is outlined which seeks to explain the results obtained and which postulates that formation factor and porosity data for consolidated sandatones may be used to determine the original porosity of the unconsolidated sands from which the consolidated sandstones were derived. It follows also that for consolidated sandstones F' = C where F is formation factor, fractional porosity and C and k are constants. INTRODUCTION All schemes of electric log interpretation implicitly or explicitly require the use of formation resistivity factors or? as they are now generally called. formation factors. 'The originator both of the concept of formation factor and of the use of formation factor data in electric log interpretation was Archie.' More recently it has been suggested that formation factors are of value in describing fluid flow in porous media. A full discussion of this problem together with adequate reference.: has been given by Wyllie and Spangler.' In spite of the theoretical and practical importance of the subject, there appear to be remarkably few basic formation factor data in the petroleum literature. A wider search reveals that this situation is nut confined to the literature of the to industry. at various times over the last century, attempts have been made to compute the theoretical relationship between the formation factor and porosity of simple systems of unconsolidated particle.. However. the formulae derived are not all identical and the experimental evidence adduced in support of each i; not wholly convincitng. Most of the experimental work has been carried out on system. of unconsolidated spheres, although some attention has been given to systems of spheroids and cylinder. Other simple shapes have received neither theoretical nor experimental investigation. The writers feel that a better understanding of the formation factors of complex systems of practical importance requires a firm foundation of reliable experimental data applicable to simple systems. Accordingly, they have reviewed the relevant literature and have determined experimentally the relationship between the formation factor and porosity of unconsolidated aggregates of particles of regular geometrical shapes. Some experiments have also been carried out to investigate the effect of cementation on the formation factor-porosity relationship. PREVIOUS WORK Although the term formation factor was not used. the relationship between the resistivity of a solution containing dielectric solids and the resistivity of a similar solution not containing solids is an old and important problem. The formation factor of a system of dispersed spheres as a function of porosity was considered by Clerk Maxwell. Maxwell arrived theoretically at the following expression: where F is formation factor and fractional porosity. Lord Rayleigh' also examined the problem of the formation factor of systems of spheres and cylinders and concluded that for spheres Clerk Maxwell'.; expression gave a value of F whirl]. at low porosities particularly, was too small. However,

Jan 1, 1953

By John R. Keith

Lead and zinc contents of elm, maple, and oak trees and of soils in which the trees grew were determined in samples from the Upper Mississippi Valley mining district, and from an area outside but contiguous to the district. The lead and zinc analyses of plant materials served to differentiate the mineralized and nonminer-alized areas. Stems contained about two times as much lead and about two to five times as much zinc as did leaves taken from the same stems. Lead and zinc analyses of all soil horizons could be used to differentiate between the two areas. Soils at most sample sites in the mineralized district seemed to be more reliable than plants for geochemical prospecting and are a more practical sampling medium. Soil samples from areas with thick loess cover, however, failed to indicate the presence of mineralized bodies whereas tree samples from the same sites contained anomalous amounts of lead and zinc. It is suggested that in areas of thick loess cover, plant samples could be used in prospecting for lead and zinc. The important part that plants play in the cycling of elements through the soil horizons is well-known. The concentration of elements in the upper soil horizons by the action of plants has been called the Goldschmidt enrichment principle.' The fact that plant species vary greatly in their ability to concentrate particular elements in their tissues is also well-known.' Agricultural literature has dealt extensively with relationships of the major nutritive elements in soils and plants3 The extent, however, to which plant actions cycle the minor nutritive and the nonmetabolic elements in the soil has not been adequately investigated. Lead is non-nutritive and toxic to plants, whereas zinc is a micronutrient in low, but toxic in high, concentrations.4 This report presents the results of a biogeochemical study concerned with the amounts of lead and zinc in some plants and soils that occurred both within and adjacent to the Upper Mississippi Valley lead-zinc district. Field work for this study was done in the summers of 1961 and 1962. SAMPLE TARGETS AND CHEMICAL ANALYSES Geologic and physiographic descriptions of' the district have been made by Heyl 5 and several other authors in a series of U.S. Geological Survey (USGS) reports and quadrangle maps.6-I Sedimentary rocks, mostly dolomite, limestone, shale, and sandstone, of Cambrian, Ordovician, and Silurian age predominate in the area. Mineral deposits are of the vein and cavity-fill type; the principal ore minerals are galena and sphalerite. Vegetation of the area was characterized by Curtis1 6 as southern hardwood forest interspersed with patches of oak savanna and prairie. Plant genera typical of the eastern United States Temperate Zone, including ash, cherry, dogwood, elm, hackberry, hickory, maple, oak, and other woody and herbaceous genera, are present. The natural vegetation has been greatly modified by agricultural, logging, and mining operations. The species of the original flora are present, but not in their former relative abundance. Soils of this district belong, for the most part, to the Brunizem and Gray-Brown Podzolic great soil groups. The Brunizems are the soils developed under prairie vegetation.'' The Gray-Brown Podzolics are the soils developed under deciduous forests,18 They are derived from both bedrock and from loess parent materials, and

Jan 1, 1970

By D. L. Pentz

The use of "probability" methods in slope stability analysis has been practised by geotechnical engineers for some time. This paper questions whether the term probability has been properly used since in many cases the term is used in a classical statistical manner only to describe frequency distributions of data. This paper proposes a definition of the term probability which includes the engineers' subjective state of confidence for all critical parameters. Such parameters may include the slope stability model, undetected structural features, strength, groundwater pressure distribution, and geological framework. This process does not make a "better" analysis but it does force the geotechnical engineer to state his opinion in such a manner that others can understand and if necessary, criticize the assumptions. Further, this technique forces the question, "What impact would failure of a slope have on the production schedule or costs of a mine?" The level of risk taken in adopting a particular slope design strategy in a mine is not a question of what Factor of Safety should be selected but, rather, what trade-offs result from steeper slopes and the associated costs of failure. This paper also presents several simple probabilistic techniques which, though widely used in other fields have been all but ignored in geotechnical slope stability analyses. These include the use of stratified sampling to optimize Monte Carlo uncertainty approaches, and the use of simple functional approximations rather than complex stability models in probabilistic analysis. The author presents a case example of this technique and discusses the results in comparison with more traditional methods.

Jan 1, 1983

By D. M. Deason, R. M. Chhatre, G. Y. Onoda

INTRODUCTION The treatment of colloidal suspensions is a subject of increasing interest in mining and benefication (1). Colloidal suspensions are not readily operated upon by mechanical and physical methods useful with coarse suspensions, such as filtration, thickening, and flotation. This is because colloids are strongly affected by interfacial and interparticle forces that may be large compared with, and resistant to, external forces. The degree and type of interactions between colloids can be modified by small additions of reagents such as coagulants, flocculants, dispersants, and immiscible liquids. These alterations in turn change the properties of the suspension and provide possible opportunities for transforming suspensions to a more favorable condition for a given processing operation. Phosphate slimes are an example of a colloidal system of interest today. In the mining and beneficiation of phosphate rock in Florida, slimes are a waste product. The phosphate ore (called matrix in the industry) is slurrified hydraulically and pumped to a beneficiation plant, where the -150 mesh material is removed by cycloning from the coarser phosphate rock and silica. The resulting -150 mesh slurry, called phosphate slime, is pumped to large impoundments. The solid content of the slime entering the impoundment is around four weight percent, and over 80% of the solids is less than one micron in size. The immediate problems with phosphate slime relate to their disposal (2, 3). The disposal problem is associated with the very large volumes and the poor dewatering characteristics of the slimes. To have sufficient impoundment volume, large earthen dams are built around the mined areas. The volume above ground level approaches and

Jan 1, 1980

By C. G. Dunn, F. W. Daniels, M. J. Bolton

IN recent papers on interface energies in metals¹,² the concept of an equilibrium of forces has been used in the measurement of interfacial tensions. Mathematically the equilibrium of three forces is given by the relations: where the 2's are the interfacial tensions (interface energies per unit area of interface) of three phases or grains meeting at angles 21 22 and 23 (212 relates to the 1-2 boundary formed by grains 1 and 2;223 to the 2-3 boundary, etc.). If these relationships are valid, one can calculate relative values of the interface energies from measured boundary angles on specimens which have been brought to equilibrium. Since Eq 1 may be derived through a mathematical process of minimizing the grain boundary energy under the restriction that the ?'s be independent of boundary orientation: the concepts of surface tensions and equilibrium of forces are not particularly essential. To deal with the general case involving dependence of boundary energy on boundary orientation, it becomes desirable to drop certain concepts formerly held (namely that energy per unit area is identical with force per unit length or surface tension) and to use the energy concept alone. It is appropriate, therefore, to use E in place of ? in deriving and using the more general equations that express the anisotropic nature of the grain boundary energy. Herring3# ' recently has derived the required general equations using the principle of minimization of energy. Specifying the boundary orientations in terms of angles (4) measured with reference to crystal axes within the grains, Herring's equations take the form E23 + E21 cos?8 + E12 cos?2 — sin ?12 + sin?2-?E12/?12 =O [2] where the partial derivatives are measured in the direction of counterclockwise rotation of the boundaries. Eq 2 implies that an infinitesimal displacement of the triple point along the 2-3 boundary produces no change in the boundary energy. Similar equations apply for infinitesimal displacements along each of the other two boundaries. From such equations Herring obtains the following general relationship (1 + E1 E2) sin?8 + (E2 — E1) cos?3 ________ E38______________ = (1+ E2 E8) sin ?1+ (E3— E2) cos ?1 __________^5____________[3] (1 + E sin ?2, + (E1 — E8,) COS ?2 1 E28 where E1 = 1/E23- E25 and PC and c8 have similar expressions. It is apparent that Eq 3 reduces to Eq 1 when the c's vanish. Eq 3 also reduces to Eq 1 when the E'S are all equal. Shockley and Read' have pointed out one limitation to these equations. When E plotted versus 4 appears as an energy cusp, as their theory requires, for example, for the energy near a twin boundary position, then Eq 3 (and therefore Eq 1 also) no longer applies if one boundary is in the minimum energy position. One of the equations of form Eq 2, however, applies if the infinitesimal displacement is along the boundary associated with the energy cusp. From the foregoing treatment it will be apparent that equilibrium angles alone are not sufficient in general for calculating relative interface energies.

Jan 1, 1951

By R. L. Stephenson

IN plants casting electric-furnace ingots and converting them immediately into blooms, billets, slabs, bars or forgings, the criterion of quality performance is the soundness of the semifinished or finished product. When rejections are necessary, it is not always obvious whether the defects were caused by an unsound ingot or by improper treatment during the heating and forming operations. To evaluate the effects of the numerous factors involved, it is necessary to accumulate a large number of detailed observations and to analyze and interpret these data properly. Even after a thorough investigation has been conducted, it is impossible, in some cases, to isolate the cause of the defect and say that it is definitely the result of an unsound condition in the ingot or mistreatment of the ingot during further processing. Two factors that are extremely difficult to evaluate are the chemical composition of the steel and time from finish pour to charge in the soaking pits or "track time," and it is necessary to evaluate their combined effects before many other factors can be studied. Plain carbon, fine-grained steel in the range of 0.18 to 0.23 pct carbon, is very susceptible to cracking and the longer the elapsed time between the pouring of the ingots and stripping for charging into the soaking pits, the higher the billet rejections for cracks are found to be. Below 0.15 pct carbon and above 0.30 pct the track time

Jan 1, 1947

By John W. Frey

[Minerals, generally of great geological age, are to a very large extent the material basis of what we know as modern civilization. In most of the so-called civilized world the use f minerals has become such a commonplace that it is easy to se sight of their importance. It was the use of minerals, obably more than anything else, that made it possible for e American people to expand from the Atlantic seaboard the Pacific in a little over one hundred years. As the 1 to use the natural wealth at hand constitutes a funda¬ental element in American life, there seems to be justification for the thought that American geography is largely mineral geography. Of all American environmental reactions, the most striking are those which have come about through the use of the metals and the power fuels. If we turn to the ancient industry of agriculture, we find very little that is unique in North America except those developments which have come about through the use of machinery and transportation, both of which are contingent upon the use of minerals. Practically every crop now grown n North America was grown in some part of Europe before merica was discovered. One can point out exceptions to statement but in general it is true. Analysis of the es of North American agriculture shows that the outstand¬ characteristics are: regional specialization (i.e., the Economic Geographer; Chief, Petroleum Section, Minerals Division, u of Foreign and Domestic Commerce.]

Jan 1, 1932

By W. O. Philbrook, C. W. McCoy

The reduction of chromous oxide from lime silica alumina slags by carbon-saturated iron behaves as a first-order process having a rate of 0.001 grams Cr min 1 cm 2 (pct Cr ) , substantially independent of slag composition and temperature over an important range for iron smelting. The equilibrium ratio (pct Cr)/[pct Crl is below 0.04 for slags having lime-silica ratios above 0.6. MANY studies have been conducted on chromium in slag-metal systems under oxidized conditions. The Purpose of these investigations has been twofold; namely, (1) to determine those conditions which lead to greater chromium recovery in electric-furnace and open-hearth practice, and (2) to determine the nature of oxide inclusions and de-

Jan 1, 1959

By R. B. Mears, E. H. Dix, R. H. Brown

In the Institute of Metals Division Lecture of 1940, E. H. Dix, J~.(I)~ discussed the acceleration of the rate of corrosion by high constant stresses. Experimental data obtained on this subject at the Aluminum Research Laboratories and a theory compatible with these facts were included in that lecture. The present paper contains data and ideas subsequently developed at the Aluminum Research Laboratories. Dix pointed out that in order for acceleration of corrosion by constant stress to occur: (1) There must exist in the alloy a susceptibility to selective corrosion along more or less continuous paths, as for in- stance at grain boundaries, and (2) There must exist a condition of high stress acting in a direction tending to pull the metal apart along these continuous paths. Acceleration of corrosion rate by stress is not confined to any one alloy system. Table I lists some of the metals and alloys and some of the corroding environments in which acceleration of corrosion by stress was sufficient to cause cracking (stress- corrosion cracking). It will be noted that the variety of alloys in which stress-corrosion cracking has occurred is rather large. Also, it will be observed that

Jan 1, 1945

By H. A. Lequear, J. D. Lubahn

A sudden change from one constant strain rate to another during a tensile test causes an unusual transient in aluminum alloy 61ST. A sudden change from one constant stress to another during a creep test does not produce an unusual transient in this material. A specially devised test shows that the nature of the previous steady-state conditions, which the sudden change disturbs, is one of the factors affecting the transient behavior. Some of the observations may be explained in terms of strain aging. USUALLY a sudden change during a tensile test from one constant strain rate to another causes a small, abrupt vertical shift from one stress-strain curve to another, parallel one. This behavior is apparently characteristic of all metals at very low temperatures and of many metals for wide ranges of temperature. It is illustrated in Fig. 1 for some early data on 61ST tested at — 195oC, and in Fig. 2 for some recent data on copper at room temperature. The greater accuracy of the results of Fig. 2 over previous ones' is due to the equipment shown in Fig. 3. Three levers apply the bulk of the load, while the changes in the small remainder load are indicated sensitively by a low capacity load scale. Refs. 2 and 3 describe the recording equipment. A test like those in Figs. 1 and 2 provides the information necessary to determine the rate sensitizrity, n,4 of the metal. ( a log s ) ? log s n = ------------------------ ----------------------------= ( a logs e, ? log e logS2-logS1 log S2/S1 log i2 — log e1 log e2/e1 where S equals stress: e is logarithmic strain or natural logarithm of (final gage length/initial gage length);" i is strain rate or de/dt: and n is rate sensitivity, rate of change of log stress with log strain rate at a given strain, or (a log S/a log i),. Normally, the rate sensitivity, n, is positive, which means that an increase in stress causes an increase in rate. However, certain exceptions, attributed to strain aging,5 have been observed. Fig. 2 indicates how rate sensitivity values are derived from the measurements. Table I summarizes the rate sensitivity values derivable from Fig. 1. In contrast to the behavior of copper in Fig. 2, the aluminum alloy 61ST, which strain ages when tested near room temperature, exhibits an unusual transient when the strain rate is suddenly changed,' as shown in Fig. 4. Initially, there is a comparatively sudden vertical shift of the stress-strain curve in a direction corresponding to the rate change, but then the curve gradually shifts back again. The initial shift is not as sudden as might be expected, because the testing machine is unable to achieve the impressed rate change instantaneously, as illustrated in Fig. 2. The behavior shown in Fig. 4 will be referred to as a tensile transient, the word tensile implying that the behavior was observed in a tension type of test. The corresponding test, where the strain rate is maintained constant except for the sudden change, will be called a tensile transient test. A creep transient, by contrast, will be defined as a temporarily abnormal behavior in a creep transient test, where there is a sudden change from one constant load to another.' In Fig. 4, a naive look at the gradually decreasing and then increasing load after a sudden rate incre-

Jan 1, 1957

By R. E. Cech, T. D. Tiemann

It has been shown that hydrogen may be made to serve as a rapid and eflicient reducing agent for Cu, Ni, Co, and Fe sulfides if a scavenging agent for hydrogen sulfide is intimately mixed with the sulfide particles being reduced. Accelerated reduction kinetics are demonstrated for nickel sulfide. Copper, nickel, and cobalt sulfides, when treated at certain temperatures in a combined reducing agent-scavenging agent system, are converted to voluminous masses of fibrous metal product. Studies have been carried out to determine the conditions which lead, on the one hand, to irregular poly crystalline fibers and, on the other, to long single crystal filaments a few microns in diameter. A mechanism is proposed to account for the formation of single crystal filuments. The sulfide minerals of Cu, Ni, Co, and Fe are an important source of these metals yet there has been comparatively little scientific effort devoted towards understanding reduction mechanisms of these minerals. This may be, in part, due to the fact that the most convenient reducing agents for carrying out such studies, viz., hydrogen and carbon, do not react appreciably with sulfides. We have found that the reaction of hydrogen with metal sulfides can be markedly accelerated by placing a scavenging agent for hydrogen sulfide in close proximity to the metal sulfide. A brief series of experiments demonstrating relative reduction rates is reported in this paper to illustrate the effect. With the reduction process thus accelerated we have observed an unusual type of reduction behavior on some of the sulfides investigated. Under certain conditions the metallic product of the reduction reaction takes the form of filaments growing outward from the sulfide particles. The present paper deals largely with efforts to classify the various types of growth forms observed. This study has shown that filamentary growths from sulfides take a much greater variety of forms than has heretofore been reported by Ercker,1 Hardy,2 and Nabarro and Jackson3 in their reviews of metallic growths from copper and silver sulfides. THERMODYNAMIC CONSIDERATIONS The thermodynamics for hydrogen reduction of metal sulfides is quite unfavorable. For the sulfides considered here equilibrium constants typically range from 10-3 to 10-5. These low equilibrium constants impose severe kinetic limitations on reduction since hydrogen sulfide must be transported out of the system at concentrations of only a few hundred ppm. Unless extremely high gas flow rates are employed the atmosphere surrounding any sulfide particle will always be essentially in equilibrium with the sulfide. If, however, one places an efficient scavenging agent for hydrogen sulfide in close proximity to the metal sulfide particles the concentration of H2S near the metal sulfide will be held to a very low value. This would permit the reduction reaction to proceed with little or no inhibition from a buildup of reaction product gas. It is well known that calcium oxide is capable of removing hydrogen sulfide from a hydrogen gas stream of low dew point.4 If a sufficient quantity of calcium oxide is mixed with the metal sulfide particles the reaction: CaO+H2S=CaS+ H2O [l] will substitute moisture in place of hydrogen sulfide in the gas stream and this will not affect, in a direct manner, the reaction: MeS +H2=Me + H2S [2] A convenient method of considering the thermodynamics of the combined reducing agent-scavenging agent system is to consider the atmosphere when the partial pressure of hydrogen sulfide is the same over both the metal sulfide and the scavenging agent, i.e., pH2S (1) =pH2S (2). As a consequence: pH2O (1) pH2(2) =K1K2 The chemical driving force for reduction will depend inversely upon the moisture content of the gas and will be 0 when, in the system, pH2O = pH2.K1K2. Table I lists values of the equilibrium constants for reduction and H2S scavenging reactions for a number of sulfides at several temperatures. Data are taken from Rosenqvist4,5 and Kelly.6 The equilibrium constant products calculated from this data show that the limiting level of gaseous reaction product has been increased by a factor of 10' to l04 as a result of substituting a reducing agent-scavenging agent system for a simple reducing agent system. One possible side effect which must be considered is the possibility that the moisture evolved in the scavenging reaction might cause the atmosphere in the system to be sufficiently oxidizing to favor the formation of oxide rather than metal. This possibility was examined by comparing the equilibrium constant products listed in Table I with equilibrium constants for hydrogen reduction of the respective metal oxides. It was found that for copper, nickel, and cobalt the combined reduction-scavenging reactions could not develop a sufficiently high oxidizing potential in the

Jan 1, 1970

By Fred Wright

IN A recent paper1 a detailed discussion is given of the possibilities. of using polarized light in the examination of opaque substances. The factors underlying the problem .are there treated from the viewpoint of the electromagnetic theory of light and the presentation is necessarily mathematical in form. The practical methods resulting from the discussion are, however, relatively simple and promise to be of value in the determination of certain ores and metals when studied in reflected light under the microscope. The results of the theoretical investigation referred to may be summarized by stating that in general the optical constants, such as refractive indices and absorption indices, cannot be satisfactorily ascertained on small, random, polished sections; that the use of polarized light enables. the observer ordinarily to determine whether the crystal plate is isotropic or anisotropic, and also to ascertain the degree of anisotropism; that for this purpose methods based either on the contrast in intensity between the two reflected components of non-polarized light, or on the amount of rotation of the plane of polarization, on reflection, of vertically incident, plane-polarized light, may be employed; that methods based on the phase difference between the two reflected components are in general of little value because of the small differences in phase which ordinarily result for a relatively large change in birefringence or biabsorption. The measurement of the optical properties of transparent minerals, even in minute irregular grains, is a simple task with modern petrographic microscope methods and is accomplished by petrologists as part of their ordinary routine work. But the determination of the optical constants of opaque substances is difficult and is rarely attempted; all observations are necessarily made in reflected light and are restricted commonly to the determination of color, of hardness, of the character of crystallization, and

Jan 2, 1920

By L. S. Darken, H. A. Wriedt

An investigation has been made of nitrogen absorption by the lattice defects in a low-carbon steel afte~ Plastic deformation. Specimens in which defects were distributed by various combinations of cold rolling and vacuum heat treatment were equilibrated with controlled ammonia + hydrogen mixtures at 300° to 450°C to study the relation between the solubility and the thermodynamic activity of nitrogen. The results are interpreted in terms of nitrogen being absorbed upon two different types of defect sites, called A sites and B sites. The concentrations of these sites are calculated for specimens with various histories of straining and annealing; and the thermodynamic relations descrihing the equilibrium distribution of nitrogen among the A, B, and ordinary interstitial sites in ferrite are evaluated as follows: THE generalization that the solute atoms in a solid solution interact with imperfections in the solvent lattice is now universally recognized and the subject of an extensive literature. All types of imperfections—point, line, or surface—exhibit these interactions, but the relative importance of each type depends upon its concentration, the strength of its interaction with the particular solute atom, and whether the interaction is attractive or repulsive. The strength and sign of the interaction vary with the vectorial displacement of the solute atom from the imperfection in the crystal. The concentration of lattice defects increases during plastic deformation and the effect of the imperfections upon the solute atoms is usually perceived only after cold work or irradiation. Two experimental methods have previously been used to observe the effects of interaction between nitrogen atoms and lattice imperfections in a iron. Internal friction, which was first used for this purpose by Dijkstra,1 has been applied more often than the electrical-resistivity method of Cottrell and Churchman.2 The method of the present investigation has not been used before.* Uniform specimens of steel with a metastable defect structure are produced by cold rolling and subsequent heat treatment below the recrystallization temperature. Variations in the defect structure are obtained by varying the amount of strain and the heat-treatment conditions. The specimens are then saturated with nitrogen at moderately elevated temperatures in ammonia + hydrogen mixtures having various thermodynamic activities of nitrogen below saturation with Fe4N. From the nitrogen contents of analyzed samples, the metastable equilibria of interactions between the defects and nitrogen can be established and the concentration of sites for nitrogen atoms in the lattice defects calculated. A steel was used in the present experiments instead of purified iron or iron alloys because the amount of nitrogen absorbed at defects is larger in the steel over a much wider range of experimental conditions and could therefore be measured more accurately. The effect of alloy composition is discussed in Part II of this paper; it is sufficient to say here that impurities and phase heterogeneity in ferritic alloys favor the generation and/or retention of larger defect concentrations during plastic deformation and annealing at 300° to 500°C. MATERIALS AND EXPERIMENTAL PROCEDURE The experimental specimens were prepared from stock of a low-carbon steel, which will be called "X steel" here, with the composition: C, 0.12 pct; Mn, 0.43 pct; P, 0.010 pct; S, 0.034 pct; Si, 0.007 pct; As, 0.086 pct; Cu, 0.022 pct; Ni, 0.009 pct; Cr, 0.003 pct. The stock was all from a single ingot made by the basic open-hearth process, which was hot-rolled to strip 0.080 in. thick.. This hot-rolled strip, given the code designation "XH", was the starting material for preparing a series of cold-rolled sheets. The latter are designated "XC27",

Jan 1, 1965

By M. Ahlers, Horace Pops

Slip features and formation of stress-induced mm-tensite have been studied in single crystals of fl phase Cu-Zn alloys in the composition range between 43 and 48 at. pct Zn. A phenomenological analysis is presented in which the glide planes and directions that me associated with the inhomogeneous shear in the martensite phase are predicted from the experimentally determined habit planes and macroscopic shear directions. It is shozun that the resolved shew component of the applied stress on the secondary shew system is a very important factor governing the formation of stress-induced martensite. A comparison is made between martensitic phases that form spontaneously upon cooling and those phases that arise from deformation. THE ß phase in Cu-Zn alloys is unstable and may transform spontaneously by a martensitic transformation1-3 during cooling. Thermoelastic and burst-type spontaneous martensitic phases have been observed3 in the composition range between 38 and 42 at. pct Zn. Martensite forms in alloys containing more than 42 at. pct Zn only by cold work below a temperature denoted as Md.4 Thus, alloys near the equiatomic composition can undergo a stress-induced transformation upon cold work at room temperature. Although data have been obtained concerning the effect of temperature5 and composition4 on the deformation of polycrystalline Cu-Zn alloys, it is rather surprising that few detailed studies6-8 on 6 brass have been conducted for single crystals where the stresses acting on crystallographic planes can be determined. A thorough understanding of transformation mechanisms requires knowledge of the role of stress and plastic strain. With this objective in mind we have made an investigation of the stress-induced rnartensite transformation in single crystals of 0 brass in the composition range between 43 and 48 at. pct Zn. Particular emphasis is given to the morphology and crystallographic features and a comparison is made between stress-induced and spontaneous martensite. I) EXPERIMENTAL PROCEDURE Master alloys having nominal zinc contents of 43, 45, and 48 at. pct were prepared from spectroscop-ically pure metals (>99.999 pct) in sealed quartz tubes under a partial pressure of helium. These alloys were cut into several pieces and converted into small rods by melting in quartz tubes. Subsequently, single crystals were grown from the rods by the Bridgman technique and homogenized for 3 hr at 820°C. Lattice parameter measurements were made from stress- relieved filings. Compositions, as determined from the reported variation of lattice parameter with atomic percent zinc,' indicated a zinc loss of less than approximately 0.25 at. pct. The single crystals were electroturned using a phosphoric acid electrolyte into tensile specimens each with a center section of 1 mm diam and 1 cm gage length. Cylindrical specimens approximately 3 mm in diam and 10 mm long and spark-machined rectangular blocks approximately 3 by 3 by 10 mm were prepared for compression studies. These blocks were stress-relieved and electropolished to eliminate any stresses introduced by spark machining. Crystal orientations were determined to an accuracy of ±2 deg primarily from back-reflection Laue photographs, and sometimes by the rotating single-crystal method. Figs. 1 to 3 show the location of the tension and compression axes within unit stereographic triangles. All specimens were deformed plastically at room temperature using an Instron machine, the crosshead speed being 0.02 or 0.05 cm per min. A hard steel hemisphere was placed at the upper end of the compression samples to achieve uniaxial loading. Trace normals of slip markings and habit planes of strain-induced martensite were determined to an accuracy of ±4 deg from the rectangular blocks by a two-surface analysis and from cylindrical specimens by measuring the angle between the tensile (or compression) axis and the tangent to the surface trace for different rotations about the deformation axis. Slip

Jan 1, 1969

By B. M. Larsen, K. Heindlhofer

THIS paper describes a relatively simple electrical apparatus that, through the close analogy between the flow of heat and of electricity, enables one to solve quickly and with satisfactory accuracy many complex problems in heat flow. This device, developed in 1935, has proved especially useful in the solution of certain practical problems relating to the design and efficiency of regenerators for an open-hearth furnace or coke oven, yielding within a few hours information that would take weeks or even months to acquire by mathematical1.2 or experimental3 methods of comparable accuracy. Its description now is prompted by growing interest in such analogues, as shown by several recent papers.4.5 The analogy between flow of heat and of electricity appears to have been recognized first by Maxwell who, in his famous Treatise on Electricity and Magnetism (1881) says: The analogy between the theory of the conduction of electricity and that of the conduction of heat is at first sight almost complete. If we can take two systems geometrically similar, and such that the conductivity. for heat at any part of the first is proportional to the conductivity for electricity at-the corresponding part of the second, and if we also make the temperature of any part of the first proportional to the electric potential at the corresponding point of the second, then the flow of heat across any area of the first will be proportional to the flow of electricity across the corresponding area of the second. .. Thus, in the illustration we have given, in which flow of electricity corresponds to flow of heat, the electric potential to temperature, electricity tends to flow from places of high to places of low potential, exactly as heat tends to flow from places of high to places of low. temperature He noted, however, that this analogy is restricted: ... there is, however, one remarkable difference between the phenomena of electricity and those of heat. Suspend a conducting body within a closed conducting vessel by a silk thread, and charge the vessel with electricity. The potential of the vessel and of all within it will be instantly raised, but however long and however powerfully the vessel be electrified, and whether the body within be allowed to come in contact with the vessel, or not, no signs of electrification will appear within the vessel, nor will the body within show any electrical effect when taken out. But if the vessel is raised to a high temperature, the body within will rise to the same temperature, but only after a considerable time, and if it is then taken out it will be found hot, and will remain so till it has continued to emit heat for some time. The difference between the phenomena consists in the fact that bodies are capable of absorbing and emitting heat, whereas they have no corresponding property with respect to electricity. According to this statement the application of the analogy would be limited to problems of steady flow that do not involve heat-capacity effects. In spite of this

Jan 1, 1945

By Eric Jette

IN thermodynamic studies of gas mixtures and liquid solutions, the respective problems have been greatly simplified by the use of two general limiting laws; Dalton's law of partial pressures and Raoult's law. It is generally recognized that these two laws have a common physical and chemical basis which may be stated as follows: The law may be expected to be strictly valid only for systems in which the different molecular species are so nearly the same in their physical and chemical properties that a molecule is unable to recognize whether its neighbor is one of its own kind or not. Positive and negative deviations from both laws are frequently encountered. The occurrence of negative deviations in both gases and liquids is ascribed to attractive forces which, in the more extreme cases, may be so large in magnitude and so highly specific in character as to lead to the formation of definite chemical compounds. Positive deviations in gases develop only at higher pressures where the intermolecular distances are so decreased that factors such as molecular size and shape, which ultimately become concerned with the repulsive forces, come into play. In liquid mixtures, positive deviations are generally considered as due to differences in the symmetrical (nonpolar) fields of force which surround the various molecular species and which are supposed to give rise to a tendency for each species to associate with its own kind and thus to "squeeze out" the other variety. Fundamentally this also involves the existence of repulsive forces between unlike molecules. If the fields of force are unsymmetrical (polar) a tendency towards compound formation results. Stated in more exact terms, strict adherence to the law means that the "activity" (or any adequate measure of this quantity) of a component in a mixture is a linear function of the molecular (or atomic)

Jan 1, 1934