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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' 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.' 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.'" 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. ' 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 E. S. Fisher, L. C. R. Alfred

The elastic anisotropy factors, c4,/c6,, c3,/cll, and c12/cl,, for hcp metal crystals vary significantly among the dgferent unalloyed metals. Significant variations with temperature are also found. The effects of elastic anisotropy on the dislocation in an elastic continuum with hexagonal symmetry have been investigated by computing the elasticity factors for the self-energies of dislocations in fourteen different metals at various temperatures where the elastic moduli have been reported. For most of the metals the effects of the orientation of the Burgers vector, dislocation line, and glide plane are small and isotropic conditions can be assumed without significant error. Significant effects of anisotropy are, however, found in Cd, Zn, Co, Tl, Ti, and Zr. The elasticity factors have been applied in the calculations of dislocation line tensions, the repulsive forces between partial dislocations, and the Peierls-Nabarro dislocation widths. It is predicted that the increase in elastic anisotropy with temperature in titanium and zirconium makes edge dislocations with (a), (a + c), and (c) Burgers vectors unstable in basal, pyramidal, and prism planes, respectively. The probability of stacking faults forming by dissociation of Shockley partials in basal planes also decreases with increasing c4,/c6, ratio, when the stacking fault energy is greater than 50 ergs per sq cm. The widths of screw dislocations with b = (a) in titanium and zirconium increase very significantly in prism planes and decrease in basal planes as c4,/c6, increases. The effects of elastic anisotropy on various dislocation properties in cubic crystals have received considerable attention during the past few years. In the case of cubic symmetry the departure from isotropic elasticity depends entirely on the shear modulus ratio, A = 2c4,/(cl, —c12); i.e., the medium is elastically isotropic when A = 1. Foreman1 showed that an increase in the ratio A produces a systematic lowering of the dislocation self-energy for a given orientation and Poisson's ratio. ~eutonico~, has shown that large anisotropy can have a marked effect on the formation of stacking faults by the splitting of glissile dislocations in (111) planes of fcc and (112) planes of bcc crystals. ~iteK' made similar calculations for (110) planes of bcc metals. Both studies of bcc metals showed that the large A values encountered in the alkali metals tend to reduce the repulsive forces between Shockley partial dislocations. In fcc metals, however, A does not vary over the large range encountered in bcc metals; consequently, the effect of A on the forces between Shockley partials is masked somewhat by the differences in Poisson's ratio between metals. The effect of A on the line tension of a bowed out pinned dislocation has also been investigated for cubic crystals, first by dewit and Koehler5 and more recent- ly by Head.6 In both cases the line energy model is applied and the core energy is not taken into account, thus making the conclusions somewhat tenuous with regard to the physical interpretation. Nevertheless, the fact that a large A decreases the effective line tension is clearly evident and the tendency for large A to produce conditions that make a straight dislocation unstable (negative line tensions) also seem evident. Head, in fact, shows visual microscopic evidence that stable V-shaped dislocations occur in 0 brasse6 For hcp metals the definition of elastic anisotropy is more complex and, furthermore, significant deviations from an isotropic continuum are found among a number of real hcp metals, especially at higher temperatures. The present work was carried out to survey the effects of elastic anisotropy on the elasticity factors, K, that enter into the calculations of the stress fields around a dislocation core. Some isolated analytical calculations have previously been carried out for several hcp metals but they are restricted in the dislocation orientations and temperature.8'9 The present computations are based on single-crystal elastic moduli that have appeared in the literature and consider various orientations requiring numerical computations. The results are then applied to survey the effects of temperature on the dislocation line tension and dislocation splitting in hcp metals. PROCEDURE Anisotropy Factors. The degree of elastic anisotropy in hcp crystals cannot be described by a single parameter, such as the A ratio in cubic crystals. The following three ratios must be simultaneously equal to unity in order to have an elastically isotropic hexagonal crystal: The magnitudes of these ratios at several temperatures, as computed from the existing data for the elastic moduli of unalloyed hcp metals, are given in Table I. There are no cases of complete elastic isotropy, but the large anisotropy ratios encountered in the cubic alkali metals are also missing. There are, however, several significant differences among the hcp metals, the most notable being the relatively small A and B ratios in zinc and cadmium and the differences in the magnitudes and temperature dependences of A. It has been noted that the temperature dependence of A has a consistent relationship to the occurrence of the hcp — bcc tran~formation. For cadmium, zinc, magnesium, rhenium, and ruthenium, A is less than unity at 4'~ and, with exception for rhenium, decreases with increasing temperature. In the case of rhenium, A has essentially no temperature dependence between 923' and 1123"~, so that it is clear that A does not approach unity at higher temperatures. Cobalt is similar to the above-mentioned group of metals in that it also does

Jan 1, 1969

By A. D. Zunkel, A. H. Larson

Equilibrium arsenic contents of Pb-As alloys in contact with PbO-As2O3 slags containing less than 30 mol pct As2O3, were determined at 650°, 700: and 750 C in an inert at?rzosphere. In this temperature range, the arsenic content of the alloy increased with increasing temperature in the single-phase liquid slag region and decreased with increasing temperature in the two-phase slag region and the single-phase solid-solution slag region. The PbO-As2O3 phase diagram below 22 mol pct As2O3 was determined by thertrzal analysis and by application of a log ?As2O3/?PbO vS log XAs2o3 /x3pbO plot determined from the equilibrium actiuity data. The resulting phase diagram was not well-defined since the eutectic temperature was not detected in the thermal analysis experiments, although a region of terminal solid solubility of As2O3 was found. Results from the phase diagram determination are compared with an existing diagram in the literature. THIS experimental investigation is an extension of a study by the authors1 on the slag-metal equilibria in the systems concerned with commercial lead refining processes such as softening and dross fuming. The first part of this investigation was a study of the slag-metal equilibria in the Pb-PbO-Sb2O3 system. The only experimental work previously done on the Pb-PbO-As2O3 system was by Pelzel2,3 in which the phase diagram for the PbO-As2O3 system was determined below 50 wt pct As2O3 and the equilibrium constant for the reaction 3Pb + As2O3 + 3PbO + 2As was determined as a function of temperature. No slag-metal equilibrium data have been determined. It is due to the scarcity of information regarding the Pb-PbO-As203 system that this work was undertaken. This paper describes the determination of the slag-metal equilibria in the Pb-PbO-As203 system by equilibrating Pb-As alloys with PbO-As2O3 slags in an inert atmosphere, the effect of 1 wt pct additions of bismuth and copper on the slag-metal equilibria, and the PbO-As2O3 phase diagram both by thermal analysis and the use of the slag-metal equilibria data. EXPERIMENTAL Materials. The materials used in this investigation were analytical reagent-grade and assayed as follows: 1) 99.8 pct PbO (0.014 pct insoluble in CHJCOOH, 0.02 pct not precipitated by H2S, 0.1 pct CaO, and 0.08 pct SiO2); 2) 99.95 pct As2O3; 3) 99.99 pct Pb; 4) 99.0 pct As; 5) 99.99 pct Cu; and 6) 99.97 pct Bi. Room-temperature X-ray patterns revealed no detectable impurities in any of these materials. Apparatus for Equilibrium and Thermal-Analysis Determinations. The resistance-heated crucible furnace used in this investigation employed nichrome elements and was mounted so that it could be raised to surround the reaction tube during each experiment and, subsequently, lowered. A schematic diagram of the apparatus is shown in Fig. 1. Each charge was heated in a 3+-in.-OD by 31/2-in.-high 416 stainless-steel crucible placed in a 41/4-in.-1D by 18-in.-long fused-silica reaction tube which was closed at one end. On a shoulder around the crucible was placed a 3: -in.-OD by 12-in.-long open-end fused-silica condenser tube. The open end of the reaction tube was covered by a water-cooled brass cap with ports for 1) admitting an inert atmosphere to the system through a stopcock, 2) introducing a stainless-steel, motor-driven, paddle stirrer into the crucible, 3) evacuating the system with a mechanical vacuum pump, and 4) sampling the melt with Vycor sampling tubes. The brass cap was fitted to the open end of the reaction tube with a silicone gasket and collar clamp. The furnace temperature was controlled by a Barber-Coleman Capacitrol controller and a chromel-alumel thermocouple. Due to the corrosiveness of the melt, the controlling thermocouple also served as the measuring thermocouple. The temperature of the melt was calibrated against the controller temperature and was checked periodically during each test with a Vycor-enclosed calibrated chromel-alumel thermocouple. The temperature measurement and control can be considered accurate to ±3°C. Procedure. The charge placed in the crucible for each experiment consisted of 1000 g of Pb-As alloy and 300 g of PbO-As2O3 slag. The crucible was then placed in the reaction tube, the condenser tube was placed on the shoulder of the crucible, the silicone gasket and brass cap were fitted on the open end of the reaction tube, and the entire system was evacuated and filled with argon ten times. After the last flushing, a positive argon pressure of 1 psig was impressed on the system. The furnace was then raised to sur-

Jan 1, 1968

By G. S. Cole, H. Biloni, G. F. Bolling

An experimental investigation of sovlze low .melting point alloys sJtows that a substvucture of isolated depressions can be the first manvestation of constitutional supercooling on solid-liquid interjaces veuealed by decanting. Electron-tni cvop vobe and wletallo gvaplic esanzinations, in tlze bulk belzind the interjace, oj the segregation associated with these isolated areas substantiate tlzei&apos;v depressed nature, since a solute of ko < 1 is enriched, and a solute of ko > 1 depleted. In contrast, the pox structuve, a set of projections often veported in the literature, leaves no trace oj. segvegation. These obserl;atims, accovlrpanied by a brief review of recent literature, point to inconsistencies between experirrental obsevvation and the idea that the fornzation of a projection is a causal step in the development of a cellular substructure. An argument is presented to show instead how it is plausible for substantial depvessiom to form in the pvesence of constitutional supercooling at dislocations threading the solid-liquid interjace. THE development of constitutional supercooling during growth from the melt leads to the formation of the cellular solidification substructure. This well-founded association between structure and instability has been basic in understanding cellular substructure and micro segregation; however, the initial formation of structure seems unclear. Rutter and Chalmers,&apos; in definitive experiments and theory, noted that in the presence of constitutional a planar interface might break down: "resulting in the formation of a small projection on an initially plane or uniformly curved interface." That is, the breakdown from a planar to a cellular interface was implied to be initiated via a projection into the unstable liquid. Later, Walton et (11. found that a structure of isolated projections, termed "pox", appeared at solid-liquid interfaces decanted under growth conditions near the onset of constitutional supercooling; the pox were taken as the indication of the instability promoted by the supercooling. Tiller and Rutter4 in their extensive work studied the shape transitions at decanted interfaces which were generally observed to proceed as— pox, "irregular cells", elongated cells, regular (hexagonal) cells, and so forth. The pox varied in size from lo-&apos; to 1CT4 cm, and tended to disappear as cells increased in number and regularity, but as noted,4 the first real array of cells did not seem to be a development from the pox. In fact these authors implied a lack of connection because they stated that the pox are denser on "irregular cells", and as cell boundaries increase in number (i.e., the cells become smaller) there is less need for the pox which do dis- appear. Thereafter, most authors dealing with either experiment or theory have accepted the reality of pox and have used them as a criterion for the onset of constitutional supercooling. In contrast, Spittle, Hunt, and smiths have now suggested that pox are irrelevant artifacts comprised of such things as entrapped oxide. This proposal invokes the observations of weinberg6 and chadwick7 each of whom have shown that the act of decanting leaves a residual liquid on a decanted interface; the remnant solid layer of the order 10 p may thus contain particles that might have been transported from the external surfaces, or elsewhere, during decanting. With the incentive of this suggestion,= some further experiments and a reexamination of the literature have been conducted, in order to question the validity of pox as evidence of an instability and to examine the initial development of the cellular substructure. 1) EXPERIMENTS Single crystals of zone-refined tin (-99.9999 pct) were grown from the melt in a controlled fashion with various, small concentration additions of lead and antimony, for which ko < 1 and > 1, respectively. The crystals were decanted at conditions near the onset of constitutional supercooling and were thus appropriate for observation of slight perturbations. It was possible to observe two types of small departure from smooth or "planar" interfaces in both cases of lead or antimony additions. Some were projections and others, if in regular array of any type, were depressions. The crystals were etched with suitable reagents progressively dissolving the decanted interface surface; projections left no record, but depressions were continuously associated with spotlike areas contrasting with the rest of the interface. Traverses were made with the beam of an electron microprobe across the regions of contrast; with lead addition the persistent spots were lead-rich, and with antimony addition the persistent spots were antimony-poor. This is consistent only with a dominant role for depressions, because if the projections had left spots but were incorrectly catalogued, a reversed observation should have been made; that is, the Pb(ko < 1) should have been depleted and the Sb(ko > 1) enriched. In the work of Cole and inegard, and elewhere, regular arrays of structure associated with the initial stage of instability have been shown, in photographs and represented as pox or projections. We believe this to be erroneous, by inference, since whenever a regular array was observed, in the present examination, it consisted of depressions, regardless of the nature of the solute, ko 1. Fig. 1 is reproduced8 as an ideal example of the possible optical illusion involved; the observer can satisfy himself from the distribution of illuminated areas that the markings are depressions. Fig. 2 from the present investigation is an interference photograph of an interface similar to that in Fig.

Jan 1, 1967

By S. S. Shen, M. J. Pool, P. J. Spencer

Heats of solution of gold and copper in dilute Au-Cu-Sn alloys have been determined using a liquid metal solution calorimeter. The self-interaction coefficient, Au - has been calculated at constant copper concentrations and n cu has likewise been determined at constant gold contents. Good experimental agreement is obtained between the interaction coefficients and nAu Cc thus demonsbating the reliability of the measured heat values. The measured data are compared with the Predictions of certain solution models. In previous publications,1,2 the results of calori-metric investigations of dilute Ag-Au-Sn and Ag-Cu-Sn alloys have been presented. The present work on the Au-Cu-Sn system concludes a program of studies of enthalpy interaction coefficients in dilute alloys of the Group IB metals with tin. Since the definition and derivation of an enthalpy interaction coefficient has been discussed previously,1,2 no restatement of this theory will be presented here. From the determination of the partial heat of solution of gold and copper in ternary alloys of various copper and gold contents, values of the interaction coefficients can be calculated. These coefficients give an insight into the various solute interactions that occur in the liquid solutions since changes in their magnitude and sign reflect bonding changes that are taking place in alloys of varying solute contents. EXPERIMENTAL Details of the design and operation of the liquid metal solution calorimeter used in this work may be found in a paper by Poo1.3 For the present studies copper of 99.999 pct purity was supplied by American Smelting and Refining Co., gold of 99.999 pct purity by A. D. Mackay, Inc., and tin of 99.99 pct purity by Baker Chemical Co. At the commencement of each series of experimental drops, a tin solvent bath consisting of between 70 and 90 g of the pure metal was inserted in the calorimeter. The weight of the bath was accurately determined and to it were added appropriate amounts of gold or copper to give alloys of the desired composition. For determinations of approximately 0.0015 g-atom samples of Cu were used and for measurements of ?HAu approximately 0.0025 g-atom additions of Au. The heat capacity of the bath was determined at regular intervals during a series of drops using tin calibration samples. Measurements were made of the heat of solution of copper in alloys containing a constant 0.01, 0.02, 0.03, and 0.04 mole fraction of Au, respectively, in order to determine ?HCu in each alloy, and the same mole fractions of copper were used to determine equivalent values for nAu at constant copper concentrations. The composition of the bath was maintained at the desired constant gold or copper content by making calculated additions of the appropriate solute throughout the experiments. The limiting values ?HAu in alloys of constant copper content and of %c, in alloys of constant gold content were studied as a function of the mole fraction of copper or gold respectively in order to determine and nCu. Heat content and heat capacity data used in calculating values of ?ºHAu and ?HCu at the experimental temperature of 720°K were obtained from Hultgren et a1.4 &apos; RESULTS AND DISCUSSION Determinations of ?HAu. The partial heat of solution of gold in pure tin as a function of gold concentration was determined in the previous study of dilute Ag-Au-Sn alloys1 and can be represented by the least-squares expression: ?HAu(l) =-8075 + 2413xAu [l] which is valid between XAu= 0.00 and xAu = 0.05. The standard error in the constant term, which represents the partial heat of solution of gold at infinite dilution in tin,?HºAu(l)is 35 cal per g-atom, while the standard deviation of the slope, which represents n Au is ± 619 cal per- agtom. Corresponding expressions for ?HAu(l) in alloys containing constant mole fractions of 0.01, 0.02, 0.03, and 0.04 copper were obtained from the data listed in Table I and are themselves given in Table II. Fig. 1 illustrates the partial heat of solution of gold as a function of its concentration in each of the alloys. For the four alloys of constant copper concentration, the values obtained for ?HºAU(l) (in order of increasing copper content) are -8141 i 36 cal per g-atom, -8210 ± 42 cal per g-atom, -8202 ± 46 cal per g-atom and -8268 ± 51 cal per g-atom. The corresponding values of the self-interaction coefficient, n Au, for these alloys are 3103 * 644 cal per g-atom, 2425 ± 676 cal per g-atom, 2574 * 717 cal per g-atom and 2523 ± 899 cal per g-atom. In Fig. 2 these values of n Au are plotted as a function of the copper content of the alloys and are seen to remain approximately constant within the experimental limits. The addition of increasing, small amounts of copper to dilute binary Au-Sn alloys thus has no apparent effect on Au-Au interactions in these dilute liquid solutions, although more exothermic values of ?HºAu(l) do result from an increase in the copper content of the alloys. Analogous behavior was observed with additions of silver to dilute Au-Sn alloys.&apos; By

Jan 1, 1970

By R. F. Krueger

Results are presented from tests of dynamic fluid-loss rates to cores from clay-gel water-base drilling fluids containing different commercial fluid-loss control agents (CMC, polyacrylate or smt,ch), organic viscosity reducers (quebracho and complex metal lignosulfonate) and oil at several different levels of concentration. In the dynamic system the most effective individual additives to the clay-gel drilling fluid, based on cost-equalized concentrutiom, were found to be starch and the viscosity reducers. These results do not conform with the rankings determined by API fluid-loss rests, which indicate CMC, polyacrylate and starch to be the most effective and comparable. Generally, minimum dynamic fluid-losr rates were attained at cost-equalized concentrations of additive (including thinner) of about $1.00/ bbl, or less. For chernically treated clay-gel drilling fluids, both the standard and the high-pressure API filter-loss tests were found to he inaccurate indicators of trends in dynamic fluid-loss rates under the test conditions used, particulurly for drilling muds containing viscosity reducers. From a practical field viewpoint, restrictions on the applicability of the API fluid-loss test are such that it is open to question whether or not results of this test can be used routinely with confidence as an indicator of control of down-hole fluid loss under field treating conditions. INTRODUCTION The petroleum industry spends large sums of money during drilling operations to control the fluid-loss properties of drilling fluids based on the standard API filter-loss test,&apos; which is a static filtration system. Laboratory studies&apos; &apos; of dynamic filtration have shown that in a given time period filtrate loss from a circulating mud stream is greater than from a static system and that it is a function of linear mud velocity, pressure and the properties of the drilling fluid. Ferguson and Klotz&apos; and Horner, et al," observed that (I) the dynamic fluid-loss rates for the drilling fluids used were not related to the extrapolated API filter loss and (2) the drilling fluids with the lowest API filter losses did not have the lowest dynamic fluid-loss rates. However, there has been no published information on the relative effects on dynamic fluid-loss rate as a given drilling fluid is treated with increasing amounts of chemical additive to reduce the API filter loss. Such information is economically important because drilling-fluid costs rise rapidly as chemical requirements increase. This paper presents the results of a study of dynamic filtratioi rates to cores from a clay-gel water-base drilling fluid treated with various commercial viscosity reducers and chemical fluid-loss control agents. The dynamic fluid-. loss rates to cores are compared with the standard API filter-loss values at several different levels of additive concentration. Dynamic filtration rates were obtained in each experiment under two different simulated wellbore conditions: (1) filtration just above the bit through a new mud cake laid down dynamically on a freshly drilled formation and (2) filtration up-hole through a mud cake formed by deposition of a static filter cake on top of the initial dynamically formed cake. The latter case corresponds to the bottom-hole conditions existing above the bit when mud circulation is restarted after a stand of pipe has been added or a round trip has been made to change the bit. Except for the short-duration, high-rate filtration beneath the bit where no mud cake can form, these two conditions probably represent the two extremes of dynamic filtration. Because thickness of a dynamic mud cake formed on freshly exposed formation is limited by the shearing action of the mud stream, the filtration rate for this condition is high. On the other hand, once circulation is stopped and a static mud cake forms on top of the dynamic cake, re-starting circulation has only a small effect on the cake properties and filtration rate is much lower thereafter. A discussion of the mechanics of mud-cake deposition and dynamic filtration is outside the scope of this paper but may be found in more detail in publications by prior investigators. APPARATUS AND EXPERIMENTAL CONDITIONS The test equipment used to simulate the dynamic flow conditions existing during drilling was a modification of that described previously by Krueger and Vogel: A schematic flow diagram is shown in Fig. 1. In general, a power-driven, high-pressure mud pump capable of delivering up to 60 gallmin was used to circulate drilling fluid parallel to the faces of 1-in. diameter sandstone cores mounted in a 2 3/4-in. ID high-pressure test cell. Pump rates were controlled by means of a magnetic clutch to maintain an average axial fluid velocity of 110 ft/min in the annular space between the cell wall and a 1 1/2-in. rod positioned on the center line of the cell. The core specimens were Berea sandstone plugs sealed with plastic inside 1 1/8-in. OD tubes and were fluid-saturated prior to use. Burettes were used to accumulate fluid discharged from the cores. The mud sump shown was used for treatment and storage of the drilling-fluid samples during a particular test. The valve arrangement permitted either (1) circulating drilling fluid through the by-pass line while treating with

By S. Sumski, M. B. Panish, R. T. Lynch

The liquidus isotherms in the gallium-rich corner of the Ga-Al-P phase diagram have been determined from 1000" to 1200°C and at I100°C the corresponding solidus isotherm was obtained. A simple thermody-namic treatment which permits calculation of the solidus and liquidus isotherms is discussed. A technique which was previously used for the growth of GaxAl1-xAs was used for the preparation of solution epitaxial layers of GaxAl1-xP and ALP. An approximate value of 2.49 i 0.05 ev for the band gap of Alp at 300°K was obtained and the ternary phase data were used to estimate a value of 36 kcal per mole for the heat of formation 0f Alp at that temperature. The Gap-A1P crystalline solid solution is one in which there exists the possibility of obtaining crystals with selected energy gaps, within the limits imposed by the energy gaps of Gap and Alp. Such crystals are of considerable interest because of their potential value for optoelectronic and other solid-state devices. Furthermore, it has been amply demonstrated for GaAs and GaP,&apos;-7 that device, or bulk materials grown from gallium solution generally have more efficient radiative recombination than materials prepared in other ways. This presumably due to the lower gallium vacancy concentration in such material.= Small crystals of GaXAl1-xP and A1P have been grown from solution,8-10 and A1P has been grown from the vapor," but neither have previously been grown by liquid epitaxy. In this paper we present the ternary liquidus-solidus phase diagram of the Ga-A1-P system in the region of primary interest for solution epitaxy, and discuss the thermodynamic implications of that phase diagram with particular reference to the liquidus and solidus isotherms in the gallium-rich corner of the GaxAl1-xP primary phase field and to the A1-P system. Several measurements of the absorption edge of GaxAl1-xP crystals have been made and the width of the forbidden gap of A1P has been estimated from these measurements. EXPERIMENTAL The differential thermal analysis technique used to determine the liquidus isotherms and the optical measurements used in this work are similar to those described previously12 for the Ga-Al-As system, ex- thermocouples in the thermopile for added sensitivity. The materials used were semiconductor grade Ga, Gap, and Al+ The composition and temperature range at which DTA studies could be done was quite restricted. The upper temperature was limited by the chrome l-alumel thermopile to about 1200°C, and the highest aluminum concentration to about 5 at. pct by low sensitivity caused by the reduced solubility of Gap with increasing aluminum concentration in the liquid. DTA studies were not possible at 1000°C and below because of the low sensitivity caused by low solubility of Gap in the Ga-A1-P system. The cooling rate for these studies was about 1°C per min. No heating studies were done because of limited sensitivity. Supercooling probably does occur, but our experience with other 111-V systems indicates that it is no greater than about 10 to 15.c. Solid solubilities were determined by analyzing epitaxial layers of GaxAl1-xP grown from the liquid, with an electron beam microprobe. The layers were grown on Gap seeds by a tipping technique in which the layer is grown over a short-temperature range (20" to 50°C) on the seed from a solution of known composition. The tipping technique reported by Nelsson1 for GaAs could not be used, particularly for solutions containing appreciable amounts of aluminum, because of the formation of an A1203 scum on the liquid surface. A system was therefore designed, which would effectively remove the oxides mechanically, so that uniform wetting and crystal growth could occur. This tipping technique has already been described in detail." The best control over the composition of the re-grown layer was obtained when the tipping was done at a temperature which corresponded to the temperature of first formation of solid for the solution being used. Generally, therefore, a solution was prepared by adding the amounts of Ga, Gap, and A1 required to yield a solution which would be completely liquid above the tipping temperature with solid precipitating below that temperature. For most of the work reported here, the 1100°C isotherm of the ternary was used. It was generally necessary to heat the solution to 50" to l00. C above the tipping temperature to dissolve all of the Gap in a reasonable length of time. The epitaxially grown layers were used both for optical transmission measurements to aid in the estimation of the way in which the absorption edge changed with aluminum concentration, and for the electron beam microprobe analyses to provide data for the determination of the solid solubility isotherm. RESULTS AND DISCUSSION Liquidus Isotherms in the Ga-A1-P Ternary Phase Diagram: Thermodynamic properties of the system. The only thermal effect studied in this work was that

Jan 1, 1970

By I. R. Kramer

A delay time for yielding in cold-worked face-centered-cubic metals was found. Slip on (123) planes was observed. Glide on these planes occurred during the delay-time period before slip starts on the (111) planes. AN important approach to the study of the anchoring and blocking of dislocations is available through the delayed-yield phenomenon which has been observed in body-centered and hexagonal close-packed metal by several investigators. Clark and his associate1-5 showed that a delay time for yielding is present in mild steels and fine-grain molybdenum. Type 302 stainless, SAE 4130 normalized, SAE 4130 quenched and tempered, and 24s-T aluminum aid not have a delay time. Kramer and Maddin6 studied the delay-yield effect. in metal single crystals. While they found a delay time in body-centered-cubic metals none could be found in the face-centered-cubic metals. Later7 a delay time was found in hexagonal close-packed metals. cottrell8 has proposed an explanation for the difference in the yield phenomena of b.c.c. and f.c.c. metals based upon the anchoring of edge dislocations by the proper types of impurity atoms (C and N). In the body-centered-cubic lattice the interstitial atoms are near a cube edge and can interact with an edge dislocation, while in a face-centered-cubic lattice the distortion around an interstitial atom is of spherical symmetry and cannot anchor a screw dislocation which has practically no hydrostatic component. Cottrell&apos;s theory seems to account rather well for the behavior of body-centered-cubic . metals. EXPERIMENTAL PROCEDURE The apparatus used in these experiments is essentially of the same design as described previously.&apos; Single crystals 1 in. long and having a diameter of % in. were placed in a pendulum which consisted of a bar 8 ft long designed with a crystal holder to accommodate the specimen at low temperatures. This portion of the apparatus was supported on fine molybdenum wires. A bar of the same diameter and length comprised the other portion of the apparatus. This bar was supported on a set of roller bearings arranged around the periphery of the bar to allow accurate alignment. This bar was propelled by means of a spring-loaded gun and allowed to strike the lead bar in front of the single-crystal specimen. SR-4 type A-8 resistance strain gages were cemented to the specimen and the strain measurements were obtained by amplifying the strain-gage output by means of a high-gain preamplifier. A tektronix 545 oscilloscope was used together with a polaroid camera to record the strain and time sweep. An Ellis Associate Bridge was used to calibrate the strain gages and calibration readings were obtained before each test. The sweep of the time signal was initiated by means of a miniature thyraton which was fired when the two bars came into contact. The single-crystal specimens were cut from single-crystal bars about 12 in. long, grown by a modified Bridgman technique. The aluminum crystals were made with material of 99.99 pct purity while the purity of the copper was 99.999 pct. A cut-off wheel was used to prepare the specimens which were then machined to the desired length. The two opposite faces of the specimen were parallel to each other and perpendicular to the axis of the specimen. The specimens were compressed 1 pct. No machining followed thereafter. In some cases prestraining was carried out in liquid nitrogen by impacting the specimens directly in the apparatus so that subsequent observations could be made without allowing the specimen to warm up to room temperature. The single crystals were compressed 1 pct at room temperature in a hand press without much control of the rate of deformation. In some cases specimens were recompressed to obtain the desired length change. As far as could be determined in these experiments this factor did not seem to influence the results. The SR-4 strain gages were glued with a cellulose type cement onto the specimen surface and baked at 45°C for 12 hr. As a check on the baking treatment gages were allowed to dry at room temperature. All delay time tests in this paper were conducted in a liquid nitrogen bath at -195°C. A schematic delay time oscilloscope trace is shown in Fig. 1. At point B the elastic stress wave caused by the impact reaches the strain gage on the specimen. The portion BC is the elastic strain. In this investigation the strain at point C was used to calculate the critical resolved shear stress by multiplying by the proper modulus depending upon the orientation of the single-crystal specimen. The time between C and D is the delay time portion of the curve. This portion of the curve is fairly flat but does have a definite microstrain associated with it. After the point D is reached the specimen deforms rapidly and the strain reaches a maximum at E. Following this, depending upon the length of the bar behind the specimen, the strain remains constant for a period and then decreases when the reflected elastic wave returns from the end of the pendulum bar. A permanent plastic strain is recorded on the oscilloscope trace and also measured by a strain-measuring bridge. The strain, E p,

Jan 1, 1960

By R. P. Laforce, ZJ. R. Low, A. M. Turkalo, D. F. Stein

The interaction of the crlloying eletnenls, nickel and chromium, with the impurity elements, antimony, pIzosphorus, tin, and arsenic, to producse reversible temper brittleness in a series of high-purity steels containing 0.40 wt pct C has been investigated. The alloyed steels contained approximately 3.5 pcl Ni, 1.7 pct Cr, and 0.05 to 0.08 pct of the particular irnpurity to be investigated. Susceptibility to teirlper embrittlement was measured by comparing the notched-bar transition temperature of each steel after quenching from the final temper and after very slow cooling (step cooling;) following the final temper. A plain carbon steel without alloying elements, bu/ ud/h 0.08 pel Sh, does not embrittle when step-cooled through the emzbrittling range of temperatures. The same embrittling treatment, applied to a steel with about the same antinzony content but with nickel and chvonziunz added, causes a 700°C increase in transition temperature. If chromium or nickel is the only alloying element, the increase in transition temperature is only 50%, again with antimony present. A carbon-free iron containing nickel, chromium, and antimony shou~s a 200°C shift in transition temperature for the same thermal treatment. Specific alloy-impurily interactions are also observed for the other impurity elements, phosphorus, tin, and arsenic. Additional investigations involving electron microscopy, trzicrohard-ness tests of vain boundaries, minor additions of zirconiutn and the rare earth and noble metals, nzainly with negative results, are also described. HE particular type of embrittlement investigated is that which is encountered in alloy steels tempered in the temperature range from about 350" to 525&apos;C or slowly cooled through this range of temperatures when tempered above this range. This type of embrittlement is sometimes called reversible temper brittleness to distinguish it from the embrittlement indicated by a minimum in the room-temperature V -notch Charpy energy vs tempering-temperature curve encountered in the range 28 0" to 350°C. Temper brittle-ness seriously restricts the use of many alloy steels since it precludes tempering or use in the embrittling range of temperatures and may significantly raise the ductile-brittle transition temperature of heavy-section forgings and castings tempered above the embrittling range, since such sections cannot be sufficiently rapidly cooled after tempering to avoid embrittlement. The very voluminous literature of temper brittle-ness up to about 1960 has been reviewed by woodfine&apos; and LOW.&apos; Of particular significance to the present investigation was the demonstration by Balajiva, Cook, and worn3 that high-purity Ni-Cr steel does not exhibit temper brittleness and the subsequent detailed and systematic study by Steven and Balajiva~ of the effect of impurity additions on the susceptibility to embrittlement of Ni-Cr steels. Steven and Balajiva showed that, of the impurities which may be found in commercial steels, Sb, As, P, Sn, Mn, and Si could all produce temper brittleness in a high-purity Ni-Cr steel. The principal purpose of the present investigation was to study the effects of particular alloy-impurity combinations on susceptibility to temper embrittlement. The steels used were high-purity 0.30 to 0.40 wt pct C steels containing 3.5 wt pct Ni and 1.7 wt pct Cr, separately or in combination. The susceptibility of these steels was then determined when approximately 500 ppm by weight of antimony, arsenic, phosphorus, or tin were added as an impurity. The melting, casting, and forging practices used in the preparation of the materials investigated are described in Appendix A. Table A-I in this appendix shows the analysis of all steels to be discussed. The steels were produced as 20- or 2-lb heats. The smaller heats were used after it had been demonstrated (see Appendix B) that a small, round, notched test specimen could be used to measure the shift in the ductile-brittle transition temperature caused by temper brittleness with about the same result as that obtained by Charpy testing. HEAT TREATMENT Unless otherwise noted, all steels were tested for embrittlement in the tempered martensitic condition. A typical heat treatment for a 0.40 C, 3.5 Ni, 1.7 Cr steel was: 1 hr at 870"C, in argon, quench into oil at 100"C, quench into liquid nitrogen, temper 1 hr at 625"C, and water-quench. The warm oil quench was used where quench-cracking was encountered; otherwise the initial quench was into room-temperature oil or water. For other compositions austenitizing temperatures were 50°C above Acs with the remainder of the thermal cycle the same. Steels in this condition, with no further heat treatment, are designated as non-embrittled. The above quenching and tempering cycle for the 0.40 pct C steels resulted in as-quenched hardnesses of 48 to 53 RC and as-tempered hardnesses of 24 to 31 Rc except in the case of the plain nickel or plain carbon steels. In these, the as-tempered hardness was as low as 80 to 90 Rg. No attempt was made to adjust the tempering temperature to obtain the same hardness in ali steels since it was felt that a uniform thermal cycle was more important than exactly equivalent hardness values. Pro- the standard quench and temper described above, the standard embrittling treatment was "step-cooling". For this the thermal cycle was: 593"C, 1 hr; furnace-cool to 538"C, hold 15 hr; cool to 524"C, hold 24 hr; cool to 496"C, hold 48 hr; cool to 468&apos;C, hold 72

Jan 1, 1969

By C. R. Whitney, G. N. Maniar, D. R. Muzyka

Previous results have shown that Pyromet 860, an Fe-Ni-base heat-resistant alloy, is stable at temperatures as high as 1500°F for aging times as long as 100 hr. This Paper describes the results of long-time creep-rupture testing at 1050" to 1400°F at various stress levels. Times as long as 37,660 hr were employed. The effects of time, temperature, and stress on the precipitates and their morphologies were studied by optical and electron microscopy, X-ray and electron diffraction, and microprobe techniques. phase, containing cobalt, nickel, and molybdenum, was detected after extended exposures from 1200" to 1400°F and careful study was performed to describe the kinetics of its formation in this alloy. µ phase formation apparently has little effect on the elevated-tem-perature properties of Pyromet 860. For times as long as 500 hr at 1300°F and below, with µ phase present, m significant effects on ambient temperature properties were noted. For longer times at 1300°F and after 1400°F exposure, the effects of u phase on ambient temperature tensile strength properties are not clear due to y&apos; effects and grain boundary reactions. Electron-vacancy, N,, numbers were calculated using different methods described in literature and correlated with the present findings. In the selection of alloys for use in gas turbine applications, structural stability ranks as a primary criterion. High-temperature strength and cost are also of major concern. With these factors in mind, Pyromet 860 alloy, an Fe-Ni-base superalloy was designed. This alloy combines the cost advantages of Fe-Ni-base alloys such as A-286, 901, and V-57 with improved strength and structural stability&apos;1,2 and no tendency to form the embrittling cellular 77 phase. A previous study3 reported on the stability of Pyro-met 860 at temperatures from 1375" to 157 5°F and times up to 100 hr. That study showed that the y&apos; precipitates increased in size and separation and decreased in number with an increase in time or aging temperature. No deleterious phases were found to occur. In the present work, samples from four production heats were subjected to long-time creep-rupture testing at 1050" to 1400°F at various stress levels. Various heat treatments were used on the starting samples and tests were run up to 37,660 hr. The effects of time, temperature, and stress on the precipitates and their morphologies were studied by optical and electron microscopy, X-ray and electron diffrac- tion, and microprobe techniques. Electron vacancy numbers, Nv , calculations were made by TRW.4 Experimental results are correlated with the Nv data used to predict occurrence of intermetallic phases such as a phase. EXPERIMENTAL PROCEDURE Mechanical Tests. Material for the present study came from four production size heats of Pyromet 860 alloy, weighing from about 3000 to about 10,000 lb. All of these heats were made by vacuum induction melting plus consumable electrode vacuum remelting. The nominal analysis for this alloy is compared with the actual analysis of the four heats in Table I. Sections of these heats were forged to 9/16-in. round bar,3/4-in. square bar, 3-in. round bar, 4-in. square bar, and a gas turbine blade forging about 16 in, long, about 6 in. wide, and weighing about 20 lb. In general, all forging of this alloy is done from a 2050°F furnace temperature. Longitudinal test blanks were cut from the centers of the smaller bars, from mid-radius positions for the 3- and 4-in. bars, and from the air foil of the gas turbine blade and heat-treated according to the procedures outlined in Table 11. Heat treatment A is the "standard treatment" recommended for this alloy for best all-around strength and ductility. Heat treatment B is a modification of treatment A for improved tensile strength at moderate temperatures. The treatment coded C was designed for treating large sections according to a procedure previously described.&apos; Heat treatment D was developed to yield optimum stress relaxation characteristics at 1050°F for a steam turbine bolting application. After heat treatment, the test blanks were machined either to plain bar creep specimens with a gage diameter of 0.252 in., to combination smooth-notched stress-rupture bars with a plain bar diameter of 0.178 in. and a concentration factor of Kt 3.8&apos; at the notched section, or to notch-only specimens. All specimens conformed to ASTM requirements. Metallography. Most of the creep-rupture tests were continued to failure. A few bars were fractured as smooth or notch tensiles after creep-rupture exposures. After fracturing, ordinary metallographic sections were made primarily in gage areas adjacent to fractures to represent a "high-stress" region and through specimen threads to represent a "low-stress" region. All metallographic sections were made in a longitudinal direction with respect to the test specimen axes. For optical microscopy, the samples were etched in glyceregia (15 ml HC1, 5 ml HNO,, 10 ml glycerol). For XRD analysis, the phases were extracted electrolytically in two media: 20 pct &Po4 in H20 for selective extraction of y&apos; and 10 pct HC1 in methanol for carbides and other phases.

Jan 1, 1970

By W. M. Yim

Experimental results are presented which indicate that transverse striations in horizontal zone-leveled Bi-Sb alloy crystals are due to irregular growth rate resulting from thermal fluctuations in the melt (Iring gowth. Thc thermal fluctutations arose from two different sources. The first type was brought about by periodic fluctuations in the furnace temperature. The second type can be attributed to turbulent therrrol conlcclion in the trzelt near the solid-liquid inteyace. Tile arrzplitlcde ond fvequency of the tetiperaticre fluctlrations vesultity from llle lhevnal con1,ecrrell. The striation spacings in Lhe crystals covvelale well with the periodicity 0.f the tempevature flueluatiors. Altliough the strialiors represenl corrlpositiozul inhoiHogeneity oh a rzicroscule, less than f.z cil. be1 S6 in Best&apos;s as deterrirzed by electron-pro be chalq&apos;sis, the slriations roerre fbund to ILUL&apos; no rrleusuanble effect on electical vesistirity rwr on weak field macgnetoresistance of. the Bi-Sb a1lu.y in the ternpevutue ),unge 4.Polo 300°K. DURING the course of an investigation on the horizontal growth of semimetals,&apos; it was found that crystals of Bi-Sb alloys contained many closely spaced parallel arrays of striations. These striations occurred perpendicular to the growth direction and parallel to the solid-liquid interface. We shall refer to them as transverse striations, or just striations&apos;&apos;, to distinguish them from lineage substructures or longitudinal striations which form parallel to the growth direction and have been known to be associated with cellular structures.&apos; Similar transverse striations have been reported previously to occur in other materials prepared by horizontal growth: metals,4 semiconductors,5 as well as their alls. - Various methods of crystal preparation have apparently little effect on the occurrence of the transverse striations. They form whether the crystals were grown by the vertical Czochralski technique, withe1&apos; or without&apos;3- rotation, or by the horizontal zoning methd.- Thus, the transverse striations are not limited to any one class of materials, nor to any particular method of preparation. It is likely, therefore, that all of the observed transverse striations may have some common cause. Previously, workers agreed that periodic changes in the growth rate bring about the striations. However, no agreement exists as to the origin of the growth-rate fluctuations. Some attributed the discontinuous growth to a purely external cause, such as fluctuations in the furnace temperature, jerky motions in the crystal pulling mechanism, or a nonsymmetrical temperature distribution in the melt (in the case of crystals grown by the Czochralski technique with rtation). Others looked for the cause in some fundamental property of the growth process itself. For instance, a certain degree of supercooling is required to initiate growth from the melt. But, with further growth, the degree of supercooling decreases because of the liberation of the heat of solidification at the solid-liquid interface. Thus, crystal growth would be brought to a halt until sufficient supercooling is resotred and the cycle begins again.3&apos;11 According to this model, periodic fluctuations in the melt temperature should exist at the solid-liquid interface. Since the periodic fluctuations in growth rate would result in changes in the segregation coefficient of solute atoms, crystals containing the transverse striations may, in some cases, show a periodic impurity fluctuation along the length, resulting in a degradation of electrical properties. The resistivity striations in doped germanium&apos;9-10 or lnsbB are well-known examples of this microsegregation. The present work was undertaken to explain the exact origin of the transverse striations, and to assess the extent of their effect on chemical homogeneity as well as on electrical properties of Bi-Sb alloy crystals. Results from our previous study of the crystal growth of Bi-Sb alloys1 indicated that the transverse striations may arise from the temperature fluctuations in the melt during growth. This paper will show that the melt temperature fluctuations are indeed responsible for the occurrence of the transverse striations. I) EXPERIMENTAL Although the transverse striations have been observed in all slow-grown Bi-Sb alloys across the entire compositional range, we selected a composition, Big3Sbs, for the present study in view of the extensive data available on the crystal growth of this alloy from a previous study.&apos; High-purity bismuth and antimony, both a 6-nine grade by the manufacturer&apos;s emission spectrographic analysis, were used throughout. Independent mass-spectrographic analysis showed, however, that the starting materials were more nearly a 5-nine grade. each containing metallic impurities of approximately 10 ppm atomic. In zone-leveled Big5Sb5 alloys, the total metallic-impurity content was slightly lower, about 7 ppm atomic, indicating that some degree of purification was achieved during the growth. None of the electrically active impurities, such as tin and lead (acceptors) and tellurium and selenium (donors), were present in significant quantity in undoped Bi95Sb5. Typical analysis of the undoped Bi95Sb5 alloy is shown in Table I. Nonmetallic impurities, such as carbon and oxygen, were detected, sometimes as much as 100 ppm, in both the starting materials and the zone-leveled alloys: but the data were only qualitative. Temperature fluctuations in the melt were monitored over 1 or more days by means of a 5-mil chromel-

Jan 1, 1967

By W. D. Robertson, W. L. Phillips Jr.

Stress-strain curves were obtained for single crystals of alpha brass in tension and in direct shear. Specimens were strained various amounts in a given slip direction, unloaded, and immediately strained in a second slip direction 60°, 120°, or 180&apos; from the original slip direction. Crystals strained in tension and direct shear had comparable critical resolved shear stresses and stress-strain curves. The density of slip lines in direct shear and in tension was essentially the same. The stress-strain curves obtained in shear were independent of initial orientation, choice of {111 } slip plane, choice of <110> slip direction, prior annealing temperature, and rate of cooling after annealing. There was no recovery after annealing for 4 hr at room temperature or 200°C; recovery was observed after 4 hr at 400°C. The crystals showed no asterism and mechanical properties were completely recoverable up to 20 pct strain. It was found that there is a barrier to slip in all latent close-packed directions, and that the magnitude of these barriers, evaluated at 3 pct strain, is proportional to prior strain and independent of the choice of latent direction in the {111} plane. The formation of Cottrell-Lomer barriers is discussed as a possible explanation for the hardening of the latent systems. AN idealized concept of plastic deformation indicates that a single crystal should yield at some stress that is dependent on crystal perfection and it should then continue to deform plastically by the process of "easy glide," which is characterized by a linear stress-strain curve and a low coefficient, ds/dE, of work-hardening. Hexagonal metal crystals generally conform to this ideal concept of laminar flow. In face-centered cubic metals the range of easy glide is always restricted in magnitude and it is strongly dependent on orientation, composition, crystal size, shape, surface preparation, and temperature. Since one of the principal differences between the two crystal systems, both of which deform by slip on close-packed planes, is the existence of secondary (latent) slip planes in the face-centered cubic crystals, it has been proposed that the transition from easy glide to turbulent flow, characterized by rapid linear hardening, is due to slip on secondary planes intersecting the primary plane.&apos;-.; However, the characteristic differences between individual face-centered cubic metals remain to be explained; in particular, it is not clear why the range of easy glide should vary so greatly in different metals and alloys similarly oriented for single slip. An investigation and comparison of different metals with respect to latent hardening on the primary slip plane should provide some of the information required to specify the necessary and sufficient conditions governing the transition from easy glide to turbulent flow. But, in order to accomplish this purpose, plastic strain must be produced by simple shear in a chosen plane and in a predetermined direction by some form of directed shear apparatus, the results of which must be correlated with the corresponding tension experiments. Two such experiments have been performed previously with zinc and with aluminum. Edwards, Washburn, and Parker" and Edwards and Washburn7 found that the strain-hardening coefficients in two latent directions in the basal plane of zinc were the same as in the primary direction. However, to initiate and propagate slip in either the [2110] or the [1210] direction, following primary slip in the [1l20] direction, it was necessary to increase the stress above that required to continue slip in the primary direction; when the direction of shear was reversed 180 deg plastic strain began at a much lower stress than that required to initiate slip in the original direction and the stress to propagate slip in the reverse direction was lower than the stress to continue slip in the forward direction, indicating a permanent loss of strain-hardening. Rohm and Kochendorfer observed softening in aluminum for all latent close-packed planes and directions. They also found that the critical resolved shear stress obtained from their direct shear apparatus was 50 pct lower than the value obtained from conventional tension tests, that the stress-strain curve was linear at 50 pct plastic strain, and that slip lines were not visible at strains less than 30 pct. At present it is uncertain whether these diverse results correspond to real differences in work-hardening characteristics of the close-packed planes of aluminum and zinc or to differences in experimental technique. In view of Read&apos;s analysis &apos;" of the stress distribution in the experimental arrangement of Rohm and Kochendorfer, there is some reason to question the significance of the latter results. In order to resolve this problem it is necessary to re-valuate the direct-shear technique and either repeat the previous measurements or investigate a third system. The latter choice seemed most likely to produce significant results with respect to work-hardening, and accordingly, it was decided to examine the hardening characteristics of the latent slip directions in alpha-brass. The choice of alpha-brass was dictated by the fact that easy glide is more extensive in this alloy than in any other face-centered cubic metal or alloy and, presumably, more nearly like the idealized hexagonal system. Experimental Procedure Crystals were made in graphite by the Bridge-man method in the form of cylinders, 11/2 in. diam and 8 to 9 in. long. Material for the crystals was 70/30 brass containing the following impurities:

Jan 1, 1959

By W. F. Chiao

With the application of dislocation damping theory an attempt was made to determine whether the generation and extension of dislocations is inherently more difficult in a brittle steel than in a ductile steel. A ductile steel was compared with a brittle stee1 by simultaneously measuring the ultrasonic attenuation and velocity during tensile test, and the density of free dislocations and their mean loop length were then calculated as a function of strain. The results showed that in the ductile steel there was always a large generation of dislocations and great extension of loop length occurring at some stage within the early plastic region. In contrast, the brittle steel showed very little or no such sudden changes in dislocation dynamic states after the onset of plastic deformation. Furthermore, a strong temperature dependence of dislocation dynamic states was also observed in the ductile steel and a hypothesis was suggested that a thermally activated process of dislocation rearrangement could occur at higher deformation temperatures. The activation energy of dislocation rearrangement at room temperature was estimated as about 2030 cal per mole.C. DUCTILITY is an indispensible property in the application of engineering materials, especially steel. During the past two decades the theoretical and experimental approach to the understanding of flow and fracture of metals has been constantly undergoing changes and progress." while the fracture behavior of metals can be influenced by many factors such as chemical Composition,3 second-phase particle mor-phology,4 and dislocation arrangement,5 it is now a general belief that the fundamental understanding of the ductile-brittle fracture phenomena of solid materials must stem from the study of dislocation dv-namics developed under stress conditions.6,7 Most of the traditional ductility tests, such as Charpy impact test, slow bend test, and tensile fracture test, cannot by themselves reveal directly the mechanisms of ductile to brittle transition of materials. In the experimental investigation of tensile ductility it would be ideal to be able to study directly the dynamics of dis-locations in a bulk specimen during the process of deformation. Since the ultrasonic pulse technique is the only satisfactory method for studying dislocations and the fine details of deformation characteristics in metals in the course of a tensile test, it would appear that a comparative study of ultrasonic attenuation changes during tensile tests of metallic materials exhibiting different ductility might be very informative. So far no work comparable to this study has appeared in the literature. Recent progress in both theory and experiment has indicated the feasibility of studying the dislocation mechanisms of ductility behaviors by ultrasonic measurements during tensile test. Granato and Lucke8 have developed a quantitative theory that enables the calculation of dislocation density and their average loop length from the measurements of ultrasonic attenuation and velocity, and several investigators, including Chiao and Gordon,9&apos;10 have shown that simultaneous ultrasonic measurements can be successfully made during a tensile test. Furthermore, many investigators11-13 have repeatedly proposed in the past several decades that deformation and fracture are mutually self-exclusive, and that the ability or inability of a material to deform plastically, i.e., to generate dislocations, is a major factor in determining whether the material will be ductile or brittle. Thus, in the present work an attempt was made to determine whether the generation and extension of dislocations is inherently more difficult in a brittle steel than in a ductile steel. This article is principally concerned with the study of the relation between the propagation of ultrasonic waves and tensile deformation in a steel series which displays quite different toughness at room tempera-turk. changes in attenuation and velocity of ultrasonic waves have been measured as a function of strain during the deformation process. The results have been interpreted in terms of the vibrating string model for dislocation damping as developed by Granato and Lucke, and it has been found that some of the more subtle predications of the model are in good agreement with the experiments. This would be especially meaningful because most of the previous experiments in testfying the model were carried out with single crystals of high-purity materials and little work has been done with polycrystalline steel alloys. EXPERIMENTAL PROCEDURES AND RESULTS Specimen Materials. The tensile specimens used throughout this experiment were of two compositions selected from a series of Fe-Mo-0.77 pct Mn-0.22 pct C steels prepared for a ductile-brittle fracture transition study. One steel contains 0.21 pct Mo and the other 1.03 pct Mo. These two compositions were chosen for the present study because they possess quite different toughness properties at room temperature. The 0.21 pct Mo steel is quite ductile while the 1.03 pct Mo steel is rather brittle, as measured by the standard Charpy impact test. The alloys had been prepared by vacuum induction melting and chill casting in steel molds. The ingots were hammer-forged into 1/2-in.-sq bars from which tensile specimen blanks were cut. These blanks were first normalized under argon atmosphere at 1700°F and then reaus-tenitized and isothermally transformed at 1050°F to a bainitic microstructure. The chemical compositions, heat treatments, hardness measurements, and Charpy transition temperatures of the two steels are listed in Table I.

Jan 1, 1970

By Pradeep K. Rohatgi, Clyde M. Adams

Dendritic aggregate of ice formed on freezing of aqueous soluitions has been studied. Chlorides of sodium, potassiutn, lithiunz , and hydroget1 were used as solutes. The spacing between ice platelets or den-drites was experimenlally found proportzonal to the square root of freezing time when the freezing rate was constant from beginrting to end of solidification; the constant freezing rates were obtained during freezing of small droplets of aqueous soliitions surrounded by relatively large heat sinks. The transverse growth velocity of the ice platelets is proportional to the square root of the freezing rate. During unidirectional freezing from a constant temperuture chill, the solution at each location is subjected to a spectrum of freezirtg rates. The freezing rate is ini- FREEZING of solutions has been a subject of investigation in many disciplines. Aqueous solutions offer the advantage of transparenty; their study is of special significance due to the increasing interest in freezing processes for desalination. In addition dendritic solidification of aqueous solutions is in many ways analogous to freezing of metallic solutions. Aqueous solutions of most ionic salts freeze with tially low, passes through a maximum, and then decreases until solidificatimz is complete. The den-drite spacing increases linearly with the distance from the chill surface; it is inversely profiortional to the square root of the maximum freezing rate. The dendrite spacings in the two systems (the constanl freezing rate and the varying freezing rate) are equal, when the maximum freezing rate of the varying freezing rate system equals the average freezing vale of the constant freezing rate system. Mass transport in interdendritic liquid duriug solidificatiotz is analyzed; the experimental observations indicate that maximum concentration difference (AC) and supercooling (AT) in the interdendritic liquid are indepexdent of freezing rate. the separation of practically pure ice crystals from the liquid phase; with very few exceptions there is no solid solubility of ionic salts in ice. As an ice crystal grows there is rejection of solute from the moving interface into the liquid. Since the rejected solute moves primarily by diffusion, concentration gradients are established in the liquid. The highest solute concentrations are found in liquid immediately adjacent to liquid-solid interfaces and lowest concentrations farthest from the interface. Two-phase equilibrium obtains only at the solid-liquid interface; at other locations the liquid becomes supercooled because temperature gradients are negligible compared to concentration gradients. This is an immediate consequence of the fact that thermal diffusivities are considerably higher than mass diffusivities.

Jan 1, 1968

By S. S. Clarke

THEN sufficient ore has been blocked out on a lease to warrant a shaft, the proposed. Location of the shaft should be carefully considered, as the old promoter&apos;s method of sinking wherever his hat landed is a sad mistake as some: of us have learned by trying to operate such mines. In some instances certain conditions exist, such as mill location, railroad right of way, etc., that necessitate a change of location from the. ideal, but under average conditions and with the knowledge of the formation gained from the drill logs and with the general trend of the orebody known, the shaft can be located from. the standpoint of its future relation to the mine with re-gard to hauling and&apos; hoisting a maximum tonnage: at a minimum cost per ton, also taking into account the minimum amount of expense and trouble- in sinking. Quite a few shafts are located in the wall of a run or just in the thin edge of the orebody: As a general rule the formation here is solid and permits rapid and safe sinking, and the shaft pillars are left in practically valueless material. This permits the withdrawal of pillars and still keeps the shaft protected. By opening a shaft in thin ground, you are not tempted to cut it high, wide, and handsome, but to shape it up-with ample clearance for lay-bys and with more of an idea of permanency, as a few hundred extra dollars spent around the shafts for proper track installation will re-turn, a good rate of interest in ease of handling "cans," quick get-away; and fewer wrecks. Nearly all the shafts in this district are sunk on a contract basis, the con-tractors furnishing all labor and explosives, and the company building the sinking-derrick, dump-track, and furnishing, all equipment, material, and power. The following costs are the averages, for three shafts sunk through good solid formation, with no water to, contend with, and approximately 260 -ft., deep, having about-100 ft. of shale. The contract price was $9 per foot with the shale and $13 per foot in the solid, making a total of $2,980 paid to the contractor. The wages paid by the contractor were, $5 per shift for the hoist-man, who also sharpened steel, $6 for the lead shaft man, and $5 for the helper;, the cribbing was sawed on contract for 40c. per shaft: foot; about. 94 board feet. of cribbing was used per foot of staggered cribbing and 168 board feet per foot of solid cribbing.

Jan 8, 1928

By Lawrence Veiller, D. Eppelsheimer

D. Eppelsheimer, * Middletown, Ohio.—The housing of employees has so many and so varied aspects that in order to reach even an approximately correct solution it is necessary to have in mind a few fundamental principles; but it is not possible as yet to write these housing principles in the clear and correct form that is possible with many of our natural laws. Manifestly, the problem depends first on the kind of people it is necessary to house. What is suitable for the Southern unattached negro is not suitable for the married skilled American. The influx of colored labor has affected quite a number of what were satisfactorily housed communities. The second important factor is the relative proportion of the number of employees to the total employable population of the community in which the industry is located. The employer of a hundred men in a large city has little responsibility in the matter of housing his employees. If he employs 75 per cent. of the employable population in a community of 27,000, as is the case of the company with which the writer is connected, it means a large responsibility. In the establishment of an entirely new plant in a more or less isolated place, the responsibility becomes greater. As engineers, we design and write the specifications for the machinery to accomplish a definite purpose, and proceed to house it, provide the necessary buildings with their accessories in the way of cranes, or heating systems, or sprinkling systems, as the case may be. There is no reason why the operating force should not be built up in very much the same way: design the organization, write its specifications so that the employment department can secure the proper men, and then house that organization with just as much thought and care as is given the plant. In the plant, the various machines will work along certain definite lines and accomplish certain results; but even if we start with the proper organization it takes considerable time to get that organization working together. One of the most important elements to this end is the proper housing of the organization. A man usually spends more time at home than at work. Proper surroundings and a comfortable, convenient house of good appearance exercise an influence that cannot be denied, and an employee situated in such surroundings is far more inclined to follow the policies of his employer and take an active part in furthering them than one dissatisfied with his home and surroundings, which feeling

Jan 1, 1919

By Mark Sheppard

DURING the winter of 1937, the writer visited a West Virginia stone quarry at which the overburden is stripped hydraulically. The quarry is in a bed of limestone, about 200 ft. thick, which outcrops on a hillside above a small river; the quarry face is 175 ft. high. The top of the stone is cut in all directions by erosion channels, which are filled with a tough, red clay. Some of the larger channels are 30 ft. deep and 8 ft. wide. The thickness of the clay overburden ranges from a few inches to 10 ft., the average being estimated as less than 3 feet. The topography of the district is rugged, and the hillside above the quarry face is not suited to the use of the usual mechanical methods of moving dirt. Until hydraulicking was started 10 years ago, the over- burden was dug by hand labor, dumped to the quarry floor and transported to the dump in quarry cars. Cleaning deep channels was a slow and expensive process. When hydraulicking was started, the top of the quarry face was over 200 ft. above the level of the river. The pipe line was carried in a semi- circle around the top of the quarry about 200 ft. from the face and about 50 ft. above it. As there is no adequate supply of water above the quarry, the water must be pumped from the river. As quarrying progressed the pipe line was moved until the discharge points are now over 300 ft. above the river. Water is pumped from the river by a four-stage centrifugal pump having a 5-in. intake and a 4-in. discharge. It is direct-connected to a 200-hp., 2300-volt, 1760-r.p.m. induction motor. At 1760 r.p.m. the rated capacity of the pump is 750 gal. per minute under a head of 600 ft. The pump is installed in a house of frame construction on the river bank, about 10 ft. above normal water level, which also houses the pump for the mill-water supply. Above the pumps are hoisting bays into which the motors are raised whenever the river reaches flood stage. An 8-in. suction line, equipped with a strainer and a foot valve, takes the water from a concrete sump at the edge of the river. The pipe line from the pump consists of 1750 ft. of 8-in. spiral steel flanged pipe and 800 ft. of 4-in. spiral steel flanged pipe. The connection from the pump

Jan 1, 1938

By L. L. Foley, C. V. Millikan

The discovery of Bromide production in the Fitts field, shallow production in Jackson County of Southwestern Oklahoma, abundant production in the Edmond field, and discovery of many small pools in all parts of the state, were the events that made petroleum history in Oklahoma in 1934. Wildcatting was much more active, as evidenced by a number of new discoveries. There was no important development in the older fields. The rapid decline of the potential of the Oklahoma City field was an important feature of the history of the year. The accompanying tabulation of oil fields (Table 1) is not complete. Many of the early records of operators and pipe line companies are lost and it will be impossible to work up complete statistics for a number of the older fields. The table includes most of the important fields of the state and includes fields of a number of different types. It is hoped that a great many additional fields may be worked up for next year&apos;s report. Fitts Pool.—The Fitts pool, in Pontotoc County, was discovered in 1933. Before the middle of 1934, the Pennsylvanian sands yielded -some oil at depths ranging from 1400 to 2800 ft. The Hunton series (Siluro-Devonian) produced most of the oil with considerable gas. In July, 1934, a well in sec. 25, T.2N., R.6E. was completed in the Bromide (Ordovician " Wilcox ") with an initial production of about 300 bbl. a day. Less than a month later a second Bromide sand well was completed in sec. 30, T.2N., R.7E., which made over 200 bbl. an hour. This started an active drilling campaign, which was accelerated when some of the major companies paid good prices for adjacent acreage. At the end of the year, 23 wells had been completed and the rate of development was increasing rapidly. It is a major oil field. The Fitts pool opened a new geological province for oil production. The structure is a faulted anticline in a graben. The producing formation (Bromide) and the Arbuckle lime below it crop out about 2 miles south of present production. The Hunton lime crops out about 2½ miles north. The field is in a sharply folded and faulted area on the northeast side of the Arbuckle uplift. Heretofore, it was generally considered not favorable for oil production, although some gas had been found in various places. The play has extended east into the McAlester coal basin, and southeast toward the

Jan 1, 1935

By Keith Leonard Sutherland

This paper is a study of the differential flotation of the sulphide minerals in the presence of salts of silver, lead and zinc. In practice, accidental activation due to these salts is more important than their use as reagents to replace copper sulphate. The general method of investigation has been based upon contact tests, the temperature of 35°C being chosen in conformity with earlier work. Potassium ethyl xanthate and potassium amyl xanthate were selected as collectors and pure sulphide minerals were used. The experimental procedure has been outlined in earlier papers and all solutions were kept carbonate-free.14 Contact, or spreading of an air bubble, at a mineral surface indicates the presence of an adsorbed collector film. Purity of Reagents The xanthates were purified in the usual manner.&apos; Neither the cyanide nor the sodium hydroxide solutions contained sufficient carbonate to give a precipitate with barium chloride solution. The silver sulphate was prepared from pure silver nitrate by evaporation with concentrated sulphuric acid until there was no evidence of brown fumes, This solution was diluted and the difficultly soluble sulphate washed with water so that unchanged nitrate was dissolved. The resultant crystalline powder was pure white. The lead and zinc salts were prepared by dissolving especially pure lead and zinc in C.P. nitric and sulphuric acid solution and the crystals drained. The standard solutions were checked by titration. It was felt desirable to use the sulphate radical wherever possible, but since lead sulphate was insufficiently soluble for the purpose of the experiments, it was necessary to use some other lead salt. A.R. copper sulphate was used without further purification. Results The results are presented in the accompanying figures; the areas of noncontact (nonflotation) are shaded in Figs. 8, 9, 10 and 11; in the remainder they lie to the right of the curve. Zinc Sulphate The curves in Fig. I are to be compared with those for Fig. 2, for which zinc sulphate is absent. This comparison shows that the influence of the zinc ion is usually small. Its influence is more marked, however, for chalcopyrite in the absence of cyanide. The influence of zinc sulphate is also marked for copper-activated sphalerite, for which tests were made only in the "absence of cyanide. The results are of importance in the separation of pyrite from copper-activated sphalerite when zinc sulphate is added in the lead flotation section (p. 204 of ref. I). Sphalerite does not adsorb the collector (i.e., become floatable) under the conditions chosen.

Jan 1, 1943

James Douglas will long be remembered as a distinguished mining engineer and metallurgist, as a scientist with broad vision, as an executive whose understanding of practical problems coupled with his knowledge of men and affairs enabled him to weld together great mining interests and to their service build railroads and bring power. More, he will be recalled as a philosopher and a writer of charm, a historian of no mean order, and one whose catholic tastes and enthusiasms led him into the fields of education, medicine and theology. His aim was to possess that which he considered made life worth while—friends and effectiveness in whatever task he undertook. In this aim he was successful to a degree exceeded by few, as thousands of his friends and associates could and can testify. Dr. Douglas was born on November 4,1837, at Quebec, Canada. His father, James Douglas, Sr., was a prominent physician and the leading surgeon of Canada. He also established the first retreat for the insane in the Dominion, the Quebec Lunatic Asylum, to which he devoted his services for years; The son followed in the footsteps of his father and studied medicine, not only in Canada but also in Scotland and in Germany. He entered the University of Edinburgh in 1855 but after two years at that institution returned to Canada and was graduated from Queens university at Kingston, Ontario, .with the degree of Bachelor of Arts. Later he went to Lava1 University, Quebec, and subsequently became professor of chemistry at Morrin College, Quebec. After he was graduated—at the time he considered his formal education completed—he traveled with his father in Europe and in the Orient; visiting Egypt, being especially interested in that country, several times. They gathered together an important archaeological collection which later was donated by them to the Metropolitan Museum of Art in the city of New York. James Douglas was also greatly interested in photography, a hobby in which he made use of his chemical knowledge. The writer can remember distinctly the descriptions he gave more than forty years ago in Arizona of the difficulties he encountered with the old wet photographic plates, especially while traveling in Egypt, when he prepared and used his own chemicals. In his humorous manner he told how he once discovered, in the nick of time, the nurse preparing to give the baby in the party a rub-down, using for that purpose the white, limpid

Jan 1, 1934