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By W.M. Peirce

The present work has been done in an endeavor to correlate and complete the data on the constitution of alloys of zinc with other common metals, dealing exclusively, however, with the zinc-rich alloys in which the zinc content is between 90 and 100 per cent. This investigation has included the systems lead-zinc, cadmium-zinc, iron-zinc, copper-zinc, aluminum-zinc, nickel-zinc, manganese-zinc, cobalt-zinc, tin-zinc, and magnesium-zinc. The important ternary system zinc-lead-cadmium and the zinc corners of other ternary systems have been investigated in connection with this work but will not be dealt with here. Zinc does not form a single homogenous zinc-rich solid solution over any considerable range of concentration with any of the metals mentioned. A limited range of solid solubility is said, by previous investigators, to occur in several cases and certain effects on the properties of zinc are attributed (with varying degrees of consistency among different writers) to the presence of certain other metals dissolved in zinc. The increasing use of rolled zinc and the possibilities offered by zinc as a casting alloy in certain fields have made it essential to determine precisely these equilibrium relationships. In carrying out this investigation reliance was placed chiefly on two methods, conductivity measurements and microscopic analysis. The first method proved valuable in determining the existence and extent of solid solubility. The second method stands alone as a means of determining structural characteristics and supplements the first method in the measurement of solid solubility. The scleroscopic hardness of all conductivity specimens was measured partly for its value from the point of view of mechanical properties and partly as a check on the conductivity curves in indicating the limits of solid solubility. No hardness curves are included in this paper, for in no case were they important in arriving at the constitution of any system. Conductivity measurements were in all cases made on cold-rolled strips 0.020 in. thick and 0.5 in. wide, both as cold rolled and after an

Jan 1, 1923

By W. M. Peirce

The present work has been done in an endeavor to correlate and complete the data on the constitution of alloys of zinc with other common metals, dealing exclusively, however, with the zinc-rich alloys in which the zinc content is between 90 and 100 per cent. This investigation has included the systems lead-zinc, cadmium-zinc, iron-zinc, copper-zinc, aluminum-zinc, nickel-zinc, manganese-zinc, cobalt-zinc, tin-zinc, and magnesium-zinc. The important ternary system zinc-lead-cadmium and the zinc corners of other ternary systems have been investigated in connection with this work but will not be dealt with here. Zinc does not form a single homogenous zinc-rich solid solution over any considerable range of concentration with any of the metals mentioned. A limited range of solid solubility is said, by previous investigators, to occur in several cases and certain effects on the properties of zinc are attributed (with varying degrees of consistency among different writers) to the presence of certain other metals dissolved in zinc. The increasing use of rolled zinc and the possibilities offered by zinc as a casting alloy in certain fields have made it essential to determine precisely these equilibrium relationships. In carrying out this investigation reliance was placed chiefly on two methods, conductivity measurements and microscopic analysis. The first method proved valuable in determining the existence and extent of solid solubility. The second method stands alone as a means of determining structural characteristics and supplements the first method in the measurement of solid solubility. The scleroscopic hardness of all conductivity specimens was measured partly for its value from the point of view of mechanical properties and partly as a check on the conductivity curves in indicating the limits of solid solubility. No hardness curves are included in this paper, for in no case were they important in arriving at the constitution of any system. Conductivity measurements were in all cases made on cold-rolled strips 0.020 in. thick and 0.5 in. wide, both as cold rolled and after an

Jan 1, 1923

By C. P. Kempter

AS part of a continuing program of liquid metals research, the densities of liquid lead, tin, zinc, cadmium, and indium have been measured by a pycnometric method. The pycnometers are made of high-density graphite to the design illustrated in Fig. l(a). In pursuing this research program, emphasis has been placed on detailed experimental care. As a result, claims are made for densities accurate to within ± 0.05 pct over temperature ranges varying from about 100± to 200°C above the melting point. A paper reporting the densities of tin, lead, and Pn-Sn alloys has recently been published,' while papers dealing with

Jan 1, 1969

By Emile Gyss

THE speed of drilling rock has become an impor-tant factor in mining operations, while the place-ment of holes, kind, and quantity of explosive used. are equally important. These are a function of the rock hardness and toughness. Both of these fac-tors must be considered in compiling a table that will enable a mine operator or engineer to estimate drilling speeds in a given rock, knowing its hardness, and from its toughness, the dynamite required. The hardness of a homogeneous rock may be defined as its resistance to a penetrating medium, such as a drill-steel bit, and toughness, its resistance to with-stand rupture by the tearing apart of its minerals or parts of the same mineral. Rock hardness, as it has here been defined, is a function of the hardness of the component grains composing it, as well as grain size, shape, arrangement, and binding minerals. Rock tough-ness depends on substantially the same factors, but is measured by a totally different method. The units in which rock hardness is usually ex-pressed are either relative values or alphabetical desig-nations which carry no definite quantitative meaning. R. M. Raymond has suggested the measurement of com-posite rock hardness, based on mineral hardness as ob-tained by the Moh scale. This is done by multiplying the percentage of each mineral in a rock by the Moh mineral hardness and dividing by 100. These values convey a clearer conception in the minds of men in-terested in rock work -and are the basis of the units used in Tables 1 and 2. The hardness of rocks as it has been variously de-fined may be determined by different methods. The first method is one in which the proportionate average of the hardness of minerals making up a rock is the basis for classification. The other factors of grain size, shape, arrangement, and binding power are not considered.

Jan 6, 1927

By E. A. Anderson

THE copper-zinc phase equilibrium diagram has been the sub-ject of many investigations. Until recently, however, the boundary of the terminal solid solution of copper in zinc (eta) has not been thoroughly investigated. This paper reports determinations of the solid solubility of copper in zinc at temperatures from 100° to 400° C., the course of the liquidus and solidus for the eta solid solution and determinations of the peritectic temperature and peritectic point for the reaction between epsilon and the melt to form eta. The liquidus of the eta phase was determined by thermal analysis and the solidus by the microscopical examination of specimens quenched from temperatures above and below the solidus. The temperature of the peritectic horizontal was obtained by thermal analysis and the com-position at the peritectic point was determined by extrapolation of the solid solubility boundary of the eta phase to the peritectic horizontal. The solid solubility boundary of the eta solid solution was investigated very carefully. Particular care was used to achieve equilibrium in the alloys at each temperature selected. The X-ray, electrical con-ductivity and microscopical methods were used in determining the solid solubility limits. The X-ray method measures the changes in the solvent lattice with increasing solute content and in this manner locates the composition of the alloy at which no further change in the solvent lattice takes place, the limit of solid solubility. The method of electrical conductivity measures the conductivity of the alloys of a graded series of compositions, whereby the solubility limit is indicated by a discontinuity in the conductivity-

Jan 1, 1934

By W. E. Bergman, P. G. Carpenter, H. B. Fisher

The conditions under which barium carbonate can be used to remove sulfates from drilling muds are limited The amount of sulfate remaining in solution in the system after treatment with barium carbonate is shown to be a function of the concentration of the carbonate and barium ions and the concentration of other electrolytes. Barium hydroxide may advantageously replace barium carbonate when the contamination is not entirely due to anhydrite (calcium in the system is then stoichiometrically less than sulfate) or when the carbonate concentration is high. The effect of substances such as quebracho, phosphates, and chromates, which form complexes or precipitates with barium, is discussed. INTRODUCTION As the complexity of the operations in drilling for oil has increased, more attention has of necessity been directed to the problems pertaining to the maintenance of good drilling mud properties. As a result, chemical treatment of muds has become an important factor in recent years. Some of these treatments have been designed to eliminate the deleterious effects of contaminants in aqueous mud systems by precipitation or other means. The most common of substances encountered during drilling include sodium chloride, cement, and calcium sulfate while various other contaminants: usually in small amounts, may be introduced from the water, clays, and other materials used in preparation of the mud. In certain cases, for example where continued salt-water flow is encountered or massive anhydrite is drilled, special muds may be used so that the physical properties of the mud will remain satisfactory for drilling. In other cases, it is desirable to remove the contaminants so that soluble electrolytes in the system are maintained at low values. For sulfate contamination, the conlmon practice in the field is to add barium carbonate to precipitate the sulfate as barium sulfate Ordinarily such a procedure gives satisfactory results. There have been important instances, however, where addition of barium carbonate was not effective in removal of soluble sulfates from drilling muds. and it is to these cases that the present paper is directed. While it is generally known that barium carbonate is not always effective in removing soluble sulfates from drilling muds, certain inconsistencies appear in the literature as to the limitations of its use, and little explanation for the limitations are given. Varnell and Kimbrel state that "the treatment (with barium carbonate for removal of sulfate) is simple and consists in maintaining a pH of 9 with caustic soda and quebracho." They caution that concentrations of quebracho greater than 1 lb./bbl. may inhibit the reaction. In another publication', a pH of 10.5 is considered "the maximum desirable," and the indication is that as much as 2.5 lb. quebracho per barrel may be present in the particular mud under discussion. Lancaster and Mitchell5 state that appreciable amounts of phosphates in the mud will inhibit the reaction with barium carbonate and that the phosphate treatment should be discontinued at least 24 hours before addition of the carbonate. Experimental work was initiated to ascertain the factors involved in using barium carbonate for the removal of sulfate contamination in drilling muds. While the experimental data herein reported are limited, they focus attention on the pertinent factors which must be considered for successful treatment. These factors are discussed from a practical and a theoretical view, the latter being supported by equilibrium data found in the literature. Further, it will be appreciated that the factors involved in this specific study will be closely analogous to those in certain of the other chemical treatments which involve a precipitation of the soluble contaminant. A thorough comprehension of these factors should result in a more fruitful application of this type of chemical reaction to the treatment of drilling muds. EXPERIMENTAL A. Reagents Two muds were used during this investigation. For one series of tests, bentonite suspensions were prepared by dilution of a stock suspension containing 8 per cent by weight of bentonite (Aquagel). For another series, a 6.4 per cent ben-tonitic mud weighted to 9.7 lb./gal. with barium sulfate (Mag-cobar) was used. Distilled water was used in all preparations. The quebracho (72% tannin extract) was obtained from the Thompson-Hayward Co. of Tulsa and contained 11.4 per cent moisture (105 C.). All other materials were reagent grade, and concentrations were corrected for water of crystallization, if any. All concentrations are expressed in pounds per barrel (42 gallons). B. Technique The systems — either mud or water — were contaminated with either sodium or calcium sulfate after treatment with the desired amounts of sodium hydroxide and quebracbo. For treatments with barium carbonate an approximately 3-fold excess (5 lb./bbl.) was used over that computed to be required to precipitate all the sulfate as barium sulfate. Barium hydroxide was used in concentrations of 2 lb./bbl. — about

Jan 1, 1949

By P. G. Carpenter, H. B. Fisher, W. E. Bergman

The conditions under which barium carbonate can be used to remove sulfates from drilling muds are limited The amount of sulfate remaining in solution in the system after treatment with barium carbonate is shown to be a function of the concentration of the carbonate and barium ions and the concentration of other electrolytes. Barium hydroxide may advantageously replace barium carbonate when the contamination is not entirely due to anhydrite (calcium in the system is then stoichiometrically less than sulfate) or when the carbonate concentration is high. The effect of substances such as quebracho, phosphates, and chromates, which form complexes or precipitates with barium, is discussed. INTRODUCTION As the complexity of the operations in drilling for oil has increased, more attention has of necessity been directed to the problems pertaining to the maintenance of good drilling mud properties. As a result, chemical treatment of muds has become an important factor in recent years. Some of these treatments have been designed to eliminate the deleterious effects of contaminants in aqueous mud systems by precipitation or other means. The most common of substances encountered during drilling include sodium chloride, cement, and calcium sulfate while various other contaminants: usually in small amounts, may be introduced from the water, clays, and other materials used in preparation of the mud. In certain cases, for example where continued salt-water flow is encountered or massive anhydrite is drilled, special muds may be used so that the physical properties of the mud will remain satisfactory for drilling. In other cases, it is desirable to remove the contaminants so that soluble electrolytes in the system are maintained at low values. For sulfate contamination, the conlmon practice in the field is to add barium carbonate to precipitate the sulfate as barium sulfate Ordinarily such a procedure gives satisfactory results. There have been important instances, however, where addition of barium carbonate was not effective in removal of soluble sulfates from drilling muds. and it is to these cases that the present paper is directed. While it is generally known that barium carbonate is not always effective in removing soluble sulfates from drilling muds, certain inconsistencies appear in the literature as to the limitations of its use, and little explanation for the limitations are given. Varnell and Kimbrel state that "the treatment (with barium carbonate for removal of sulfate) is simple and consists in maintaining a pH of 9 with caustic soda and quebracho." They caution that concentrations of quebracho greater than 1 lb./bbl. may inhibit the reaction. In another publication', a pH of 10.5 is considered "the maximum desirable," and the indication is that as much as 2.5 lb. quebracho per barrel may be present in the particular mud under discussion. Lancaster and Mitchell5 state that appreciable amounts of phosphates in the mud will inhibit the reaction with barium carbonate and that the phosphate treatment should be discontinued at least 24 hours before addition of the carbonate. Experimental work was initiated to ascertain the factors involved in using barium carbonate for the removal of sulfate contamination in drilling muds. While the experimental data herein reported are limited, they focus attention on the pertinent factors which must be considered for successful treatment. These factors are discussed from a practical and a theoretical view, the latter being supported by equilibrium data found in the literature. Further, it will be appreciated that the factors involved in this specific study will be closely analogous to those in certain of the other chemical treatments which involve a precipitation of the soluble contaminant. A thorough comprehension of these factors should result in a more fruitful application of this type of chemical reaction to the treatment of drilling muds. EXPERIMENTAL A. Reagents Two muds were used during this investigation. For one series of tests, bentonite suspensions were prepared by dilution of a stock suspension containing 8 per cent by weight of bentonite (Aquagel). For another series, a 6.4 per cent ben-tonitic mud weighted to 9.7 lb./gal. with barium sulfate (Mag-cobar) was used. Distilled water was used in all preparations. The quebracho (72% tannin extract) was obtained from the Thompson-Hayward Co. of Tulsa and contained 11.4 per cent moisture (105 C.). All other materials were reagent grade, and concentrations were corrected for water of crystallization, if any. All concentrations are expressed in pounds per barrel (42 gallons). B. Technique The systems — either mud or water — were contaminated with either sodium or calcium sulfate after treatment with the desired amounts of sodium hydroxide and quebracbo. For treatments with barium carbonate an approximately 3-fold excess (5 lb./bbl.) was used over that computed to be required to precipitate all the sulfate as barium sulfate. Barium hydroxide was used in concentrations of 2 lb./bbl. — about

Jan 1, 1949

By E. T. Stephenson

Wert and Marx1 pointed out that a straight-line relationship exists between the activation energy of a relaxation process and the temperature at which the maximum relaxation occurs. The data available at the time indicated that this relationship held for a number of Snoek peaks, several grain boundary peaks, and pair relaxation in a brass. Theoretical justification for the observed relationship was found in the following equation, which Wert and Marx derived from the theory of interstitial atomic diffusion coefficients:' where AH is activation energy, R is the gas constant, T is the internal friction peak temperature, v is the interstitial atomic frequency, f is the frequency of the applied stress, S is entropy of activation. More accurate internal-friction data on interstitial diffusion in bcc metals have become available since Wert and Marx's paper. Table I gives activation energies calculated by several authors from a combination of elastic aftereffect data and the peak temperatures at several frequencies of measurement. (In the case of Fe-C and Fe-N, the referenced authors5'7'8'10 also used high-temperature diffusion data.) However, diffusion experiments at 150°C and above1'-13—rather than anelastic techniques—were used to determine the activation energy of hydrogen diffusion in Fe-H. In order to plot this recent data as a AH vs T graph we calculated the peak temperatures of the systems listed in Table I (with the exception of Fe-C, Fe-N, and Fe-H) by using published values3'' of AH and Do. These calculated peak temperatures varied by only a few degrees from experimentally determined peak temperatures. The calculated values were felt to represent the better average. A number of investigators have found the peak temperatures in Fe-C and Fe-N to be 38 to 40°C and 20° to 24°C, respectively. The values of 39" and 22°C (312° and 295°K in Table I) were determined by carefully executed experiments.6'8 The hydrogen peak temperature has been measured at 1 cps,12 20 cps,14 and 35,000 cps.15 All hydrogen peak temperatures were adjusted to 1 cps for Table I using AH = 3000 cal per mole. As Fig. 1 shows, the data of Table I fit a straight line at least as well as the earlier data used by Wert and Marx. Linear-regression analysis was applied to the data in Table I. The Fe-H data was omitted because the activation energy has not been experimentally determined in the temperature range of the peak. The analysis yields the equation: with a standard error of 860 cal per mole. The agreement of the data in Table I with the Wert-Marx equation is excellent. Strict application of Eq. [I] forces the linear regression analysis through the origin. In this case, the analysis gives a slope of 62.1 cal per mole per deg, and a standard error of *890 cal per mole. With this value, it follows from internal-friction theory that Hence, Do varies by only 30 pct among these bcc-interstitial systems. Thus, a concept suggested originally by Wert and Marx1 is confirmed by recently published data. The

Jan 1, 1965

By Frederick N. Rhines, Robert F. Mehl

IT has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), ‡ in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Zedele and of Zedele.§ These data are essentially for one temperature alone and do not furnish any information on the variation of the activation heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a singles olid solution field. 11 Much of the argument concerning the properties of metals that determine D and Q has been drawn from data in which variations of the quantities with concentration are unknown, for these data have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concentrations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

When the writer first began his search for the early history of coal he was amazed at the paucity of information in literature about it, and while after six years many of the reasons for such a scarcity are understood, there are still many cases, even within the last two centuries, when one who can appreciate the tremendous part coal has played in the development of modern times, finds it hard to realize how little attention was paid to this material in those early clays. Occasionally a traveller or observer is found who foresaw how valuable coal was to be when industries were developed, but these were few and to most of those recording its occurrence it was just another mineral. George Washington was farsighted in his view of the development of this country and the need for means of transportation across the mountain barrier, but it was at least sixteen years after he must first have known of coal before he made any reference to it in his journals. He did, however, knowingly or not, select some valuable coal properties in the lands lie obtained in the West. This was then almost entirely an agricultural country, and what industries there were found a great abundance of wood fuel within easy access, there were no steam plants, and all iron was made with charcoal; in fact, the "captive mines" of the iron industry then were large timber "plantations," and when these were exhausted the furnace usually was abandoned and another one built elsewhere, as transportation of charcoal was quite expensive. Along the seaboard the cities and industries began to import coal from England and Nova Scotia early in the eighteenth century, but until the war of the Revolution began the total quantity of coal used yearly in this continent did not exceed nine thousand tons. In 1800 only two places, Pittsburgh and Richmond, Virginia, were using coal to any extent for domestic purposes and it was much later. than this that the amount of coal used in Philadelphia, New fork, and Boston exceeded that of wood. Practically all of the early travellers and writers mentioning coal are noted in the following pages. Several Englishmen who were evidently familiar with its use and value at home, mention its presence as being of great future promise to the young nation, but to nearly all it was more or less of a curiosity and the smoke caused by its use an abomination, and it

Jan 1, 1942

By F. Pošepný

Part I.—General Facts and Theories. PAGE 1. Systems of Classification Employed Hitherto, . . 199 2. Standpoint and View of the Present Paper, . . . 206 3. The Xenogenites in General, ...207 4. The Subterranean Water-Oirculation, . . . 212 A. The Vadose Underground Circulation, . . . 213 Filling of Open Spaces Formed by Vadose Circulation, . . 217 B. The Deep Underground Circulation, . 220 Ascending Waters Encountered in Mines, , 222 Related Phenomena near the Surface, . 225 Mineral Springs at the Surface,. . 230 Chemical Constitution of Mineral Waters, . 232 Minute Metallic Admixtures in Mineral Waters, . . . 238 Alterations Produced by Mineral Springs, . 240 Structural Features of the Deposits of Mineral Springs, . . 244 5. Origin of Ore-Deposits in the Deep Region, . . . 247 Manner of Filling of Open Spaces in General, . . . 254 Part II.—Examples or Classes of Deposits. 1. Ore-Deposits in Spaces of Discission, .. 264 General Features and Illustrations, a. Ore-Veins in Stratified Rocks, .. 269 Clausthal, 269; Andreasberg, 270. b. Ore-veins in the Neighborhood of Eruptive Masses, 271 The Erzgebirge, 271; Przibram, 272. c. Ore-Veins Wholly Within Large Eruptive Formations, 274 Hungary, 274; Dacian Gold-field. 275; Verespatak, 276; Vulkoj, 276 ; Comstock lode, 278.

Jan 1, 1894

By N. Christensen, B. Augland, T. H. Johansen

Samples of an Fe-Nb alloy were brought to equilibriurtr with hydrogen-methane mixtures in the temperature range from 950° to 1050°C, and subsequently analyzed on their carbon contents. The solubility pvoduct L = [%Nb] [%C] may be represented by the equation Approximate solubilities indirectly assessed through hardness measurements have been included from a previous report. These data are shown to be in a fair agreement with the present solubility measurements. IN an investigation based on hardness measurements by de Kazinczy, Ms, and pachleitnerl the molal heat of solution of NbC was estimated to 11.5 kcal per mole. This value was considered rather small, and an investigation using a similar technique was carried out. The results indicated a heat of solution about 35 kcal per mole.2 At this stage it was decided to determine the solubility under conditions of true equilibrium . During the course of this work a similar investigation was published by Smith. 3 His heat of solution, 41.6 kcal per mole, is not very different from the value resulting from the present work (42.5 kcal per mole). Our solubility product, on the other hand, is at considerable variance with that reported by Smith. Possible reasons for these differences are discussed below. Mori, Tokizane, and saheki 7 have studied the behavior of niobium in commercial steels, with special attention to the formation of niobium carbide, nitride, and sulfide. Assuming a carbide composition Nbco.87 based on X-ray diffraction and chemical analysis of residues extracted from Fe-Nb-C-S alloys, the molal heat of solution of niobium carbide was estimated to 35.2 kcal per mole. MATERIALS AND EQUIPMENT The chemical analysis of the materials is given in Table I. Electrolytic iron* was used in the preparation of

Jan 1, 1968

By L. W. Davies

A problem often encountered is the provision of materials which have impurity contents below a certain specified level. This problem is in some cases solved by making use of the segregation of the impurity with respect to the liquid and solid states of the material: an ingot of the material is subjected to directional solidification and the ends of the ingot. which are richer in solutes which respectively raise and lower the melting point of the solvent, are removed. An important extension of this process is the zone-refining process invented by pfann,' in which molten zones are passed successively along the length of an ingot and displace solutes towards the ends. Pfann's process is particularly appropriate in cases for which the segregation coefficient k does not differ greatly from unity, or when the impurity content must be kept extremely low (-=,6 atom fraction); it is widely used, particularly in the purification of materials for use in semiconductor electronic devices. It is the purpose of this paper to investigate theoretically the efficiency of the above refining processes; that is! we determine the most economic method of attaining a given yield of solvent of specified purity, taking into account the variables of the process. One variable of interest is the effective value of the segregation coefficient. which depends on the rate of movement of the liquid-solid interface and on the degree of stirring in the liquid; in addition to this, in the zone-refining process we are also interested in the choice of zone length for most efficient operation. A mathematical determination is made here of the lengths of successive molten zones which give, for an initially uniform distribution, the most efficient removal of a solute of arbitrary distribution coefficient. In order to be able to give a quantitative treatment of efficiency, we first define figures of merit applicable to a given distribution of solute. FIGURE OF MERIT Let an ingot of length L contain a distribution y(x) of solute: we confine our discussion to mono-tonic distributions, in order to avoid inconsistencies in the subsequent analysis. The first moments of the distribution about the origin and x = L are respectively L F = hy{x)dx [I] G = f(L -x)y(x)dx = YoL2-F, [21 where yoL is the total amount of solute present. We shall see that the quantities F and G are useful figures of merit for a discussion of the efficiency of zone-refining processes. In the first place, it is

Jan 1, 1960

By L. W. Davies

A problem often encountered is the provision of materials which have impurity contents below a certain specified level. This problem is in some cases solved by making use of the segregation of the impurity with respect to the liquid and solid states of the material: an ingot of the material is subjected to directional solidification and the ends of the ingot. which are richer in solutes which respectively raise and lower the melting point of the solvent, are removed. An important extension of this process is the zone-refining process invented by Pfann,' in which molten zones are passed successively along the length of an ingot and displace solutes towards the ends. Pfann's process is particularly appropriate in cases for which the segregation coefficient k does not differ greatly from unity, or when the impurity content must be kept extremely low (=10-6 atom fraction); it is widely used, particularly in the purification of materials for use in semiconductor electronic devices. It is the purpose of this paper to investigate theoretically the efficiency of the above refining processes; that is! we determine the most economic method of attaining a given yield of solvent of specified purity, taking into account the variables of the process. One variable of interest is the effective value of the segregation coefficient. which depends on the rate of movement of the liquid-solid interface and on the degree of stirring in the liquid; in addition to this, in the zone-refining process we are also interested in the choice of zone length for most efficient operation. A mathematical determination is made here of the lengths of successive molten zones which give, for an initially uniform distribution, the most efficient removal of a solute of arbitrary distribution coefficient. In order to be able to give a quantitative treatment of efficiency, we first define figures of merit applicable to a given distribution of solute. FIGURE OF MERIT Let an ingot of length L contain a distribution y(x) of solute: we confine our discussion to mono-tonic distributions, in order to avoid inconsistencies in the subsequent analysis. The first moments of the distribution about the origin and x = L are respectively L F = hy{x)dx [I] G = f(L -x)y(x)dx = YoL2-F, [21 where yoL is the total amount of solute present. We shall see that the quantities F and G are useful figures of merit for a discussion of the efficiency of zone-refining processes. In the first place, it is

Jan 1, 1960

By Frederick N. Rhines, Robert F. Mehl

It has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Jedele and of Jedele. 8 These data are essentially for one temperature alone and do not furnish any information on the variation of the activation heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a single solid solution field. 11 Much of the argument concerning the properties of metals that determine D and Q has been drawn from data in which variations of the quantities with concentration are unknown, for these data have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concentrations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

By Frederick N. Rhines, Robert F. Mehl

It has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Jedele and of Jedele. 8 These data are essentially for one temperature alone and do not furnish any information on the variation of the activation heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a single solid solution field. 11 Much of the argument concerning the properties of metals that determine D and Q has been drawn from data in which variations of the quantities with concentration are unknown, for these data have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concentrations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

By W. E. Forsythe

WHEN measuring ordinary temperatures, the instrument is generally placed in very close contact with the body the temperature of which is desired. However, if the temperature of the source is continually raised, a point is soon reached where no known substance will, in general, remain constant in any of its temperature-measuring properties if placed in direct contact with the source. Also, it is occasionally necessary to measure the temperature of a source that 'is so small or so situated that it would be very hard to bring the measuring instrument into direct contact with the source. When these conditions exist, advantage is taken of the well-known fact that all bodies, when at sufficiently high temperatures, send out radiation in amounts readily measurable. This radiation has been found to be related to the temperature. The temperatures of very hot bodies have probably always been judged by the color, or the brightness, of the light given off. With practice, one can estimate probably within 50° to 100° C. of the correct value. However, if judgment is left to the eye alone, very much larger errors are sometimes made, due to

Jan 9, 1919

By W. H. Adams

Shortly after becoming one of the van-guard of mine-developers in the State of Virginia, during the year 1883, I called the attention of the Institute to certain deposits of pyrites, which have been largely worked since. In all cases these deposits are covered with iron-ore (limonite), extending 40, 50 or 60 feet from surface to water-level. The several classes of brown iron-ores are found almost continuously along a prominent ridge of mineral-bearing slates, which can be traced from the James river northeasterly to the North Anna, the Rappahannock and the Potomac rivers, crossing the counties of Louisa, Spottsylvania and Stafford. Outcrops are plainly discoverable from end to end of this belt, also, in places, to the right and left of it, and at intervals there are evidences of workings, some of them for known purposes and others of unknown age and meaning. These old workings have an interest aside from the minerals they may contain or may have yielded. I have been engaged during the past five years in the collection of facts concerning them, which might determine definitely the site of those iron-furnaces, placed by tradition within reach of " the towne called Germanna," which were the first ever built in this State or on this continent. The events which led to the establishment of this important industry are sufficiently narrated in a paper written by Mr. R. A. Brock, Secretary of the Virginia Historical Society, and printed in the Proceedings of the National Museum, 1885, page 77, from which I quote the following : " To Virginia, the first of the English settlements in America, belongs the honor of inaugurating within her limits, as a colony, that most important industry, iron manufacture. "The London Company contemplated a variety of manufacturing enterprises from the very beginning of its authority; prominent among them was that of iron. In 1610 Sir Thomas Gates testified before the council of the Company at London, that in Virginia ' there were divers minerals, especially iron-oare,' lying upon the

Jan 1, 1892

By A. B. Kinzel

ALTHOUGH the iron-carbon diagram has undergone many changes in the last 20 years, the region below the eutectoid line and up to approxi-mately 1.7 per cent carbon has been little affected. This region is generally considered to consist of cementite and ferrite. Graphite has been noted occasionally in the hypereutectoid steel region, and the ready formation of graphite nodules in malleable cast iron is a phenomenon difficult to interpret in the light of cementite, supposedly stable at sub-eutectoid temperatures. In this case the graphite formation has been partly explained by the presence of silicon, and many have believed that silicon acts to change the stable state rather than to accelerate reactions so as to arrive at the stable state in a briefer period of time. Consider-ation of this phenomenon indicates that cementite is not the stable phase in the temperature composition zone referred to. In the course of examining a low-carbon steel tube taken from a petroleum cracking still, which had been in service for approximately three years at temperatures somewhat below the eutectoid temperature, observations were made that shed light on this entire subject. The tube in question analyzed:1 C, 0.15 per cent; Mn, 0.49; Si, 0.02; S, 0.023; P, 0.015. The microstructure of the tube after service is shown in Figs. 1 and 2. From these it is evident that cementite as such is absent, and that in its place nodular graphite has been formed. In order to check this observation further, samples taken from the tube were heated at 850° C. for varying periods of time. The small samples were put into a large hot furnace, and the total time is recorded. The structure of the

Jan 1, 1934

By T. A. Rickard

"The chief aim in style ought to be absolute precision", said Flaubert. "There is only one noun that can express your idea, only one verb that can set that idea in motion, and only one adjective that is the proper epithet for that noun." Let this be your motto. The engineer tries to be exact in all his measurements; he should measure his language with similar exactness. The technical term is a word of precision. It is not only precise, it is a word-saver. To the unscientific the earth is "a ball slightly flattened at the poles, something like an orange". To the scientific it is "an oblate spheroid". A similar contrast between the precision of the technical term and the vagueness of common words is afforded by a conversation between Ivanhoe and Rebecca: "' What device does he bear on his shield?' asked Ivanhoe. 'Something resembling a bar of iron, and a padlock painted blue on a black shield.' 'A fetterlock and shacklebolt azure', said Ivanhoe "-using the technical terms of heraldry. It is good style in writing, however, to adapt your manner of expression to the intelligence and experience of the person or persons to whom the writing is addressed. The description of a mine should be worded differently according as it is intended to inform a mining engineer, a director, or a bishop. REMEMBER THE READER. It is as incorrect to write in a technical way for a non-technical reader as to write in a popular way for a technical or scientific reader. That style is best which enables the writer to place himself in the closest mental touch with his reader, to establish the maximum of sympathetic understanding. Let your precision be\ proportioned to your accuracy. You should not try to be precise in matters that do not admit of

Jan 1, 1931