Search Documents

By S. L. Craig, C. Orr, H. G. Blocker

WITHIN recent years gas adsorption methods have been developed for measuring the surface area of finely divided materials and have become extremely valuable in research on the corrosion and the catalytic activity of metals. Rather elaborate apparatus is required, and a single determination is so time-consuming that these methods have not been utilized to the fullest extent; the methods are un-suited for most routine control work such as that encountered in powder metallurgical operations and in processes employing metal catalysts. These difficulties are largely eliminated, and surface area is reduced to a routine determination if the liquid-phase adsorption of a surface-active agent such as a fatty acid can be used. When the affinity of the fatty acid carboxyl group for the solid surface is greater than its affinity for the solvent, a unimolec-ular layer of orientated fatty acid molecules will be formed at the solid-liquid interface in a manner similar to that of a compressed fatty acid film on a water surface. The measurement of surface area is then reduced to a measurement of fatty acid adsorption. This propitious circumstance, first investigated by Harkins and Gans,¹ has been employed with somewhat inconclusive results by a number of investigators in evaluating the surface properties of metals, metal catalysts, and metal oxides. The specific surface area values for nickel and platinum catalysts, determined from the adsorption of a number of fatty acids from various solvents, were found by Smith and Fuzek² to agree with values calculated by the gas adsorption technique of Brunauer, Emmett, and Teller," he so-called BET technique. And recently Orr and Bankston4 have also reported good agreement between nitrogen gas and stearic acid adsorption results in the measurement of the surface areas of clay materials. On the other hand, Ries, Johnson, and Melik5 found only order-of-magnitude agreement between these two methods in studying supported, cobalt catalysts having specific surface areas as great as 420 sq m per g; the reason is partially attributable to the very porous nature of the materials. Greenhill,6 investigating the adsorption of long-chain, polar compounds in organic solvents on a number of metal powders, concluded that a uni-molecular layer of stearic acid was formed on exposure of the solid to the acid solution and that the presence of an oxide or another film did not alter this result. Furthermore, the adsorption process appeared to be the same whether or not the sample was degassed prior to exposure to the solution. Greenhill estimated the surface area of one of the powders he investigated from microscopic diameter measurements, and obtained a rough check with surface area evaluation. Russell and Cochran7 found moderate agreement for alumina surface area results by fatty acid and gas adsorption methods. In addition, they also found that the prolonged heating and evacuating pretreatments previously used by investigators were unnecessary. The present work, however, considerably extends these previous investigations, shows that fatty acid adsorption can be used to determine the surface area of a variety of metals and metal compounds, offers further confirmation of the correctness of gas adsorption methods, and presents a simplified technique for the determination of the metal surface area which is suitable for routine work. Experimental Technique Basically, the fatty acid adsorption method is quite simple. It consists of exposing a sample of the material of which the surface area is desired to a fatty acid solution of known concentration. By analysis of an aliquot of the solution, the concentration after adsorption has occurred may be determined. The difference between the initial quantity of acid in solution and the final quantity is that quantity of acid adsorbed by the sample. The specific surface area of the adsorbent material may be calculated from the quantity adsorbed and the weight of the sample. In agreement with the findings of others as outlined above, it was found entirely unnecessary to degas or pretreat the nonporous materials employed other than by drying them thoroughly. However, precaution was necessary so that the dried sample entered the fatty acid solution with little exposure to moisture. The effect of moisture on the interaction of stearic acid with finely divided materials has been thoroughly investigated by Hirst and Lancaster." They found the presence of water merely reduced the amount of acid adsorbed by powders such as TiO2, SiO2, Tic, and Sic. With reactive materials such as Cu, Cu2O, CuO, Zn, and ZnO, however, water was found to initiate chemical reaction. Only with ZnO was reaction observed when the solid and the solu-

Jan 1, 1953

By L. H. Van Vlack, T. Y. Tien, R. J. Martin

The phase relationships of the MnTe-MnS system were studied by DTA procedures. There is an eutectic at 810°C with about 10 mole pct MnS-90 mole pct MnTe. An eutectoid occurs at about 710°C with approximately 7 mole pct MnS where the MnTe(NaCl) solid solution dissociates on cooling to MnTe(NiAs) and MnS. There is very little solid solubility of MnTe in MnS. ALTHOUGH MnS may exist in three different crystal forms,' only the NaC1-type phase is stable.2 Above 1040°C, MnTe also has the cubic NaC1-type structure. Below that temperature, MnTe changes to the NiAs-type structure.3 This phase transition is rapid for both heating and cooling. As a result the high-temperature crystal form of MnTe cannot be retained at room temperature. Because MnO, MnS, and MnSe are all stable with the NaC1-type structure, and MnTe has this structure at high temperatures,4 solid solution formation could be expected among these compounds. It is interesting to note, however, that a complete series of solid solutions exist only in the MnS-MnSe system,' and that the solid solution is quite limited in the MnO-MnS system.' The MnSe-MnTe system possesses a complete series of solid solutions at high temperatures with separation at lower temperatures.7 Although ion size may be critical in the miscibility of MnO-MnS, it is quite possible that the bond type plays a more important role with the miscibility of MnSe-MnTe. This would permit us to speculate that the miscibility gap would be extensive in the MnTe-MnS system. EXPERIMENTAL Preparation. The samples were prepared by mixing and compacting MnTe and MnS powders. The MnS was previously prepared through the sulfur reduction of Mnso4.8 The MnTe had been prepared by mixing and compacting double vacuum distilled metallic manganese and high-purity tellurium in stoichiometric ratio modified with 1 wt pct excess tellurium. The compacted powders were put in a graphite crucible which was sealed in an evacuated vycor tube. The free space in the vycor tube was made minimal to reduce the loss of tellurium. The sealed assembly was then heated slowly to about 500° C where the free manganese and tellurium reacted vigorously, melting the MnTe which formed. Only one phase, MnTe, was detected by X-ray powder patterns and metallographic techniques. Each compact of MnTe-MnS was placed in a graphite crucible and then sealed in an evacuated vycor tube. The samples were heated at 1250°C for 4 hr and furnace-cooled. Microscopic examination revealed no third phase beyond MnS and MnTe. A typical microstructure is presented in Fig. 1. Identification. X-ray powder patterns were obtained using 114.6 mm Debye-Scherrer camera and Fe-Ka radiation. Mixtures of cubic MnS and hexagonal MnTe were observed in all of the compositions prepared. No lattice parameter change was noticed among different compositions, indicating no solid solution could be retained at room temperatures between these two end-members. A lattice parameter of 5.244Å for MnS was obtained by the Nelson and Riley9 extrapolation method using the diffraction lines of (h2 + k2 + 12) equal 12, 16, 20, and 24. The values, a = 4.145Å and c = 6.708Å, for hexagonal MnTe were obtained from the (006) and (220) lines in the back-reflection region. These values agree well with the values reported by Taylor and Kag1e.10 Differential Thermal Analysis. A differential thermal analysis procedure was used to determine phase relationships since the high-temperature equilibrium conditions could not be retained for examination at room temperature, even when the sealed samples (~0.5 g) were quenched in water. The samples were sealed in an evacuated 4 mm vycor tube with a recess in the bottom to accept a thermocouple. An Al2O3 reference was similarly prepared and the two placed within a piece of insulating fire brick to dampen spurious temperature changes within the furnace. The furnace was controlled by a mechanically driven rheostat which increased the temperature at a rate of about 15°C per min. Known phase changes in the Pb-Sn system1' and the a-to-ß quartz inversion12 were used for calibration

Jan 1, 1969

By A. H. Daane, A. S. Wilson

The U-Cr system is of the simple eutectic type with some solid solubility of chromium in r and ß uranium. The eutectic occurs at 20 atomic pet Cr and melts at 859°C. The maximum solubility of chromium in y uranium is 4 atomic pet at the eutectic temperature, and in ß uranium the solubility is estimated to be 1 atomic pet. y-ß and ß-a transformations were found to occur at 737°estimatedt° and 612°C respectively. DURING 1944 and 1945, the U-Cr constitution diagram was studied in this laboratory as a part of a research program on uranium metallurgy in the Manhattan Project, and the work was described in a Manhattan Project report issued in December 1945. This paper is based on that report, which has been declassified. Prior to this study, it had been shown by other Manhattan Project workers that the low Cr-U alloys could be quenched to retain the form of uranium. Experimental The uranium used in this work was massive metal prepared in this laboratory and contained less than 0.1 pct of other elements. The chromium was 200 mesh powder obtained from the A. D. McKay Co. and was found on analysis to be 99.5 pct Cr with 0.3 pct Fe the major impurity. Alloys, weighing 400 to 600 g, were prepared by induction heating the components to 1700°C in slip-cast ZrO, crucibles in a vacuum of 3x103 mm Hg. TO prevent too violent agitation of the melt by the induction field with subsequent crucible breakage and sample loss, the ZrO2 crucible was placed in a graphite crucible, which was surrounded by a layer of powdered carbon insulation 2 to 3 cm thick. Polished vertical sections of the alloys were examined microscopically to confirm their homogeneity. Heating and cooling curves were taken on the alloys by reheating them in ZrO, crucibles to 1200°C and inserting a mullite-protected chromel-alumel thermocouple into the melt by means of a slip seal in the vacuum head of the furnace. A recording potentiometer traced the curves which had a slope of from 3" to 6" per min. Samples of the alloys were prepared for metallo-graphic examination by conventional mechanical polishing techniques followed by an electrolytic polish in an ethylene glycol-phosphoric acid-ethyl alcohol bath. The structure of the alloys was brought out clearly by this procedure so that no further etching was required. Samples for chemical analysis were taken from drillings from the top, center, and bottom sections of the alloys. The uranium was determined by titra-tion with Ce(SO1)2, while the chromium was titrated with FeSO,; the uranium and chromium totaled at least 99.6 pct in all of the alloys prepared. X-ray samples were prepared by filing bulk specimens in a helium-filled glove box and annealing the resulting powder in a zirconium-gettered helium atmosphere. A 114.6 mm diam Debye-Scherrer camera and a Weyland nonsymmetrical self-focusing camera were used with filtered copper radiation to obtain the powder X-ray diffraction data. Results The data obtained in this study have been combined to construct the constitution diagram of the U-Cr system shown in Fig. 1 where the arrests observed in cooling curves are indicated by dots. The liquidus arrest was quite distinct in thermal data taken on alloys in the range 0 to 20 atomic pct Cr. The eutectic arrest was not observed in studies on the 2.5 and 4.5 pct Cr samples but appeared in the 7.5 pct samples, which suggested some solubility of chromium in y uranium. On quenching from 859 °C, the 2.5 pct sample showed but one phase while the 4.5 pct sample contained a small amount of the eutectic along the grain boundaries; see Figs. 2 and 3. From this the maximum solubility of chromium in r uranium has been set at 4 pct. X-ray studies on these samples showed that the r phase was not retained at room temperature by quenching, but in each case a pattern was observed .which has been identified with the ß phase of uranium. Thermal data show the y-ß transformation of uranium lowered to 737°C as a consequence of this solubility. On quenching from the ß range (660°C), precipitation of chromium in the primary uranium is observed in the 2.5 and 4.5 pct Cr samples (see Figs. 4 and 5),

Jan 1, 1956

By P. C. Johnson, B. A. Stein

This paper describes a study of the effects of combined heat treatment and explosive loading on the mechanical properties of high-strength steels. nis program investigated two distinct areas: 1) the effect of shock waves, without gross irreversible defmmution, on a 3-Cr steel at various stages of heat treatment; and 2) the effect of rapid deformation (explosive forming) on H-11 and D6-AC steels in the metastable austenitic state. The mechanical properties of these steels were improved, in some cases markedly, as a result of these treatments. ,AUSFORMWG, which requires the plastic deformation of metastable austenite, is a process which can appreciably improve the properties of selected alloy stee1s.l,2 The Ausform process significantly increases the strength of these steels without decreasing their ductility. The properties at high temperatures are also improved through a change in the response of the steels to tempering. Although the mechanism by which ausforming alters the properties of these steels is not fully understood, it appears that the dislocation arrays produced by deformation of the metastable austenite influence the structure of the martensite on subsequent transformation. This, in turn, affects the strength, ductility, and tempering response of the martensite. This research used chemical explosives to deform steels at various stages in their heat treatment in order to improve the properties of these steels. The explosive energy is used in two ways; 1) high-pressure shock waves are propagated through the steel to produce extensive microscopic shear strain without causing a large irreversible change in shape, and 2) explosive energy is used to cause extensive macroscopic plastic strain in the metastable austenitic state (explosive forming). I) AUSFORMING WITH INTENSE SHOCK WAVES The steel used in this phase of the research was an alloy having a nominal composition 0.43 pct C, 3.0 pct Cr, 1.5 pct Ni, and 1.5 pct Si. The steel was subjected to intense shock waves in three conditions: 1) in the metastable austenitic state, 2) in the tempered mar tens itic state, and 3) in the tempered martensitic state after ausforming by conventional techniques. The specimens were in the form of disks 2.75 in. in diam and 5/16 in. thick. These were incorporated into a specimen assembly consisting of two disks pressed into a 5 by 5 by 1 in. block of stainless steel, Fig. 1. Spalling (or scabbing) is confined to the front disk. The specimen is protected from oxidation and decarburization by the surrounding metal. The temperature of the assembly is monitored by a thermocouple inserted into one side of the stainless steel block. The assembly is positioned over an oil reservoir which serves both as a means of catching the disks and as quenching medium for the disks shocked under ausforming conditions. Plane shock waves are introduced into the assembly by a metal driver plate impacting the top surface of the block. The driver plate is accelerated by a chemical explosive sheet supplied by E. I. du Pont de Nemours & Co. All the specimens were subjected to plane shock waves having a peak pressure of approximately 430 kbar. The pressure is that quoted by G. E. Dieter for the plane wave generator used in this work.' The driver plate used was 1/4 in. thick, so that the initial pulse was essentially a l/2-in.-wide square wave. The attenuation of the peak pressure during the subsequent 1/4 in. is estimated to be less than 5 pct. The shock front induces a temperature rise, a portion of which is irreversible. Rough estimates (+25 pct) of this temperature rise have been made for iron shocked at room temperature.4 For a 500-kbar shock wave, the temperature rise in the shock front is about 700°F, and is held for a time of the order of microseconds. The irreversible temperature rise, which remains after the shock wave passes, is about 450°F.4 The disks are quenched to room temperature within a few seconds of the shock treatment. It should be emphasized that the temperature rises given above are estimates for pure iron at room temperature, and are not necessarily true for the tests made in this work. The disks shocked at temperatures in the metastable austenitic range were austenitized in the stainless steel assembly in a furnace protected from the firing area. The assembly was removed from the furnace and placed over the recovery reservoir. The plane wave generator was then positioned and

Jan 1, 1963

By E. T. Turkdogan, Klaus Schwerdtfeger

OelSEN and Maetz1 detected some 20 years ago the existence of a miscibility gap in iron oxide-CaO-P2O5 slags melted in iron crucibles at about 1400°C. Because of the importance of this system for the dephos-phorization of steel in the basic Bessemer process, equilibria between liquid iron and selected iron oxide-CaO-P2Q slags have been measured since by numerous investigators.2-5 When in equilibrium with metallic iron, the iron oxide of the slag is present mainly as FeO. In connection with oxygen-blowing steelmaking processes, it is useful to know the phase relations in the slag system at higher oxygen pressure, when major parts of the iron oxide are present as Fe2O3. This problem was investigated by Turkdogan and Bills7 by equilibrating the oxide mixtures contained in platinum crucibles with CO2-CO mixtures at 1550°C. It was found that increasing the Fe2O3 content decreases the composition range of the miscibility gap strongly so that the miscibility gap has almost disappeared at pco2/pco = 75. This result was refuted by the careful work of Olette et a1.,''' who equilibrated their slags with controlled Ha-H2-Ar gas mixtures. Their equilibrium measurements, at 1600°C and at oxygen pressures of 5 x 10"* and 10"5 atm, showed that the oxidation state of the iron has almost no influence on the formation of the miscibility gap. The present experiments were undertaken to check the previous results of Turkdogan and Bills. The experiments were performed at 1625°C in the strongly oxidizing atmosphere of air (PO2 = 0.20 atm) for which no experimental data are available. About 10 g of slag were melted in platinum crucibles and held at constant temperature for 1 hr. After equilibration, the crucible was rapidly pulled out of the furnace and cooled in air. The platinum crucible was removed from the sample. The two slag layers were carefully separated with a small diamond disc, and the surface of the top layer, which may have changed its oxidation state during cooling, was removed. The slags were crushed and analyzed chemically for CaO, P2O5, Fe2+, and Fetotal. The starting mixtures were prepared by sintering the desired amounts of reagent-grade 2CaO . P2O5 - H2O, CaCO3, and Fe2O3. Sintering and subsequent crushing were done three times to ensure homogenization. Molybdenum wire resistance heating was used. The furnace was provided with a recrystallized alumina reaction tube which was left open to air at the top. The temperature was controlled electronically. The reported temperature was measured with a Pt/Pt-10 pct Rh thermocouple and is estimated to be accurate within +5°C. The composition of the equilibrated melts is given in Table I. For the graphical illustration of these quaternary slags the type of projection suggested by Trömel and Fritze10 was used. In this representation, Fig. 1, the composition point of a mixture within the tetrahedron Fe2O3-CaO-P2O5-FeO is projected into the Fe2O3-CaO-P2O5, triangle (triangle I) so that the direction of projection is parallel to the side FeO-Fe2O3, and into the triangle Fe2O3-P2O,-Fe0 (triangle 11) so that the direction of projection is parallel to the side CaO-P2O5, of the tetrahedron. The projected point has the coordinates wt pct CaO, wt pct P205, and wt pct (FeO + Fe2O3) in triangle I and wt pct FeO, wt pct Fe2O3, and wt pct (CaO + PzO5) in triangle 11. Both triangles are turned into the same plane around the Fe203-P20, side of the tetrahedron. An illustration of the projection of a quaternary point in the present system is shown in Fig. 1. The advantage of this type of projection is that all four components for an equilibrium curve can be read directly from the diagram. The present results are shown graphically in Fig. 2. The curves depicting the miscibility gap are dashed in parts where no experimental points were obtained. The composition range covered by the miscibility gap

Jan 1, 1968

By Norman Lamont

The evaluation of certain reser-voir properties, such as porosity and fluid saturation, from electrical well surveys has been widely accepted in petroleum engineering. Various investigators have established relationships between these properties and certain parameters which affect the response of the electrical log. Among these are the resistivities of the mud, its filtrate, and its filter cake. In 1949, Patnode1 established a relationship between the resistivities of the mud and filtrate. The well logging service companies have contributed relationships for the mud-mud cake resistivities2,3 These have been valuable since it was the practice to measure only resistivity of mud at the well site. During the mid-1940's the industry began drilling wells with oil-emulsion drilling fluids. These were conventional aqueous muds with a dispersed oil phase. Since 1950, oil-emulsion muds have been used on an increasing number of wells each year. However, the practice of measuring only the resistivity of the mud at the well site has continued, and the mud filtrate and mud cake resistivities have been determined by the above-mentioned relationships. Service companies are now equipped to measure all three resistivities at the well site. An investigation was conducted on the resistivities of oil-emulsion muds, mud filtrates, and mud cakes to determine if these values conformed to the relationships for aqueous muds. TYPES OF MUDS Fifty-one oil-emulsion mud samples were prepared in the laboratory following a standard manual' published by a leading mud company. The diesel oil in the samples varied from 5 to 50 per cent, the majority of the samples being in the 10 per cent region. The basic aqueous mud types which were converted to oil-emulsion muds were commercial clay and bentonite muds, low pH and high pH, caustic-quebracho treated muds, and lime treated muds. The emulsions were stabilized by dispersed solids, lignins, lignosulfo-nates, sodium carboxymethyl cellulose, or sulfonated petrolatum. It is worthy of note that after a quiescent period of two weeks at room temperature all samples, regardless of emulsifying agent, remained stable. The make-up water for the muds was from the laboratory tap. Resistivities were varied by the addition of table salt to the water. A range of mud resistivities from 0.44 to 3.9 ohm-m was obtained in this way. Twenty-three field muds were tested. These covered the same range of mud types as did laboratory muds. Oil provinces of the Gulf Coast, South Texas, West Texas, Oklahoma, Montana, and Canada were represented. MUD TEST PROCEDURE Each mud was tested for density, viscosity, pH, and filter loss by standard testing techniques. The resistivity measurements were obtained with a Schlumberger EMT meter. This meter required small volumes of sample, e.g., 2 mm. Filtrate was obtained from a Standard Baroid fil-ter press at the end of a 30-minute test. The filter cake from the same test was used for cake resistivity measurements. Mud, filtrate, and cake samples were heated to 100" F in a constant temperature water bath prior to measurement of resistivities. RESULTS The relation between mud resistivity (Rm) and mud filtrate resistivity (Rmf) is shown in Fig. 1. The solid line represents an average for the data. The equation of this line is Rmf =0.876 (Rm) 1.075 . . (1) Arbitrary limits, indicated by the dashed curves, have been set. The majority of the data falls within these limits, but some points do lie outside the limits. The approximate equation Rmt = 0.88 Rm , . . . . (2) will give satisfactory results within these limits. The data on mud cake resistivity Rmc is shown in Fig. 2. The solid line is an average for the data. The equation for the line is Rmc = 1.306 (Rm)0.88 The dashed lines are arbitrary limits on the data. Within these limits, Eq. 3 may be simplified to Rmc = 1.31 Rm . . . . (4) DISCUSSION The limiting curves in Figs. 1 and 2 represent maximum deviations of ±25 per cent. Thus the use of the average curves can introduce considerable error. There is no substitute for accurate measurements of mud, mud cake, and mud filtrate resistivities at the well site. The mud sample tested should be representative of the mud opposite the formation being logged. The average mud filtrate resistivity curve of Fig. 1 is reproduced in Fig. 3 with two curves which have been published for clay-base aqueous muds2,3. The latter curves were determined from average values of a large number of drilling fluids. The three curves have essentially the same slope and the differences between them are from 7 to 22 per cent. Comparison is made only to illustrate the possibility of error

Jan 1, 1958

By R. O. Williams

Analytical representation of the thermodynamics of solutions is highly desirable from the standpoint of accuracy, compactness, and numerical manipulations. In particular, computer calculations are greatly implemented. Mathematical considerations show that previous expressions have one or more serious defects. This investigation shows a Fourier series to be satisfactory but that it is also possible to derive a new series which fits certain additional conditions. Included examples show the value of analytical expressions in giving a simple characterization of each system using some two to five parameters, the elimination of the Gibbs-Duhem integration, and the es timation of the error for the experimental function as well as derived functions. It is further shown that the present characterization provides easy comparison between systems. IN the past, thermodynamic calculations have depended to a considerable extent on tabular and graphical methods. As the volume and precision of such data increase such methods become less satisfactory. Specifically, the selection of the optimum representation and the estimation of errors require statistical methods which in turn require analytical representation. The utilization of such data require further manipulations which are best done analytically for maximum precision. For example, phase equilibria are determined by common tangents to free-energy curves: a graphical determination is normally of low accuracy. As computers are increasingly used analytical representations become almost mandatory. Insufficient mathematical consideration has been given previously to the selection of empirical expressions. Those expressions having some theoretical justification are generally too inflexible and mathematically unattractive. We consider the problem in some detail and show that a Fourier series can be effectively used. Also a new series is defined which has certain advantages. ANALYSIS We wish to consider the analytical representation of the heat of mixing, AH, the excess free energy, ?Gxs, and the excess entropy, ?sXS, as a function of composition, X, for binary solutions relative to the pure components in the same state. When a distinction is not required, we use W to denote any one of the above functions. One may use a Taylor expansion around X = 0 to generate a power series. As the derivatives are un- known we represent the series as W = A + BX + CX2 + DX3 + EX4 + ... [l] where the constants A , B, C , ..- are to be selected to provide some optimum fit. For the extremes of composition W is necessarily zero so it follows that A = 0 [2a] B +C + D + E +••• = 0 [2b] Nonelectrolytes, which we are considering, appear to satisfy the condition that d3W/dx3 = 0 [3] in the terminal regions. This is the basis of the a, ß, and Q functions used by Hultgren et al.' and others. While this condition does not have a strong theoretical basis it does appear desirable that any analytical relation should satisfy this condition. Darken2 and Turk-dogan and Darken3 have shown that many systems exhibit this behavior over an extended range from each terminal region, departure being restricted to a limited intermediate region. Since we have no a priori knowledge as to where this transition occurs we can require that this condition be satisfied only as a limit at the extreme compositions as a general condition. We will show later how more restricted conditions can be included in specific solutions. Darken2 has called this behavior the quadratic formalism; we call our application the limiting quadratic formalism, LQF. This condition applied to the above power series requires that D = 0 [4a] 4-3-2E +5-4-3_F + 6 • 5 . 4G + ••• =0 [4b] The form of the power series normally used, due to Margules,4 is W=X(1-X)(A + BX + CX2 + DX3 + EX4 + •••) [5] where A, B, C, --. are a new set of constants. (Guggenheim5 has given a variation of this expression in a more desirable form. Since, however, it is contained in the above expression it does not require separate consideration.) This form is precisely what results by incorporating the conditions in Eq. [2] into the power series and regrouping the constants. The LQF requires that B =C [6a] and 4.3.2(D-C) +5-4-3(E-D) + ••• =0 [6b] Thus, the correct form of the Margules expression with two adjustable parameters is w =X(1-X)[A + B +X2-2/3x3)] 171 and the EX4 term must be included before three adjustable parameters are permitted.

Jan 1, 1970

By E. M. Porbansky

DURING the investigation of the electrical transport properties of copper, it became necessary to prepare large single crystals of the highest obtainable purity. In an effort to meet these demands, single crystals of copper have been grown by the conventional pulling technique—as has been used for the growth of germanium and silicon crystals.' Low-temperature resistance measurements made on these crystals show that, as far as their electrical properties are concerned, they are generally of significantly higher purity than the original high-purity material. The use of these pure single crystals with very high resistance ratios has made possible the acquisition of detailed information regarding the electron energy band structure of copper2-' and has stimulated widespread effort on Fermi surface studies of a number of other pure metals. It is the purpose of this note to describe our method of preparing very pure copper crystals by the Czochralski technique. Precautions were taken to prevent contamination of the melt from the crystal growing apparatus. A new fused silica growing chamber was used to prevent possible contamination from previous groqths of other materials such as germanium, silicon, and so forth. A new high-purity graphite crucible was used to contain the melt. This crucible was baked out in a hydrogen atmosphere at -1200°C for an hour, prior to its use in crystal growth. Commercial tank helium, containing uncontrolled traces of oxygen, was used as the protective atmosphere. A trace of oxygen in the atmosphere appears to be necessary for obtaining high-purity copper single crystals. A 3/8-in-diam polycrystalline copper rod of the same purity as the melt was used as a seed. The copper rod was allowed to come in contact with the melt while rotating at 57 rpm. When an equilibrium was observed between the melt and the seed (that is, the seed neither grew nor melted), the seed was pulled away from the melt at a rate of 0.5 mils per sec. As the seed was raised, the melt temperature was slowly increased, so that the grown material diminished in diameter with increasing length. When this portion of the grown crystal was -1 in. long and the diameter reduced to less than 1/8 in., the melt was slowly cooled and the crystal was allowed to increase to - 1-1/4 in. diam as it was grown. By reducing the diameter of the crystal in this manner, the number of crystals at the liquid-solid interface was decreased until only one crystal remained. Fig. 1 shows a typical pulled copper single crystal. The purity of the starting material and the crystals was determined by the resistance ratio method: where the ratio is taken as R273ok/R4.2ok. The starting material, obtained from American Smelting and Refining Co., was the purest copper available. Most of the pulled copper crystals had much higher resistance ratios than the starting material. The highest ratio obtained to data is 8000. Table I is an example of the data obtained from some of the copper crystals. Note that Crystal No. 126 had a lower resistance ratio than its starting material and this might be due to carbon in the melt. The melt of this crystal was heated 250" to 300°C above the melting point of copper. At this temperature it was observed that copper dissolved appreciable amounts of carbon. The possible presence of carbon at the interface between the liquid and the crystal will result in reducing conditions and negate the slight oxidizing condition required for high purity as discussed below. The possible explanations of the improvement in the copper purity compared to the starting material are: improvement in crystal perfection, segregation, and oxidation of impurities. Of these, the latter seems to be most probable. A study of the etch pits in the pulled crystals showed them to have between 107 and 108 pits per sq cm. The etch procedure used was developed by Love11 and Wernick.10 The resistivity of the purest copper crystal grown was 2 x 10-10 ohm-cm at 4.2oK; from the work of H. G. vanBuren,11 the resistivity due to the dislocations would be approximately 10-l3 ohm-cm, which indicates that. the dislocations in the copper crystals would contribute relatively little to the resistivity of the crystals at this purity level. Segregation does not seem likely as the reason for purification of the material, since the resistivity of the first-to-freeze and the last-to-freeze portions are approximately the same, as was observed on Crystal No. 124. On most of the crystals that were examined, the entire melt was grown into a single crystal. If the

Jan 1, 1964

By W. Rostoker, A. S. Yamamoto, K. Anderko

ALTHOUGH the corrosion resistance of magnesium and its alloys is closely related to iron content, there has been no direct measurement of the solid solubility of iron in magnesium. Bulian and Fahrenhors;1 and Mitchel]2 agree that pure iron or a limited terminal solid solution crystallizes from the Mg-rich liquid. For this reason a magnetic-moment method was selected to estimate that portion of the total iron content which is not in solid solution. Since iron in solid solution in magnesium cannot contribute to ferromagnetism, the difference between chemical and magnetic-iron analyses should yield the solid solubility. By experimentation it was found that the melting of pure sublimed magnesium (99.995 wt pet purity) in Armco-iron crucibles at about 800°C is a convenient way to introduce small amounts of iron. Melts retained 5, 10 and 20 min at 800°C analyzed 0.003,, 0.005,, and 0.018 & 0.001 weight pet Fe, respectively, after being stirred, heated to 850°C, and cast into graphite molds. The as-cast alloys were pickled in acid (dilute HC1 + HNO3), annealed at 600°C for 3 days, scalped on a lathe to remove the pitted surface, pickled again, extruded at about 100°C to 3-mm wire, reannealed 41/2 days at 500°C, and water-quenched. The specimens were again scalped, pickled, and used both for chemical and for magnetic analysis. Most of the precautions described were intended to prevent iron pickup by contact with tools or superficial iron enrichment by volatilization of magnesium during heat-treatment. It is believed that the specimens ultimately used for test were homogeneous and characteristic of phase equilibria at 500°C. Magnetic Analyses A susceptibility apparatus of the Curie type was used for magnetic analyses. Field strengths of up to 10,400 oersteds could be generated. By this method, an analytical balance measures the force of attraction which a calibrated magnetic field exerts on a suspended specimen. The force equation is as follows f/m = M dh/dy where f/m = force per unit mass of sample M = magnetic moment per unit mass dH/dy = magnetic field gradient The dH/dy characteristic of the instrument is determined by the use of a standard palladium sample, and the calibration is made independently for all values of H. Since a large finite field is required to saturate an assembly of ferromagnets, it is necessary to measure the apparent magnetic moment for increasing steps of H until a saturation value is obtained. The percentage of iron in the sample as free ferromagnetic iron may then be computed simply C= 100 (M1/M1) where C = percent content of undissolved iron in sample M1 = saturation magnetic moment of sample per unit mass M1 = saturation magnetic moment of iron per unit mass taken as 217 emu-cm per gm There is no serious difficulty in applying this method except for the unusual magnetic behavior of very fine particles of ferromagnetic substances. It has been found and is the basis for a widely accepted theory that with sufficient subdivision, the magnetic fields required to saturate and the coercive force after saturation rise to exceedingly high values. Recent work on precipitates of Fe and Co from copper solid solutions8 showed that about 5000 oersteds were necessary to approach saturation. The magnetic moments as a function of field strength measured in the present investigation are listed in Table I. Only the 0.018 wt pet Fe alloy yielded a magnetization curve with a fairly well-defined saturation plateau at 3.76x10 -2 emu-cm/ gm. This corresponds to 0.017 & 0.001 wt pet Fe in the alloy. This indicates that the solid solubility must be of the order of 0.001 wt pet Fe. The magnetic-moment data of the other two alloys are badly scattered, indicating that the amount of ferromagnetic iron in these samples is so low that the magnetic forces acting on them cannot be measured accurately by the analytical balance used. Nevertheless, the fact that even the 0.003, wt pet Fe alloy shows ferromagnetism indicates that the solid solubility must be below that value. Acknowledgment This work was sponsored by the Pitman-Dunn Laboratory of Frankford Arsenal, Philadelphia, Pa. The support and permission to publish are gratefully acknowledged. References W. Bulian and E. Fahrenhorst: Zeic. Metallkunde, 1942, vol. 34, pp. 116-170. 2 D. W. Mitchell: AIME Transactions, 1948, vol. 175, pp. 570-578. 3 G. Bate, D. Schofield, and W. Sucksmith: Philosophical Magnsine, 1955, vol. 46, pp. 621-631.

Jan 1, 1959

By T. L. Chu, G. A. Gruber

Silica films hare been rleposited 011 silicon substmtes at 400° to 600°C by a chemical-transport technique using hydrogen fluoride as the transport agent ill a closed system. This transport takes place from a source materia1 1071: temperature to substrates at higher temperatures, as indicated by the thermochemistry of the transport reaction. The experimental variables of- the transport process, such as the substrate temperature, the pressure pi the transport agent, and so forth, have been studied. The rate -determining step of the transport process appears to he the ),ale of chemical reaction in the source region. The transported films are similar to thermally grown silica films in physical proper-ties with the exception of 'some what higher dissolrrtion rates. SILICA films deposited on suitable substrates serve many purposes in electronic devices. They are used for the fabrication of tunneling devices, the surface passivation of devices, and the shielding of devices from nuclear radiation: and as selective masks against the diffusion of specific impurities into semiconductors. Doped silica films can also be used as sources for the diffusion of impurities into semiconductors. Several oxidation and deposition techniques for the preparation of silica films have been developed to meet the requirements of these applications. The therma1 oxidation of silicon by oxygen or steam at temperatures above 900 C is commonly used in silicon technology. The deposition techniques are perhaps more advantageous since they usually require lower temperatures and are not limited to silicon substrates. Silica films have been deposited on silicon and other substrates by reactive sputtering and chemical reactions. The sputtering of silicon in an oxygen atmosphere is capable of depositing good-quality silica films on silicon' and gallium arenide. Many chemical reactions are known to yield silica at room temperature or higher. These reactions may involve intermediate steps. However, the final step yielding silica should take place predominately on the substrate surface in order to produce adherent films. When silica is formed in the gas phase by volume reactions, no adherent deposit can be obtained. Generally, the experimental conditions of a reaction can be varied so that the surface reaction predominates over the volume reaction. The chemical reactions which have been used successfully for the deposition of silica films are briefly as follows. The pyrolysis of alkoxysilanes in an inert atmosphere or under reduced pressure has been employed to deposit silica films on germanium3 and silicon4 at 650" to 750°C in a flow system. The deposition of silica films from alkoxysilanes has also been achieved at nearly room temperature by a low-pressure plasma. Device quality silica films have been deposited on germanium and gallium arsenide by the deposition of an amorphous thin silicon film followed by oxidation at 600" to 700" . Silica films for high-temperature capacitors have been produced by the hydrolysis of silicon tetrabromide at 950°C in argon and hydrogen atmospheres.7 We have developed a chemical-transport technique for the deposition of silica films on semiconductor substrates at relatively low temperatures. The thermochemistry of the transport reaction, the experimental variables of the transport process, and the properties of the transported silica films are described in this paper. THERMOCHEMICAL CONSDERATIONS The transport of solid substances by chemical reactions in the presence of a temperature gradient has been used for the preparation of films and crystals of many electronic materials. In this technique, a gaseous reagent is chosen so that it reacts reversibly with the solid substance under consideration to form volatile products. Since the equilibrium constants of most reactions are temperature-dependent, the transport of these products to regions of suitable temperature in the reaction system would cause the reverse reaction to take place. depositing the original solid. When the equilibrium is shifted toward the formation of the solid as the temperature is decreased, the solid is transported from a high-temperature zone to a lower-temperature region, and vice versa. This chemical-transport technique can be carried out in a closed or gas-flow system. In a closed system, chemical equilibrium is presumably established in the different temperature regions of the system, and the transport agent regenerated in the deposition region repeats the transport process in a cyclic manner. The local chemical equilibrium may not be approached in a flow system: however, this system offers a greater degree of flexibility. Silica reacts reversibly with hydrogen fluoride and this reaction was chosen for the transport process. The over-all reaction between silica and hydrogen fluoride may be written as: SiO2(s) + 4HF(g-) = SiF4Ur) + 2H2O(^)

Jan 1, 1965

By Shiou-Chuan Sun

THE presence of an excessive amount of tough froth in the flotation of minerals, particularly coals, may create trouble in dewatering, filtering, and handling. Froth is also a nuisance in many chemical industries.' This paper presents a study on the destruction of extremely tough froths with intense high-frequency sound. The data indicate that sound waves can be employed for continuous atandsoundwavescan instantaneous defrothing. A powerful high-frequency siren was used in obtaining the data. Also tested was an ultrasonorator of the crystal type with a frequency range of 400, 700, 1000, and 1500 kc per sec and a maximum power output from its amplifier of 198 w. The results, not presented, indicate that as now designed this machine is not suitable for defrothing. Although the sound generators of the magnetostriction type2,3 and of the electromagnetic type'.' were not available, it is beelectromagneticlieved they are capable of producing the required sound intensity for defrothing. The use of ultrasonics for defrothing was suggested by Ross and McBain1 in 1944. Ramsey8 reported in 1948 that E. H. Rose mentioned a supersonic device that broke down flotation froth but with low capacity. The writer has not been able to find any published literature containing practical experiments. Theoretical Considerations The mechanism of defrothing by sound is attributed to the periodically collapsing force of the propagated sound waves and the induced resonant vibration of the bubbles. The collapse of froth is further facilitated by the sonic wind and the heat of the siren. Sound waves can exert a radiation pressure'," against any obstacle upon which they impinge. When a froth surface is subjected to the periodic puncturing of sound waves, the bubbles are broken. According to Rayleigh9 and Bergmann,12 the radiation pressure of sound, P, in dynes per sq cm is given as: P = 1/2 (r+1)i/v where r is the ratio of the specific heats of the medium through which sound is traveling and is equal to 1 on the basis of Boyle's law; i is the sound intensity in ergs per sec per sq cm, and v is the sound velocity in cm per sec. In this case, the accuracy of the formula is only approximate, because a perfect reflection can hardly result from a column of froth. In addition to the radiation pressure, the propagated sound waves cause the bubbles of the froth to have a resonant vibration.'" he vibratory motion of the bubbles causes collision and coalescence, thereby weakening if not breaking the bubble walls. Sonic wind and heat were also generated." The sonic wind can exert pressure on the froth surface, and the heat can evaporate the moisture content of the bubble walls as well as expand the enclosed air. Apparatus The defrothing apparatus, shown in Figs. 1 and 2, consists of a powerful high-frequency siren, a glass or stainless steel beaker of 2-liter capacity with 12.4 cm diam and 17.1 cm height, and a metal reflector. The beaker was placed 2 in. above the top point of the siren. The metal reflector was adjusted to reflect and focus the generated sound waves into the central part of the beaker. Fig. 2 shows the crystal probe microphone used to measure the acoustic intensity and the mandler bacteriological filter employed to introduce compressed air into the beaker for frothing. The apparatus was enclosed in a soundproof cabinet equipped with a glass window. The siren, shown in Fig. 3, consists of a rotor that interrupts the flow of air through the orifices in a stator. The rotor, a 6-in. diam disk with 100 equally spaced slots, is driven by a 2/3 hp, Dumore W2 motor at 133 rps. The frequency of the siren can be varied from 3 to 34 kc. The maximum chamber pressure is about 2 atm, yielding acoustic outputs of approximately 2 kw at an efficiency of about 20 pct. The siren itself is relatively small and can be operated in any orientation. A detailed description of the siren has been given by Allen and Rudnick.11 Collapse of Froth To study the sequence of the collapse of froth, the glass beaker was partially filled with 920 cc water, 100 g of —150 mesh bituminous coal, 0.3 cc petroleum light oil, 0.2 cc pine oil and 1.54 cc Pyrene foam compound. This mineral pulp was agitated for 5 min and then aerated through a mandler filter until the empty space of the beaker, approximately 9 cm high, was filled completely with min-

Jan 1, 1952

By C. W. Sherman, N. J. Grant

The correlation of the high temperature chemical properties of slag-metal systems with some easily measured property of either slag or metal at room temperature has been the goal of both process metallurgists and melting operators for many years. There are several rapid methods for estimating various constituents in steel in addition to the conventional chemical methods which are quite fast, but these do not reveal the nature of the slag as a refining agent, which is of primary interest to the steelmaker. Furthermore, there are several methods for examining slag, the three principal ones being slag pancake, petrographic examination, and the previously mentioned chemical analysis. The main objection to the last two is the lime required to make a satisfactory estimate of the mineralogical or chemical components. The objection to the first is the inadequacy of the information obtained. A new technique has been developed by Philbrook, Jolly and Henry1 whereby the properties of slags are evaluated from an aqueous solution leached from a finely divided sample of slag. It is known that the pH or hydrogen ion concentration (of saturated solutions that have dissolved certain basic oxides, notably calcium oxide) will indicate a pronounced basicity. Philbrook, Jolly and Henry devised the pH measurement technique in order to supply open hearth operators with a fast, reasonably accurate method of estimating slag basicity. They offered the method as an empirical observation and made no claims as to its theoretical justification. The results were presented as an experi-metally observed relationship which applied over an important range of basic open hearth slags. They found that, in plotting the measured pH against the basicity, the best relationship existed between the pH and the log of the simple V ratio, CaO/SiO2. Extensive investigation also showed that there were several variables in the experimental technique that influenced the results and necessitated following a standard procedure to obtain reproducible pH readings. These variables were: 1. Particle size of the slag powder used. 2. Weight of sample used per given volume of water. 3. Time of shaking and standing allowed before the pH was measured. 4. Exclusion of free access of atmospheric carbon dioxide to the suspension. 5. Temperature of the extract at the time the pH was measured. In subsequent investigations of the pH method by Tenenbaum and Brown2 and by Smith, Monaghan and Hay3 the general conclusions of Philbrook's work were reaffirmed. It was the object of the present investigation to extend the technique to a point where it could be used to evaluate slags of all types. Experimental Results PARTICLE SIZK OF SLAG POWDER A large sample of commercial blast furnace slag of intermediate basicity (V-ratio 1.15) was selected for the study. The slag had been put through a jaw crusher until all of it passed through a 20 mesh screen. Five fractions of this crushed material were separated, -20 to +40, -40 to +60, -60 to +100, -100 to +200, and -200 mesh. A representative sample of 0.5 g was removed from each fraction and the pH determined using the method of Philbrook. Check pH analyses on the sample fractions varied due to the different amounts of shaking. To eliminate this variable, a mechanical shaker was employed. In order to know the exact time of contact between the slag and water, it was found necessary to filter the extract at the end of the shaking period. Using the mechanical shaker and a filtering apparatus, similar runs were made on the five fractions for contact times of 5, 10, 20, and 40 min. Random checks gave reproducible results within 0.02 pH. The data are plotted in Fig 1. It can be seen from the plot that each slag fraction is hydrolyzed to an extent that is roughly proportional to the surface area exposed to the water. The (—100 to +200) mesh material changed very little in pH after 10 min. shaking time. The curves are symmetrical and lie in proper relation to one another. The —200 mesh curve appears to be somewhat flatter than the others, but this can be attributed to the portion of very fine material that is not present in the other fractions. The closeness of the (-100 to +200) mesh curve to the —200 mesh curve and the fact that a —100 mesh sample would contain amounts of slag down to 1 or 2 microns in diam were considered sufficient reasons for selecting a —100 mesh sample as representative of the whole sample of slag for the purposes of this investigation.

Jan 1, 1950

By C. C. Templeton, J. C. Rodgers

A key step in feed water treatment for generating wet steam for thermal oil recovery is the removal of calcium and magnesiunt hardness by cation-exchange series softening. Knowing the solubility of any scale forming salts in brines at elevated temperatures is necessary for fixing the level to which the feed water must be softened. Such calcium sulfate solubility data, previously not available above 392F, were determined by the authors in a flow equilibrium apparatus mud will be reported elsewhere. These data were used to develop a method for predicting the solubility of anhydrite in hot water or steam droplets for saturated steam pressures as high as 2,000 psig (637F). (The calcium sulfate solubility product is represented by a combination of two factors, one reflecting the effects of ionic strength and the other accounting for the effects of complex ion formation in either calcium-magnesium-rich or sulfate-rich brines.) The method is applied to a calcium-magnesium-rich brine If moderately high salinity from a pilot hot-water flood, I nd to several sulfate-rich, low-salinity feed waters and l lowdown (cooled steam droplets) samples from steam s ak operations. The predicted calcium hardness levels corresponding to the calcium sulfate solubilities agreed reasonably well with the results of laboratory solubility determinations run on the field samples. Further testing of the method is needed for brines of other composition classes. Existing field cation exchange softeners in the cases tested are performing adequately since all the samples were found to be undersaturated with respect to calcium sulfate at their operating temperatures. Introduction Prevention of scaling caused by precipitation of calcium sulfate (anhydrite) is of considerable concern in connection with thermal recovery processes using wet steam or hot water. To avoid anhydrite precipitation in a heated system, an engineer must keep the product of the calcium and sulfate concentrations in the water or steam droplets below the value of the solubility product of anhydrite for the temperature and brine composition in question. Usually it is most practical to keep the concentration product lower than the solubility product by keeping calcium low in the presence of high sulfate, or by keeping sulfate low in the presence of high calcium. This can be done by a choice of combinations of natural waters and water treatment processes (such as series cation exchange softening to remove calcium). Until recently, few anhydrite solubility data, particularly for solutions containing other salts, were available for temperatures above 392F (211 psig steam); Marshall, Slusher and Jones' studied the CaS0,-NaCI-H,O system up to 392F and surveyed the work of previous investigators. To model natural brines, one needs to study the solubility of anhydrite in aqueous solutions of sodium chloride, sodium sulfate, calcium chloride, magnesium chloride and their mixtures. Since steam pressures as high as 2,000 psig (637F) may be involved in thermal oil recovery projects, a solubility study was conducted between 482 and 617F.' Discussed in this paper is the application of these data to the prediction of anhydrite precipitation in some practical steam soak and hot-water injection projects. Any simple method for predicting the solubility of an inorganic compound over a wide range of temperatures and solution compositions must be based on some assumptions, and therefore must yield approximate results. On the one hand, natural brines contain too many ionic species for all to be included in a simple scheme; on the other hand, there is no adequate theoretical basis for the exact prediction of solubility in even simple solutions of mixed electrolytes. However, it is possible at a given temperature to base a reasonable prediction scheme on two phenomena:'-' the increase in solubility with increasing total concentrations of all ions (as measured by the ionic strength; see the Appendix), and an increase due to formation of cornplexes between calcium ions and sulfate ions and between sulfate and magnesium ions. Stiff and Davis' developed such a scheme for predicting the solubility of gypsum (CaSO, ¦ 2H,O) in brines at temperatures u~ to 212F. However, for the higher temperaturei of present interest, the stable solid phase is anhydrite (CaSO,). This study involves a two-part method for predicting anhydrite solubility products. First, one predicts a value K, for a given ionic strength I and a given temperature T corresponding to mo./msr, = 1 from data of the CaS0,-NaCI-H,O system. Second, one determines a group of factors F .= F(Ca) • F(Mg) • F(SO,), where the individual factors account for increases in the solubility product due to complex formation by high concentrations, respectively, of calcium, magnesium and sulfate. Combining the two parts, one obtains the solubility product in molalities as

Jan 1, 1969

By C. E. Tsoutrelis

A new method for determining rock drillability in diamond drilling is discussed; the method takes into consideration both penetration rate and bit wear. The method is based on drilling a rock specimen under controlled laboratory conditions using a model bit. The technique used for determining the experimental variables is extremely simple, quick, and reliable. Drillability is then determined by the mathematics of drilling. In considering the different factors that affect diamond drilling performance, the nature of the rock to be drilled is of outmost importance since it affects significantly the drilling costs and such other variables as bit type and design, drilling thrust, and bit rotary speed. Many attempts have been made to study this effect by correlating actual drilling performances either to certain physical properties of the rock being drilled1-? or to test drilling data obtained under laboratory conditions.7-13 These attempts were aimed at providing a reliable method of predicting by simple means the expected rock behavior in actual drilling, thus giving the engineer a tool to use in estimating drilling performances and costs in different types of rock. The purpose of this paper is to describe such a method by which rock drillability (a term used in the technical literature to describe rock behavior in drilling) could be determined in diamond drilling. It is believed that the proposed simple and reliable method will cover the need of the mining industry for a workable method of measuring the drillability of rocks. It should be emphasized, however, that since drill-ability depends on the physical properties of rock and each drilling process (diamond, percussive, rotary) is affected by different or partly different rock properties,14-l6 the proposed method of determining rock drillability cannot be extended to the other drilling processes. The results presented in this paper form part of an extensive three-year research program carried out by the author in the laboratories of the Greek Institute of Geology and Subsurface Research. During this period the effects of the physical properties of rocks and of such operational variables as drilling thrust and bit rotary speed in diamond drilling were investigated in detail. DRILLABILITY CONCEPT The literature is not devoid of drillability studies. While there are a number of investigators1,3,5-7,9-0,12-13,17 who have attempted to establish by direct methods (i.e., drilling tests under laboratory conditions) or indirect (i.e., through a physical property of rock) an index from which the drilling performance in a given rock may be estimated, very few6-7,9,12, of the proposed methods seem to be of much practical value to the diamond drilling engineer and none to date has been universally accepted. Commenting on the proposed methods for assessing rock drillability, Fish14 remarks that "for a measure of drillability to be accepted it is essential that penetration rate at a given thrust and bit life are elucidated as otherwise the method is of little value." This statement should be examined in more detail by making use of the penetration rate-drilling time diagram obtained in drilling a rock under constant operational conditions. Furthermore, the merits of using this diagram to describe rock drillability will be pointed out. At the same time reference will be made to this diagram when discussing some previously proposed methods. Fig. 1 illustrates such a diagram for three rocks,A, B, and C, which have been diamond drilled under identical conditions. It is assumed here that rocks A and B have the same initial penetration rate, i.e., VOA = Vog, but since rock B is more abrasive than A, rapid bit wear occurs and as a result the fall of its penetration rate with respect to time is more vigorous than in rock A. This is shown graphically by a steeper V = f(t) (0 curve in this rock than in rock A. Rock C has a lower initial penetration rate, due to higher strength properties16 but since it is not very abrasive, only a slight fall of its penetration rate occurs during drilling (in this category are some limestone and marbles with compressive strength above 1000 kg per sq cm). It follows from the foregoing considerations that the characteristic for each rock curve (I) is a function of (i), the penetration rate of the rock Vo recorded at the instant of commencing drilling, which determines the starting point of the curve (1) on the y-axis and (ii), the abrasive rock properties which determine the rate of fall of Vo with respect to time. Thus, curve (I) provides an actual picture of the rock behavior in drilling for given operational conditions, and it can be used with complete satisfaction to assess rock drillability. It can be seen clearly from Fig. I that proposed methods for assessing rock drillability by measuring the

Jan 1, 1970

By Paul F. Kerr, Raymond F. Robinson

Uranium mineralization occurs in the footwall of the Sunshine vein from the 2900 to the 3700 level. Veinlets of uraninite associated with pyrite and jasper have been so extensively divided and recemented that units more than a few feet in length are seldom observed. The wall rock is St. Regis quartzite of the Belt series. The age of the uraninite, on the basis of isotopic analyses, is 750 * 50, which agrees with geological data suggesting that phases of the Sunshine mineralization are pre Cambrian. THE Sunshine mine in the Coeur d'Alene district, Idaho, is well known for its silver-bearing veins but prior to the summer of 1949 had not been recognized as a possible source of uranium. At that time, during a geiger counter reconnaissance by T. E. Gillingham, R. F. Robinson, and E. E. Thurlow, high radioactivity was noted and radioactive specimens were collected from the footwall of the Sunshine vein.' The detection led to the identification of uraninite-bearing veins, since explored jointly by the Atomic Energy Commission and the Sunshine Mining Co. After the occurrence was noted, the geology of the uranium deposit was studied by the Sunshine staff, and a laboratory examination of the ores was conducted at Columbia University. Several types of laboratory work were undertaken. Differential thermal curves were made of selected siderite samples and results from many more were secured through the work of Mitcham.2 X-ray diffraction and X-ray fluorescence analyses were employed on uraninite, jasper, and siderite. Chemical analyses were made through the cooperation of the Division of Raw Materials of the Atomic Energy Commission. General Geological Features Several silver-bearing veins cut the overturned north limb of the Big Creek anticline as mapped by Shenon and McConne1,³ while the Osburn fault, a long-recognized regional feature about a mile away, marks the north boundary of the Silver Belt. The Sunshine vein, Fig. 1, has a south dip more or less parallel to the 60" axial plane of the fold and cuts rocks of the Belt. Series, starting with the Wallace formation near the surface, continuing downward through the St. Regis formation, and probably extending into the Revett quartzite which lies below the bottom or 3700-ft level. The limb of the anticline is locally modified by secondary folds, one being prominently exposed in the uranian area along the Jewel1 crosscut near the Sunshine vein. Crumpling of the limb resulted from compression which formed the anticline and probably preceded the faults in which the vein deposits accumulated. Evidence of drag along these faults points to reverse movement in the uranium-bearing area and elsewhere. This is true of major faults in the mine workings, and the majority of faults which can be mapped, as pointed out by Robinson.' The St. Regis formation, as measured in the mine, appears to have an initial thickness of some 2000 ft, but the apparent thickness due to thickening during folding is some 3400 ft. Along the Sunshine vein the purple and green rocks characteristic of the Wallace formation in the nearby Military Gulch section p. 37 of ref. 5) have been completely bleached because of introduced sericite. Hydrothermal solutions acting on the wall rock have substituted for the original color a pale greenish cast, although no pronounced mineralogical change has resulted, as Mitcham has observed.' The silver and the uranium depositions appear to belong to distinct epochs resulting from several periods of emplacement. Likewise, multiple periods of deformation account for the faulting. Uraninite is generally associated with silicification, while silver . mineralization accompanies carbonate veins. Rarely, uraninite may be found in a matrix of siderite. Ordinarily uraninite formed prior to ar-gentian tetrahedrite. Where clusters of veins form a stockwork, uraninite-jasper veins often favor one trend while tetrahedrite-siderite veins favor another. During deformation, brecciation of the St. Regis quartzite provided openings between broken rock fragments for precipitation from vein-forming solutions. Fractures due to major breaks were filled during the first stages of vein formation, while later deformation displaced the first veins and provided new channels along which further mineralizing solutions proceeded. The uraninite veins, as the first formed, have suffered fracturing, displacement, and segmentation. Uranian vein segments uncut by faults and more than a few feet in length are rare or nonexistent. Siderite veins are more massive and often extend without a break for tens and even hundreds of feet. In general they show much less segmentation. While the siderite is usually later, there is an overlap in the periods of deposition, some earlier siderite veins being extensively segmented in much the same way uraninite veins have been broken. Vein silica is more extensively distributed than the uranium and iron mineralization it carries. Along the vein course concentrations of uraninite frequently fade away and barren white quartz continues, the transition often occurring within a few feet along strike or down dip. An example appears on the 3700-ft level where a uraninite vein, see Fig. 2a,

Jan 1, 1954

By Joseph R. Stephens

Deformation substructures of' polycrystalline tungsten, W-2, 9, and 24 pct Re, and W-3 pct Ta were studied by tra?zsrnission electron microscopy. The stress-strain curve for unalloyed tungsten showed gradual yielding followed by work-hardening. Electron nzicrographs indicated a gradual increase in dislocation density with increase in strain up to 5.0 pct. Dislocations, although frequently jogged, were straight over moderate distances and were in a randorn array. Stress-strain curves for alloy specimens of W-2 and 9 pct Re and W-3 pct Ta exhibited a drop in stress at yielding followed by only slight work-hardening. Electron micrographs of these specimens after strains of 0.05, 0.1, and 0.5 pct revealed no change in dislocation substructure from the unstrained specimens. After 2.0 pct strain, the three alloys exhibited dense networks. W-3 pct Ta was characterized by straight, frequently jogged dislocations comparable with the dislocation structure in unalloyed tungsten after a similar amount of strain. In contrast, W-2 pct Re exhibited dislocations that contained widely spaced jogs, while W-9 pct Re had developed a cell structure after the relatively srnall strain of 2.0 pct. The W-24 pct Re alloy contained a few dislocations after 0.1 pct strain, while after 0.5 pct strain twins were evident. Dislocation slip bands apparently preceded the twins. The stress-strain curve for the alloy indicated that twinning commenced after approximately 0.25 pet strain. These results indicate that the primary effect of low rhenium concentrations (2 and 9 pct) in tungsten is to increase dislocation multiplication after macroyielding by reducing the Peierls-Nabarro force (lattice resistance to dislocation motion). The dislocation bands that precede twins in W-24 pct Re may be caused by localized internal stresses resulting fro a metastable structure, for example, clustering of rhenium atoms. The effect of high rhenium additions (22 a 65 pet* Rproperties of tungsten. Klopp, Witzke, and Raffo5 reported bend transition temperatures as low as -100°F (200°K) for dilute electron-beam-melted W-Re alloys tested in the worked condition. Recrystalliza-tion increased the bend transition temperature, but alloys with 2 to 4 pct Re were still markedly superior to unalloyed tungsten. Fractographic examinations of tungsten and W- 3 pct Re and W- 5 pct Re alloys by Gilbert 6 revealed that these low rhenium alloys showed a greater tendency toward cleavage failure than did tungsten. Garfinkle 7 showed that rhenium additions, up to 9 pct, to (100) oriented tungsten single crystals increased the proportional limit stress and decreased the flow stress and the rate of work-hardening. In addition, while deformation in unalloyed (100) oriented crystals apparently involved both (110)100) and (112) slip, crystals with rhenium contents of 5 andpct or more deformed primarily by (112) slip. The mechanism by which high and low rhenium additions affect the mechanical properties of tungsten is still not well-established. The present investigation was undertaken to determine by transmission electron microscopy the effects of low rhenium additions, 2 and 9 pct, and a high rhenium addition, 24 pct, on dislocation substructure in the early stages of deformation of polycrystalline electron-beam-melted tungsten. Unalloyed tungsten and a W- 3 pct Ta alloy were included for comparison. EXPERIMENTAL PROCEDURES Materials. Triple electron-beam-melted tungsten, W-2, 9, and 24 pct Re, and W- pet Ta were used for this investigation. Chemical analyses of the cast ingots are given in Table I. A description of the starting metal powders and melting and fabrication pro-cedures for unalloyed tungsten and the W-Re alloys is reported.5 The W-3 pet Ta alloy was processed in a similar manner. Compression specimens measuring 0.300 in. (7.6 mm) in length by 0.130 in. (3.3 mm) in diam were machined from swaged rods. All alloy specimens were annealed in a vacuum of 8 x 10- 6 Torr (10'2iVper sq m) for 1 hr at 3600°F (2255°K). The recrystallized grain size ranged from 0.06 to 0.08 mm diam for the alloy specimens. Unalloyed tungsten was annealed at 2400° F (1589°K) for 1 hr to produce a recrystallized grain diameter of approximately 0.12 mm. Specimens were electropolished in a 2 pet NaOH solution to a diameter of 0.125 in. (3.18 mm) to remove surface notches resulting from grinding and to improve reproducibility of t data. The ends o the compression specimens were ground flat, parallel to each other, and perpendicular to the longitudinal axes with 4/0 emery paper. Compression Tests. The compressive stress-strain apparatus used for compression tests is described in detail by Stearns and Gotsky.9 Room-temperature compression tests were conducted at a crosshead speed of 0.01 in. per min (0.25 mm per min).

Jan 1, 1969

By G. M. Yocom

Blowing acid Bessemer converters with oxygen-steam produces steel of below 0.002 pct N2 content. This method of blowing, combined with a dephosphorizing treatment in the steel ladle, results in low-carbon steels of low nitrogen and low phosphorous (under 0.035 pet) contents, which has physical properties equivalent to open-hearth steels of similar analysis. Using a 50-50 mixture of oxygen and steam, the refinitzg rate is increased 25 pct over blowing with natural air, and scrap charge increased from 3 to 10 pet. Bottom life is normal with proper tuyere area and arrangements, fumes are decreased, yields increased, and hydrogen content is normal. THE acid Bessemer plant at the South Works of Wheeling Steel Corp., consists of two 15-ton bottom blown converters with a monthly capacity of 57,000 N.T. The product of the shop is skelp billets for continuous welded pipe and slabs for ordinary drawing and forming quality sheets. Approximately 50 pct of ingot production is regular Bessemer steel of natural Phos content and the remainder is a dephosphorized grade of steel made by a special treatment of the blown metal as it is poured into the steel ladle. The low Phos grade of steel has certain advantages over the higher Phos grade but since both grades were produced by blowing natural air, the N2 content was in the range of 0.015 pct which limited its application. In 1954 it was decided to explore the possibilities of blowing with a steam-oxygen mixture for the production of steel of both low N2 and low Phos contents. The necessary equipment was installed to operate one converter in this manner and early in 1955 an experimental run of 160 heats was made by blowing with a steam-oxygen blast and excluding natural air entirely. During this period the proper operating techniques were established, such as blast pressures, steam-oxygen mixtures, valves and instrumental control equipment, tuyere arrangement in the bottoms, blowing times and production rates, and a thorough study made of the final steel quality. Also during this experimental period the dephosphorizing practice was improved by the use of a tap hole below the lip of the vessel. This provided a clean separation of the acid converter slag and blown metal which made the dephosphorizing treatment more effective. The results of this experimental run dictated further development of this practice and a second run of 720 heats was made in 1957. The quality features and conversion cost results were in line with expectations and accordingly a 400-ton per day oxygen plant is now being installed. The plant is scheduled for completion in September of this year. This will provide sufficient oxygen to operate both vessels on steam-oxygen blast and delete natural air blowing entirely. The steel will then be below 0.002 pct N2 bar content and the dephosphorized grades will be between 0.015 and 0.040 pct Phos. STEAM-OXYGEN BLOWING The steam for the process is fed to the plant at 220 psig pressure through a 6-in. line. The high-purity oxygen is compressed to 200 psig and conducted through an 8-in. line. The oxygen from the main line is valved down to 100 psig and passed through a steam heated heat exchanger. The heat exchanger is regulated to supply oxygen at 300°F to the steam-oxygen mixing station. It is essential that the incoming oxygen be held at this temperature to avoid condensation of the steam with resulting excessive erosion of the clay tuyeres in the vessel bottom. Oxygen is admitted to the mixing chamber by a 6-in. hydraulically operated valve driven by the ratio control regulator on impulse from the flow of steam. Steam is admitted to the steam-oxygen mixture station through a 2 1/2-in. hydraulically driven valve. The ratio control regulator acts to increase or decrease oxygen input as the steam flow increases or decreases with changing positions of the Blower's control lever. The important point to note here is that steam flow always precedes the oxygen flow as a safety measure. The control valves have sufficient capacity to afford protection should blow pipe trouble develop. A 50-50 mixture for these 15-ton heats demands an oxygen flow of 3800 standard cu ft per min along with 317 lb of steam. The Blower's stations is provided with an indicating blast pressure gage, and indicating steam and oxygen flow meters. Signal and warning lights indicate the valve positions and line pressures. A control room at the real of the Blower's pulpit room houses the ratio control and pressure regulators, as well as the various meter bodies. The hand actuated wheels used to change the conditions are mounted on a panel on the front of the meter control house. The recording steam and oxygen meters used for totalizing and accounting purposes are also mounted on this panel.

Jan 1, 1962

By R. L. Bell, T. G. Langdon

A technique was developed- for determining the grain strain, and hence the grain boundary sliding contribution, occurring during the high- temperature creep of a magnesium alloy, from the distortion of a grid photographically printed on the specimen surface. The results were compared with those obtained from measurements of grain shape, both at the surface and interrwlly, and it was concluded that the grain shape technique may substantially underestimate the grain strain and overestimate the sliding contribution due to the tendency for migration to spheroidize the grains. ALTHOUGH a considerable volume of work has been published on the role of grain boundary sliding in high-temperature creep, many of the estimates of Egb (the contribution of grain boundary sliding to the total strain) have been in error due to the use of incorrect formulas or inadequate averaging procedures.' One of the most easy and convenient measurements from which to compute Egb is that of v, the step normal to the surface where a grain boundary is incident. Unfortunately, this parameter is also the one associated with the treatest number of pitfalls. Values of v have been used to calculate Egb from the equation: egb =knrVr [1] where k is a geometrical averaging factor, n is the number of grains per unit length before deformation, v is the average value of v, and the subscript ,r denotes the procedure of averaging along a number of randomly directed lines. If the dependence of sliding on stress were assumed, it would be possible, in principle, to calculate k from the known distribution of angles between boundaries and the surface. This in itself is difficult because the distribution depends on the history of the surface,' but the problem is even further complicated by the fact that v depends on other factors such as the unbalanced pressure from subsurface grains.3 However, the great simplicity of the measurement procedure for v makes it highly desirable that this problem of k determination should be overcome. In the present experiments, this was achieved by the use of an indirect empirical method in which the grain strain, eg, at the surface was determined by the use of a photographically printed grid. The assumption here is that the total strain, et, is simply the sum of that due to grain boundary sliding, egb, and that due to slip or other processes within the grains, eg. SO that: Et = Eg + Egb [2] Thus k is given by: In practice, it is customary to indicate the importance of sliding by expressing it as a percentage of the total creep strain; this quantity is termed y (= 100Egb/Et). The determination of Eg from a printed grid within the grains avoids the difficulties due to boundary migration which should be considered when the grain strain is calculated from measurements of the average grain shape before and after deformation. As first pointed out by Rachinger,4,5 however, this latter technique has the particular advantage that it can also be applied in the interior of a polycrystal. Recently, several workers have produced evidence on a variety of materials6-'' to support the observation, first made by Rachinger on aluminum,4,5 that 7 can be very high, 70 to 100 pct, in the interior, even when the surface value, determined from boundary offsets, is very much lower.10'11 Although there have been criticisms both of the shortcomings of the grain shape technique'' and of the different procedures used to determine y at the surface,' it seemed important to check whether measurements of sliding by grain shape gave values of y which were truly representative of the material. In the present experiments, grain shape measurements were therefore made both at the surface and in the interior for comparison with one another and with the independent measurements of grain strain using the surface grid technique. EXPERIMENTAL TECHNIQUES The material used in this investigation was Magnox AL80, a Mg-0.78 wt pct A1 alloy supplied by Magnesium Elektron Ltd., Manchester. Tensile specimens, about 7 cm in length, were prepared from a 1.27-cm-diam rod, with two parallel longitudinal flat faces each approximately 3 cm in length. The specimens were annealed for 2 hr in an oxygen-free capsule, at temperatures in the range 430° to 540°C, to give varying grain sizes, and, prior to testing, the grain size of each was carefully determined using the linear intercept method. This revealed that the grains were elongated -0.5 to 5 pct in the longitudinal direction. Testing was carried out in Dennison Model T47E machines under constant load at temperatures in the range 150" to 300°C. At temperatures of 200°C and below, tests were conducted in air with the polished flat faces coated with a thin film of silicone oil to prevent oxidation; at higher temperatures, an argon atmosphere was used. To determine v,, each test was interrupted at regular increments of strain and the specimen removed from the machine. At the lower strains, when v, was less than about 1 pm, measurements were taken on a Zeiss Linnik interference microscope;

Jan 1, 1969

By R. R. Judd, H. W. Paxton

The rate of dissolution of cementite was studied in three low-carbon materials: a zone-refined Fe-C alloy, an Fe-0.5pct Mn-C alloy, and a commercial low-carbon steel. The materials were spheroidized, ad then held isothermally at temperatures above the Al. The isothermal anneal was interrupted periodically by a water quench and the specimens were analyzed by quantitative metallography for the amount of aus-tenite formed during the anneal. The results of this study were compared with an analytical model for the process, which assumes that carbon diffusion in aus-tenite is the rate-controlling step for the cementite dissolution process. The correlation between the model and the experimental data is excellent for the zone-refined Fe-C alloys; however, the Fe-0.5 pct Mn-C alloys and the commercial steel deviate from the calculated model. This deviation is thought to be a result of manganese segregation between the carbide and the matrix. The rate of nucleation of austenite at carbide interfaces was reduced by the manganese addition and enhanced by the presence of ferrite-ferrite grain boundaries. PREVIOUS investigations of the nucleation and growth of austenite from ferrite-carbide aggregates are not entirely satisfying for at least one of several reasons. The most prevalent of these is a lack of quantitative data. Engineering studies have been run on many steels with little control over important parameters such as composition and initial aggregate structure. The data obtained are valid only for material with identical chemistry and thermal history. A more informative approach to the problem of aus-tenitization would be to determine the mechanism that controls the rate of solution of carbide in austenite and how it is modified by alloying elements. This information could then be used to calculate an austeniti-zation rate for any material, provided its composition and structure are known. The object of the present work is to establish the rate-controlling step for cementite dissolution in Fe-C austenite and to investigate the modification of this rate by small manganese additions. The composition and structure of the material used were carefully controlled and all measurements were designed to allow a quantitative analysis of the kinetic process that controls the austenitization rate. A MODEL FOR DISSOLUTION OF CEMENTITE Cementite dissolution has been analyzed mathematically by a model that approximates the material used in the experiments. This model postulates a regular ar-array of identical cementite spheroids with 4 C( diam, embedded in a grain boundary- free ferrite matrix. The analysis provides a detailed description of the dissolution of one carbide spheroid and a generalization of the solution by summation over all the carbides in the material. The carbides may be isolated by defining identical, space-filling cells of ferrite around them. If the cell dimensions are greater than the diameter of the austenite sphere resulting from complete dissolution of the carbide, and no interaction (through diffusion in ferrite) takes place between cells during the dissolution process, the model need concern only one cell, since the solution in each cell is identical. In the experimental material, the dimensions of the cell, the carbide, and the final austenite sphere are approximately 24, 4, and 8 p, respectively; use of the single cell is therefore justified. The experimental observations are made on the austenite nodules that form around each carbide during the dissolution process. The model concerns the growth of these austenite nodules. The attendant shrinking of the carbide can be obtained from the same analysis by an extension of the calculations. Several a priori assumptions are necessary to make the analysis of the growth problem tractable. They are: 1) carbon diffusion through the austenite nodule is the rate-controlling process; 2) local equilibrium exists at all interfaces, 3) the austenite nucleus that forms on each carbide instantaneously envelops the carbide; 4) during the austenite growth process, the diffusion flux of carbon in ferrite is insignificant; 5) a quasi-steady state exists in the austenite concentration field; that is, at any instant during the dissolution process, the austenite carbon concentration gradient closely approximates that for a steady-state solution; and 6) the effects of capillarity on the dissolution rate of the carbides can be neglected. Referring to Fig. 1, a mass balance at the y-a interface for an infinitesimal boundary movement gives: Where rb is the outer radius of the austenite shell, C1 and C are carbon concentrations at the interface in austenite and ferrite, respectively, see Fig. 2, is the diffusion coefficient of carbon in austenite for the concentration of carbon at the interface, and t is time. The fifth assumption permits the austenite carbon concentration to be approximated by the Laplace solution for the spherical case. Therefore, where C(Y) is the carbon concentration at r, and A and B are constants. Local interfacial equilibrium fixes the boundary conditions for the diffusion problem. They are:

Jan 1, 1969

By Carl J. McHargue

Mechanical twins were produced in electron-beam melted columbium by high-speed impact at room temperature and by slow or fast compression at -196°C. The composition plane of the twins was { 112} and the shear direction was <111>. Notches in the twin bands often corresponded to traces of {110) of the matrix and appeared to be untwinned regions. Markings within the twin bands were interpreted as resulting from {110} slip in the twins. THERE has been much work in recent years concerning plastic deformation by glide, and the dislocation theory relating to glide has reached a relatively high degree of development. On the other hand, there have been fewer studies of deformation by mechanical twinning, and understanding of this process is far from satisfactory. This method of deformation is of interest for at least two reasons. First, it provides a mechanism in addition to glide for the relief of stresses, and, in the bcc and hexagonal close-packed metals may result in significant amounts of plastic flow. Secondly, there is the possibility that twins may act as barriers for dislocation movement, resulting in pile-ups which could nucleate cracks. As might be expected, the bulk of the literature on mechanical twinning in the bcc metals is concerned with iron. A good summary of the work done prior to 1954 is contained in the book by all.&apos; Recently the refractory bcc metals have become increasingly important. Limited studies have shown that tantalum,2,3 molybdenum,4,5 vanadium,6,7 tungsten,&apos; and columbium9-11 deform by mechanical twinning under some conditions. Alloys of molybdenum with rhenium and tungsten with rhenium show extensive deformation by twinning at room temperature.I2-l4 Most of these studies have dealt primarily with mechanical properties at low temperatures or have shown the existence of twins, and there is only a small amount of information concerning the conditions under which they form. The subject of the present paper is the formation of twins under stress in columbium with a consideration of their morphology. EXPERIMENTAL PROCEDURE The material used for these studies was taken from an ingot of columbium which had been melted twice by the electron-be am-method. The analysis of the ingot was (in ppm): B < 1, C = 10, Fe < 100, The cast ingot contained very large grains, and it was possible to obtain single-crystal prisms which measured from ¼ to 3/4 in. on a side. A few experiments were conducted on polycrystalline plate which was prepared by rolling material from the same ingot at room temperature and annealing at 1000 in a dynamic vacuum of 10-6 mm Hg. This gave a plate in which the grains had an average diameter of 3 mm. After the specimens were cut from the ingot, the six faces were metallographically polished and elec-tropolished to remove all traces of cold work. Most of the observations were made on the surfaces of the deformed specirllens without further treatment. Occasionally, etching after deformation was desirable. In these cases, an etchant of the composition 50 parts H2O, 5 parts HNO3 25 parts HF, and 10 parts H2SO4 was found to delineate the twins very well. Unless considerable care was taken to ensure the removal of all disturbed metal left by the mechanical polishing, etching failed to reveal many of the features discussed in this; paper. The specimen&apos;s were deformed either by impact or slow compression at 77°K (liquid-nitrogen coolant), 198°K (dry ice and acetone coolant), and 298°K. The impact load was delivered by a hammer except in one case where the load was delivered by a bullet. Slow compression was carried out on a hydraulic testing machine equipped with a chamber to hold the coolant. EXPERIMENTAL RESULTS It has been generally believed that the conditions favoring the formation of deformation twins are large grains, low temperature, and impact loading. In fact, Barrett and Bakish2 found twins in tantalum only after impact deformation at 77°K, and Adams, Roberts, and Smallman10 observed twins in columbium only at 20 For these reasons, the initial experiments of this study used impact loading. Hammer blows caused many bands resembling twins in single crystals a.t 77" but not at 198°K. Only a few slip lines were observed on any of the single-crystal specimens of this study—essentially all the deformation occurred by twinning. The appearance of the twins on the as-deformed surface is shown in Fig. 1. Although both Figs. 1(a) and l(b) are photomicrographs of twins taken at the same magnification and from the same crystal, they are startlingly different in appearance. Fig. 1(a) was taken from the crystal face approximately perpendicular to the shear direction, whereas Fig. 1(b) was taken from

Jan 1, 1962