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By J. J. Tietien, R. O. Clough

A technique previously used to prepare alloys of InAs1-xPx and GaAsl-x Px, miry: the gaseous hydrides arsine and phosphine, has been extended to grow single -crystalline GaAs 1-x Sb x by replacing the phos-phine with stibine. Procedures were developed for handling and storing stibine which now make this chemical useful for vapor phase growth. This represents the first time that this series of alloys has been grown from the vapor phase. Layers of P -type GaSb and GaSb-rich alloys have been grown with the carrier concentrations comparable to the lowest ever reported. In addition, a p-type alloy containing 4 pct GaSb exhibited a mobility of 400 sq cm per v-sec which is equivalent to the highest reported for GaAs. RECENTLY, interest has been shown in the preparation and properties of GaAs1-xSbx alloys, since it was predicted1 that for compositions in the range of 0.1 < x < 0.5, they might provide improved Gunn devices. However, preparation of these alloys presents fundamental difficulties. In the case of liquid phase growth, the large concentration difference between the liquidus and solidus in the phase diagram, at any given temperature, introduces constitutional supercooling problems. It is likely that, for this reason, virtually no description of the preparation of GaAs1-xSbx by this technique has been reported. In the case of vapor phase growth, problems are presented by the low vapor pressure of antimony, and the low melting point of GaSb and many of these alloys. In previous attempts1 at the vapor phase growth of these materials, using antimony pentachloride as the source of antimony vapor, alloy compositions were limited to those containing less than about 2 pct GaSb. This was in part due to the difficulty of avoiding condensation of antimony on introducing it to the growth zone. A growth technique has recently been described2 for the preparation of III-V compounds in which the hydrides of arsenic and phosphorous (AsH3 and pH3) are used as the source of the group V element. With this method, GaAs1-xPx and InAs1-xPx have been prepared2&apos;3 across both alloy series with very good electrical properties. Since the use of stibine (SbH3) affords the potential for effective introduction of antimony to the growth apparatus, in analogy with the other group V hydrides, this growth method has been explored for the preparation of GaAs1-xSbx alloys. In addition to GaSb, these alloys have now been prepared with values of x as high as 0.8. In the case of GaSb, undoped p-type layers were grown with carrier concentrations equivalent to the lowest reported in the literature. Thus it has been demonstrated that, with this growth technique, all of the alloys in this series can be prepared. EXPERIMENTAL PROCEDURE A) Growth Technique. The growth apparatus, shown schematically in Fig. 1, and procedure are virtually identical to that described2 for the growth of GaAs1-xPx alloys, with the exception that phosphine is replaced by stibine.* HCl is introduced over the gallium boat to *Purchased from Matheson Co., E. Rutherford,N+J. transport the gallium predominantly via its subchlo-ride to the reaction zone, where it reacts with arsenic and antimony on the substrate surface to form an alloy layer. The fundamental limiting factors to the growth of GaAs1-xSbx alloys from the vapor phase, especially GaSb-rich alloys, are the low melting point of GaSb (712°C) and the low vapor pressure of antimony at this temperature (<l mm). Thus, relatively low antimony pressures must be employed, which, however, imply low growth rates. To provide low antimony pressures, very dilute concentrations of arsine and stibine in a hydrogen carrier gas were used. Typical flow rates (referred to stp) were about 4 cm3 per min of HC1 (0.06 mole pct)+ from 0.1 to 1 cm3 per min of ASH, (0.002 to 0.02 mole pct), and from 1 to 10 cn13 per min of SbH3 (0.02 to 0.2 mole pct), with a total hydrogen carrier gas flow rate of about 6000 cm3 per min. Although no precise data on decomposition. kinetics exist, it is known4 that stibine decomposes extremely rapidly at elevated temperatures. However, the high linear velocities attendent with the high total flow rate (about 2000 cm per sec) delays cracking of the stibine until it reaches the reaction zone and prevents condensation of antimony in the system. To improve the growth rates of the GaSb-rich alloys, growth temperatures just below the alloy solidus are main-

Jan 1, 1970

By John W. Wagner, Robert K. Willardson

Single crystals of Pbl-xSnxTe have been grown from nonstoichiometric, cation-rich melts with the objective of producing as-grown, bulk material containing carrier concentrations ranging from 1016 per cu cm to 1018 per cu cm. Three specific crystal composi-tions were investigated in detail; x = 0.00, 0.10, and 0.17. Pull rates of from I to 3 mm per hr were used. Single crystals were successfully pulled from melts containing as little as 30 at. pct Te. Hall coefficients, resistivities, and carrier mobilities of these materials were determined. The relationship between the composition of the melt and the carrier concentration in the as-grown crystal has been studied for the three crystal compositions of interest. BULK single crystals of Pb,-,Sn,Te have previously been grown from stoichiometric melts.1,2 Such crystals are p-type and have relatively high carrier concentrations ranging from -9 x 1018 per cu cm for PbTe to -8 x l020 per cu cm for SnTe at 77°K. These carrier concentrations result from deviations from stoichiometry (lead vacancies) in the as-grown crystals. Since lower carrier concentrations are desirable for electrooptic device applications, these crystals are usually subjected to long-term, isothermal anneals.&apos; This paper reports on the growth of Pbl-xSnxTe single crystals from nonstoichiometric melts with the primary objective of producing as-grown material containing relatively low (1016 to 1018 per cu cm) carrier concentrations and also reports on the general characteristics of these crystals. The phase relationships in the Pbl-xSnxTe systems are such that materials solidifying from nonstoichiometric, cation-rich melts will have smaller deviations from stoichiometry than materials grown from stoichiometric melts. Fig. 1 is the T-x phase diagram for PbTe in the vicinity of the stoichiometric composition.3 A crystal grown from a stoichiometric melt will solidify at a melting point maximum at which the solid will contain -0.5002 atom fraction of tellurium. PbTe single crystals grown in our laboratories from stoichiometric melts have carrier concentrations of 9 x 10" per cu cm, indicating that the excess tellurium in the crystals is as expected from this phase diagram. However, growth of PbTe from a lead-rich melt will result in material having a more nearly stoichiometric composition. Although the addition of Sn to the melt shifts the solidus curve further toward the tellurium-rich side,4 the general discussion given for PbTe applies to the Pbl-xSnxTe systems as well. EXPERIMENTAL Single crystals of Pb1-xSnxTe have been grown in our laboratories from nonstoichiometric, cation-rich melts using the Czochralski technique and boric oxide liquid encapsulation. The details of the growth apparatus and growth technique have been reported in a previous paper on growth of these alloys from stoichiometric melts.2 In the present study, three specific crystal compositions were investigated in detail; x = 0.00, 0.10, and 0.17. Growth of alloy crystals from nonstoichiometric melts requires considerable care, and good quality single crystals were obtained in this study only by optimizing the mechanical and thermal stability of the growth system and by using pull rates of from 1 to 3 mm per hr (Pbl-xSnxTe crystals are easily pulled from stoichiometric melts at rates of from 5 to 10 mm per hr). The liquid encapsulation technique was found to yield near-ideal conditions, since the B2O3 layer increased the thermal stability at the growth interface, permitted easy attainment of near-ideal thermal gradients, and dampened vibrations at the melt surface. The hygroscopic character of the B2O3 was a slight problem and vacuum heat treating was necessary to completely remove the water from the boric oxide. During initial growth, the seed diameter was reduced and a narrow neck (1 to 2 mm diam) of several millimeters length was grown. The latter steps were found to be necessary for the growth of single crystals, i.e., if either of these two requirements were

Jan 1, 1970

By L. F. Mondolfo, W. T. Collins

A study of the relationship between undercooling for nucleation and structure in Sn-Cu alloys with 0.1 to 5 pct Cu has shown that in hypereutectic allojls the halo of tin that surrounds the primary crystals of Cu3Sn5 is larger, the larger the undercooling for nucleation o,f the tin. This increase of halo size results in a decrease of coupled eutectic, and, in alloys far from the eulectic composition, may produce its complete disappeavance, with the formation of a divorced eutectic structure. This was confirnred by the excrrnination of other alloys in which divorced eutectic slructuves are formed, and leads to the conclusion that they ave only an extrenle case of halo forrtzalion , which results when the two phases freeze one at a time and solidification of the first is completed Defove the second starts. It was also found that under proper conditions of nucleation all types of eutectic structures can be formed in the sartte system , and therefore divorced eutectics, like normal and anomalous, are not characteristic of the syslett~, but are mainly controlled by nucleatiorz. Dizlovced eutectics are formed when the phase that tutcleates the eulectic vequires a large undevcooling for ils nucleation and when the cotnpositiorz of the alloy is far from the eutectic., on the side of the primary phase that does not nucleate the other phase. It is recommended that the tevm "divorced" be used in preference to degenerate because it is more desct-iptice of the morphology and mode of forinalion of the structures. ThE variety of structures found in eutectic alloys has been extensively investigated and classified. The most accepted classification is the one by ~cheil,&apos; in which three different types of eutectic were distinguished: 1) normal, 2) anomalous, 3) degenerate (divorced). ATornlal eutectics are typified by the simultaneous growth of the two phases ("coupling") by which the two phases appear as interpenetrating crystals. The presence of a crystallization front, in which the two phases grow side by side, creates the eutectic grains, with the boundaries where the fronts meet. The presence of eutectic grains is the .distinguishing feature of a normal eutectic, according to Scheil. Straumanis and Brakss2 examined the Cd-Zn system and showed that there was a crystallographic relationship between the phases. Later, others4 also investigated additional systems and found definite crystallographic relationships in the coupled eutectics. The anornalous eutectic shows much less coupling than the normal; the two phases are intimately mixed but &apos;grow without a uniform crystallization front—a consistent crystallographic relationship— and the eutectic grain is conspicuously absent. As in the normal eutectics faster rates of growth result in a finer structure, but there is not the typical uniform spacing of normal eutectics. The degenerate eutectic shows no coupling; in fact the two phases attempt to minimize their area of contact and to form separate crystals. It has been suggested5" that slow cooling may favor this type of structure. Scheil believes that normal eutectics are formed when the two solid phases are present in more or less equal proportions, whereas both anomalous and degenerate eutectics form when one of the phases is present only in small amounts. spengler7 extended much farther this qualitative relationship between the eutectic type and the ratio of the two phases, and added a relationship to the melting point of the constituents. On this basis he proposed two equations for determining into which of Scheil&apos;s classifications an alloy belongs. The first equation is: where TI is the melting temperature of the lower-melting component, Tp of the higher-melting component, and Te the eutectic temperature. The second equations is: where is the volume percent of the lower-melting phase and $2 of the higher-melting phase at the eutectic composition. If 0 and/or 4 are in the range 0.1 to 1, a normal eutectic is formed; if in the range 0.01 to 0.1, anomalous; if less than 0.01, degenerate. Although the examples given by Spengler show a good agreement with the formulas, chadwick found that the Zn-Sn eutectic is normal to all growth rates, even though the volume ratio is 12/1, and Davies9 reports that the A1-AlgCo2 eutectic is normal, with a volume ratio of more than 30/1. Many more discrepancies of this type can also be found. Neither Scheil nor most of the other investigators have considered nucleation as a factor in the formation of divorced eutectics. Daviesg states that divorced eutectics form when neither phase acts as

Jan 1, 1965

By E. S. Bumps, M. Baeyert, W. F. Craig

SOME time ago during a study of impact properties of tempered martensite,1 it was postulated that the consistently good ductility of tempered martensite might be caused by its relatively small and peculiarly shaped ferrite grains. The fer-rite grains of tempered martensite have approximately the same size and shape as the martensite "needles." Thus they form an interlocking mass of needle-shaped grains quite different from equiaxed or lamellar ferrite grain structures. When the common mechanical test methods are applied to steel, variations are often observed in the ductility of specimens that have closely similar hardness and tensile strength values. The ductility so measured appears to be structure dependent. When steel from the same heat has been heat treated to produce different structures with the same hardness, the elongation and reduction of area values from the tensile test and the transition temperature determined by the notched-bar impact test vary according to whether pearlite, tempered martensite, or other structural constituents were produced by the heat treatment. It has been widely recognized that tempered martensite gives a consistently good performance, when tempered to the same hardness as many other structures with which it has been compared. In recent years the isothermal transformation of austenite to specific structural products and the quantitative evaluation of the character of these products with respect to their nature and response to deformation has received considerable attention. The objective of the present study was to pursue somewhat further the dependence of ductility upon structure; specifically, it was desired to ascertain whether ferrite grain structure, including both shape and size of the grains, can account for the consistently good performance of tempered martensite in the notched-bar impact test. It was thought that a simple experiment would indicate whether the ferrite grain structure plays any part in the good ductility exhibited by tempered martensite in contrast to other steel structures with different types of ferrite grains. By determining the impact transition temperature, it was proposed to compare spheroidites having similar carbide particle size and spacing but obtained in such a manner that their ferrite grain structures would be very different. Spheroidite obtained by tempering martensite, with its small, needle-shaped grains, was to be compared with spheroidite from pearlite. If the latter is produced by sub-critical annealing, the ferrite grains correspond to the pearlite colonies. Thus, if the pearlite was not too coarse, the ferrite grains of spheroidite from pearlite are equiaxed in contrast to the needle-shaped grains of spheroidite from martensite. It was thought that the ferrite grain structure of spheroidite from martensite might depend to some extent upon the grain size of the prior austenite. The austenite grain boundaries limit the maximum attainable size of the martensite needles and thus of the ferrite grains in the derived spheroidite. In order to evaluate any possible influence of prior austehite grain size, spheroidites were to be prepared from martensites that had been formed from fine-grain austenite and also from coarsened austenite. As the carbide particle size and distribution were to be essentially alike in the various spheroidites, the difference would be in the ferrite grain size and shape. Thus any marked difference in transition temperature could be attributable to the character of the ferrite grain structure. There are certain considerations in assuming that these spheroidites would be equivalent in all respects except ferrite grain structure, and an attempt was made to take them into account. One of the considerations was the choice of the carbon content of the steel. An approximately eutectoid steel was selected for two reasons. First, the pearlitic structure would contain no proeutectoid ferrite which might complicate the picture by producing a non-uniform ferrite grain structure in the resulting spheroidite. Then, too, the high-carbon content would inhibit ferrite grain growth during the sub-critical treatment. Another factor to be taken into account was the choice of an alloying element to assure a martensitic structure throughout on quenching the impact specimens. Nickel was chosen, because it is a common alloying element and resides in the ferrite both upon its formation from austenite and throughout tempering. The formation of alloy carbides, or even a large solubility of the alloying element in cementite, would have complicated the interpretation by changing the composition of the ferrite .during spheroid-ization. The possibility of temper brittleness was minimized insofar as possible by using a tempering temperature as high as consistent with the 1 pct of nickel in the steel, namely, 1150°F. While it certainly is not claimed that no difference other than ferrite grain structure could exist between the spheroidites, nevertheless, reasonable precaution has been exercised within the limits of steel metallurgy. It is believed that any large difference in transition temperatures would reflect the difference in ferrite grain structure and that relatively good ductility in the spheroidites from mar-

Jan 1, 1951

By J. Leja, J. H. Schulman

FROTH flotation is usually effected by the addition of a collector agent and a frothing agent to an aqueous suspension of suitably comminuted mineral ores. The action of collectors is to adsorb onto the surfaces of minerals to be separated, sensitizing them to bubble adherence. The action of frothers has, in the past, been accepted as that of froth formation only, brought about by a lowering of the air/water interfacial tension. Substances capable of producing froth are classed1a,b according to their relative capacities for production of froth-volume and froth stability in the simple frother-water system. The purpose of this paper is to show that the surface active agents acting as frothers become effective only when there is a suitable degree of molecular interaction taking place between collector molecules and frother molecules at the air/water and solid/ water interfaces. Further, the discussion will demonstrate that the actual mechanism of adherence of an air bubble to a suitably collector-coated particle is due to the molecular interaction collector-frother. This leads to the formation of a continuous interfacial film of associated molecules, anchored to the mineral by polar groups of the collector, and enveloping the whole bubble. The tenacity of adhesion mineral-to-bubble results from the strength and the visco-elasticity of this mixed film. Some 20 years ago Christman2 postulated mutual dependence of collector and frother in effecting flotation. This view was, however, strongly opposed by Wark,3 who pointed out that an addition of frother had no effect on the value of contact angle once this was established in the solution of collector. More recent work by Taggart and Hassialis&apos; indicated that the presence of frother, namely, cresol, leads to the immediate establishment of a contact angle on sphalerite, partially coated with xanthate, whereas an air bubble fails to make contact in potassium ethyl xanthate solution alone, even after 60 min induction time. Wrobel5 raws attention to the selectivity of frothers in flotation. Many instances of antagonistic effects of certain mixtures of frothers (or collectors and frothers) on flotation froth have been known to flotation operators and have been reported in literature. Taggart6 and Cooke7 give several examples of incompatibility of certain ratios of frothers and collectors, e.g., oleate and long-chain sulphates, pine oil and soaps. Monolayer Penetration. Properties of insoluble films produced by molecules of surface active agents orientated at the air/liquid interface are conveniently studied by the Langmuir trough technique, described fully by Adam.&apos; Using the trough technique Schulman and Hughes" and Schulman et al.10a. b, c, d,e established the existence of molecular interactions occur- ring between certain types of surface active agents. Their experiments revealed the phenomenon of penetration of an insoluble monolayer (e.g., a film of a long-chain alcohol) by a soluble agent (e.g., sodium alkyl sulphate) injected into the substrate (water or salt solution). The degree of molecular interaction taking place on penetration is determined by changes in the surface pressure of the resulting film, changes of its surface potential and its mechanical properties (viscosity and rigidity). When the interaction takes place between both polar groups and both hydrophobic groups of the two participating amphipathic molecules a molecular complex is formed. Complexes formed on penetration of the monolayer at interfaces are not necessarily true chemical compounds: they are labile in solution, the activity and reactivity of individual components are greatly different from those of the molecularly associated complex, and on crystallization they usually separate out into components. However, when formed in the orientated state at interfaces they are found to be very stable, although some mixed films spread as monolayers of stoichiometric complexes can show further penetration by subsequent additions of the soluble component injected into the substrate.&apos;" The degree of association between two or more types of surface active agents is very sensitive even to small changes in electric (dipole) moment of the polar groups of the amphipathic molecules as influenced by magnitude and position of neighboring ions or dipoles, their size, concentration, and stereochemistry. In addition, the molecular association is greatly influenced by concentration and type of inorganic salts in the substrate, by its pH, and by temperature. The nonpolar groups of interacting molecules greatly affect the stability of molecular complexes. Progressive shortening of the aliphatic chain of one of the reacting molecules weakens (at an increasing rate) its tendency to form stable complexes. Similarly, introduction of a double bond of cis-form into one of the reacting chains, which changes the straight hydrocarbon chain into a kinked one, or introduction of a branched chain, reduces the stability of the associated complex. Monolayer Adsorption. Using the trough technique and injecting metal ions into the substrate (water or salt solution) underlying insoluble films of fatty acids, alkyl amines, and sulphates, Wolsten-holme and Schulman11a,b,e. &apos; and Thomas and Schulman" have established conditions, namely, pH, concentration. and steric factors, under which molecular interactions take place between the polar groups of the surface active agents and the metal ions. These interactions are marked by great changes in the solubility and mechanical properties of the monolayer of the agent; no surface pressure increases are observed as in monolayer penetration experiments. The results of these adsorption studies, correlated with flotation experiments, indicated that in the case of fatty acids and alkyl sulphates their adsorption onto minerals of base-metals takes place by a similar

Jan 1, 1955

By J. J. Frawley, W. J. Childs

The dynamic nucleation of supercooled bismuth and Bi-Sn alloys has been studied over a frequency range of 15 to 20,000 cps. For low-frequency vibration, a minimum vibrational energy was required for enhancement of nucleation. Above this critical energy, the dynamic supercooling was less than static supercooling showing that vibration promoted nucleation. The amount of dynamic supercooling continued to decrease with increasing vibrational energy until a minimum or threshold value was reached. This minimum value of supercooling for nucleation remained constant joy all further increases in vibrational energy. For higher frequencies, similar results were observed. This behavior has been related to the necessity of cavitation for dynamic nucleation. When a liquid is cooled to a temperature below its equilibrium melting point, the solid phase is more thermodynamically stable. However, for solidification to occur, a two-step process, nucleation and subsequent growth of the solid phase, must occur. When a liquid is supercooled, that is cooled below the equilibrium melting point, the controlling process for solidification to begin is the rate of nucleation. Once nucleation has occurred, the solidification process is controlled by the rate of growth. Nucleation can be induced by two factors: either by a catalyst or by the use of mechanical shock. Numerous investigators1-4 have studied the effect of nucleation catalysis but much less systematic study has been made of nucleation by mechanical shock waves. The influence of vibrations on grain size in castings and ingots has been studied by many authors but no clear understanding of the mechanism or accurate prediction of the effect has been presented.5 It would be intuitively expected that the further the departure from equilibrium (i.e., the greater the supercooling), the easier it would be to induce nucleation. This has been quantitatively demonstrated both by walker6 and later by Stuhr,7 that the greater the degree of supercooling the easier it is to nucleate by a shock wave. Stuhr also attempted to obtain the mechanical energy required for nucleation of bismuth as a function of supercooling. He vibrated a crucible containing supercooled metal at low frequencies and various amplitudes and noted the corresponding dynamic supercooling obtained. The amount of supercooling was inversely proportional to the mechanical energy applied. Limitation of his experiment was the problem of the confinement of the liquid in the crucible without splashing and minimizing other unwanted modes of vibration. Tiller et al.8,9 did similar work on tin and Sn-Pb alloys using an electromagnetic stirring device. Their conclusions were that the magnitude of the magnetic field strength did not affect the amount of undercooling at which nucleation was initiated. While conclusive experimental results have been lacking to explain this effect of mechanical vibration on inducing nucleation, a number of theories have been proposed. Two of these theories are discussed below. 1) The Change in Melting:- Point Locally Due to the Change in Pressure (Clapeyron Equation). According to Vonnegut10 the most plausible explanation for the nucleation of a supercooled melt by cavitation is the effect of changing the melting point by a change in pressure. For materials where the volume decreases on solidification, an increase in pressure raises the melting point; for materials which expand on solidification, the melting point is raised for a decrease in pressure, i.e., rarefaction. Using the Clapeyron equation, the melting point of a metal can be calculated as a function of pressure. If it is assumed that the equation can also be used to calculate the temperature of nucleation of a supercooled melt as a function of pressure (i.e., the temperature of heterogeneous nucleation will increase with pressure at the same rate as the melting point), the amount of supercooling required for nucleation will be constant at all pressures as shown in Fig. 1. It is obvious that an isothermal change which results in an increase in melting point results in an equal increase in supercooling. This increase in supercooling may now be sufficient for nucleation. A pressure of 80,000 atm was calculated, using the Clapeyron equation, as the pressure required to increase the temperature of nucleation of nickel by 200°C. According to Lord Rayleigh,11 this very large pressure could be generated for a very brief period of time by the collapse of a cavity. This pressure wave is radiated in all directions from the collapsed cavity. If the temperature of the melt is slightly below its equilibrium melting temperature at atmospheric pressure, stable growth can follow; that is, once nucleation occurs, growth becomes the main driving force of the solidification process. This proposal has been extended to water which expands on freezing by assuming that nucleation occurs during rarefaction following the pressure pulse. This negative pressure pulse should follow immediately after the positive pressure pulse with its magnitude approaching the critical tensile strength of the liquid. The negative pressure developed during this period would raise the melting point of water and thus promote nucleation. Hunt and jackson12 have suggested this for water. Similarly, it could be postulated that bismuth which also expands on freezing could be nucleated during the negative pressure pulse. 2) Nucleation by a High-pressure Phase. An extension of the Clapeyron equation to systems where density decreased on freezing at atmosphere pressure has been proposed by Hickling.13 The phase diagram for water initially shows the well-known decrease in

Jan 1, 1969

By L. R. Shoenberger

Boron has been used to produce nonaging low-carbon sheet steel. Retention of the necessary minimum amount of about 0.006 pet partially killed the steel. Amounts exceeding about 0.012 pet increased the degree of deoxidotion, piping tendencies, and possibility of hot tearing in primary rolling. Semikilled practice resulted in good ingot yields and satisfactory surface quality. Aluminum added with the boron provided a protective de-oxidizer. Good drawobility was indicated by performances of the steel in a limited number of deep-drawing trials. Some problems with hot-tearing and boron-analysis procedures were overcome. Metal lographically, the boron semikilled steels revealed some structures not usually found in plain low-carbon steels. IN 1943 Low and Gensamer1 reported that strain aging, which hardens and embrittles ordinary low-carbon rimmed steel, was due to nitrogen and carbon, and that oxygen played a relatively unimportant role. Since then, many investigators have substantiated their findings and indicated that nitrogen is particularly potent. Commercially, today&apos;s most widely produced non-aging sheet steels for deep drawing are either aluminum killed or vanadium rimmed types. The difference in deoxidation practice, alone, is evidence that oxygen is apparently not an important consideration in control of strain aging. The fact that nitrogen is important is apparent in the consideration that has been given, knowingly or unknowingly, to the amount combined with aluminum and vanadium. Patents were granted to Hayes and Griffis2 for the processing of aluminum-killed steel, and to Epstein" for the manufacture of vanadium rimmed material. Certain prescribed steps in producing these steels can be correlated with the formation of the respective nitrides within certain temperature ranges below the usual hot-finishing temperatures. The potential nonaging properties of either type can be reduced or suppressed by cooling too rapidly to permit the aluminum or vanadium to combine with nitrogen. Subsequent suberitical annealing of the cold-rolled strip, however, normally forms the nitrides and produces the resistance to strain aging. Titanium-killed nonaging steel, described by Comstock,1 forms a nitride in the molten state and is essentially nonaging throughout its processing. Zirconium-killed steel, which was investigated briefly by the author,* appeared to have similar nitride- forming characteristics. It is known" that chromium can produce nonaging rimmed steel, but relatively little is known of the potentialities of some of the other nitride-forming elements such as boron, silicon, columbium, and cerium. In attempting to develop a new nonaging cold-rolled sheet steel with good drawability, the following factors were considered pertinent. Such a steel would necessarily have a low carbon content and therefore have a relatively high degree of oxidation when made in a basic open-hearth furnace. If the denitriding element were also a deoxidizer, a part of the addition would be lost as oxide. The degree of deoxidation would determine whether the steel is rimmed, semikilled or killed, and also could be expected to have an important bearing on ingot yields and ultimate surface quality. Assuming that the pattern for the production of cold-rolled sheets would not be changed to any great extent, the nitride must form in the molten steel, in hot rolling, in subsequent cooling, or in annealing. The nitride, once formed, should resist dissociation and be stable in the final product. Usually an excess of the nitride-forming element is required to combine with sufficient nitrogen. If the element used is a strong ferrite strengthener, a small excess may markedly decrease drawability. With aluminum and vanadium, about 0.03 to 0.05 pct in the steel is preferred. Epstein has said" that about 0.30 pct chromium is required. Titanium nonaging steels are hard unless a sufficient amount (about 0.30 pct) is added also to combine with the carbon. The cost of the necessary amounts of these latter two elements discourages commercial acceptance. Silicon was considered as a possible nitride former, but since amounts up to 0.10 pct in rimmed and semikilled steels do not induce marked resistance to strain aging, larger amounts are apparently required, which would tend to harden and strengthen the ferrite. Of the other elements mentioned, all but boron are expensive heavy-metal elements. Stoichi-ometrically, almost an equal weight of boron would be required to combine with the nitrogen—-ordinarily about 0.003 to 0.006 pct in scrap-practice open-hearth steels. Boron is a slightly stronger deoxidizer than carbon but is less powerful than zirconium, aluminum, or titanium. Thus a rimmed-steel practice might be possible. There is much in the technical literature concerning the hardenability effects of minute amounts of boron in killed steels but very little about its behavior in low-carbon material—particularly as a ferrite strengthener. The available data indicated a need for better information concerning the effects of boron in low-carbon strip steels. Experimental Work Development of a Boron-Treated Nonaging Strip Steel—Initial attempts to produce a boron-rimmed strip steel employed 3-ton basic open-hearth heats which could be teemed into molds large enough to sustain a normal rimming action. Boron as ferro-boron was added to the ladle in small amounts because of the reported hot-short character of aluminum-killed heat-treating grades containing more than about 0.005 pct boron. Actually, the amounts used, i.e., 1/8 and 1/4 lb per ton, would be large for

Jan 1, 1959

By S. G. Cupschalk, F. A. Dahlman, J. J. Wert

Studies have been undertaken to determine the indicidual effects of particle size, degree of long-range ovder, antiphase domain size, and root mean square stran on the microhardness and yield strength of ordered alloys. Dnta have been analyzed for Cu3Pt initzally ordered to a value of 0.82 and after deformations of 1 and 6 pct. It was observed that deformation fleatly reduced the degree of long-range order. Furtherrnore, wztkin this range of relatively small deforntntlons, the average particle size changed very little while the antiphase domain size was greatly reduced. Smultaneosly, the mcrohardness changed by a factor of two durzng the deforrtation process. PREVIOUS studies have reported some of the effects of cold work on the broadening of X-ray diffraction peaks. These investigations were performed on powder and wire samples representing both ordered and disordered states; i.e., the specimens were initially studied in a severly cold-worked condition. By comparing the difference in line shape between the annealed and cold-worked peaks, fundamental information was obtained concerning particle size, strain distribution in different crystallographic directions, degree of long-range order, and change in antiphase domain size. Considerable theoretical work has been done concerning the analysis of diffraction data obtained from cold-worked metals. Stokes&apos; expressed the change in diffraction profiles in terms of Fourier coefficients. Much of the work in this area has been summarized by warren2 in an extensive review article concerning the analysis of plastic deformation by X-ray diffraction. Cohen and Bever3 applied these techniques in studying the effects of cold work on alloy systems exhibiting long-range order. They utilized the Fourier coefficients of fundamental peaks in conjunction with those of the superlattice peaks to determine the change in antiphase domain size. Little work of this nature has been reported for ordered systems that have undergone small degrees of plastic deformation. The purpose of this investiga-tion was to determine the effects of small deformations in such a material with respect to particle size, strain distribution in various crystallographic directions, antiphase domain size, degree of long-range order, and hardness. EXPERIMENTAL PROCEDURE CusPt was used for the initial investigation since the order-disorder transformation takes place with- out a change in crystal structure. The transformation is readily detectable via X-ray diffraction techniques due to the large difference in the scattering factors of copper and platinum. Additionally, the alloy is relatively low melting (approximately 1300°C) and is easily deformable in both the ordered and disordered states. 1) Specimen Preparation and Cold Working. A 100-g, 12-in. diam., cylindrical specimen of Cu3Pt was prepared by melting and casting 99.99 pct pure Cu and Pt i.n vacuo. Prior to any mechanical working, the material was homogenized in a vacuum for 60 hr at 100O0C, and surface defects were removed by machining to a depth of approximately 116 of an in. The material was then cold-rolled, with an intermediate anneal, into a strip approximately 12 in. wide by 14 in. thick. Straightening and flattening removed another 0.025 in. from the thickness. After a recrystallization treatment at 750°C for 30 min, the specimen was slow-cooled from 55OoC, at the rate of 6°C per hr, down to 150°C to induce superlattice formation. This treatment yielded an ASTM grain size of 7 and a degree of long-range order equal to 0.83 0.06. After obtaining X-ray and Knoop hardness data, the sample was cold-rolled approximately 0.75 pct in one pass through a hand-operated jewelers&apos; mill. X-ray and hardness data were again obtained and the specimen was reduced an additional 5.41 pct in a single pass through the mill. 2) X-Ray Measurements. The specimen was examined in the ordered condition and after the two degrees of cold working previously mentioned using a General Electric XRD-5 unit equipped with a spectrometer and scintillation counter. Using Mo-Ka radiation with a zirconium filter, six orders of the 100 reflection were obtained. It was anticipated that point counting would be necessary for an accurate determination of the low-intensity peaks and tails: however, it was demonstrated that, by using a scanning speed of 0.2 deg per min and the appropriate time constant, the recorded data were sufficiently accurate. Thus, for ease of experimental procedure, all peaks were recorded on chart paper. Specimen position in the holder was considered to be insignificant after making a series of measurements of the same peak area in different positions with respect to the beam. Since peak overlapping did occur at high values of 20, it was necessary to separate the peaks graphically prior to analyzing the data in order to minimize this source of error. The peak tails were also carefully drawn to obtain the best possible data. Fourier coefficients of the line profiles were calculated on an IBM 7072 computer, and graphical meth-ods2j3 were employed in analyzing the results. For this type of calculation, in which the line profile is represented by intensities taken at set intervals, the intervals selected must be sufficiently small to give an accurate representation of the line profile. It was decided that for 20 = 0.02 deg the line profiles were

Jan 1, 1967

Fred. T. Greene, Rossland, B. C. (communication to the Secretary): At the beginning of his gaper, Mr. Herzig refers to an article of mine in the Engineering and Mining Journal of January 27, 1900. I would like to add that the method de-

Jan 1, 1901

By Richard W. Smith

THERE are three distinct varieties of phosphate rock, in Tennessee, known commercially as: (a) the "brown" rock, which is the residual pro- duct of the weathering and natural concentration of certain phosphatic Ordovician limestones; (b) the "blue " rock, which is an unaltered phosphatic stratum of Mississippian or Devonian age; and (c) the "white" rock, which is the result of chemical replacement and deposition. Before 1894, South Carolina and Florida had supplied most of the phosphate of the United States, South Carolina leading until that date and Florida from then until the present time. In December, 1893, the blue phosphate of Tennessee was discovered almost simultaneously on Swan Creek, in Lewis County, by two independent parties-by one as the result of a careful and systematic search for a workable deposit of the long known kidney phosphate, and by the other through mistaking it for a "bloom" of coal. Leases were taken and, with further prospecting disclosing other deposits in the region, the development progressed as rapidly as &apos;could be expected without railroad transportation

Jan 1, 1924

By E. DeGolyer

WAR has wrought sharp and sudden changes in the pattern of the oil industry. The most obvious and most striking of such changes have been in the fields of transportation and refining. A third of the world&apos;s total oil production formerly started to market, tanker-borne, over the waters of the Gulf and Caribbean. Most of this oil went to our North Atlantic ports, supply points for the world&apos;s greatest consuming center. This tremendous traffic, disrupted by the loss of tankers as a result of requisition for military purposes and by the activity of enemy submarines, has had to be substituted largely by such lines of supply as could be improvised without loss of too much time. No single solution for this gigantic problem has been found nor is it likely to be entirely solved for some time to come. It has been solved in part, however, by rearrangement, reversals, and patching up of existing pipe-line systems; by overland transport of crude and products in tank cars on a scale never before attempted; by barging over inland waterways; and through the construction at long last of the "big-inch" line, the first leg of which is just being put into operation as far as Norris City, III. The tank-car traffic alone, reaching a peak of deliveries of 856,710 barrels per day into District 1 during the week ending Sept. 19, 1942, and accomplished at an expense of millions of dollars in extraordinary transportation costs, defrayed by the Defense Supply Corp. and by the mobilization of tank cars from all over the nation, is a story worth the telling but by some of those who directed it.

Jan 1, 1943

By George F. Weaton

Although an almost continuous campaign had been carried on by various experimenters since 1885 to find a commercial process of smelting zinc by electrothermic means, no commercial success was attained in the United States. The St. Joseph Lead Co., appreciating the theoretical possibilities of such a process, such as the ability to construct units of large capacity, quality control, and the possibility of treating complex and refractory ores, decided in 1926 that the process was worthy of further investigation, and in that year, at one of its southeast Missouri plants, began the development of the electrothermic zinc-smelting process according to the invention of the late Earl C. Gaskill. Late in 1929 the process reached a stage of commercial significance, and in 1930 the erection of a modern electrothermic zinc smelter was begun, at Josephtown, Beaver County, Pa. The site is 3 miles from Monaca, which is on the main line of the Pittsburgh & Lake Erie Railroad, and a spur of the railroad has been constructed to the plant site. The site borders upon the Ohio River, which is navigable for 600 to 800-ton barges. This district was selected for the plant after an economic survey involving such questions as cost and availability of electric power, reduction fuel, transportation facilities, and the transportation charges on raw and finished materials, labor conditions, and taxes. The initial unit of the plant was designed to treat daily 120 tons of 58 per cent zinc sulphide concentrates from the company&apos;s mines in St. Lawrence County, New York. The plant equipment is housed in seven modern steel-frame buildings, and includes: Roasting and Acid Plants 3000-ton concentrate storage. Two Nichols-Herreshoff 21 ft. 6-in. diameter, 12-hearth roasters with usual cast-iron airshaft supporting chromium-alloy rabble arms and rabbles. SO2 gas purification system consisting of: One double-compartment hot-dust Cottrell precipitator. Cast-iron sinuous air-contact gas cooler.

Jan 1, 1937

By J. D. Livingston, H. E. Cline

Cu-Pb alloys in the vicinity of the monotectic composition have been directionally solidified under a high temperature gradient at rates up to 2 X l0-&apos; cm per sec. Over a wide range of compositions, high growth rates yield a composite structure consisting of continuous rods of lead in a copper matrix. This range of compositions increases with increasing growth rate, in agreement with arguments based on the relative velocities of composite growth and the growth of copper dendrites or lead drops. The breakdown of the composite structure at slow growth rates is explained in terms of the relative interphase surface energies. The observed interrod spacings of the composite structure are large compared with the predictions of the Jackson-Hunt equations of eutectic growth. ThE directional solidification of many eutectic alloys produces fine composite structures of parallel lamellae or rods. There has been considerable interest not only in the fundamentals of this two-phase solidification process,&apos;-3 but also in the interesting physical properties produced by such regular and aniso-tropic microstructures. Composite structures can be grown only over a limited range of composition, beyond which coarse primary dendrites of one phase appear. In organic eutec-tics, this composition range of composite structures has been shown to increase with increasing growth rate.7"10 These results were explained in terms of the relative velocities of composite (coupled) growth and dendritic growth. Although similar arguments should apply to metallic eutectics,11-13 suitable experimental results are lacking. In contrast to the work on eutectics, the directional solidification of monotectic alloys has received little attention. (The monotectic reaction is similar to the eutectic reaction, except that one of the resulting phases is a liquid, which subsequently solidifies in a separate reaction at a lower temperature.) Directional solidification of some monotectic alloys&apos;4715 yields regular rodlike microstructures, whereas in other cases macroscopic separation of solid and liquid phases occurs.16 chadwick17 rationalized these results in terms of the probable relative magnitudes of the various interphase surface energies. A recent study of chill-cast Cu-Pb alloys18 revealed a fine rodlike microstructure in alloys near the monotectic composition. It was decided to investigate the directional solidification of such alloys, and to determine the range of composition and growth conditions yielding composite structures. The Cu-Pb system is convenient for such a study, both because it is simple metallurgically, with no compound formation and negligible solid solubilities, and because its basic properties are well-documented. Recent literature on the Cu-Pb system includes studies of bulk thermo-dynamic properties,&apos;g surface energies,20"21 densi-ties,25 and diffusion constants.a6 A similar study of the directional solidification of Cu-Pb alloys was recently undertaken, independently, by Kamio and Oya." EXPERIMENTAL Alloys were prepared by melting 99.999 pct Cu and 99.999 pct Pb in a graphite crucible, stirring well, and pouring into a cold graphite mold. Rods 0.175 in. in diam were machined from the ingots. Alloy compositions studied ranged from 25 to 55 wt pct Pb. Samples were placed in graphite crucibles 5 in. long with 4 in. OD and 0.035-in. walls. They were melted under flowing argon in a vertical, two-zone. platinum -wound furnace. A voltage stabilizer was used to minimize fluctuations in input power. The narrow specimen diameter minimized convection. Directional solidification was achieved by driving the crucible downward into a +-in. hole in a water-cooled copper toroid. The toroid was located immediately below the narrow end zone of the furnace. The end zone was separately powered to maintain high local temperature. Therefore a high temperature gradient (approximately 300 deg per cm) was maintained in the specimen throughout the run. The crucible motion was screw-driven. and a wide range of drive speeds were available. The limited rate of heat removal caused a thermal lag in the specimens at high drive rates. However. temperature-time curves from thermocouples imbedded in a representative sample indicated that the average growth rate still approximately equaled the drive rate. Although the specimens were initially homogeneous, melting and re solidification redistributed the lead. producing composition variations of several percent along the specimen length. (During melting. lead melted first and ran down the sample surface. Rapid freezing tended to reproduce the resulting composition gr~dient, but slow freezing did not because a slow-moving interface tended to reject lead. as discussed later.) To determine local composition. ;-g samples were cut from regions exhibiting various microstructures and were chemically analyzed for lead content. Micrographs were taken on as-polished or lightly etched surfaces. Three-dimensional structure of the lead network was viewed with a scanning electron microscope after removal of some of the copper matrix with nitric acid. RESULTS Several different microstructures are observed, depending on composition and drive rate. Because melting and resolidification produced composition gradients, results are best presented in t&ms of final local composition, rather than initial or average composition. The ranges of local compositions and drive

Jan 1, 1970

By YANG TSANQ WOO

THE method of making coke that has been adopted at the Kaiping and other collieries in northern China resembles, to some extent, the familiar bee-hive oven process of the United States, except that a kiln with permanent sides is used instead of a closed oven, and the products of combustion are drawn off at the bottom, In building coke-kilns in China, two circular holes, 8 ft. 6 in. in diameter at the bottom and 13 ft. in diameter at the top, are excavated in the ground, both being .connected at the bottom by a flue as shown in Fig. 1. The sides and bottom of the kiln are lined with fire-bricks, and covered with a layer of fire-clay, and a rectangular opening, 6 in. by 8 in., connects the bottom of each kiln with the main flue. Around the edge of the hole, and overlapping the lining, is a wall of fire-brick extending .2 ft. 6 in. above the level of the ground. An open space 5 ft. wide is left in this wall, through which the coal is carried into the kiln and the resultant coke removed. This space, of course, is bricked up during the time that the coking operation is being carried on. The wall is pierced with nine flue-openings uniformly placed around the circumference, each intervening space in the wall being strengthened with a brick buttress, as is shown in Figs. 2 and 4. The floor of the kiln, as well as the main flue, is lined with fire-brick. Before charging the coal, it is first placed in shallow bamboo sieves, 2 ft. in diameter, and immersed in a trough 10 ft. long, and 3 ft. wide, fed with pit-water; in which it is washed by hand. Fig. 3 shows the manner in which the washing is done. From 25 tons of good " dust" coal, 22.5 tons of washed coal are obtained. When ready to charge the coal into the kiln a temporary cone-shaped flue of fire-wood and lump coal is first built to a

Nov 1, 1905

By AIME AIME

The Bulletin. As already announced in the January Bulletin, this publication will be issued during the coming year monthly instead of bi-monthly as heretofore. Among other reasons for this change, it is desired to effect thereby the earlier transmission to members of important papers, lists of candidates for membership, and other items of timely information. The New Haven Meeting. As already announced in special circular, the XCVIth meeting of the Institute for the reading and discussion of papers will be held at New Haven, Conn., beginning Feb. 23, 1909. The Secretary of the Local Committee is Prof. J. D. Irving, Box D, Yale Station, New Haven. The program embraces visits to many interesting works in New Haven, Ansonia, Bridgeport, etc. The leading topics for discussion at the sessions will be: The Conservation of Natural Resources; A Sea-Level Canal at Panama; and The Technical Education of Mining Engineers. But papers on other subjects also are announced. A supplementary session of this meeting will be held in New York City, at some time during March, 1909, as a joint session with other national engineering societies, for the further discussion of the subject of The Conservation of Natural Resources. A Pacific Coast Meeting. The XCVIIth meeting will be held on the Pacific Coast, including a visit to the Exposition at Seattle, and various other points en route going or coming, depending upon the route and program finally adopted. More definite information will be announced at the New Haven Meeting, or at the earliest possible date thereafter.

Feb 1, 1909

By H. J. Maguire

(Presented by invitation at a meeting of the Spokane Local Section, Feb. 17, 1912.) THOSE familiar with mill-practice understand the work required of an average bucket-elevator, but I wish to call special attention to the wear on the buckets. I have been studying in what manner the life and service of the bucket might be improved, and I feel that an adjustable lip, attachable to each bucket without the aid of rivets, will be of material advantage. For illustration, consider the feed-elevator of a typical mill in the Cur d&apos;Alène district. The ore is carried by water in a launder from the feed-rolls and dumped in the "boot" of the elevator, directly in front of the ascending bucket. Middlings from the return-rolls are similarly handled. Under this condition the bucket not only carries the ore, but also picks it up, and this latter requirement determines the life and service of the bucket. It might be said that it would be better practice to convey the feed to the elevator and dump it directly into the bucket, but at one mill at which this plan was tried the results were disappointing and the rubber belt was badly worn. The wear of the bucket is confined to the lip and the corners which have to pick up the material. When the lip on a corner of a 7- by 12-in. malleable cast-iron bucket is worn down about 3 in., the bucket is of no further value as a carrier and has to be replaced. The worn bucket, containing about three¬quarters by weight of the metal of the original bucket, has a scrap value of about 10 per cent. of that of a new bucket. To the cost of the bucket, however, should be added the time-cost of replacing the old bucket by a new one. This time-cost is considerable when the loss per hour, to cease operating the mill, is about $200. It is out of the question to put lips on a bucket unless the latter was originally fitted with this device. For if it is attempted to fit lips upon buckets not originally provided with

Sep 1, 1912

By Edmund J. Pryor

DURING the war years restrictions on travel, pressure of work, and the irregular arrival of technical literature from abroad combined to severely isolate Great Britain in a period of intense war expansion of the art and practice of mineral dressing. Many British technicians were fully occupied with the day-to-day problems of improvising substitutes as regular sources of supply failed. and with mastering the strange demands and working conditions of wartime. After a long day spent between ones laboratory and production work, the rest of the waking hours were often filled with fire watching or home guard patrol activities, substituting for a night-shift manager, or "resting" in a dugout while the bombs came down. There was no time for serious study of such technical literature as survived the Atlantic crossing.

Jan 1, 1947

Ira B. Joralemon, one of the world&apos;s most noted mining geologists, died last year at the age of 91. "His long professional career," says Donald H. McLaughlin, chairman of the executive committee at Homestake Mining Co., "covered an epoch in the history of mining that was unique in its opportunities and achievements," adding that many mining companies (Bunker Hill, Bralorne Mining, Copper Range, Anaconda, Newmont, Phelps Dodge, Homestake, etc.) greatly benefited from Joralemon&apos;s experience and wisdom.

Jan 12, 1976

By Fred C., Bond

IN CYANIDE milling, little attention has been paid to the effect of the viscosity of the mill solution on the extraction speed. The viscosity of the solution varies with the amount of dissolved salts present as impurities. These salts build up to a maximum depending on the character of the ore, the grade of cyanide used, the lime and salts added, and the impurities originally in the water. The viscosity will change from month to month and week to week as these factors vary; and that this variation affects the extraction is unquestioned, although methods for calculating it are lacking. The character of the ore is probably the most important of the four factors, as the amount of minerals present that are soluble in cyanide solution will vary constantly, and each variation affects the viscosity of the mill solution. When the cyanide consumption increases as the character of the ore changes, the viscosity of the solution will increase and the extraction will decrease, for the cyanide consumption is usually a measure of the impurities dissolved from the ore. In other words, as the difference between the total and free cyanide increases the extraction will decrease, other factors remaining constant.

Jan 1, 1926

By WALTER M. DAKE

WITH the renewal of the contract between bituminous miners and operators, whereby a period of three years is assured without the devastating effect of irregularity of operation due to general strikes; and, with the increasing comprehension on the part of the large consumers as to the stabilizing effect of adequate storage upon prices; the coal industry has reached that period of its history in which permanence of purpose towards necessary changes is being crystallized, and these changes accomplished by the industry. It is to be hoped that during this era the phrase- " Our National Coal Problem "-will be relegated to the limbo of&apos; antiquated expressions. That this epoch is upon us is evinced by the fact that operators are turning to consolidations, whereby financially sound companies will acquire smaller production units and place themselves in position to maintain constant supervision and control of their development and output; and, as further proof of the arrival of these changes, may be cited the entrance of additional members of the engineering profession into the many phases of management and operation, where- by the cost per ton of output will be, constantly reduced through the increasing use of modern methods and equipment. As an instance, attention is specifically called to the developments in mechanical loading, proposed and actual continuous underground transportation systems and betterment in methods of preparation.

Jan 1, 1924