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By Jos. J. Walsh

Ventilation within a coal mine is essential to the welfare of those employed therein, from the standpoint of health, safety, and efficiency. While the saving of life and the preserving of health are the chief reasons for ventilation, efficiency and production are increased. In spite of the fact that we speak of air as having a certain composition, the proportions of oxygen, nitrogen, and carbon dioxide are not fixed, but vary between small limits. The different elements are not chemically united, they are merely mixed and each is free and can be separated with little energy. For this reason air in the mine workings is seldom found in a pure state. Factors that necessitate ventilation in coal mines are those that change the composition of pure air. Contamination of mine air results from the burning of oil-fed flames, the use of explosives, the oxidation of coal, and the liberation of gases by the coal. The extent to which these factors exist governs the size and general plan of the ventilating applianccs required. An efficient ventilating system is one that will furnish air at the working faces in sufficient volume to dilute and render harmless noxious gases and at the same time maintain an oxygen content closely approaching that of pure air. In a well-ventilated mine, the oxygen seldom falls more than 0.5 per cent. below normal. The carbon-dioxide content of the air in the average coal mine will vary from 0.1 to about 0.8 per cent., which amounts are not harmful. Three per cent. of carbon dioxide in air doubles the frequency and the depth of breathing; it is plainly noticeable and if breathed continuously for several hours its effect would probably be harmful. Slight reductions in the oxygen content of the air, such as occur in well-ventilated mines, have no debilitating effect on the worker. A person not exerting himself would fail to observe any unusual physical effect in an atmosphere: containing 17 per cent. of oxygen. This condition, however, or even a condition showing an oxygen content below 20 per cent., would indicate poor ventilation and that the elements which tend to reduce the efficiency of the worker are present, namely water vapor and a high wet-bulb temperature.

Jan 1, 1923

By Jos. J. Walsh

Ventilation within a coal mine is essential to the welfare of those employed therein, from the standpoint of health, safety, and efficiency. While the saving of life and the preserving of health are the chief reasons for ventilation, efficiency and production are increased. In spite of the fact that we speak of air as having a certain composition, the proportions of oxygen, nitrogen, and carbon dioxide are not fixed, but vary between small limits. The different elements are not chemically united, they are merely mixed and each is free and can be separated with little energy. For this reason air in the mine workings is seldom found in a pure state. Factors that necessitate ventilation in coal mines are those that change the composition of pure air. Contamination of mine air results from the burning of oil-fed flames, the use of explosives, the oxidation of coal, and the liberation of gases by the coal. The extent to which these factors exist governs the size and general plan of the ventilating applianccs required. An efficient ventilating system is one that will furnish air at the working faces in sufficient volume to dilute and render harmless noxious gases and at the same time maintain an oxygen content closely approaching that of pure air. In a well-ventilated mine, the oxygen seldom falls more than 0.5 per cent. below normal. The carbon-dioxide content of the air in the average coal mine will vary from 0.1 to about 0.8 per cent., which amounts are not harmful. Three per cent. of carbon dioxide in air doubles the frequency and the depth of breathing; it is plainly noticeable and if breathed continuously for several hours its effect would probably be harmful. Slight reductions in the oxygen content of the air, such as occur in well-ventilated mines, have no debilitating effect on the worker. A person not exerting himself would fail to observe any unusual physical effect in an atmosphere: containing 17 per cent. of oxygen. This condition, however, or even a condition showing an oxygen content below 20 per cent., would indicate poor ventilation and that the elements which tend to reduce the efficiency of the worker are present, namely water vapor and a high wet-bulb temperature.

Jan 1, 1923

By Edward W. Mehal

This paper presents a review of the technologies which have been used in the application of III-V compound semiconductors to integrated circuits and arrays. These materials have properties which make them useful for various devices such as: light emitters, sensors, microwave sources, and microwave diodes. Technologies for incorporating these devices into integrated circuits have been reported and processes developed for fabricating planar devices using selective epitaxial deposition or selective diffusions. Isolation methods utilizing semi-insulating GaAs, oxide isolation, and ceramic insulation have also been reported. These techniques, and the devices and circuits produced or proposed are discussed. AFTER the invention of the silicon-integrated circuit, methods for utilizing compound semiconductors for integrated circuit applications were proposed. The scope of applications was potentially much broader because of the range of properties available from these materials. There also was the opportunity of coupling these properties with germanium and silicon devices to realize functions and circuits which could not be produced with silicon monolithic circuits. Table I exemplifies the range of electrical properties available in III-V compound semiconductor materials which are currently being widely used. A wide range of sensor and emitter applications result from the range of band gap. The band structure of GaAs and GaAsxP1-x permits their use as microwave oscillator source, and the high electron mobilities further facilitate their utility in microwave devices. The concept of "integrated functions"1 results from the availability of these materials and methods for utilizing their special properties. Heteroepitaxial growth allows the fabrication of a monolithic block of these materials. Semi-insulating GaAs permits the attainment of electrical isolation between components in a monolithic block without resorting to p-n junction biasing or oxide isolation methods. An "integrated function" is a unit which can perform a system or subsystem role and perform a number of electromagnetic functions. These functions could include sensor or input transducer, signal processing, interconnections, and control or output function. Two examples which demonstrate this concept are an optoelectric processor and a microwave receiver front end. The optoelectronic processor, Fig. 1(a), would consist of a light sensor, signal processor, and output emitter. The sensor could be InSb or InAs which would be IR-sensitive. The signal from this sensor would then be amplified and transmitted to the light emitter. The amplifier could utilize GaAs bipolar or field effect transistors. A Gap emitter would then produce visible radiation. The microwave receiver front end, Fig. l(b), would consist of a local oscillator section and a mixer section. A signal input from an antenna is mixed with the signal from the local oscillator. The local oscillator signal is produced by a Gunn oscillator. The single-ended mixer utilizes one Schottky barrier mixer diode. The IF signal would then be amplified further and suitably displayed. A further extension of the capability of utilizing the

Jan 1, 1969

By D. T. Peters, S. Floreen

The age hardening behavior of an Fe-8Ni-13Mo alloy was studied after the matrix had been varied to produce either ferrite, cold u~orked ferrite, or nzassive nzartensite. The aging behavior of the cold worked ferrite and murtensite structures were very similar. The martensite aging kinetics were much different from those observed in earlier studies of aging of maraging steels, even though the martensite wzatri.r had the same dislocation structure as those found in maraging steels. The results suggest that the previously observed precipitation kinetics of maraging steels ?nay have been controlled by the nucleation be-haviov, which in turn were dictated by the alloy compositions and the resultant identities of the precipitating phases. IT is well known that the rate of precipitation from solid solution depends not only on the degree of super-saturation, but also on the density and distribution of dislocations in the matrix structure. These imperfections often act as nucleation sites, and may also enhance atomic mobility. 'Thus, the presence of dislocations is important since the type and distribution of precipitates may be determined by them. The precipitate density and morphology in turn affects the mechanical properties of the alloy. A number of studies have been devoted to the precipitation characteristics in various types of maraging steels.'-" These are iron-base alloys containing 10 to 25 pct Ni along with other substitutional elements such as Mo, Ti, Al, and so forth, that are used to produce age hardening. The carbon contents of these steels are quite low, and carbide precipitation is not believed to play any significant role in the aging reactions. After solution annealing and cooling these alloys generally transfclrm to a bcc lath or massive martensite structure characterized by elongated martensite platelets that are separated from each other by low angle boundaries, and that contain a very high dislocation den~it~.~~~~~~~~-~~ Age hardening is then conducted at temperatures on the order of 800" to 1000°F to produce substitutional element precipitation within the massive martensite matrix. Most of the aging studies to date have revealed several common traits in these alloys, regardless of the particular identity of the precipitation elements. Generally hardening has been found to be extremely rapid, with incubation times that approach zero. The agng kinetics, at least up to the time when reversion of the martensite matrix to austenite begins to predominate, frequently follow a AX/~~ = ktn type law, where x is hardness or electrical resistivity, t is the time, and k and n are constants. The values of n are frequently on the order of 0.2 to 0.5, which are well below the idealized values of n based on diffusion controlled precipitate growth models. Finally, the observed activation energy values are typically on the order of 30 kcal per mole, and thus are well below the nominal value of about 60 kcal per mole found for substitutional element diffusion in ferrite. The common explanation of these observations is that the precipitation kinetics are controlled by the massive martensite matrix structure. Thus, the absence of any noticeable incubation time has been attributed, after ~ahn," to the fact that the precipitate nucleation on dislocations may occur without a finite activation energy barrier. The low values of the activation energy are generally assumed to be due to enhanced diffusivity in the highly faulted structure. If this explanation that the precipitation kinetics are dominated by the matrix structure is correct then one should observe a distinct difference in lunetics between aging in a martensitic matrix and aging the same alloy when it has a ferritic matrix. Such a comparison cannot be made with conventional maraging compositions, but could be made with the alloy used in the present study. In addition, the ferritic structure of the present alloy could be cold worked to produce a high dislocation density so that one could determine whether ferrite in this condition would age similarly to martensite. EXPERIMENTAL PROCEDURE The composition of the alloy used in this study was 8.1 pct Ni, 13.0 pct Mo, 0.10 pct Al, 0.13 pct Ti, 0.012 pct C, bal Fe. The alloy was prepared as a 40 lb vacuum induction melt. The heat was homogenized and hot forged at 2100°F to 2 by 2 in. bar, and then hot rolled at 1900°F to $ in. bar stock. The aging lunetics were followed by Rockwell C hardness and electrical resistivity measurements. Samples for hardness testing were prepared as small strips approximately 2 by $ by 4 in. thick. Electrical resistivity was studied on cylindrical samples approximately 2 in. long by 0.1 in. diam. The method for making the alloy either martensitic or ferritic was based on the fact that the alloy showed a closed y loop type of phase diagram. At high temperatures, above approximately 24003F, the alloy was entirely ferritic. Small samples on the order of the dimensions described above remained entirely ferritic after iced-brine quenching from this temperature. In practice, a heat treatment of 1 hr in an inert atmosphere at 2500°F followed by water quenching was used to produce the ferritic microstructure. These samples were quite coarse grained and usually en-

Jan 1, 1970

By R. V. Smith

The theory for unsteady radial flow of gas, as simplified by Aronofsky and Jenkins, has been reviewed and compared with actual well performance. This study indicated that the theory should be modified by the introduction of an empirical "rate of flow" function "Y(q)". The expansion of the theory on the flow of gas to include a Y(q) term bridges the gap between the theory of unsteady-state flow of gas and actual gas-well behavior. Apparently, the Y(q) term is a function only of the rate of flow for a given well. The completion factor or skin effect is associated with the Y(q) function in such a manner that at least two or more sets of drawdown or pressure build-up tests are needed to separate the Y(q) function and the completion factor. Since the Y(q) function used in this report represents an energy loss dependent on rate of flow near the well-bore of a gas well which is in addition to the loss required by Darcy's law, the Y(q) function is related to the exponent of the back-pressure curve for a gas well. Techniques and equations are presented which permit the estimation of stabilized and "short-time" deliver-abilities. INTRODUCTION The published theory of radial unsteady-state flow of gas through porous media may be divided into papers1-" which use Darcy's law as a premise and other papers4-7,16-10 which recognize that Darcy's law may not hold for flow into gas wells. Miller8 compared theory based on Darcy's law with actual gas-well behavior and concluded that flow into gas wells deviates from Darcy's law. Houpeurt4,5 in a thorough investigation of flow into gas wells concluded that the flow rate into a gas well is proportional to the difference between the squares of upstream and downstream pressures elevated to a power between 1.0 and 0.5. Houpeurt also concluded that the deviation from Darcy's law is caused by irreversible, kinetic energy exchange between the flowing gas and the porous media. Tek9 presented a complete evaluation of the flow problem in gas wells. Several investigators state that the inclusion of gas compressibility into flow equations based on Darcy's law does not begin to explain the flow problems suggested by gas-well behavior. For many years, natural-gas engineers have realized that gas wells by actual test exhibit behavior which cannot be explained entirely by Darcy's law. Many tests on gas wells have indicated that a value of 0.85 for the exponent in the back-pressure equation is a fair average for many wells. However, Darcy's law either for steady or unsteady-state conditions indicates that the exponent should be 1.0. The purpose of this paper has been to examine this deviation from Darcy's law and to present a reasonable mathematical means of evaluating the deviation. The method presented in this paper combines previous theory with an empirical function to provide a description of gas-well behavior. All equations in this report are for constant terminal-rate-of-flow conditions. While present methods of testing wells usually are not based on this concept, they are believed to approach the constant terminal-rate conditions closely in many tests. However, several gas wells were tested by holding the rates of flow constant in order to approach more closely the constant terminal rate of flow; the results confirm the concepts presented in this paper. REVIEW OF THEORY FOR UNSTEADY-STATE FLOW OF GAS The basic partial differential equation for the flow of natural gas has been given in technical literature; the equation for a cylindrical reservoir with the well in the center is

By W. L. Staker

The Bureau of Mines investigated selective extraction of Au and Ag from a low-grade Au ore containing Hg. Gold and silver were extracted from the ore in cyanide slurries, and Hg extraction was suppressed with sodium or calcium sulfide. Maximum Au extraction and minimum Hg extraction were obtained using solutions containing 0.34 lb NaCN/ton of solution. Increasing the cyanide concentration increased Hg extraction without increasing Au extraction. Mercury extraction from the ore was suppressed with 0.5 to 2.9 lb CaS/lb Hg in the ore. Gold-to-mercury ratios of 100:l to 400:l were obtained in the leach solution, and on the activated carbon in a CIP circuit.

Jan 1, 1984

By J. Russ, C. L. Clark

For many years attempts have been made to develop a laboratory test that would serve to indicate the proper temperatures to be used in the various hot-working applications to which metals may be subjected as they are being processed from the cast ingot to the desired finished products. That these attempts have not been very successful is indicated by the fact that most of the temperatures in use today in these operations have been developed over a period of years by trial and error. In other words, the selection of the proper temperatures for the hot-working of metals is generally an art rather than a science. Our knowledge with respect to the behavior of metals at elevated temperatures has been greatly extended during the past several years. While most of the work in this field has been done at proposed operating temperatures of equipment, rather than at processing or fabricating temperatures, one outstanding fact has been developed, which is applicable to the entire high-temperature range; that is, that the rate of deformation to which the metal is subjected is of the same order of importance as the temperature. The failure to properly recognize this fact has greatly retarded the development of a suitable laboratory test for determining hot-working temperatures. Influence of Rate of Deformation on High-temperature Properties It is not the intent of this paper to survey all the work that has been done On the effect of deformation rate On the properties of metals. The importance of this factor, however, was shown by Zay Jeffries' as early as 1919, when he called attention to the existence of the so-called equicohesive temperature and to the effect of certain factors on the location of this temperature' Fig. I is a diagrammatic sketch showing the effect of temperature On the relative strength of the crystals and grain boundaries and the type of fracture that will res depnding On the location of the test, or Or temperature with respect to the equicOhesive temperature. Since the type fracture varies, it also follows that at temperatures below the equicohesive temperature the major deformation occurs in the grains: while at temperatures above, the deformation results either from the movement of the grains with respect to each other or recrystallization of the strained material occurs almost instantaneously, producing new crystals at the fracture. As previously indicated, it is an established fact that the position of this equicohesive temperature for any given metal is dependent On the deformation rate' For example, in 0.15 per cent plain carbon steel the location of this temperature under

Jan 1, 1947

By C. L. Clark, J. Russ

For many years attempts have been made to develop a laboratory test that would serve to indicate the proper temperatures to be used in the various hot-working applications to which metals may be subjected as they are being processed from the cast ingot to the desired finished products. That these attempts have not been very successful is indicated by the fact that most of the temperatures in use today in these operations have been developed over a period of years by trial and error. In other words, the selection of the proper temperatures for the hot-working of metals is generally an art rather than a science. Our knowledge with respect to the behavior of metals at elevated temperatures has been greatly extended during the past several years. While most of the work in this field has been done at proposed operating temperatures of equipment, rather than at processing or fabricating temperatures, one outstanding fact has been developed, which is applicable to the entire high-temperature range; that is, that the rate of deformation to which the metal is subjected is of the same order of importance as the temperature. The failure to properly recognize this fact has greatly retarded the development of a suitable laboratory test for determining hot-working temperatures. Influence of Rate of Deformation on High-temperature Properties It is not the intent of this paper to survey all the work that has been done On the effect of deformation rate On the properties of metals. The importance of this factor, however, was shown by Zay Jeffries' as early as 1919, when he called attention to the existence of the so-called equicohesive temperature and to the effect of certain factors on the location of this temperature' Fig. I is a diagrammatic sketch showing the effect of temperature On the relative strength of the crystals and grain boundaries and the type of fracture that will res depnding On the location of the test, or Or temperature with respect to the equicOhesive temperature. Since the type fracture varies, it also follows that at temperatures below the equicohesive temperature the major deformation occurs in the grains: while at temperatures above, the deformation results either from the movement of the grains with respect to each other or recrystallization of the strained material occurs almost instantaneously, producing new crystals at the fracture. As previously indicated, it is an established fact that the position of this equicohesive temperature for any given metal is dependent On the deformation rate' For example, in 0.15 per cent plain carbon steel the location of this temperature under

Jan 1, 1947

By C. L. Clark, J. Russ

FOR many years attempts have been made to develop a laboratory test that would serve to indicate the proper temperatures to be used in the various hot-working applications to which metals may be subjected as they are being processed from the cast ingot to the desired finished products. That these attempts have not been very successful is indicated by the fact that most of the temperatures in use today in these operations have been developed over a period of years by trial and error. In other words, the selection of the proper temperatures for the hot-working of metals is generally an art rather than a science. Our knowledge with respect to the behavior of metals at elevated temperatures has been greatly extended during the past several years. While most of the work in this field has been done at proposed operating temperatures of equipment, rather than at processing or fabricating temperatures, one outstanding fact has been developed, which is applicable to the entire high-temperature range; that is, that the rate of deformation to which the metal is subjected is of the same order of importance as the temperature. The failure to properly recognize this fact has greatly retarded the development of a suitable laboratory test for determining hot-working temperatures. INFLUENCE OF RATE OF DEFORMATION ON HIGH-TEMPERATURE PROPERTIES It is not the intent of this paper to survey all the work that has been done on the effect of deformation rate on the properties of metals. The importance of this factor, however, was shown by Zay Jeffries1 as early as 1919, when he called attention to the existence of the so-called equicohesive temperature and to the effect of certain factors on the location of this temperature. Fig. I is a diagrammatic sketch showing the effect of temperature on the relative strength of the crystals and grain boundaries and the type of fracture that will result, depending on the location of the test, or working temperature with respect to the equicohesive temperature. Since the type fracture varies, it also follows that at temperatures below the equicohesive temperature the major deformation occurs in the grains; while at temperatures above, the deformation results either from the movement of the grains with respect to each other or recrystallization of the strained material occurs almost instantaneously, producing new crystals at the fracture. As previously indicated, it is an established fact that the position of this equicohesive temperature for any given metal is dependent on the deformation rate. For example, in 0.15 per cent plain carbon steel the location of this temperature under

Jan 1, 1945

By R. A. Burmeister, G. P. Pighini, P. E. Greene

An open tube vapor phase epitaxial growth system has been used for large area (multiple substrate) growth of GaAs1-xPx on GaAs substrates. The GaCl-GaCl transport reaction is used with either a GaAs or Ga (nonsaturated) source. Selenium and tellurium have been used for donor impurities, and zinc as an acceptor. The useable substrate area in this system is approximately 20 sq cm. The uniformity of thick-ness of the epitaxial layers are typically better than ±5 pct across a given wafer. Electrical and optical measurerments indicute comparable uniformity in electrical and luminescent properties within a wufer. The application of this system to the large scale pro-duction of GaAs1-x Px for display devices, both discrete and arrays, is discussed. Typical electrical and luminescent properties of light emitting diodes fabricated front material produced by this technique are presented. THE most promising materials currently being utilized for visible injection electroluminescence are GaAs1-xPx, Ga1-xAlxAs, and Gap. All have reasonably efficient emissions in the red portion of the visible spectrum at room temperature; Gap also has an efficient green emission.' At present, GaAs1-xPx has a technological advantage over Ga1-xAlxAs and Gap for display applications, since relatively large (several sq cm) areas of GaAs1-xPx suitable for use in electroluminescent devices may be readily grown by vapor phase growth techniques. In contrast, the preparation of Gap and Ga1-xAlxAs for electroluminescent device applications generally employs solution growth techniques which are at present not well suited for the growth of large areas of uniform thickness and doping level. The capability of uniform growth over large substrate areas and the use of multiple substrates is necessary for the practical utilization of electroluminescent devices. This is particularly important when quantity production or monolithic devices are required. Furthermore, in many display applications arrays of light emitting devices are used, the individual elements of which are of a size resolvable by the unaided eye. Thus the overall dimensions of display are substantially larger than those of most semiconductor devices. It is also necessary to achieve a high degree of control over the growth parameters to attain the required degree of reproducibility of materials properties for electroluminescent devices. In the case of GaAs1-xPx it is necessary to accurately and precisely control the phosphorus content of the alloy, both on a macroscopic and microscopic scale, in addition to the parameters generally associated with epitaxial growth such as thickness and doping level. This value is critical, as it has a major effect on the performance of electroluminescent devices. This paper describes the epitaxial growth of GaAsl-xPx suitable for electroluminescent display devices using a system developed specifically for this purpose, and which contains several novel features. The results of studies of selected physical properties of the epitaxial layers are also discussed. Finally, a brief summary is given of the characteristics of display devices fabricated from GaAsl-xPx grown in this system. EXPERIMENTAL A) Reactants. A number of techniques suitable for the vapor phase epitaxial growth of GaAs1-xPx have been reported in the literature.'-' The method selected for this investigation is that in which the Ga is transported by the GaC1-GaCI3 reaction in an open tube process. The results reported here were obtained using either the combination of GaAs, AsC13, and pH3, or Ga, AsH3, pH3, and HC1 as the initial re-actants.* The ASH3 and pH3 were obtained as dilute *Several different sources of supply were used for these reactants, y~elding comparable results._____________________________________________________ mixtures in HZ; the HC1 was obtained from the reduction of AsC13 by Hz at elevated temperatures. Both selenium and tellurium were employed as donor impurities, and zinc as an acceptor impurity. Selenium was introduced in the form of H2Se, tellurium in the form of tellurium-doped GaAs, and zinc in the form of diethy1 zinc. B) Apparatus. The prinicipal difference between the apparatus used in the present study and that of Tietjen and Amick,8 in addition to size and other related design features, is that RE induction heating is utilized in place of resistance heated furnaces. Induction heating was selected for this application because it appears to have several advantages, including: 1) It is possible to keep all fused silica portions of the apparatus at temperatures well below those of the reaction zone, thus minimizing a possible source of contamination. 2) The thermal mass of an induction heated system can be made small, thus reducing the total time required for the growth process. 3) Sharp temperature profiles (desirable for high deposition efficiency) are easily achieved. 4) The volume of the system for a given substrate area can generally be made smaller than a comparable resistance heated unit. This results in shorter time

Jan 1, 1970

By A. W. Schlechten, Ernest J. Breton Jr.

Experiments on the separation of copper and zinc ions by selective action of ion exchange resins showed the carboxylic type to be more effective than the sulphonic resins. The latter demonstrated a greater capacity over a wider pH range. Data show the effectiveness of resins as a means of concentration. IN recent years the restrictions of stream pollution laws and the high price of metals have created an interest in ion exchange as a means for metal recovery. Some applications have proved successful. In Germany during World War 11, 17 tons of copper per day were recovered from rayon mill wastes by means of ion exchange resins;' and for some time in this country a large ion exchange unit has been in operation for the recovery of copper from rayon waste water. The possibilities of applying ion exchange to the recovery of metals occurring in plating rinse water is particularly promising. In most of these applications only the metal being recovered occurs in the waste. The ion exchange resins act merely as a means of concentrating the metals to a point where they can be recirculated. It would be highly desirable to use ion exchange as a means of not only concentrating but also of separating metals. With the exception of the impressive separations accomplished in connection with the atomic energy program, very little has been done on metal separations.' Therefore, an investigation was undertaken at the Missouri School of Mines and Metallurgy to determine if either of the two main types of ion exchange resins could be used to separate metal ions in solution. The selective removal of copper ions from a mixture of copper and zinc on carboxylic and sulphonic-type resins was investigated as a function of flow rate, pH, copper-zinc ratio, and concentration. It was shown that zinc can be separated from copper and that very large ratios of concentration can be obtained using ion exchange resins. Since ion exchange is relatively new to the field of metallurgy, a brief review of the subject will be included. Theory of Ion Exchange A comprehensive theory for ion exchange has not been developed as yet, but the mechanisms are analogous to metathetical reactions: R Na + Cu++ *=? K(SO3)2 Cu + 2Na+ R is the designation for the ion exchange resin. If a copper solution is passed over a resin bed in the sodium form, two ions of sodium will be released for every ion of copper removed. For the most part this reaction follows the laws of mass action and of electrical neutrality. Consequently, if an excess of sodium ions is passed over a bed containing copper, the reactions will be reversed, and the resin will be regenerated to its original form. A few empirical rules governing the exchange reaction have been set forth: 1—In general ions with a high valence will replace ions with a lower valence. 2—Ions having higher activity coefficients have a higher replacement potential. 3—In a series of mono-valent ions, those with the smallest radii of hydra-tion will tend to replace those having larger radii of hydration. 4—Where ions are similar in most respects, those with the higher atomic weight sometimes will take precedence. This last rule is not as definite as some of the others. These rules apply to rather dilute solutions at moderate temperatures and assume all ions to be present in about equal concentrations. Higher concentrations and temperatures may in some cases reverse the normal exchange reactions. Ion exchange materials are unique in that their efficiency increases as the concentration of the solution decreases. For many exchangers, most efficient operation is obtained at concentrations in the order of one thousandths of a percent. Most applications, though, are made in solutions containing considerably higher concentrations than this. Coste9 as shown that ion exchange resins will remove aluminum and iron effectively' from solutions of up to 10 pct chromic acid. Ion Exchange Resins Ion exchange resins are insoluble, porous, resinous structures to which active groups have been attached. Active groups such as (—SO,,)- and (COO)- pick up cations; hence structures saturated with groups such as these are called cation exchangers. Structures saturated with groups such as (—NH,)' which pick up anions, are referred to as anion exchangers. The resinous structure of necessity is resistant to strong acids, bases, oxidizing, and reducing agents, and most of the common organic solvents. An idea of the stability can be gaged from the fact that resins last for many years under constant use without detectable chemical or physical breakdown. The ion exchange reaction is not confined to the surface of these synthetic resins. Its porous structure permits active groups in the center of a particle as well as those on the surface to remove ions. A high capacity resin such as Amberlite IR-120 will remove up to 3.3 lb Cu per cu ft of resin. In this investigation several approaches to the problem of separating copper from zinc by ion exchange were considered. First, if a reagent could be found which would complex one of these metals and not the other, then by passing this reagent through a bed of exchanger containing copper and zinc, the

Jan 1, 1952

By R. G. Webber, F. C. Langenberg

During the course of some magnetic investigations which the authors have under way, six bars of 0.43-carbon steel were tested, a permeameter designed after the Hopkinson yoke type being used. The results obtained were of some interest and although far from complete serve at least to show the necessity for a careful investigation of the previous history of the samples under study as well as the chemical composition. A steel of given chemical composition may assume a great variety of structures, depending on its treatment. Professor Sauveur has devised a very clear and effective means of illustrating this point. The accompanying microphotographs show some of the possible structures assumed by a 0.30 carbon steel (Fig. 1). It is now a well-established fact that a structural change is accompanied by changes in the tensile strength, elastic limit, hardness, etc., and it seems reasonable to assume also, a change in the magnetic properties. Six bars of a 0.43-carbon steel were used, all the bars being taken from the same rod and treated as follows: Bar 1. Heated to 1,100° and cooled in the furnace. Bar 2. Heated to 1,000° and cooled in the furnace. Bar 3. Heated to 900° and cooled in the furnace. Bar 4. Heated to 1,000° and cooled in air. Bar 5. Heated to 900° and cooled in air. Bar 6. Untreated. The bars were then turned to 13 mm. diameter and tested by the Hopkinson yoke method. After testing, three specimens were taken from each bar, one from each end and one from the middle. The homogeneity of the bars was tested in this manner and in no instance could any difference in structure in the three specimens1 be detected. Bars 1 to 3 inclusive are pearlitic in structure. The white areas are ferrite (iron with certain impurities in solution) and the dark areas pearl-

Jan 1, 1915

By Robin O. Williams

Robin 0. Williams (Oak Ridge National Laboratory)— The authors have questioned the degree to which the coherency strains between the iron-rich and chromium-rich phases are isotropic as proposed in Ref. 5 on the basis of the difference between the elastic properties of the two phases. The relative magnitude of the stresses is determined by the moduli as shown by Eqs. [2], [3], and [4] of Ref. 34. However, the moduli of the two phases have no direct bearing on the uniformity of either the stress or strain within either phase. The idea that the strains are isotropic within each phase (but normally of different magnitude and always of different sign) is based entirely upon the experimental observation that X-ray line broadening has not been detected even when the particles become rather large. It has not proven possible to grow the particles sufficiently large that they lose coherency. Based upon this lack of line broadening one can estimate an upper limit for the nonuniformity of the strains within each phase as follows. It is considered possible to detect line broadening if it is as great as 10 pct of the separation of the K, doublet for the (211) line using chromium radiation. The doublet separation would correspond to a total strain of 0.0017 such that the total variation of lattice parameter relative to the average lattice is now k0.05x0.0017 or something less than ± * For the present case the strain in each phase is roughly 0.002 such that the variation of strain within a phase will not exceed 5 pct. It is stated that the expression derived for strengthening for the hydrostatic straining as observed in this system would substantially overestimate the magnitude due to dislocation flexure. This is contrary to the conclusion reached in the original paper34 for the present range of particle sizes. What is the lowest temperature at which a has been observed to form in this alloy? M. J. Marcinkowski, R. M. Fisher, and A. Szirmae (nutlzors' reply)— -Williams' arguments based on X-ray findings for a chromium-rich precipitate and an iron-rich matrix strained to a common lattice parameter are certainly convincing. This being the case, there are no shear components of strain associated with the precipitate-matrix aggregate to interact with the shear components of the dislocation stress fields, contrary to the opinion expressed by the present authors. On the other hand, the present authors, in spite of this error, did not expect the shear interactions to be significant. The chief objection to Williams' model in the present case is that the various segments of the dislocation line are assumed to pass from one potential valley to the next independently of neighboring segments. This is only true for a highly flexible dislocation line, i.e., one whose radius of curvature is something less than the center to center distance between precipitate particles which amounts to about 90A in the present alloy. In order to maintain this curvature, an externally applied shear stress of at least 230,000 lb per sq in. would be required or about four times the observed stress. It is therefore concluded that the dislocation lines move rather rigidly through the lattice. This being the case, the forces on the dislocation resulting from the hydrostatic interaction between the stress fields of the edge-dislocation components and the precipitate particles should average out to zero; that is particles above the below the slip plane produce forces on the dislocation of opposite sign and therefore will cancel when averaged over the entire length of the dislocation. On the other hand, since the dislocation is not perfectly rigid, Williams' model may lead to some strengthening, but far less than that predicted. A second and equally serious objective to using Williams' strengthening model for the present alloys is that profuse wavy slip due to the motion of screw dislocations played a predominant role not only in the unaged alloys but in the fully aged ones as well. Since the screw dislocation has associated with it only shear components of stress the hydrostatic strengthening model no longer applies. In view of these arguments the present authors must reject Williams' model of strengthening as being pertinent to the present alloy system. The present authors have made no detailed study of the lowest temperature at which a forms in the quenched ferritic alloys. None was ever observed n the alloys aged at 500°C so that forma-tion must occur at temperatures higher than this and was therefore not a factor in the present study.

Jan 1, 1965

By Clarence Zener

THE internal friction of nonferrous metals vibrating at low stress amplitudes has so far always been successfully interpreted in terms of inhomogeneities of one sort or another. Examples are the fluctuation of stress across a specimen vibrating transversely,1,2,3 the stress inhomogeneities due to the elastic anisotropy and partial random orientation of the individual crystallites,4,5 localized weak regions introduced by cold-working,6,7 grain boundaries and possibly twinning planes.8,9 Perfect single crystals are, by definition, homogeneous. Actual single crystals usually, perhaps always, contains some imperfections. The present investigation. was undertaken to determine whether the internal friction of single crystals may likewise be attributed to inhomogeneities. This study was made possible through the gift of a large single crystal of 70-30 alpha brass by H. L. Burghoff, of the Chase Brass and Copper Co. The specimen, ½ in. in diameter and 10 in. long, was similar to samples previously described by Mr. Burghoff.10 EXPERIMENTAL METHOD The experimental method used has previously been described in Institute papers.5,6,9 The measure of internal friction adopted here, 1/Q, is (1/p) X the logarithmic decrement, a measure used by some writers, and is also (1/2p) X the specific damping capacity, a measure used by other writers. In all measurements the stress level was kept so low that the measurements were independent of stress level. In all measurements in which the temperature was varied, observations were made as the specimen slowly cooled from its highest temperature. The specimen was vibrated transversely. Observations were made at the funda¬mental frequency and at the first overtone, of about 620 and 1710 cycles per second, respectively. No attempt was made to avoid acoustical losses. EXPERIMENTAL RESULTS The specimen was annealed for several hours at 450°C. The temperature dependence of the internal friction was then determined from room temperature to 400°C. As shown in Fig. 1, the internal friction increased by only a factor of 2 from room temperature to 300°C., then by a factor of l00 during the next 100° interval. These measurements are consistent with the view that the observed internal friction is the superposition of two distinct parts. One, dominant at room temperature, is nearly independent of temperature. This part may be accounted for by acoustical losses and by transverse thermal currents. It was not further investigated. The second part, when plotted in the manner of Fig. I, lies upon a straight line. Therefore it has a heat of activation H; i.e., it varies with temperature as Internal friction e~H/RT [I]

Jan 1, 1942

By Ralph H. Sweetser

AT the end of 1943 the charcoal pig iron capacity of the United States was at the lowest point in over 1110 years, with only one strictly charcoal blast furnace in operation, and all others permanently out of blast except one in Tennessee d reported to he running on part charcoal and part coke. Such a decrease in production has taken place in spite of the O.P A.'s high-premium price on charcoal pig iron of +34 per ton f.o.b. furnace in Michigan. Depletion of the hardwood supply within fifty mlles or inure of the blast furnace is the reason why; the deplorable lack of reforesting is the cause.

Jan 1, 1944

By Lewis T. Wright

It is commonly believed by metallurgists that in copper-smelting, the copper in the slags, which is irreducible by continued " settling," is retained in the form of " prills " of matte. I have frequently held well-settled slag in a molten condition for a long period without being able thereby to reduce the copper-content. The slag acted as though it contained a minimum of dissolved or combined copper that could not be settled out by gravity. I have used reagents, but without satisfying myself in what form this copper existed. The same slags, by fine grinding and elutriation, could not be separated into portions containing more or less copper than the average content. By treating copper-slags in an electric furnace a button of metallic iron and copper was produced, but the high temperature and the strong reducing-action of the furnace mere influences that suggest an explanation of a result not obtainable with ordinary smelting-temperatures. If all the copper in the slag were in the form of copper-matte, and not existing as a dissolved compound with some of the elements of the slag, then the other metals in the matte, such as gold and silver, should occur in the slag in the same ratio to the copper as to the copper in the accompanying matte. This reasoning led me to study the ratio of metals in the products of smelting, and, apart from the issues discussed in this paper, the research has proved both interesting and illuminative. On the assumption of a similar ratio of metals in matte and slag, if the percentage of copper in the slag accompanying a matte containing 50 oz. of silver and 1 oz. of gold per ton of copper was 0.3 per cent., or 96 oz. per toll of slag, there should be found 0.15 oz. of silver and 0.003 oz. of gold per ton of slag; but, in my experience, there is less silver and much

Jan 1, 1910

By Oscar T. Marzke

Four alloys that precipitate the alpha phase from the beta of the copper-zinc system were heat-treated in various ways to develop as many forms of the segregate as possible. It was found that the precipitate may have the form either of plates or of needles. Plates usually result when precipitation occurs at low temperatures and needles when precipitation takes place at high temperatures. The needles tend to align themselves along certain planes in the matrix and to coalesce into plnte-like structures. The two phases were found to be related so that a (111) plane and [Oil] direction of the precipitate are parallel to a 10111 plane and 11111 direction of the matrix. DISCUSSION (E. A. Anderson presiding) D. W. Smith, Pittsburgh, Pa. (Written discussion).—Tllis report by Dr. Marzke covers completely all possible heat treatinents over a considerable range of compositiol~s in which a1pha precipitates from beta brass, and may be said to complete the Inctallographic part of this problern The lining up of ncedles of segregate to form plates, espeeially as shown in Fig. 5, appears to he regular, although the author's frequency plot in Fig. 11 makes it appear rather irregular. Has the author attempted anY correlation between some of the major dircetions and the oricntntaion of the parent grain as determined by X-ray analysis? Also, in Figs. 4, 5 and 6 the cross-sections of the needles appear to be straightsided and regular. Have these directions been correlated with the matrix latttice? Dr. Mnrzkr 's method of interpretation of the orientation rclationships between the alpha. and beta phases is a bit uncertain and seems to wed more explanation. If this relationship, as staited is such that :L (1111 plane and a [I 10] direction of that plane in the precipitate is parallel to a. {110} p1ane and a [111] direction of that, plane in the matrix, there mill be a maximum of 24 possible orientations of the alpha phase within a. single grain of the beta phasc. This relationship is expressed strercographical1y in Fig. 13, ill which the locations of a11 of the alpha {111} poles for the 24 orientations of alpha me given. Fig. 12 chccks fairly closely with this thcoretical plot,. with a few exeeptions which may be due to the inaceuracy inherent in the method used by the anthor in determining the orientations of the segregates. The method might have been refined somewhat had corrections been made for the displacement of the slip p1ancs upon deformation.

Jan 1, 1933

By L. D. Jaffe

THE data recently published1-" on heat treatment of titanium alloys have not been readily systematized into an overall picture. When the ß titanium phase transforms isothermally at low temperatures, the hardness follows a typical age-hardening pattern, going through a peak as schematized by the "hardness" vs "time of isothermal transformation" coordinates of Fig. 1. As the temperature is raised, the peak will decrease in height and occur at shorter times; slowing must however take place as the /3 transus is approached. The brittle microconstituent in the region of peak hardness has been termed /3'. Its structure is still undetermined but it is clearly a transition stage from soft /3 to the £ + a that is found at the right of the peak. On continuous cooling, high cooling rates correspond to short times on Fig. 1; abscissa labeling has been added accordingly. Extremely rapid cooling will retain soft /3; very slow cooling will precipitate soft a; intermediate rates give hard 8'. Increasing distance from the water-quenched end of a Jominy hardenability bar corresponds to slower cooling (right on Fig. I), but the range of cooling rates covered by a Jominy bar is only a small portion of that shown in the figure. The p-stabilizing alloying elements retard the transformation process, moving the material to the left on Fig. 1. A lean alloy is harder water-quenched (P') than air-cooled (/3 +a); a rich alloy is harder air-cooled (/3') than water-quenched (/3). Examples of the position of various compositions with respect to the curve, based on limited data in the literature, are given at the top of the figure. Oxygen and carbon accelerate the transformation process, moving the material to the right on Fig. 1. If an alloy quenched quickly enough to retain soft /3 is reheated below the £ transus (tempered), it ages, going through a hardness maximum as time increases (moving right on Fig. 1). Material which after cooling from the /3 range lies on or right of the hardness peak, will move still further right on tempering, and so soften. Since the rate of the tempering (aging) reaction increases with temperature, the figure also may be used to represent the variation in properties with tempering temperature, at short tempering times. The simple picture given here neglects martensite transformation, as well as differences between decomposition products of /3 formed by direct isothermal transformation and those formed by quenching and tempering. It may nevertheless be of use as a guide for practical heat treatment and for further research.

Jan 1, 1955

By Clarence Zener

THE internal friction of nonferrous metals vibrating at low stress amplitudes has so far always been successfully interpreted in terms of inhomogeneities of one sort or another. Examples are the fluctuation of stress across a specimen vibrating transversely,1,2,3 the stress inhomogeneities due to the elastic anisotropy and partial random orientation of the individual crystallites,4,5 localized weak regions introduced by cold-working,6,7 grain boundaries and possibly twinning planes.8.9 Perfect single crystals are, by definition, homogeneous. Actual single crystals usually, perhaps always, contains some imperfections. The present investigation was undertaken to determine whether the internal friction of single crystals may likewise be attributed to inhomogeneities. This study was made possible through the gift of a large single crystal of 70-30 alpha brass by H. L. Burghoff, of the Chase Brass and Copper Co. The specimen, 3-s in. in diameter and 10 in. long, was similar to samples previously described by Mr. Burghoff.10 EXPERIMENTAL METHOD The experimental method used has previously been described in Institute papers.5,6.9 The measure of internal friction adopted here, I/Q, is (p) X the logarithmic decrement, a measure used by some writers, and is also (I/2p) X the specific damping capacity, a measure used by other writers. In all measurements the stress level was kept so low that the measurements were independent of stress level. In all measurements in which the temperature was varied, observations were made as the specimen slowly cooled from its highest temperature. The specimen was vibrated transversely. Observations were made at the fundamental frequency and at the first overtone, of about 620 and 1710 cycles per second, respectively. No attempt was made to avoid acoustical losses. EXPERIMENTAL RESULTS The specimen was annealed for several hours at 450°C. The temperature dependence of the internal friction was then determined from room temperature to 400°°C. As shown in Fig. i, the internal friction increased by only a factor of 2 from room temperature to 300°°C., then by a factor of 100 during the next :too' interval. These measurements are consistent with the view that the observed internal friction is the superposition of two distinct parts. One, dominant at room temperature, is nearly independent of temperature. This part may be accounted for by acoustical losses and by transverse thermal currents. It was not further investigated. The second part, when plotted in the manner of Fig. I, lies upon a straight line. Therefore it has a heat of activation H; i.e., it varies with temperature as Internal friction ~ e-HI/RT [I]

Jan 1, 1942

By E. H. Crabtree

Research on the iron ranges begins to bear fruit in big plant construction -Big coppers raise capacity, build at new Arizona, Michigan, Nevada, properties - Hydrometallurgy comes to fore with new uranium ore treatment and the Chemico process for nonferrous metals -

Jan 2, 1953