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By Fred C. Bond

AN improved method of measuring the surface area of a comminution product down to any desired particle size has been developed. The method is largely graphical, and requires relatively little calculation. It can be used with materials containing large amounts of clay, or excess fines of any kind. The surface area S is expressed in terms of square meters per100 c.c. of solids. This expression is based upon volume rather than weight, and is considered to be more suitable for crushing and grinding problems, where the machines ordinarily are operated under constant volume conditions. It has the advantage that surface areas of different materials can be compared directly, even though their specific gravities may be unknown. The "specific surface" of a material, or the number of square centimeters of surface area per gram, is equal to 100S divided by the specific gravity. Particle diameters are expressed in microns, K being the diameter of the largest particle present and L the grind limit, or lower size limit of the particles formed directly by grinding. The value of K does not always coincide exactly with the diameters of the largest particles retained on the coarsest testing sieve, since the largest particles formed in crushing and grinding are often slabby, or have other irregular shapes. L has been chosen as 0.700 microns, or number 27.5 in the size number series,1 for reasons to be explained later. S is the total surface area of all particles larger than L microns in diameter. When a homogeneous comminution product is separated into fractions whose diameters bear a constant geometrical relationship [p] to each other, and the log per cent weight retained upon each size and passing the next larger size is plotted against the log diameter, a straight line results, which is called the distribution line, and which has a slope in called the distribution modulus. The distribution line can be extended to any desired limiting size, and the total surface area of all particles larger than that size can be calculated. The equation of the distribution line is w = Cxm [I] where w is the per cent weight retained on each successive sieve; x is the particle diameter; and C is the per cent weight retained on an opening of unit diameter.2 Theoretically, the distribution line can be extended to include infinitely small particles. When it is so extended, and the assumption is made that no fine particles are present other than those accounted for by the equation; the log per cent cumulative weight passing any series of sizes, plotted against the log diameter passed, will result in a straight line lying parallel to and above the plotted distribution line.

Jan 1, 1941

THERE are three chief production zones of tungsten ore in China. In the Province of Kiangsi mines are located at Kanchow, East River, and West River. Their combined production is understood to amount to 300 to 350 tons of ore per month, and their original exportation is made through the port of Kiukiang, largely to Shanghai. The second zone is in Kwangtung Province, the mines there being at Tayulin. Produc-tion reaches about 200 tons per month and cargo is gen-erally exported through the port of Hong Kong. In the Province of Hunan approximately 25 tons of ore are produced monthly in the mines at Ton-on. Tungsten ore from Kiangsi and Kwangtung Prov-inces is generally about 70 per cent WO, (tungstic acid), while that from Hunan is of lower quality, run-ning about 65 per cent WO3. Kiangsi ore is received from the mines in 100-1b. and Hunan in 224-lb. gunny sacks. No repacking is done except as it is made neces-sary by the condition of the sacks. Kiangsi Province contains the Chinese districts pro-ducing the largest amount of salable wolframite or tungsten. Many districts west and south of Kiangsi have been found to have wolframite deposits.-Com-merce Reports.

Jan 1, 1928

By W. A. Vine

When a hole is made in a stressed solid, such as rock pierced by mine openings, equilibrium of the solid is destroyed. To restablish that equilibrium the stress condition in the rock surrounding the opening becomes rearranged. This rearrangement may or may not develop local stresses in the vicinity of the opening which exceed the elastic strength of the rock. Since stability of the opening depends, therefore, on the strength of the naturally occurring rock surrounding the opening, this rock is an engineering material of construction, and all rock affected by the associated opening or system of openings may be considered a structure. The term invert is chosen to describe the formation of the structure built from the inside, as it were, and a consequence of mining rather than an entity built for a purpose. By definition, an invert structure is formed when openings are made underground and is com- posed of that material on the solid side of a rock-air interface wherein the stress condition is affected by the associated opening or system of openings. The shape of an invert structure is never clearly defined; the skin of the structure may be mapped, and even described, but the boundary of the structure within the solid rock mass must be arbitrarily set.

Nov 1, 1955

By A. L. Mular

lnput energy-size modulus relation at small reduc-tion ratios is expressed by Et = (M, -Mt) k;. In some cases 13 is close to Schuhmann's distribution modulus a in value. Experimental results in conjunc-tion with the equation demonstrate the fact that energy input which produced fracture is not expended on unbroken starting material inside the mill at any time. Recently, schuhmann1 derived the Charles equation2 using the postulate that complex com-minution operations can be considered as a summa- tion of many comminution events. The fragments resulting from each event are assumed to follow the Gaudin-Schuhmamn distribution. In his derivation, Schuhmann implies that the size distribution of the total mass of a material is determined by the fraction of that mass actually subjected to comminution. Consider a feed to contain a volume, Vo, of uni- formly sized homogeneous material. After t seconds of grinding, let the volume of broken material be Vo - Vt where Vt is the volume of starting material not yet broken. The size distribution of the broken material is given by: where V is the cumulative volume less than size X, and k, is the size modulus of the broken material at time t. The distribution for the total volume at this

Jan 1, 1962

By David R. Poirier

THE activity of carbon in Fe-C-Cr liquid solutions has been measured by Richardson and Dennis,1 Fuwa and chipman,2 and Goto et aL3 Fuwa and Chipman2 have presented their data along with data of Richardson and Dennis1 and utilized an interaction parameter. However, the interaction parameter is only valid for dilute solutions of carbon, because, as indicated, the same interaction parameter does not apply to more concentrated solutions of carbon (i.e., the effect of chromium on the saturation of graphite in liquid iron). Ohtani4 has attempted to account for the effect of carbon concentration on the interaction parameter; however even his analysis does not apply to the saturation data. Also, the effect of temperature on interaction parameters must be taken into account. Therefore, in any process where the concentration of carbon and/or the temperature changes (such as solidification), the use of an interaction parameter is not adequate to know the activity of carbon. The purpose of this communication is to make use of the existing data on the effect of chromium on the activity of carbon in liquid iron solutions in such a way that the activity can be described as a function of both composition and temperature. The method is an extension of Rist and chipman's5 analysis for the binary Fe-C solutions. As in Rist and Chipman's analysis, the activity coefficient is assumed to obey the relation: log y1 = at(l -X1)2 + It [1]

Jan 1, 1969

By Herman Dykstra, Irving Fatt

Relative wetting phase permeabilities calculated from capillary pressure-saturation data are compared with measured relative permeability data. The equation relating relative permeability to capillary pressure-saturation data is derived by assuming that a porous medium is analogous to a bundle of capillary tubes. The equation includes a term to correct for the difference between fluid path length and length of core. Relative oil permeability data in the water-oil-gas system are presented, and it is shown that if the water is considered part of he rock matrix, the relative oil permeability curve is typical of a wetting phase relative permeability curve. Apparatus for measuring two and three-phase relative permeabilities are described. INTRODUCTION The difficulty in measuring relative permeability of cores has made it desirable to have a correlation between relative permeability and some more easily measured property of porous media. Such an easily measured property is the capillary preisure-saturation relation. In the past there has been a tendency to separate the capillary pressure concept from the very complex pore geometry and to consider that the capillary pressure-saturation curve give? only some characteristic distribution of interfacial curvature between two fluids.' Recently, however, it has been realized that if capillary pressure data are to yield information concerning pore size distribution2 and fluid flow in porous media. the pore must be assumed to have a simple shape such as a cylinder or a sphere. Childs and George' showed that relative water permeability could be calculated from the capillary pressure-water saturation curve by assuming that the pores are cylinders in which the fluid flowing obeys Poiseuille's Law, and that the capillary preisure curve indicated the size and number of pores. Purcell5 derived an equation relating the permeability of a porous medium to the capillary pressure curve by assuming the porous medium to he analogous to a bundle of capillary tubes. Gates and Lietz6 calculated relative permeability by an equa-tion derived from Purcell's equation. In this paper an equation is derived giving the relative water permeability as a function of water saturation by as-sulning that the core sample can be represented by a bundle of capillary tubes in which the fluid path length is not the same as the bulk length, and in which the fluid path length varies with saturation. THEORY For a bundle of N capillary tubes the flow through dN tubes will be dQ = qav dN ..........(1) where Q is the total flow rate through all the tubes and q., is the aberage flow rate through the tubes in the interval dN. If the interval dN is made small the average flow rate through a tube in the interval dN is given by Poiseuille's Law, 8 nl where ?P is the pressure drop across the tube of length 1 and radius r, and µ is the viscosity of the fluid. Substituting for qav in Equation (1), dQ =pr4 ? P/8µl dN.........(3) Darcy's Law for linear flow of an incompressible fluid in a porous medium is Q = KA?P/µL...........(4) where K is the permeability and ?P is the pressure drop across a bundle of tubes which has replaced the porous medium of length L and cross-sectional area A. Differentiating Darcy's Law with A, ?P, µ, and L constant, dQ = A?P/µL dK.........(5) Equating (3) and (5) gives dK------------dN.........(6) 8Al If the pores are assumed to be cylinders dV =pr2ldN..........(7) where V is the volume of flowing fluid in the pores. Substituting for dN in Equation (6) gives dK = —dV..........(8) 8AI' By definition the saturation, S, of the core is v v S =V/Vp..........(9) Vv -PAL

Jan 1, 1951

By Irving Fatt, Herman Dykstra

Relative wetting phase permeabilities calculated from capillary pressure-saturation data are compared with measured relative permeability data. The equation relating relative permeability to capillary pressure-saturation data is derived by assuming that a porous medium is analogous to a bundle of capillary tubes. The equation includes a term to correct for the difference between fluid path length and length of core. Relative oil permeability data in the water-oil-gas system are presented, and it is shown that if the water is considered part of he rock matrix, the relative oil permeability curve is typical of a wetting phase relative permeability curve. Apparatus for measuring two and three-phase relative permeabilities are described. INTRODUCTION The difficulty in measuring relative permeability of cores has made it desirable to have a correlation between relative permeability and some more easily measured property of porous media. Such an easily measured property is the capillary preisure-saturation relation. In the past there has been a tendency to separate the capillary pressure concept from the very complex pore geometry and to consider that the capillary pressure-saturation curve give? only some characteristic distribution of interfacial curvature between two fluids.' Recently, however, it has been realized that if capillary pressure data are to yield information concerning pore size distribution2 and fluid flow in porous media. the pore must be assumed to have a simple shape such as a cylinder or a sphere. Childs and George' showed that relative water permeability could be calculated from the capillary pressure-water saturation curve by assuming that the pores are cylinders in which the fluid flowing obeys Poiseuille's Law, and that the capillary preisure curve indicated the size and number of pores. Purcell5 derived an equation relating the permeability of a porous medium to the capillary pressure curve by assuming the porous medium to he analogous to a bundle of capillary tubes. Gates and Lietz6 calculated relative permeability by an equa-tion derived from Purcell's equation. In this paper an equation is derived giving the relative water permeability as a function of water saturation by as-sulning that the core sample can be represented by a bundle of capillary tubes in which the fluid path length is not the same as the bulk length, and in which the fluid path length varies with saturation. THEORY For a bundle of N capillary tubes the flow through dN tubes will be dQ = qav dN ..........(1) where Q is the total flow rate through all the tubes and q., is the aberage flow rate through the tubes in the interval dN. If the interval dN is made small the average flow rate through a tube in the interval dN is given by Poiseuille's Law, 8 nl where ?P is the pressure drop across the tube of length 1 and radius r, and µ is the viscosity of the fluid. Substituting for qav in Equation (1), dQ =pr4 ? P/8µl dN.........(3) Darcy's Law for linear flow of an incompressible fluid in a porous medium is Q = KA?P/µL...........(4) where K is the permeability and ?P is the pressure drop across a bundle of tubes which has replaced the porous medium of length L and cross-sectional area A. Differentiating Darcy's Law with A, ?P, µ, and L constant, dQ = A?P/µL dK.........(5) Equating (3) and (5) gives dK------------dN.........(6) 8Al If the pores are assumed to be cylinders dV =pr2ldN..........(7) where V is the volume of flowing fluid in the pores. Substituting for dN in Equation (6) gives dK = —dV..........(8) 8AI' By definition the saturation, S, of the core is v v S =V/Vp..........(9) Vv -PAL

Jan 1, 1951

By John Chipman

The concentration of a solute in a dilute ),zetallic solution may be measured by any of several parame- ters including weight percent, atom fraction, atom ratio, and lattice ratio. The ratio of filled to unfilled interstitial sites is useful for interstitial solutes. A variable 2 proportional to this ratio is used as a measuve of concentration. For component 2 irz a bitzary solution z2 = n2/Ym - nz/b) where b is the numberber of interstitial sites per lattice atom. For a t~lul-ticortzporzent solution this becomes zz = n2/(nl + Cvjnj) in which Vj = - l/b for an interstial solute and +1 for a substitulional solute. In the infinitely dilute solution the activity of an interstitial solute 2 is proportional lo z2. At finile concentration the departure from this limiting law is expressed us an activity coefficient, his coefficient is a function of concentra1io)z expressed as tevactiolz coeffcient 8; is analogous to the jark~iliar e£ bul is found to be independent of concentvation in certain solutions for which data are available. It is found that the same equations may be used to express the activity of a nonmetallic solute, sulfur, in liquid solutions of iron containing other solutes, both metallic and nonmetallic. For a nonmetallic solute or for one which strongly increases the actiuity of sulfur, it is convenient to assign arbitvarily a value vj = — 1. When this is done the derivative is found to be constant in each of the ternary solutions studied. The activity coefficient of sulfur in a complex liquid iron solution may be expressed as where nk is a second-order cross product determined in the quaternary solution Fe-S-j-k. The equation is used to calculate tlze activity of sulfur i)z three sevetl- component solutions. IN thermodynamic calculations concerning dilute solutions it is unnecessary to invoke laws and relations which extend across the concentration range to include concentrated solutions. In most binary metallic systems, as arkeen&apos; has recently pointed out, there exist two terminal composition regions of relatively simple behavior, connected by a central region of much greater complexity. When the solute is a nonmetal there is only one such region and in many systems the concentration range is extremely limited. It is the purpose of this paper to suggest a method for the calculation of activities in such a terminal region in which one or more solutes are dissolved in a single solvent of predominantly high concentration. HENRY&apos;S LAW In the usual textbook statement of Henry&apos;s law, concentration is stated in mole fraction. This has the advantage that it makes Henry&apos;s law thermodynamically consistent with Raoult&apos;s law. Since all measures of concentration at infinite dilution are related by simple proportion it follows that mole fraction, molality, atom ratio, weight percent, or any other unit of concentration can be used with the appropriate constant. At finite concentrations, however, calculations based on the law depend upon the unit employed. Deviations from Henry&apos;s law at finite concentrations depend upon the composition variable employed. They are evaluated in terms of activity and interaction coefficients2 which have become familiar features of metallurgical thermodynamics. It is the purpose of this paper to propose a measure of concentration for metallic solutions containing interstitial or nonmetallic solutes by means of which the calculation of activities in complex solutions may be simplified. The discussion will be restricted to free-energy interaction coefficients3 typified by Wagner&apos;s c|a BINARY SOLUTIONS The several measures of concentration which are to be considered are shown in line a of Table I. The corresponding activity coefficients are in line b and the deviation coefficients, sometimes called self-interaction coefficients, are in line c. Henry&apos;s law simply states that the activity coefficient approaches a constant value at infinite dilution. By adoptihg the infinitely dilute solution as the reference state and defining the "Henrian" activity as equal to the concentration in this state, the activity coefficient is always unity at infinite dilution. This convention is far sim~ler and more useful in dilute solution than emploiment of the &apos;Raoultian" activities and it will be used in the following discussion. The several definitions and equations of Table I will be referred to by means of their coordinates in the table. Early observations of deviations from Henry&apos;s law in metallic solutions were shown graphically4 rather than analytically. For the case of sulfur in liquid iron5 the slope of a plot of logfs vs (%S) was constant in the range 0 to 4.8 pct S, indicating constancy of eh2&apos; in Ic. He was proposed by wagnerz and has been widely adopted. The a function of IIIc recently employed by ~arkenl was designed specifically for dilute solutions. Darken has shown that the value of a12 remains essentially constant for many binary solutions within a substantial range of compositions. The atom ratio is directly proportional to the molalitv.<, a conventional measure of concentration. IVb and C served as the basis for smith&apos;s6 classic studies of

Jan 1, 1968

By J. G. Faller, L. P. Skolnick

The distribution of cobalt and vanadium over non-equivalent crystallographic sites in C14-type Zr(VCo), alloys has been investigated. An anomalous X-ray scattering technique developed by Skolnick, Kondo. and lavine7 by which the separation in the scattering factors of two similar atoms can be enhanced was employed. Six alloys spanning the pseudobinary section ZrV1.6Co0.4-ZrVO.6CO1.4 at 10pct steps showed a nonrandom compositionally dependent distribution. Specifically, at high vanadium content cobalt preferentially occupied sites of type (6h) and vanadium, sites of type (2a; at low vanadium content the reverse was observed. In addition to the distribution fraction the structural parameters x and z were obtained. There was no significant deviation of these parameters from those obtained in the ideal C14 structure. Certain suggestions are made to account for the observed nonrandomness in the distribution of atoms on the two types of sites. INTERMETALLIC compounds of formula AB2 iso-morphous with MgCu2, MgZn2, and MgNi2 are known as Laves phases. Because Laves phases exhibit high symmetry and coordination numbers, the highest possible for an AB2-type compound,1 they are among the most frequently observed compounds in nature. In recent years interest has centered about the purely transition metal Laves phases2-&apos; in efforts to understand the function of atomic size and electronic structure in the formation of these compounds. It has been observed that pseudobinary Laves phase systems often show a variation of structure across the phase diagram. Such a system is the ZrV2-ZrCo2 in which the structure varies from cubic MgCu2 to hexagonal MgZn2 to cubic MgCu2.4 Some understanding about the conditions under which the second modification is stable can perhaps be gained by studying the distribution of cobalt and vanadium atoms on lattice sites in the MgZn2 modification of the system ZrV2-ZrCo2. In both the MgZn2 and MgNi2-types there exist nonequivalent positions open to occupancy by the B element, whereas in the MgCu2 prototype all sites are equivalent. Skolnick, Kondo, and La-vine7 have developed an anomalous scattering technique suitable for this type of investigation. Whereas the influence of size on the formation of a Laves phase is well recognized, no substantial evidence has been put forth in support of the size ratio dependence of a particular prototype. Berry and Raynor8 suggested that RA /RB ratio does indeed affect the type of structure that is chosen, MgZn2 compounds tending to cluster about 1.225 while MgCu2 compounds were found at larger deviations from this ratio. Dwight,3 however, from a study of 164 Laves phases does not believe this generalization to be justified. Electronic effects are certain to play a part in the stability of Laves phases in general and in the choice of a structure type in particular. For example, size along would favor the formation of Laves compounds of Ti, Zr, Hf, Ta, or Nb as the A element with nickel or copper as the B element. The absence of such is attributed to an unfavorable electron : atom ratio by Elliott and rostoker.4 Early experiments of Laves and witte9 with pseudobinary and pseudoternary systems of the three prototypes established the dependence of crystal structure upon electron: atom ratios. They observed that the MgCu2 structure dissolved elements of higher valency until the electron: atom ratio of =1.8 was reached; the MgZn2 likewise dissolved elements of lower valency replacing zinc. witte,6 from calculations of the electron : atom volumes of Brillouin Zones, obtained limits of stability for the prototypes MgCu2 and MgZn2. Elliott and Rostoker4 used these limits with considerable success in the all-transition element Laves phases they investigated. According to witte,6 compounds between the electron :atom ratios of 1.80 and 2.32 were of the MgZn2 type; those above and below exhibited the MgCu2-type structure. On the basis of these limits and an assumed valency of zirconium based upon the near tetra-valence of titanium, Elliott and Rostoker obtained valencies for the first transition series elements. For the Laves phases with which this investigation is concerned, ZrV2 and ZrCo2, the authors calculated electron :atom ratios of 2.54 and 1.56, respectively. These ratios are for the MgCu2-type structure and straddle the stability band of the MgZn2 modification. One could, therefore, predict that a pseudobinary system ZrV2-ZrCo2 should pass through the MgZn2 modification in traversing the composition diagram from one end to the other. Implicit in this assumption is a smooth change of the electron: atom ratio from 2&apos;54 to 1.56. MOSS10 states that his finding the low temperature structure of ZrCr2 to be C15 instead of C14 alters greatly Elliott&apos;s valency of zirconium and hence the assumed valencies of the other metals. Such a quantitative correlation of structure with electron : atom

Jan 1, 1963

F. L. Clerc, Chicago, Ill. (communication to the Secretary): On page 681 in Mr. Winslow&apos;s paper, he refers to me as having "advocated the view that the ores were derived from the patches of Coal-

Jan 1, 1895

By Leonard Grimshaw

THE idea of bonding two dissimilar ferrous metals, and making use of both, is an old one. Tips have been brazed onto tool shanks for many years. The bonding of larger pieces to form whole bars and sheets has also been accomplished, but has received little attention in the technical literature, although a number of patents have been issued covering various methods for its accomplishment. There are three main motives behind the manufacture of composite steels. One is that the physical properties of one steel may supplement those of another; a useful, but at the same time, hard, brittle steel may be backed by a soft ductile one, or a stainless steel may be backed by a steel possessing greater strength. Another motive is direct lowering of cost; an expensive steel may be backed by a less expensive one, bringing down the cost of the piece as a whole. The third motive is an indirect lowering of cost, as when a useful steel is backed by a steel that is easier to machine, so that machining cost on a finished product is lowered considerably. Often more than one of these motives lead to a decision to use a com-posite steel.

Jan 1, 1936

By E. H. Bunce

CONTINUED progress in zinc metallurgy has been shown during 1933 by the adoption of new methods as well as the modernization of old processes and equipment, and by the initiation of new fields of activity for future advancement. The use of suspension roasting continued to grow as its advantages and adaptability became increasingly, apparent. The process developed by the National Smelting Co., Ltd., several years ago, of completely roasting on large sintering machines with utilization of the gas for acid manufacture has worked so successfully that an additional machine was installed during the year. At both the Swansea and the Avonmouth Works all of the ore for smelting is now roasted on the large sintering machines, thereby completely eliminating the old hearth-roasting furnaces. Work continued on obtaining partial purification of zinc ores from lead and cadmium by close control of conditions on the sintering machine, and in a few instances by chlorine additions to the ore before sintering. Ores so treated were either partially roasted or com-

Jan 1, 1934

United Engineering Trustees, Inc. TAMES L HEAD, &apos;50 E C MEAOHER, &apos;52 R M ROOSEVELT, &apos;49 The Engineering Foundation F F COLCORD, &apos;50 E A PRENTIS, JR , &apos;48 R M ROOSEVELT, &apos;49

Jan 1, 1952

By Amitava Gangulee, Michael B. Bever

The effects of changes in short-range order on some thermodynamic, electrical, and mechanical properties of the silver-rich Ag-Mg solid solutions have been investigated. The heats of formation at 273°K of several alloys after two different thermal treatments were measured by liquid metal solution calorimetry. Their electrical resistivities were measured at temperatures ranging from 4° to 773°k. Tensile tests and microhard-ness measurements were carried out at room temperature. An effective short-range order parameter and an effective interaction energy are defined. The measured changes in the properties are interpreted in terms of these quantities. The short-range order parameter is evaluated separately from calorimetric and X-ray data; the results are in fair agreement. Increasing short-range order lowers the resistivity of- the silver-rich Ag-Mg alloys but does not measurably affect the temperature dependence of the resistivity. Short-range order increases the yield stress of these alloys but does not affect the ultimate tensile stress. Changes in the effective short-range order parameter independently obtained from measured changes in the heat of formation, resistivity, and yield stress are in fair agreement. THE thermodynamic, electrical, and mechanical properties of solid solutions have been investigated as functions of composition in many alloy systems, but the effects of configurational variables, such as short-range or long-range order, on these properties have received much less attention. The silver-rich terminal solid solutions in the system Ag-Mg are well-suited for the investigation of the effects of order. The composition of these solid solutions may be varied over a range extending to about 27 at. pct Mg.1 Appreciable short-range ordering is likely to take place in these solid solutions; the degree of short-range order can be varied by suitable thermal treatments. In the alloy Ag3Mg long-range ordering is possible.2 This paper is primarily concerned with the effects of short-range order on some thermodynamic, electrical, and mechanical properties of the silver-rich Ag-Mg solid solutions.-The long-range ordering transition is the subject of a concurrent paper.3 1) EXPERIMENTAL PROCEDURES 1.1) Preparation of Specimens. Ag-Mg alloys containing up to 26.4 at. pct Mg were prepared by melting 99.99 pct pure Ag (obtained from Baker Chemical Co.) and 99.99 pct pure Mg (obtained from Eastman Chemi- cal Co. or Johnson Mathey & Co.) in graphite crucibles under molten potassium chloride. The solidified ingots were homogenized at 823°K for 10 days in evacuated Vycor capsules. A surface layer 6 in. thick was then removed by machining. The ingots were swaged into rods (2.5 mm diam) which were drawn into wires (1.0 mm diam). The wire specimens were annealed at 773°K for 24 hr in vacuum and either quenched into iced brine or cooled to room temperature over a period of 15 days. The average grain diameter (obtained from the linear intercepts) was about 0.1 mm. 1.2) Calorimetry. The heats of formation of the alloys were measured in a tin solution calorimeter as the difference in the heat effects of alternate additions of samples of an alloy and the mechanical mixture of its component elements. The additions were made from 273°K to the bath at about 623°K. The heat effect on addition of the alloys was approximately 5.5 kcal per g-atom. The procedure and the method of calculation have been described.4 1.3) X-Ray Diffraction. Short-range order parameters of two alloys were calculated from diffuse scattering intensities,&apos; obtained with briquettes made from powdered specimens. A GE-XRD 5 diffractometer with filtered copper radiation was used. The absolute intensities were based on calibrations with paraffin. 1.4) Resistivity Measurements. The electrical resistivities were measured by a potentiometric method in which the potential drop across the specimen was compared with that across a standard resistance. For measurements below room temperature, the specimens were immersed in liquid helium (4°K), liquid nitrogen (78°K), dry ice and trichloroethylene (195°K), or ice and water (273°K). Measurements above room temperature were made on specimens held in a furnace under helium or in vacuum. The resistivity measurements were reproducible to ±0.5 pct or less. 1.5) Mechanical Tests. Tensile tests were carried out at room temperature with a Tinius-Olsen XY elec-tromatic Universal testing machine. Wire specimens (nominal gage length 1 in.) were used. The strain was measured with an extensometer, which had a sensitivity of 4 x 10-5; the strain rate was 10-3 min-1. Microhard-ness measurements were made with a square-pyramid indenter and a 100-g load.11 2) RESULTS AND DISCUSSION All measurements were made on two parallel sets of specimens, one quenched and the other slowly cooled from 773°K. The reported values are the averages of at least three measurements. In the range of magnesium concentration substantially below that of the composition Ag3Mg, quenched alloys have less short-range order than slowly cooled alloys. As the magnesium concentration approaches that of Ag3Mg, slow cooling develops long-range order. Quenching sup-

Jan 1, 1969

By David A. Thomas, Eugene S. Meieran

MECHAMCAL, electrical, and other property measurements are often more easily made on wires than on sheets. In order to carry out transmission electron microscopy on the same material used for property determinations, we have developed a method for preparing thin foil specimens of wires. The technique was developed for 0.030 in. diam tungsten wires, and is a modification of the thinning techniques used by Wilsdorf, et al 1 A length of wire is first ground to about 0.010 in. thick by mounting the wire in low melting temperature wax, hand grinding a longitudinal flat, removing and reversing the wire in the mount, and then grinding a second parallel flat. The 0.030 in. wide and 0.010 in. thick strip is cut into 1/8 in. lengths to fit in the specimen holder of the electron microscope. Next the specimen is gripped in platinum-tipped tweezers (the anode) and placed 2 mm below a hol- low copper cathode with a 0.010 in. ID nozzle. Electrolyte, 10 pct NaOH, flows by gravity feed through the nozzle onto the specimen, as shown in Fig. l(a). Polishing is carried out until a shallow impression is made on one surface, and then the specimen is turned over and the opposite surface indented. The metal between the two impressions should be about half the specimen thickness, as is shown by the heavy line in the cross section in Fig. l(b). The entire specimen is then electropolishedin 2 pct NaOH until a hole appears at the location of the indentations. The apparatus is shown in Fig. 2, and is essentially the same as that used by Wilsdorf et al. at The Franklin Institute. Light is reflected by a mirror onto the bottom surface of the specimen! which is viewed by a stereoscopic microscope placed above it. Polishing is carried out until light is seen, indicating that a hole has formed, and then immediately stopped. The specimen is washed in water. alcohol, and ether, and is then ready for examination. The specimen should be reversed in its platinum clip during electropolishing to insure equal polishing on both sides of the impression. For tungsten, indenting at 120 v and 0.04 amp takes less than 1 min, and final polishing, at 10 v and 1 amp, less than 5 min. The portion of the specimen available for transmission microscopy surrounds the hole, as is seen by the dashed lines in Fig. l(b). Slight electroetch-ing accompanying electropolishing reveals the mi-crostructure, as seen in Fig. 3(a) by light microscopy. Low-magnification electron microscopy, as in Fig. 3(b), enables the same areas and grains to be viewed and identified when subsequently examined at high magnification. Fig. 4 is a typical structure of

Jan 1, 1963

By M. L. Fuller

IN connection with an investigation in this laboratory on the high-zinc side of the copper-zinc system, it was observed that well developed segre-gate structures of the Widmanstätten type were formed when a secondary phase precipitated from the solid solution of copper in zinc. This paper presents an analysis of the crystallographic relationship between the segregate and the solid solution matrix. The data to be presented are an interesting addition to the literature on segregate structures in that the plane of segregation is one of the less densely populated planes. In agreement with the generalization of C. H. Mathewson and D. W. Smith1 the plane of segregation in the matrix con-tains the direction of closest atomic packing of the lattice. Furthermore, the matrix and the segregate are both hexagonal close-packed, which has not been reported hitherto in the literature.2 The increasing com-mercial importance of zinc alloys containing copper makes this funda-mental study of value to the metallography of zinc alloys.

Jan 1, 1933

By Earl G. Alexander, W. R. Runyan

The nature of silicon growths which form on amorphous silicon dioxide during epitaxial deposition in unmasked areas was investigated. Octahedral silicon crystals nucleate and grow on the oxide at pinholes, adjacent to foreign matter, and probably at oxygen-deficient sites. Generation of these oxygen-deficient sites on the oxide surface is shown to be thermody-namically favorable under usual deposition conditions. The conditions which affect saturation (SiCl4 concentration, flow rate, temperature) determine the number of sites on which silicon will nucleate and grow. Reaction product HCl is likely responsible for suppressing silicon growths on the oxide near exposed areas of silicon. Evidence is given that the oxide-silicon interaction occurs in hydrogen only and involves water as a transport agent. SINCE shortly after the first epitaxial layers of silicon and germanium were grown over large areas, efforts have been underway to grow selectively on specified portions of the surface. Such selective growth should be particularly applicable to monolithic integrated circuits. Usually the approach has been to use a mask to delineate the desired area,&apos;-7 but the VLS methoda can also be used, and direct programmed atomic beam deposition has been suggested.9 The masking techniques may embody two forms: in one the mask is a material which can later be removed along with any growths attached to it; in the other, attempts are made to prevent growth on the mask, so that over a whole slice the only deposition that will occur is in the unmasked regions. The present work is concerned with only the latter case, and specifically with silicon. Joyce and Baldrey1 suggested the use of thermally grown silicon dioxide as a mask material and showed that for the proper choice of operating conditions (total flow, SiCl4 concentration, total deposition time, and temperature) spurious growth could be minimized and that if the deposition times were not too large, and the criteria not too stringent, a usable process occurred. Later Schnable et al 4 observed that after extended deposition times, during which most of the silicon dioxide became covered with growth, there was always a band of oxide around the exposed silicon area that was quite free of spurious silicon crystallites. This latter observation is particularly intriguing since it extends the hope that with proper precautions masking can be much more versatile than it presently is. EXPERIMENTAL PROCEDURE Silicon substrates oriented to within 1.5 deg of a (111) plane were prepared by etch polishing lapped

Jan 1, 1967

By John E. Sherborne

Much valuable scientific research has been performed in recent years on the subject of phase behavior of hydrocarbons.l-11 Engineers employed in petroleum production are interesting themselves in this work as well as in methods of applying the fundamental data available to the solution of their various problems. Recently a number of papers have been published in which applications of phase behavior have been made to specific cases pertaining to critical phenomena.l2-16 Little effort, however, has been made in the literature to show the relation between changes occurring in the critical region and the more common phase behavior, therefore it is believed that a presentation of the fundamentals of phase behavior with reference to hydrocarbons is timely. Study of phase behavior is not new. In the metallurgical field, knowledge of heterogeneous equilibria has advanced tremendously, particularly with reference to solid-solid and solid-liquid behavior. Much is known about vapor-liquid equilibria too, but few engineers are familiar with this subject. Definition of Terms In a discussion of this sort, a definition of terms used is most important. Such terms as "pressure," "temperature" and "volume" need little definition other than mention of the units in which they are considered. Pressure is expressed in pounds per square inch absolute. Temperature is usually expressed as degrees Fahrenheit or degrees Rankine. In considering thermodynamic and phase behavior, the use of the absolute, Rankine, scale is desirable. Volume is expressed as specific volume, such as cubic feet per pound. This will be recognized as the reciprocal of the specific weight. In considering systems composed of more than one component, it is sometimes desirable to consider molal

Jan 1, 1940

By John E. Sherborne

Much valuable scientific research has been performed in recent years on the subject of phase behavior of hydrocarbons.l-11 Engineers employed in petroleum production are interesting themselves in this work as well as in methods of applying the fundamental data available to the solution of their various problems. Recently a number of papers have been published in which applications of phase behavior have been made to specific cases pertaining to critical phenomena.l2-16 Little effort, however, has been made in the literature to show the relation between changes occurring in the critical region and the more common phase behavior, therefore it is believed that a presentation of the fundamentals of phase behavior with reference to hydrocarbons is timely. Study of phase behavior is not new. In the metallurgical field, knowledge of heterogeneous equilibria has advanced tremendously, particularly with reference to solid-solid and solid-liquid behavior. Much is known about vapor-liquid equilibria too, but few engineers are familiar with this subject. Definition of Terms In a discussion of this sort, a definition of terms used is most important. Such terms as "pressure," "temperature" and "volume" need little definition other than mention of the units in which they are considered. Pressure is expressed in pounds per square inch absolute. Temperature is usually expressed as degrees Fahrenheit or degrees Rankine. In considering thermodynamic and phase behavior, the use of the absolute, Rankine, scale is desirable. Volume is expressed as specific volume, such as cubic feet per pound. This will be recognized as the reciprocal of the specific weight. In considering systems composed of more than one component, it is sometimes desirable to consider molal

Jan 1, 1940

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

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

Jan 1, 1944