Search Documents

By D. J. Weintritt, R. G. Hughes

Statistics show arz increase in the average depth of wells drilled in recent years. As a corollary to this trend, drilling fluids have been improved in an effort to meet the problems inherent at temperatures approaching 500°F. Of importance are (1) deterioration of mud components and (2) the effect of solids on filtration and rheological properties. High-temperature, stable water-base and oil-bare muds are discussed. Those areas in which differences exist are pointed out. Results are based on data taken from the Fann consistotneter, rheometer and shear-strength measurements, static and dynamic filtration tests, methy-lene blue test for bentonite solids and specific heat measLrrenlents of muds. INTRODUCTION Higher well temperatures go along with the fact that the average depth of wells continues to increase. Recent data by Gardner' lists 137 completions deeper than 15,000 ft for the first half of 1964 with a record second-half total of 167 wells drilling or proposed. In addition, there has been an increase in drilling for steam for power production or mineral recovery. In this application the depths are modest, but the mud may approach the critical pressure and temperature of water. Scearce and Magnon' report drilling mud used at temperatures of about 700°F in the Salton Sea area of California. Most deep wells have been drilled with water-base muds. In recent years, however, there has been a substantial increase in the use of oil-base muds because of technological advances in effective additives. The significance of this development was dealt with in considerable detail by Simpson and his co-workers.3 Additiona1 field data have now been obtained to indicate that oil muds are competitive in control, performance and cost with the best types of water muds for use at high temperaturc. This parallel offer of two very different fluid systems, each offering a similar variability in performance, cost and convenience, has created the need to evaluate the merits of these fluids under specified conditions so that the advantages and disadvantages of each can be weighed in relation to the over-all drilling program. This paper is not intended as a review of all the factors. Rather, it attempts to emphasize: (1) important condltions and facts peculiar to high-temperature drilling muds, (2) that more than one imposed test condition or testing method is necessary to describe the quality of a mud at high temperature and (3) that elaborate experimental precautions are necessary whenever laboratory data are used in selection of a mud for field use. WHAT IS A HIGH-TEMPERATURE DRILLING FLUID? For the purpose of this discussion, a high-temperature drilling fluid is any system so formulated or treated to economically minimize the effects of temperature on the properties of the fluid. Our experience in drilling fluids suggests that these effects become obvious for many mud materials at temperatures of 300F or higher. It is understood that hydrolysis of starches, depoly-merization of certain organic thinners, or irreversible chemical reactions (such as that of clay and lime) can affect filtration, viscosity and shear strength at less than 300F. However, the temperature level is not a serious point and in no way affects the precautions and techniques used in this study. An up-to-date review of the literature on high-temperature drilling fluids and the many variations was treated by Rogers'in 1963. EXPERIMENTAL REQUIREMENTS TESTING EQUIPMENT AND PROCEDURES With the advent of deeper drilling and increased demand for temperature-stable drilling fluids, new testing equipment and laboratory techniques were devised for the evaluation of drilling fluids subjected to elevated temperature and pressure. While the equipment has not been standardized, it is in widespread use. Milligan et al. Qescribe a filtration cell for determining the filtration properties of drilling fluids at temperatures in excess of 300F. They showed the effect of variations in temperature and pressure on oil and water muds filtered in the 300 to 400F range. The dynamic filtration apparatus described by Simpson6 permits the study of the filtration properties to temperatures of 350F for drilling fluids circulated over sandstone cores. Watkins et al.' describe the use of pressure bombs for studying the effect of prolonged periods of elevated temperature upon the gelation or solidification of drilling fluids. Chisholm et a1.' describe the use of a modified cement consistometer adapted for use in drilling fluid evaluations. A similar consistometer is used in this study, although the application and data-recording method have been changed. The consistency of a mud sample is measured by timing the movement of a soft iron bob which is magnetically moved up and down in the sample container.* Changer in the time of travel and the temperature of the mud at that moment are plotted with a two-point Brown Elec-tronik Recorder. A 10-in. chart with a speed of 4-in./hr is used. Fia.- 1 is a generalized internretation of the data ob-

Jan 1, 1966

By J. D. Embury, R. M. Fisher, A. S. Keh

An investigation of the defect structure and properties following large strain deformation has been carried out using transmission electron microscopy and mechanical testing for a range of ferrous materials and for copper. It is shown that, for a variety of ferrous materials, a cellular substructure is developed during the initial stages of working and on further deformation the dimensions of this substructure are reduced. Quantitative measurements of the flow stress and the scale of the substructure indicate that the strength of heavily worked materials is largely determined by the spacing of cell walls. These cell walls act as dislocation barriers in a manner analogous to grain boundaries. FCC materials do not harden as extensively as bcc after cold working and the present observations on copper indicate that the dimensions of the substructure in fcc materials are not markedly reduced on deformation. The differences between the fcc and bcc structures produced by large plastic strains are ascribed to differences in the extent of dynamic recovery. It is tentatively proposed that the greater stability of substructural barriers in bcc structures results from strong interstitial Pinning effects. It is proposed that for large plastic strains the work-hardening process may be considered in terms of the reduction of substructural-barrier spacing during the working process. This pvovides a simplified hut useful analysis of the strain hardening occurring during mechanical processes. THE mechanisms of strain-hardening processes have occupied the attention of numerous investigators over the past three decades and a multitude of theories have emerged in this field. The majority of previous work has been concerned with the development of a description of the plastic behavior of single crystals in terms of dislocation theory.'" In contrast, scant attention has been given to the strengthening mechanisms operative during mechanical working processes such as rolling and drawing. The large plastic strains involved in these processes make it difficult to correlate the observations with any elementary dislocation theory. Further, as Bullen and coworkers3 have opined, for large plastic strains both hardening and recovery occur simultaneously and thus it is extremely difficult to estimate the effect of plastic strain on the ambient internal stress field. It is probable that for large plas- tic strains any theoretical estimate of the internal stress field must be made in terms of complex dislocation groups. Although some valuable theoretical work has been done toward calculating the elastic properties of dislocation groups4 any detailed self-consistent model for large plastic strain is as yet impossible. With these limitations in view it is still of value to examine the mechanical properties of highly strained materials as a function of their substructure. This relationship is explored in the present communication for a variety of materials subjected to rolling, drawing, or swaging. The primary object of this investigation has been to establish the validity and the limitations of the substructural strengthening mechanism proposed by Embury and eisher' for drawn pearlitic wire and by Meieran and Thomas for drawn tungsten wire. No attempt has been made to delineate the basic interaction mechanism which occurs between a slip dislocation and the substructure and the authors believe that a great deal more experimental evidence must be compiled before these fundamental aspects can be explored. Also, no specific attention has been given to the detailed formation of substructure during working. Experimental Details. A variety of materials were used in this investigation, the compositions and heat treatment of which are tabulated in Table I. The commercially pure iron is referred to throughout this report as Ferrovac E. The mechanical working processes were all performed at room temperature. The wire drawing was performed on a manual drawing bench. Reductions of between 10 and 20 pct in area per pass were used in both swaging and drawing. The experimental parameter used to evaluate the mechanical properties of the materials was the 0.2 pct proof stress. This was determined for wire samples using an Instron tensile machine at a crosshead speed of 0.02 in. per min. The techniques for preparation of samples for transmission electron microscopy have been described previo~sl~.~ Specimens from wire samples were prepared from longitudinal sections and in some cases from transverse sections. To evaluate the substructural characteristics of rolled materials, thin foil samples were prepared of both the face and edge sections. Results. One of the more familiar ways of expressing work hardening in mechanical working is by the flow stress as a function of reduction in cross-sectional area. Fig. 1 shows such a plot for Ferrovac E eutectoid carbon steel and for copper. The curve for Ferrovac E is characterized by an initial stage of rapid work hardening and a final stage of rapid work hardening separated by an intermediate stage with a low rate of work hardening. This behavior is typical of many ferrous materials and the drawn pearlite wire previously investigated by Embury and Fisher is a more pronounced example. Copper shows an initial

Jan 1, 1967

By A. W. H. Morris, G. H. Laurie, J. N. Pratt

Using- galvanic cells of the form Sn(liq)/Sn" (LiCl-KC1-SnCl,)/Sn-Ag (alloy), measurements have been made of relative thermodynamic properties of the a, C, E, and liquid phases of the Ag-Sn alloy system. Partial heats of solution of the components in the liquid alloys lzave also been observed by direct cal-orimetric measurement in an isoperibol calorimeter. The thermodynanzic quantities are disczlssed in relation to structural and other properties and the existence of anomalous minor fluctuations in the partial heats and entropies of solution in liquid alloys is tentatively suggested. In the course of a recent electro motive-force study of the thermodynamic properties of Sn-Ag-Pd liquids,' some measurements were also performed on the Ag-Sn binary system. Most previous thermodynamic studies of this system have been concerned with the liquid state. Measurements confined to the limiting heat of solution of silver in liquid tin have been made by many calorimetric workers2 while high-temperature calorimetric measurements of the heats of formation of the full range of liquid alloys are reported in the early work of Kawakami~ (1323°K) and more recently by Wittig and Gehrin~(1248°K). Electromotive-force studies on liquid alloys have been made by Yanko, Drake, and Hovorka' (606" to 686°K; 86 to 99.4 at. pct Sn) and by Frantik and Mc Donald' (900°K; 30 to 90 at. pct Sn). The only known measurements on the solid state are of heats of formation of the a, £, and c phases; these values were obtained using tin-solution calorimetry, at 723"K, by Kleppa,~ whose investigation also yielded heats of formation of liquid alloys containing more than 64 at. pct Sn. The present experiments on the Ag-Sn alloys include a re-examination of the liquid phase and, because of the dearth of free-energy data for the solid state, attempted measurements on the a, c, and E phases. The principal new feature of electromotive-force results obtained for the liquid phase was an indication of anomalous fluctuations in the partial heats and entropies of solution of tin at certain compositions. However, since the values for these thermodynamic quantities were determined from the temperature coefficients of cell potentials, which are commonly subject to considerable error, confirmation by calorimetric measurements was considered desirable. A detailed investigation of the partial heats of solution of the components in the binary liquids was made using a liquid metal solution calorimeter. I) GALVANIC CELL STUDIES a) Experimental Details. Measurements were made, as a function of alloy composition and temperature, of the potentials of reversible galvanic cells of the form: ~n(liq)/~n++/~n-Ag (solid or liquid alloy) Details of the apparatus and experimental techniques have been given elsewhere.' so that a brief account will suffice here. Molten salt, 58 mole pct LiC1-42 mole pct KC1, containing small amounts (1 to 2 mole pct) of stannous chloride was used as the electrolyte. The salts were dehydrated by pre-electrolysis and vacuum -drying techniques. Cells were established under an argon atmosphere by immersing tin and alloy electrodes in the molten salt contained in a large silica tube, heated in a vertical resistance furnace. The tube was sealed at the top by a head plate provided with openings permitting the simultaneous insertion of six electrodes, a central thermocouple sheath, and connections to vacuum and argon lines. Temperatures were controlled to *0.2"C over prolonged periods, with maximum variation over the electrodes at any time of 0.l°C. Temperatures were measured with a standardized Pt/13 pct Rh-Pt couple. The electromotive force of this and the cell potentials were measured on a Cambridge Vernier potentiometer and short-period galvanometer. Alloys were prepared from Pass "S" tin (99.999 pct) and Johnson-Matthey high-purity silver (99.999 pct) by melting in evacuated silica capsules and quenching in cold water. For liquid phase experiments, pieces of the resulting alloys were remelted into prepared silica electrode units, while solid electrodes were prepared by remelting into 3-mm bore tubing, inserting a cleaned molybdenum lead wire, and quenching to produce uniform rods about 3 cm in length, with soundly attached leads. In all cases remelting was done under an argon atmosphere. The solid electrodes were subsequently annealed in evacu ated silica tubes for 14 days at about 20°C below the solidus and quenched. Analyses showed that these techniques produced uniform electrodes with no significant change from weighed out compositions. b) Results and Discussion. Measurements were made on about forty alloys in the solid and liquid states, over varying ranges of temperature between 550" and 1050°K. Stable, mutually consistent, and reproducible electromotive-force data were obtained with most liquid alloys and these are shown in Fig. 1. Investigations were extended below the liquidus tem-

Jan 1, 1967

By C. A. Stickels

A heat of electrolytic iron, to whzch alunzinutn and nitrogen had been added, was hot-rolled, cold-rolled 90 pct, and recrystallized at temperatures from 500" to 700°C. Primary recrystallization textures appear to arise from competitive growth of two types of nuclei: 1) those having orientations belonging to the "usual" primary recrystallization texture found in riming steel, and 2) those with the {111} (110) ovientation. Development of a (111}(1 10) component in the primary recrystallization texture occurs only over a certain interval of isothermal recrystallizatzon temperatures when the material is supersaturated with respect to the precipitation of AlN. Lowering the degree of supersaturation depresses the temperature interval in which a (111)(110) component occurs. An elongated, 'pancake-shaped" recrystallized pain structure and a marked delay in the start of recrystallization were found in all specimens which were supersaturated with respect to A1N precipitation after cold work, regardless of their recrystallization texture. ONE of the consequences of killing low-carbon steel with aluminum is a significant change in recrystallization behavior. About 15 years ago, Solter and eatttiel showed that this behavior was largely controlled by aluminum and nitrogen in the steel. If complete precipitation of A1N was prevented before cold rolling, an increased "recrystallization temperature" was observed in subsequent. annealing, and the recrystal-lized grains were not equiaxed. Leslie et a1.2 studied this phenomenon in some detail and clearly demonstrated the relationship between A1N precipitation, recrystallization kinetics, and the development of "pancake-shaped" grains. It has also been known for some time that aluminum-killed steels, processed to produce elongated "pancake" grains, develop a (11 I}( 110) primary recrystallization texture. This texture has not been found in iron or low-carbon rimming steel as a primary texture4j5 but has been observed following grain growth in electrolytic iron.5 The present work was undertaken to study in more detail the effect of A1N supersaturation on recrystallization textures in iron. LITERATURE REVIEW The deformation texture in heavily rolled iron has been studied in detail by Bennewitz.~ The texture consists primarily of a partial fiber texture about a (110) axis in the rolling direction, designated here as fiber texture A. It includes the range of orienta- tions (111)[110] - (001)[ 110] - (11l)[110]. A weak secondary texture also is present.6 This is a duplex partial fiber texture about two (110) fiber axes located 60 deg from the rolling direction and 30 deg from the sheet normal. The range of this texture, designated here as fiber texture B, about the [101} fiber axis is (112)[110] - near (545)[252] - (211:1[011] *The range given here follows Bennewit~.~ A few pole figures from re-crystallized material indicate a broader range than this.' However, the components which are strongest in the recrystallization texture are in this range.'________________________________________________________ Primary recrystallization textures in unkilled steels can be accounted for by growth of members of fiber texture B present in the deformed metal.5 However, while members of fiber texture B dominate the primary texture, other orientations survive primary recrystallization as well. In particular, some {111}(110) members of fiber texture A must also grow during primary recrystallization, because a well-defined {1ll)( 110) texture develops during subsequent grain growth at 700°C.5 The unusual recrystallization behavior of deformed supersaturated solid solutions has been attributed to: 1) retention of the solute in solution,' 2) formation of coherent, preprecipitation solute clusters prior to and during re~r~stallization,~ and 3) formation of a precipitate prior to and concurrent with recrystallization.'~-'~ When aluminum is supersaturated with iron, the difference in grain boundary mobility between general high-angle boundaries and certain special coincidence site boundaries is apparently eliminated.' In aluminum-killed steels, precipitation of A1N can take place at ordinary subcritical recrystallization temperatures. The rate of precipitation increases with increasing aluminum or nitrogen contents.2'13 There is some doubt, however, as to whether true precipitates form during the time at temperature needed to complete recrystallization. Leslie ef a1.2 found that precipitation in one steel was complete after about 100 min at 700GC, or after about 1000 min at 650GC, as measured by chemical analysis for AlN. Aoki et a1.,13 using internal friction for dissolved nitrogen, showed that a large fraction of the dissolved nitrogen was removed from solution within a few minutes annealing time at temperatures from 400" to 800°C. However , the rate of formation of AlN, as detected bv chemical analvsis. was much slower than the apparent rate of nitrogen removal. Hasebe,'~~ using carbon extraction replicas, has identified A1N precipitates by electron diffraction in a 0.2 C steel, solution-treated at 1300°C and annealed 2 hr at 700°C. Borchers and kim,I6 also using a replication technique, observed precipitates after annealing treatments as short as 2 min at 640°C. However, Leslie et a1.' state that no A1N precipitate can be seen while recrystallization is being inhibited in aluminum-killed steel.

Jan 1, 1967

By H. I. Aaronson, H. A. Domian, G. M. Pound

Zener's two-parameter theory of the y a reaction in Fe-X alloys is extended to encornpass austenite-stabilizing as well as fewite-stabilizing elements, and is then cottzbitzed with statistical thermodynamic theories of Fe-C alloys to permit development of a ther-modynamic description of the proeutectoid fewite reaction in Fe-C-X alloys. Equilibrium tielines are calculated for tile a + y rep'on from experimental data and frort extrapolations of the y/y +a equilibrium surface. Sectzovs of the y/y + 0 surface are calculaled for the tzetastable sstuation LYL u-kich alloyrtg eleitzents do not partition betzseen azrstenite andfer-rite. The finding that the metastable y/a + y curves Lie close to their equilibriuwz counterparts when X = Si, .Vo, Co, Al, and Cu but well below them when X = A/ln or Ari pr-elides a thermodunamic explanation for the expcri1?7e?ztally obserted absence of partition during the proeutec toid ferrite reartlon in the fortner alloys and for the occurrence of partition at hzgher ternperatures in the latter alloys. Cotarison ofno- patitzoa free-energy changes and y/y i a curr,es in Fe-C-X alloys with the equilibrium 11al1es of these quantities in Fe-C alloys furnishes additional qualitative insight into the irqluence of allojling elements upon the kinetics of the proeutectoicl ferrite reaction. THE introduction of a substitutional alloying element, X, appreciably complicates calculation of the thermodynamics of the formation of proeutectoid ferrite from austenite. As noted in the preceding paper,' the positional entropy of the interstitial species is the principal component of the free energy of an interstitial solid solution with which theory has so far been able to deal. One would expect, however, that other components of the free energy of this type of solid solution may be significantly altered by the addition of a substitutional alloying element. Even if the assumptions are made, by analogy to the case of Fe-C alloys,' that changes in the positional entropy of carbon represent a significant part of the thermodynamic effects of an alloying element, and that the remaining effects can be taken into account by fitting the equations developed on this basis to experimental data on Fe-C-X phase diagrams or on the activities of carbon in alloyed austenite and ferrite, the experimental information available on either of these quantities is not yet sufficiently accurate or extensive, respectively, to make such an approach useful. An attempt made by Zener on the former basis to explain the effects of alloying elements on the thermodynamics of Fe-C alloys in terms of a temperature-independent "free-energy change" (actually enthalpy hane') required to transfer 1 mole of an alloying element from austenite to ferrite, in which the "free-energy change" was determined by fitting the theoretical relationships developed to Fe-C-X phase diagrams, thus proved inadequate in part because of deficiencies in the available ternary-phase-diagram data.= Other difficulties of a more fundamental nature, however, also indicated the desirability of a different approach to the problem.3y4y6 zener6 subsequently proposed that the free-energy change associated with y — a transformation in pure iron can be decomposed into magnetic and nonmagnetic components. Alloying elements were assumed to affect those components separately. One parameter was used to describe the quantitative effect exerted on each component. These parameters were evaluated from Ms (martensite-start) temperature data and from other experimental information usually either readily available or measurable with acceptable accuracy. Zener applied this treatment only to the calculation of Fe-X phase diagrams in which X is a ferrite-stabilizing element. In the present study, this treatment is extended to include austenite-stabilizing elements, and then combined with treatments previously considered for Fe-C alloys1 to permit calculation of the thermodynamic quantities of interest in the austenite - proeutectoid ferrite transformation in Fe-C-X alloys, where a number of representative, and commonly used alloying elements are chosen for X, including Si, Mn, Co, Mo, Al, Cr, and Cu. The results are used to explain important features of the partition of alloying elements between austenite and proeutectoid ferrite, as reported in a companion paper7 on the basis of electron-probe analysis, and to provide some additional understanding of the influence of alloying elements upon the kinetics of nucleation and growth of proeutectoid ferrite. Portions of this treatment6 have been clarified in the course of a review by Kaufman and Cohen.3 The consolidated summary of these developments with which this section is begun provides a basis for further clarification of the treatment, from which extension to include austenite- as well as ferrite-stabilizing elements is a natural consequence. The division of the free-energy change associated with the 7 - a transformation in pure iron, into two independent components is formally stated as:

Jan 1, 1967

By Harry C. Gatos, Frank J. Bachner

It was shown through high-pressure experiments that tin loss by volatilizatim is necessary for the degrada-tion of the superconducting transition temperature of Nb,Sn associated with high-temperature annealing. Crystallochemical analysis of the degraded Nb3Sn showed that it constitutes a new phase with ordered niobium-site vacancies, created by the migration of niobium atoms to vaccnt tin sites. This new phase was found to form when 4 pct Nb-site vacancies were present. It has a transition temperature of 6'K and a lattice parameter of 5.283A. A similar degradation effect was observed in Nb,Al. Its superconducting transition temperature dropped from 16.5" to 8" K following a high-temperature annealing. The superconducting temperature degradation in these 0-tungsten structure compounds is attributed to the disruption of the interchain d bonding by the periodic interruption of the niobium atom chains. By annealing the degraded Nb, Sn at 1000 C in nitrogen its normal superconducting behavior is restored most likely due to the incorporation of nitrogen atoms causing the elimination of the ordered vacancies. HANAK et al.' have observed low superconducting transition-temperature values (T, - 9"K) in some NbsSn samples deposited from the vapor phase. They attributed such low T, values to disorder in the 0-tung-sten structure. Much lower T values (down to 5.6"K) were reported by Reed et al.zC for NbsSn samples annealed at high temperatures. These authors also attributed this degradation effect to disorder (random occupation of the A and B sites by niobium and tin) but pointed out that such disorder could be brought about (by high-temperature treatment) only in samples containing niobium in excess of the stoichiometric composition NbsSn. Both groups reported that the normal superconductivity behavior could be rever-sibly restored by appropriate heat treatment. Courtney et al., also found that degradation in NbsSn requires excess niobium brought about by the loss of tin during the treatment. However, these investigators proposed that the degradation is due to niobium-site vacancies resulting from the migration of the niobium atoms to the vacated tin atom sites. They did not consider the reversibility of the effect. The present study attempts to establish the nature of the above degradation phenomenon. EXPERIMENTAL PROCEDURES All compounds prepared for this investigation were made from the powders or filings of the elements which were intimately mixed, cold-pressed into a cylindrical pellet at approximately 50,000 lb per sq in., and then submitted to the desired heat treatment. The samples annealed under high pressure were placed in a MgO sample container which was mounted in a pyrophyllite tetrahedron designed for a tetra-hedral-anvil press. Details of the experimental arrangement are given elsewhere. This setup allowed heating at 1800°C or above under pressures in excess of 30kbars for 3 hr. The samples annealed in a vacuum were prepared in a high-temperature vacuum furnace which could reach temperatures up to 2400°C under a pressure of 2 x lo-' Torr. For annealing in a reactive atmosphere, a quartz tube was placed in a clamshell furnace and the desired gas ambient passed through the tube. Lattice parameters were determined using a Debye-Scherer 114.6-mm camera. Cohen's method, programmed for the IBM 7094 computer, was used to calculate the lattice parameter from the measured d spacings. X-ray integrated intensity measurements were made on several samples. These samples were ground to -400 mesh and the powder mixed with a solution of collodion in amyl acetate. The mixture was poured into a depression milled in a bakelite disc. When the mixture dried, the surface of the disc was ground flat leaving a diffraction surface defined by the face of the disc. The disc was mounted in a Philips rotating specimen holder which allowed the rotation of the sample in the plane of the diffraction surface and the integrated intensity measured using a scintillation counter and a pulse-height analysis sys-tem. The superconducting transition temperatures were determined by means of self-inductance techniques.' EXPERIMENTAL RESULTS AND DISCUSSION The Role of Tin Loss in the Degradation of Super-conductivity. The loss of tin during high-temperature annealing can be effectively suppressed by annealing under high hydrostatic pressures. Accordingly, a series of experiments were performed under pressures of approximately 30kbars. This pressure was the minimum under which high-temperature experiments could be safely performed in the particular pressure apparatus employed. Experiments were also designed to test high-pressure effects on the superconductivity behavior of NbJSn. The results of the high-pressure annealing experi-ments are summarized in Table I. All samples were prepared as described earlier. They were reacted and homogenized at 1000°C for 24 hr under argon at-

Jan 1, 1967

By E. Miller, J. M. Eldridge, K. L. Komarek

Aclivilies of magnesium in liquid Alg-Si alloys have been delermined between 5 and 60 at. pcl Si, close to the melling point of Mg2Si, by an improved isopieslic melhod. Silicon specinrens, held in alumina crucibles and graplrile conlainevs of special design, were healed in a letrlpevalure gvadient and equilibrated with mag-nesilcrrl rapor in a closed lilanium system. The ther-madynamic Junctions were calculated and compared with the thermodyuamic properties of the other three mg- Gvoup IVB systems. Lattice paramelers of three Mg2X compounds were measured. The bonding in the Mg2X compounds is largely covalent with small and uarying amounts of metallic and ionic conlvibutions. The Mg-Si phase diagram1 has one congruent melting compound, Mg2Si, of essentially stoichiometric composition, two eutectics, and very limited terminal solid solubilities. Little information is available on the thermodynamic properties of this system. The free energy of formation of Mg2Si has been determined by the Knudsen cell technique2 in the range 572" to 680oC, by the transportation method3 between 858" and 950oC, and by the electromotive-force method4 in the range 400o to 600°C. Kubaschewski and villa5 and caulfield6 have measured the heat of formation of Mg2Si. An electromotive-force study of magnesium-rich liquid alloys was recently published by Sryvalin el al.7 The present investigation was undertaken to complete a general survey of the thermodynamic properties of the homologous series of Mg-Group IVB systems, i.e., Mg-Pb,a9,Mg-Sn,10,11 mg-Ge,12and Mg-Si. An isopiestic technique, previously developed for similar measurements on liquid Mg-sn11 and Mg-Ge alloys,12 was modified for the Mg-Si system. Specimens of the nonvolatile component, silicon, were contained in dense alumina crucibles placed inside covered graphite crucibles which were heated in a temperature gradient in an evacuated and sealed titanium reaction tube and equilibrated with magnesium vapor of known vapor pressure. The alumina crucibles prevented contact between the highly corrosive liquid Mg-Si alloys and graphite. The graphite cruci- bles effectively preserved the high-temperature equilibrium composition of the liquid alloys containing highly volatile magnesium on termination of the experiments during the quench to room temperature. EXPERIMENTAL PROCEDURE Silicon of semiconductor-grade purity (E. I. du Pont de Nemours and Co., Brevard, N.C.) and 99.99+ pct Mg (Dominion Magnesium Ltd., Toronto, Canada) were used. Graphite crucibles with press-fitted lids were machined from high-density (1.92 g per cu cm) rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The alumina crucibles had a purity of 99.7+ pct (Triangle RR grade, Morganite, Inc., Long Island City, N.Y.). In preliminary runs the liquid alloys were contained in graphite crucibles following the exact procedure developed for the Mg-Ge system.'2 These runs failed due to appreciable reaction between the molten Mg-Si alloys and graphite, and the results have been discarded. The procedure was then modified and the Mg-Si alloys were subsequently held in alumina crucibles. For most of the runs alumina crucibles of known weight and approximately 6.3 mm ID, 12.5 mm height, 1.0 mm wall thickness were loaded with weighed amounts of silicon and encapsuled in tightly covered weighed graphite crucibles 5/16 in. ID, 2 in. helght, 3/32 in. wall thickness). The graphite crucibles were machined from rods which were 85 pct of the theoretical density. These crucibles were therefore sufficiently porous so as to permit magnesium vapor to effuse through the silicon under the experimental conditions of approximately 970O to 1220°C and 1 day equilibration time. However, negligible magnesium was lost from the crucible during the quench due to the slow effusion rate through the pores of the graphite. The inner alumina crucible prevented the liquid alloys from contacting the graphite, and the very tightly fitting graphite crucible lids served to retain any magnesium vaporizing from the alloys inside the crucibles during the quenching step.12 The loaded silicon-alumina-graphite cells were positioned, one above another, on a 16-in.-long titanium thermocouple well and tied securely to the titanium tube with thin molybdenum wires held in grooves around the circumference of the graphite crucibles. A thin (0.005-in.) molybdenum strip prevented contact between the graphite crucibles and the titanium. This assembly was lowered into a titanium reaction tube (la in. ID, 16 in. long, $ in. wall thickness) closed on one end which contained a 11/2-in.-long cylinder of magnesium at the bottom. The inner titanium thermocouple well was positioned eccentrically in the large tube because of the eccentric mounting of the cells on the well. Appropriate modifications of the titanium cap"'12 were made to join the inner and outer titanium

Jan 1, 1968

By E. S. Tankins, G. R. Belton

A simple solution model, based upon the formation of molecular species, is developed for strongly electronegative dilute solutes in liquid binary-metallic solvents. Two approximations are considered for the relative concentrations of the species: the random and the quasi-chemical. Equations are presented for the partial molar free energy, enthalpy, and entropy of mixing of the solute. An experimental study has been made of equilibrium in the reaction H2 6) +0 (dissolved) = H2O(g))for the liquid Cu-Co alloys. The standard free energy of solution of oxygen is presented as a function of composition for the alloys at 1550°C and as a function of temperature for five of the alloys. The experimental results for these alloys and also for Cu-Ni alloys are shown to be in reasonable agreernent with the theory in the random approximation. A knowledge of the thermodynamic behavior of dilute solutes in liquid metals and alloys is of importance in understanding and designing refining and alloy-making processes. Accordingly, several attempts have been made to derive suitable solution models to forecast the effect of a third component on the activity coefficient of such a solute in a metal. Alcock and Richardson' reviewed the literature prior to 1958 and also showed that a regular solution model gave a reasonable description in the case of metallic solutes but failed to account for the behavior of the more electronegative solutes sulfur and oxygen. These same authors2 later modified their model by using the quasi-chemical approximation3 to calculate the average composition of the first coordination shell surrounding each solute atom. This modified model was shown to lead to a better qualitative description of the behavior of the electronegative solutes; however, quantitative agreement with experimental data for oxygen in alloys could only be achieved by assuming a very small coordination number. The authors concluded that the major source of error in the model was the assumption that pairwise interaction energies were independent of composition. Substitutional and interstitial random solution models by Wada and saito4 are essentially similar to the first model except that the required interchange energies were derived from the modified solubility parameter equation of Mott, instead of from experimental binary data. Most recently Hoch5 has presented a statistical model for interstitial solutions and has applied the model to the Fe-C-O system. However, as the various interaction energies needed in the model had to be derived from the ternary data, the model does not promise well as a means of forecasting ternary behavior. Each of the above models carries the assumption that the strongly electronegative solutes have the same configurational environment as metallic solutes; i.e., the solute can be treated as a substitutional or interstitial atom in a quasi-crystalline lattice and is surrounded by a normal coordination shell of solvent atoms. There are, however, a number of facts which suggest that this is unlikely. First, the heats of solution are large, being more typical of molecule formation rather than alloying. For example, the heats of solution of monatomic oxygen and sulfur in liquid iron are -90 kea16,8 and -74 kea1,7, 8 respectively. These are to be compared with maximum heats of solution of metallic solutes in liquid iron of about -13 keal (silicon is an exception with -28.5 kea17). The large depression of the surface tension of liquid iron by trace amounts of the electronegative solutes oxygen, sulfur, and selenium9 suggests, by analogy with aqueous systems, the possible existence of polar molecules in the liquid. The effect of these solutes is at least three orders of magnitude greater than normal metal solutes.10 As has been pointed out by Richardson,11 the electron affinities and ionization potentials of oxygen and sulfur are such that it is likely that they exist in metallic solution as negatively charged ions. If this is so, and it is assumed that electrostatic forces play an important role in determining the configuration, it is unlikely that the stable configuration will be that of an isolated ion surrounded by a symmetrical coordination shell of solvent ions. It is more likely that the energy of the system would be lowered by the formation of solute-solvent screened dipoles. The above arguments suggest the formation of "molecular species" between solute and solvent atoms. The idea of the existence of molecular species in such solutions is not new, however', for Marshall and chipman12 have explained in a semi-quantitative manner the C-O equilibrium in liquid iron by postulating the species CO. Chen and Chip-man13 interpreted their measurements on the Cr-O equilibrium in iron in terms of the species CrO. Zapffe and sims14 have also postulated the existence of such species in liquid-iron alloys.

Jan 1, 1965

By R. D. Taylor, Jim Douglas Jr., H. H. Rachford Jr., P. M. Dyke

A major obstacle to the use of wetting agents in .secondary recovery by water flooding is the adsorption of the agents on the sand. As a result of adsorption, the surfactant always lags behind the floodwater front. Consideration of the chromatographic theory of adsorption indicates that the detergents will not lag as much if used in very high concentrations. An investigation was made of the possibility of using high concentrations economically by flowing slugs of wetting agents followed by normal flood water. The experiments consisted of adsorption studies on Alundum powder and Berea sandstone. Flow rests on a 12-in. Alundum core and 22-in. Berea core were used to determine rate of detergent movement. The results of the flow experiments indicate that the relative rate of surfactant advance is, indeed, sensitive to the concentration of the agent. A 10 per cent slug moved with a rate that war 78 to 95 per cent as fast as the rate of advance of the flood water. By contrast, one with 25 ppm (the number of parts of commercial detergent in a million parts of water on a weight basis) concentration moved less than one-fourth as fast as the flood water, and calculations indicate that in very long porous systems the rate of movement of the lower concentrations will be a small fraction of the rate of advance of the flood front. The results. of the adsorption studies were utilized to calculate the rate of advance of the detergent when only the initial concentration was known. The calculated rates showed substantial agreement with the experimental flow tests in the high concentration ranges. The adsorption results were also used to estimate the cost of the materials for a slug-type surfactant flood in the field. In addition to the faster rates of movement, the concentrated detergent slugs removed much more oil than the dilute solutions. However, the effectiveness of the slug process depends on many variables. The quantity of oil removed is increased markedly by increasing the flooding rate. The efficiency is also influenced by the type of crude, type of reservoir rock and initial water saturation. Therefore, a careful analysis of each reservoir system is required before the economic value of the process can be determined. INTRODUCTION It is well known that the displacement of oil by invading water during water flooding is far from complete. It is generally agreed that the unrecovered oil is retained in the porous medium by the capillary forces which may be relatively large compared to the forces generated by the flowing water. Therefore, it was logical that some early workers should turn to surface-active materials to reduce the capillary forces to facilitate the release of oil. As early as 1927,' a patent was granted for the use of surface-active materials in water flooding. In 1932, when soap solutions were passed through Bradford and Venango sands, it was reported that the results were inconclusive, erratic and that "further investigation is needed to determine exactly the function of the solution and to obtain a clearer insight into the phenomena involved."' Some of the modern scientific reports conclude with a similar statement,' showing that the lack of agreement on the mechanism of oil removal by wetting agents is still very widespread even though several comprehensive studies have been reported.'." Although there is a lack of agreement as to the general effectiveness of the detergents for water flooding, most investigators do agree that all of the common detergents are strongly adsorbed onto the solid surfaces of the reservoir. In the early calculations it appeared that all additives would be lost before reaching much of the formation area which contained the additional oil to be removed. Experiments indicated that if the usual small waterflood concentrations of wetting agents were used, the rate of advance of detergent through the formation would be only a small fraction of the rate of advance of the flood front. Indeed, some investigators4 felt that the use of wetting agents would never be economically feasible because of their adsorption. For example, DunningG estimated that the wetting agent in concentrations of 25 ppm, would advance only 0.05 times as fast as the flood front. Ojeda, et al,' found that a surfactant in a concentration of 10 ppm moved less than 0.01 times as fast as the flood front. It is significant, however, that both investigators found that increased concentrations of wetting agents moved faster, relative to the flood front, than solutions at the lower concentrations. Ojeda showed that an extrapolation of his data indicated a relative rate of 0.5 at 1 per cent concentration, while Dunning6 estimated a relative rate of 0.46 for a 1 per cent concentration. It was obvious that these concentrations could not be used for continuous injection because the cost of the injected detergent would far exceed the value of additional oil produced. Traditionally, detergents are used in very low concentrations for they show good

By A. E. Jenkins, L. A. Baker, N. A. Warner

Rates oj decarburization of levilated Fe-C droplets conlaining 5.5 to 0 pct C have been measured at 1660°C. Gas mixtures of 1, 10, and 100 pct 0, with helium diluenl were used at velocities of 12.5 and 62.5 cm per sec. Rates were independent of carbon concentration in the mell and in good agreement with the calculated rule of oxygen diffusion through the gas boundary layer. The effects of flow rale and total pressure are as predicled and the rates are approxitnalely 2.5 times those with CO2 as oxidant. The mass-transfer correlation used incorporaled the efject of natural convection as well as forced conrection. Graphile spheres are shown to oxidize at the same rate as Fe-C droplets under the same experimental codlions. It is concluded that, for high carbon concentrations in the melt, the rate of- decarburizalion is controlled wholly by the rate of gaseous diffusion. Rate measurements with pure CO, are reported for low carbon concentrations where CO bubbles nucleate within the droplet. Under these circumstances the decarburi-zation decreased with carbon concentration and it is proposed that carbon diffusion is significant in conlrolling the decnvburization rate. In an earlier paper1 decarburization rate measurements were reported for levitated Fe-C alloys at 1660°C but with CO2 as the oxidant. The decarburization rate was found to be independent of carbon concentration in the melt but slightly affected by total pressure. The authors were unable to explain the slight pressure effect but in all other respects the results were consistent with control by diffusion in the gas boundary layer. Subsequent work has been directed at finding the reason for the slight pressure effect and whether the kinetics with oxygen as oxidant parallel those with CO2. Recently Ito and Sano2 have shown that with water vapor-argon atmospheres the decarburization rate is gaseous diffusion controlled until an oxide film appears on the surface. In this work the melts were contained in crucibles. MASS TRANSFER IN THE GAS PHASE In the earlier analysis1 only forced-convection mass transfer was considered. Subsequent recognition of the existence of some free-convection mass transfer explained the observed small effect of total pressure on the decarburization rate. Steinberger and Treybal3 and Kinard, Manning, and Manning4 have developed correlations involving the linear addition of the contribution of radial diffusion, free and forced convection. Steinberger and Treybal&apos;s correlation was chosen as the most applicable to the present work since it correlated most of the data available in the literature and handled the low Reynolds number region exceptionally well. The correlation for (Gr&apos;Sc) < 108 is where Nu&apos; is the Nusselt number for mass transfer based upon the total surface of a sphere in an infinite medium, G&apos; is the mean Grashof number for mass transfer defined by Eq. [2], Sc is the Schmidt number (µ/pDAB)f, Re is the sphere Reynolds number (dpu,pf/µf), p is the viscosity of the gas (poise), p is the density of the gas (g cm-3), Dab is the binary diffusivity for the system A-B (sq cm sec-&apos;), dp is the sphere diameter (cm), u is the approach velocity of the gas (cm sec-I), and subscript f denotes the property value is computed at the film temperature Tf defined by Tf = +1/2(To + Tr) where To is the specimen temperature and T, is the approach gas temperature (oK). Natural convection occurs when inhomogeneities exist in gas density. These may be caused by concentration gradients, temperature gradients, or both. In the present work the temperature gradient between the sphere and the bulk gas was very large and in some cases, for example the runs with pure oxygen, the concentration gradient was also appreciable. The Grashof number defined by Mathers, Madden, and piret5 was used since it took account of both temperature and concentration gradients: where Gr&apos; is the Grashof number for mass transfer (p2fgd3|-yA-yA|/µ2f), Gr is the Grashof number for heat transfer (p2f gd3p|To - T,]/µ2fTf), Pr is the Prandtl number (cpµ/k)f, g is the acceleration due to gravity (cm sec-&apos;f, a is the concentration densification coefficient (1/p)(ap/ayA)T, yA is the mole fraction of component A at the gas-metal interface, yA is the mole fraction of component A in the bulk gas stream, cp is the heat capacity of the gas per unit mass at constant pressure (cal g-I OK-&apos;), and k is the thermal conductivity of the gas (cal cm-&apos; sec-1 OK-1). Mathers et al. tested this combined Grashof number

Jan 1, 1968

By R. L. Moment

The anisotropic elastic behavior of rolled beryllium sheet has been measured, using a pulse echo technique, and compared with X-ray diffraction data. Calculated elastic stiffness constants compared favorably with published values for beryllium single crystals which were attributed to the strong (0002) rolling plane texture. Variations of Young&apos;s modulus in the yolling plane could be associated with the velative distribution of (0002) planes out of their ideal position in the rollitzg pkule. WHEN a metal is subjected to cold working such as drawing, forming, or rolling, a crystallographic texture develops which can significantly alter its physical properties. One method for detecting this texture is X-ray diffraction, but Alers and Liu&apos; have recently pointed out how the prediction of anisotropic physical properties from pole figures alone is not always accurate due to differences in interpretation. Variations in Young&apos;s modulus with orientation or, more completely, the values of the effective elastic constants of the worked metal, also serve to indicate the presence of a texture. In fact, as Alers and Liu&apos; pointed out, calculated variations in Young&apos;s modulus for assumed orientations, when compared with experimental data, can be used to eliminate some of the uncertainty in interpretation of X-ray pole figures. Thus, elasticity measurements can serve not only to clarify any unusual elastic behavior of worked metal, but also to detect and in part determine the nature of its texture. X-ray determination of the texture of rolled beryllium has been reported by Smigelskas and Barrett,2 who found a strong texture of (0002) in the rolling plane with (1070) planes normal to the rolling direction. In the case of metal rolled at room temperature, they reported that [1010] directions also appeared at positions 60 and 120 deg from the rolling direction in the rolling plane, while in more recent work Keeler3 found these directions were also tilted towards the rolling plane. The texture for beryllium rolled at 80O0C, however, only showed (1010) planes normal to the rolling direction and the spread of (0002) planes out of the rolling plane was less. In looking for elastic anisotropy one might consider unidirectional rolling of a metal as introducing an or-thorhombic symmetry through reorientation of the grains, since the three deformations, compression, extension in the rolling direction, and extension in the cross direction, are orthogonal to each other and unequal in magnitude. Thus the rolled sheet could be treated like an orthorhombic single crystal and the nine stiffness constants of the elasticity tensor used to calculate the anisotropy of Young&apos;s modulus, the shear modulus and Poisson&apos;s ratio. In this case we could write: which is symmetric about its diagonal. Borik and Alers4 have recently used this approach on rolled die steel with very good results. They found, however, that instead of displaying orthorhombic elastic symmetry their specimens could be considered tetragonal in which case Cr1 = c22, c13 = Ca, and c44 =cjj. This conclusion was made solely on the basis of the measured tensor elements, and serves to point out the advantage of this method for studying the anisotropy of rolled metals. Their calculated values for Young&apos;s modulus as a function of angle in the rolling plane also checked very well with direct measurements made on different specimens using the resonance technique. In the present study, cross-rolled beryllium was used which had been unidirectionally rolled about 11 pct for the final reduction. This imparted a slight anisotropy in the rolling plane which was detected both by X-ray techniques and elasticity measurements. For purposes of discussion in this paper, the rolling direction is that direction in which the most reduction passes were made and cross direction is the normal to the rolling direction in the rolling plane. It was also decided to consider the rolled sheet as displaying orthorhombic symmetry for the purpose of obtaining elasticity samples with the direction defined as in Table I. Any change in the final symmetry attributed to the sheet would then be made on the basis of the measured elastic stiffnesses. The final data would then be compared with that expected from the X-ray study and that reported for beryllium single crystals. EXPERIMENTAL PROCEDURE Rolling Schedule. The samples used in this study were taken from a large sheet which, because of its size, had to be unidirectionally rolled for the final reduction. The resulting texture was that of cross-rolled metal with a slight unidirectional texture superimposed. A cast beryllium ingot, 9.500 in. sq by 3.325 in. thick, was cross-rolled to 81 pct reduction followed by unidirectional rolling for an additional 11 pct to give a total reduction of 92 pct. The thickness of the final sheet ranged from 0.265 to 0.280 in. Reduction up to 67 pct was done at 980°C and the final 25 pct at 870°C. Analysis for metallic impurities showed aluminum 0.06 pct, iron 0.19 pct, and silicon 0.11 pct, giving a beryllium purity of 99.64 pct.

Jan 1, 1968

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

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

Jan 1, 1970

By Larry Kaufman, Joan B. Berkowitz-Mattuck, Edward V. Claugherty

The oxidation characteristics of hafnium and zirconiunr diboride were measured between 1200 and 2200&apos;K by a thermal- conductivity method which continuously ttzeasures the rate of reaction of oxygen with the diboride and by a metallographic air oridation method zuhich provides a measure of the total arr7ount of bovide conuerted to oxide for a given time interval. The oxidized specimens obtained from the tl~eritaal-coi~ductitrity method were also examined by quantitatire metal-lographic procedares. The significant results obtained in this investigation reveal that metal-rich compositions of lzafi~iutil diboride proride the most oxidation-resistatzt material up to 2000°K; hafnium diboride is tmre oxidation- resistant titan zirconium diboride at all tempevatures examined; the morphology of the oxide formed on H/B2 and Llie temperature coefficient qi. the oxidation rate constants change at the temperature of ttze monoclinic to tetragonal phase transition] in HfO2; the oxidation of neither HfB2 nor ZrB2, results iN catastrophic Jazlure at lorc. oxygen pressures; and pvefevetztial gvaLti boundary oxidation was not obsevued for either HfBi or ZYB, A comprehensive study of the high-temperature characteristics of refractory transition-metal di-borides is currently in progress. This program has included investigation of the physical, thermal, and thermodynamic properties of TiB2, ZrB2, HfB2, NbB2, and TaB2. In addition, aspects of the synthesis and fabrication of such materials have been studied. In view of the diverse nature of this research, a number of other laboratories have actively participated and contributed specific capabilities for analysis and characterization of these materials. As a consequence, an extensive description of the relevant properties of these compounds has emerged which is central in evaluating their high-temperature (1200" to 2500°K) performance. To date, information on thermodynamic stability, specific heat, and vaporization characteristics,1 hot hardness and electrical resistivity,1, 3 therma1 expansion:&apos;4 and thermal conductivity 1, 5 has been presented. This information has been generated on materials of the highest purity (98.5 to 99.9 wt pct Me + B) and density currently available. Samples fabricated by zone melting6 and high-pressure hot pressing"3&apos;7 techniques have been used to generate suitable specimens for all of the aforementioned studies. dation characteristics of the most oxidation-resistant of these materials, hafnium and zirconium diboride, is presented and a description of the synthesis and the experimental procedures used to prepare and characterize specimens is given. The high-temperature range under consideration (1200" to 2200°K) and the known dependence of oxidation characteristics on sample chemistry, density, and oxidation conditions required a close coupling of the synthesis, fabrication, and evaluation procedures.8 This was accomplished by continual surveillance of chemical composition of starting materials before and after specimen fabrication and by evaluation of density, phase constitution, and microstructural features prior to and after oxidation exposure. I) PROCUREMENT AND CHARACTERIZATION OF STARTING MATERIALS In view of the current state of the art in fabricating refractory boride materials, the methods used in preparing samples for the present study are given in detail as follows: starting materials were purchased in high-purity powder form and fabricated by high-pressure hot pressing into 0.40 by 1.00 in. bars from which oxidation specimens were obtained. The hafnium diboride used in this study was purchased from Wah Chang Corp.; the zirconium diboride from U.S. Borax and Chemical Co. These powders were routinely characterized by quantitative chemical analyses for metal, boron, carbon, oxygen, nitrogen, and iron, by qualitative emission-spectrographic analysis for trace impurities, by X-ray procedures for extraneous phase identification, and by powder densitometry for comparison with X-ray (theoretical) density. Hafnium and zirconium metal and elemental boron were also purchased as high-purity powders and characterized for impurities by emission-spectrographic analyses. The hafnium diboride was procured in three shipments which were designated as HfBl.g7(1), HfB1.88(2A), and HfB2.12(2). The indicated stoichiometry is based on the atomic ratio of total boron to total hafnium; the number in parentheses identifies the shipment number. Shipment 1 was 5 1b, shipment 2A, 1 1b, and shipment 2, 8 1b. The zirconium diboride was procured as a 20-1b shipment and designated as ZrB1.89(1). A small quantity of purified zirconium diboride was also supplied and designated ZrB1, 9(P). The averaged results for chemical analyses which were generally performed according to the procedures set forth in the compilation by KrieGe9 are presented in Table I. Qualitative spectrographic analyses indicated that Ca, Cr, Ti, Si, Zr (in H~B~), and A1 were present at levels between 0.01 and 0.10 wt pct. Other metallic elements were found to be less than 0.01 wt pct. Since it is virtually impossible to purchase these materials in the desired quantities (5 to 20 lb) as single-phase compounds it is necessary to obtain

Jan 1, 1968

By J. W. Spretnak, J. N. Cordea

The gain boundary relaxation in high-purity aluminum, nickel, copper, and silver was studied by means of a low-frequency torsion pendulum. Both internal friction and creep at constant stress tests were conducted. A lognormal distribution in relaxation times was found to account for the relatively wide experimental internal friction peaks and the gradual relaxation behavior during the creep tests. This distribution was separated further into a lognormal distribution of relaxation time constants and a normal distribution in activation energies. A spread of up to ±6 kcal per mole in the activation energies accounted for the major part of the distribution. A "double-peak" internal friction phenomenon was observed in silver. The activation energies in kcal per mole derived from the grain boundary relaxation phenomena are 34.5 for aluminum, 73.5 for nickel, 31.5 for copper, and 41.5 for silver. It was found that the rain boundary relaxation strength in these metals increases with the reported stacking-fault energy. GRAIN boundary relaxation phenomena have been observed in a large number of polycrystalline metals and alloys. Numerous investigations have been conducted to study the structure of the grain boundary through this relaxation process. One of the first investigators was Ke1-4 who observed that the activation energy for grain boundary relaxation in aluminum, a brass, and a iron was about the same as that for volume diffusion. He concluded that the grain boundary behaved as if it were a thin liquid layer with neighboring grains sliding over one another. Leak5 conducted experiments on iron of a higher purity and observed that the grain boundary activation energy is comparable with that of grain boundary diffusion. He suggested that, in metals where this relationship holds, the damping may be caused by a reversible migration of grain boundaries into adjoining grains. Nowick6 has presented an interesting view of inter-facial relaxation with his "sphere of relaxation" model. A relaxed interface is represented as one where the shear stress is greater than the normal value along the edges and zero in the interior of the interface. The region of the stress relaxation is pictured as a sphere surrounding the interface. From his calculations Nowick concluded that the slip along an interface is directly proportional to its length. Therefore, the time of relaxation, T, depends on the size of the relaxation interface. This means that in the Arrhenius relationship, t = TO exp[H/RT], valid for atom movements, the relaxation time T is predicted to be proportional to the grain diameter through the pre-exponential term, TO. Since the internal friction can be given as Q-1 = ?j wt/(1 + w2r2), where ?J is the relaxation strength and w is the angular frequency, an increase in grain size at a constant frequency will shift the peak to a higher temperature. A great deal of work has been done to determine the exact relationship between the internal friction and grain size.1,5,7,8 In metals, the grain boundary peaks are found to be lower and broader than predicted theoretically.&apos; The above model can explain this by a distribution in the size of the interface areas, represented by a distribution in the parameter tO, and an overlap of spheres of relaxation, represented by a distribution in activation energies. Both these phenomena result in an over-all distribution in the relaxation time, which could affect the internal friction peak height, breadth, and also position. This relationship between the experimental data and theoretical calculations appears very promising in the study of interfacial relaxation mechanisms. THEORY A lognormal distribution in t can sometimes be used to adequately describe the spectrum of relaxation times governing an anelastic relaxation. wiechert9 originally suggested such a distribution to explain the elastic after-effect in solids. This choice is particularly applicable to grain boundary relaxation when considering Saltykov&apos;s work.&apos;&apos; He found a lognormal distribution in the grain sizes within a metal. Recently Nowick and Berry11 have introduced a log-normal distribution in T into the theoretical internal friction equations. The form of the distribution function is where z = In(r/rm), and Tm is the mean value of t. The parameter ß is a measure of the distribution and is the half-width of the distribution when is l/e of its maximum, IC/(O). Nowick and Berry have described the methods to obtain the parameters Tm, ß, and ?,J from experimental internal friction and creep test data. In the idealized case, where only one relaxation event occurs with one relaxation time, only ?J and T are necessary to completely describe the event, and 0 = 0. For the broader internal friction curves 6 is some positive number greater than zero. The larger the 6, the greater is the half-width of the distribution in In t.

Jan 1, 1967

By G. R. Heckman, H. J. Murphy, C. T. Sims

An incestigation has been made of the effects of heat treatment and alloy composition on the long-time stress-rupture properties and structural stability of the similar nickel-base alloys Udimet-500, Lrdimet-520, and Udimet-700. Rupture test data are presented at stresses ranging from 4 to 50 ksi at temperatures from 1450° to 1900°F for times up to 14,000 hr. Ductility response is emphasized. Optical and electron tnicroscopy were complemented by X-ray diffraction analyses of extracted phases to relate microstructural stability to the observed rupture properties. Particular attention is paid to Udimet-520 since structural characteristics of this alloy appear to vary somewhat from its sister alloys. Both cast and wrought performance of Lrdimet-500 are discussed. The computerized PHACOMP calculational technique, based on electron-vacuncy theory, is discussed and related to structural stability where appropriate. Electron microscopy and microprobe techniques were used to conduct evaluation of the oxidation characteristics of Udimet-500 exposed in air for 16,100 hr. The steady advance in strength and reliability of nickel-base superalloys continues to be one of the high points of modern metallurgy. The stress capability of these materials has increased steadily, allowing higher and higher operating temperatures in the highly sophisticated aircraft and industrial gas turbines now on the market. The attendant increase in efficiency, of course, means greatly improved power output. Gas turbines for industrial and marine use have long been designed with these objectives paramount the usual design requirements in terms of time of service being 100,000 hr. High-efficiency, long-life aircraft such as the supersonic transport require superalloy engine materials with high-strength and long-time structural stability. Thus, materials studied for and operating experience from industrial gas turbines provide a good reservoir from which technology of high value to the SST program can be drawn. This study is one such case. Three prominent nickel-base super alloys—Udimet 500, Udimet 520, and Udimet 700 were extensively evaluated for industrial gas turbine bucket use. Particular attention was directed toward structural stability as a requisite property. Within the present context, structural stability is defined as freedom from the propensity to form strength-robbing or embrittling phases such as u,p,x,or Laves, and the ability to maintain useful rupture strength and ductility throughout design life. MATERIALS The three alloys, cast Udimet 500 (U-500C), Udimet 520, and Udimet 700, were chosen for detailed evaluation based on preliminary studies which indicated that U-500C and U-520 possessed comparable rupture strength capabilities, and that U -700 had a greater strength capability but somewhat poorer ductility than wrought U-500. The nominal compositions of the three alloys, along with the compositions of the heats investigated, are presented in Table I. PROCEDURE Dimensionally rejected U-520 buckets from Special Metals Corp. heat 63370 were heat-treated using the four cycles delineated in Table 11. Cycle A was investigated to determine the effects of a shortened 1700°F primary age. Cycle B was considered a "standard" treatment. Cycle C investigated a higher solution temperature in combination with a shortened primary age, while cycle D assessed the effect of the higher solution temperature alone. These heat treatments were designed to produce optimum combinations of rupture strength and ductility through maximum y&apos; development, the development of a y&apos; grain boundary cushion, promotion of MC carbide degeneration reactions, and agglomeration of resultant M23CB. Since one of the premises of the evaluation of U-520 was that rupture strength would be equivalent to U-500, forged U-500 buckets from Special Metals Corp. heat 62916 were heat-treated with cycles A, B, and C to provide comparison. The heat-treated structures of U-520 and U-500 are illustrated in the 8700 times electron micrographs of Fig. l. The U-700 tested was all from 3-in.-diam hot-rolled and centerless-ground rod from Special Metals Corp. heat 2-1426. Two heat-treatment cycles were employed, E and F of Table 11. Cycle E is a standard four-step, triple-age treatment intended to provide an optimum match of strength and ductility through well-developed matrix and grain boundary y&apos;, as recommended by U-700 vendors. Treatment F is a shortened , single-age cycle which could provide a significant processing cost reduction should adequate strength and ductility be maintained. Following heat treatment, rupture specimens of U-500 and U-520 were machined from the buckets and tested. Standard rupture bars of U -700 were machined from the heat-treated rod and rupture-tested. Failed and withdrawn rupture bars were prepared and examined by optical and electron microscopy. Select specimens were electrolytically digested, and the residues analyzed for carbide and topologically close-packed phases using CrKa or CoKo radiation. Of the six different U-500C heats evaluated, five were cast by Misco Precision Casting Co. and one was cast by Haynes Stellite Co. Cast-to-size rupture bars

Jan 1, 1968

By N. Mungan

Laboratory imbibition and displacement experiments were performed using crude oil and cores drilled with water and preserved under anaerobic conditions. The purpose of these tests was to determine reservoir rock wettability and to find out if more oil could be recovered by use of NaOH solution than by conventional waterflooding. The preserved cores were found to be oil-wet. Contrary to work in the literature, these cores changed to water-wet upon contact with air. After exposure to air for a week, the cores yielded more oil by waterflooding than when preserved under exclusion of air. At reservoir temperature of 160F, flooding the preserved cores with 0.5N NaOH solution recovered more oil than an ordinary wa-terflood, and additional oil when following a waterflood. When the caustic solution was used from the beginning, all the extra oil was obtained before breakthrough; when the caustic followed a conventional waterflood, the extra oil was produced in the form of an oil bank ahead of the injected caustic. The increase in oil recovery resulted from wettability reversal. Also, use of caustic reduced the volume of injection required to flood out the cores. At room temperature, however, the caustic solution did not reverse the wettability and gave no additional oil recovery. Cores which had become water-wet by air exposure or caustic flooding were restored to their original oil-wet state when saturated with crude oil and allowed to equcilibrate at reservoir temperature for two weeks. Therefore, in the absence of preserved cores, it may be possible to restore weathered cores to their original wettability for use in laboratory floods. INTRODUCTION Waterflooding has been in use since 1865, and is by far the simplest of secondary recovery methods. Unfortunately, most waterfloods are inefficient in recovering oil, often leaving half or more of the original oil in place un-recovered. The low oil recovery generally results from low sweep efficiency and low displacement efficiency. Consequently, to increase oil recovery by waterflooding, sweep and displacement efficiencies should be improved. Sweep efficiency is primarily affected by reservoir heterogeneities and mobility ratio, while displacement efficiency is affected by the capillary forces between fluids and rock surfaces. For petroleum reservoirs, the capillary forces are expressed in terms of interfacial tension and wettability. If oil recovery is to be improved significantly in water- flooding, the capillary forces holding the oil in the raervoir porous matrix must be reduced or eliminated. One way to reduce capillary forces is to inject commercial surfactants ahead of the injection water into the reservoir. Laboratory tests of this method have shown no promise of an economical process yet, and no increase in oil recovery was obtained in the field trials which have been reported. Work is continuing in many companies to find surface-active agents which, in workable concentrations, can yield substantial added oil recovery. Another way to change capillary forces operating in petroleum reservoirs is by changing the pH of the injected water. Wagner et al.&apos; showed that change in the pH sometimes activates the surface-active materials natural to some crudes and brings about gross wettability change. Since pH alteration can be obtained with cheap chemicals, such as hydrochloric acid or sodium hydroxide, the process shows promise of being economical in a field application. Pan American Oil Corp. reported oil recovery by use of caustic solution from a flooded-out reservoir.&apos; Their test, conducted at a small additional cost, yielded results which were so sufficiently favorable and encouraging that the wettability reversal flood was expanded to portions of the field not previously flooded.13 It is important to bear in mind that changes in the pH of the water not only can reverse wettability but also can lower the interfacial tension between water and crude oil. Reisberg and Doscher4 have studied the pH dependency of the interfacial tension of Venture crude using sodium hydroxide solutions of various concentrations. Their data show that the interfacial tension was lowered from 23.0 to 0.02 dynes/cm by increasing the NaOH concentration from 0.005 to 0.5 per cent by weight. Thus, the use of NaOH may lead to additional oil recovery due to both wettability reversal and lowering of interfacial tension. Whether alteration of pH results in wettability reversal from oil-wet to water-wet and increases oil recovery depends on wetting properties of the reservoir rock and the crude. This necessitates delicate laboratory experiments, with suitable core and fluid samples from a field. Although many investigators have studied wettability reversal floods in the laboratory,1,2,5,6 these studies have been carried out with synthetic porous media, refined laboratory fluids and surface-active chemicals to simulate the process. The study presented in this paper is the first time that wettability reversal by pH alteration has been accomolished in laboratory core floods using carefully preserved natural cores, live crude and with experiments performed at reservoir pressure and temperature.

Jan 1, 1967

By R. A. Flinn, R. D. Pehlke, D. R. Glass, P. O. Hays

Knowledge of the depth of penetralion of an oxygen jet into the bath of the oxygen converter and of the correlation of penetration with driuing pressuve, lance heighl, and nozzle throat area is vital to the understanding of converter operation. If the penetration is too shallow, then severe and hazardous slopping takes place. On the other hand, if the jel penetrates entirely Lhvough lhe bath for an apprcciublc period of time, bottom damage occurs. In addilion to measurement of the penetralion of the jel, knou~ledge of the circulatory movement in the bath is also of interest in order to evaluale various theories oj-concerter operating behavior which have been published. In this investigation, experimental converters were buill of IOU- , 300-, and 4000-lb capacity. Four independent methods were used to determine penelralion: the onset of bottom marking, a nitrogen bubbler probe, observation througlt an optical syslew built into the oxygen lance, and direcl viewing of the jet issuing from the bottom of the vessel. Good correlation zuas obtained, and empirical relalions for pvedicling perletration were found. These relations were conjzrmed by bottom marking tests in 55- and 110-ton vessels. Within the operaling conditions employed in these tests, the depth to which a single oxygen jet penetrated zuas found lo vary according to the relatiorl ThE technical literature is replete with data concerning the successful use of the basic oxygen furnace or converter in steelmaking. Experimental data are lacking, however, on the vital factors of the depth of penetration of the jet into the bath and the induced circulation. Commercial operating conditions usually have been the result of cut and try experiments in lance manipulation until satisfactory results were obtained. There have been, however, two hotly argued opposing theories concerning desirable depth of penetration and these are exemplified by the Schwarz and Miles patents1,2 on one hand and the Suess patent3 on the other. The Schwarz patent teaches that the jet, issuing from the nozzle at supersonic speed, penetrates deeply "so that the reactions between the iron and the oxygen and between the oxygen and the rest of the smelting components take place in the center of the bath". Specific operating suggestions are given by Miles.2 By contrast, the Suess patent calls for surface Circulalion was investigated by lour methods: by direct observation in 200-lb open baths, by the use of graphite rudders in the 300- and 4000-lb converlers, by direct observalion through an oplical system in the lance, and by various models al room temperature. All were in excellent agreement and indicated that the motion of the bath ulas up at the center, radially outluavd at the surface, and down at the sides. Experi-ments in small and in commercial vessels indicate that it is essential to operate with a jet penetration of approximately 50 pct of the bath depth. Surface blowing results in low oxygen eficienty and in hazardous conditions which may render the process inopeuable. RejYactory dartzage al the bottom of the vessel is only encountered when the jet penetrates to the bottom, and this can be avoided by properly applying the penetration formula. The application of this en/pirical formula in commercial peraations is best when limited to combinations of lance size, pressure, and height which are typically encounteved in the use of a single-hole lance. blowing so that "...the oxygen jet does not penetrate deeply into the molten metal bath and is confined to an impingement area at the central portion of the bath surface". These references are given merely to illustrate the basic differences between the two schools of thought and to point out the need for measurement of penetration for the sake of the operator. For example, it is shown later that inefficient and even dangerous conditions can arise if improper blowing conditions are used. Differences are also evident between the two schools of thought as to the mixing, circulation, and agitation which is to be accomplished by the jet. The Schwarz patent states that "surface contact is not sufficient in most cases to bring about quick reaction, the same as the blowing of the gas over the bath surface or the mere blowing of the gas onto the bath surface". The patent goes on to call for active mixing. In contrast the claims of the Suess patent call for "discharging a stream of oxygen ... to an extent to avoid material agitation of the bath by the oxygen stream". In this patent the circulation is said to be downward in the center and up at the sides of the vessel. A number of investigators4-12 have explored penetration and circulation in transparent models. In general, it is agreed in these tests that the circulation is upward at the center (along the sides of the jet cavity),

Jan 1, 1968

By C. G. Dunn

According to a recently suggested effect of silicon on the re recrystallization textures of high-purity Fe-Si alloys with (111)[112] type rolling textures, the recrystallization texture for a rolled (110)[001] oriented iron crystal probably should be entirely different from that of a (110)[001] oriented 3 pct Si-Fe crystal. Comparative studies of iron and 3 pct Si-Fe crystals, however, show that both have (110)[Ool] recrystallization textures when the rolling textures are the (111)[112] type after reductions in thickness of about 70 pct. Qualitatively the results from the iron crystal are like those of polycrystalline high-purity 3 pct Si-Fe and not like polycrys-talline high-purity iron. The large effect previously noted probably involves unknown impurities or processing variables rather than silicon itself. Some problems on experimental and analytical procedure for a spherical X-ray specimen, which was machined from a laminated composite of sheet specimens, are treated in the Appendix. A possible strong effect of silicon on the textures produced in cold-rolled high-purity Fe-Si (HPFe-Si) alloys during primary recrystallization and normal grain growth was suggested in a recent paper.&apos; All the textures were far from the random-orientation type, but that of iron, or of Fe-Si alloys of low silicon composition, was entirely different from the texture of 3 pct Si-Fe. The same effect was noted for the textures obtained prior to normal grain growth, i.e., for primary recrystallization.2 It is the main purpose of the present paper to provide some clarification of this silicon effect. All the HPFe-Si alloys from zero to 3 pct Si, which were rolled by two or more stages separated by anneals, developed (111)[112] type rolling textures.2 Thus, there was no effect of silicon on the rolling textures. Earlier, Gensamer and Mehl3 also found no effect of silicon on the rolling textures of Fe-Si alloys; they obtained the Kurdjum.ow and Sachs (K-S) rolling texture for iron,4 which is characterized as the three ideal components: (100)[011], (112)[li0], and (111)[112]. There is a difference between the HPFe-Si multiple-stage rolling texture and the K-S single-stage rolling texture, but this is a variable processing effect. Of interest here is the fact that the recrystallization textures from (111) [llZ] type rolling textures were different depending on the amount of silicon in the alloy. There was a relatively strong (110) [001] component in the recrystallization texture of HP 3 pct Si-Fe5,8,2 but no such component in HP 0.6 pct Si-Fe, for example; the recrystallization texture for the latter was two (111) [110] type components and a (111) fiber component 1,2 Several publications have shown that a strong (110) [001] recrystallization texture is derivable from a (111) [112] type rolling texture for 3 pct Si-Fe crystals reduced in thickness by about 70 pct.7-10 Furthermore it appears that the strongest of these (110) [001] recrystallization textures occurred when the orientation of the crystal prior to rolling was (110) [001].7 Barrett and evensoon11 found that the rolling texture of a (110)[001] oriented iron crystal was (111) [llj]. Accordingly, it seemed desirable to determine whether a (110) [001] oriented iron crystal, upon rolling and annealing, would behave like the 3 pct Si-Fe crystal (or the polycrystalline HP 3 pct Si-Fe) and thus produce a (110) [001] recrystallization texture contrary to the suggested silicon effect, or would behave like the polycry stalline HP iron or HP 0.6 pct Si-Fe and thus produce (lll) [110] type components in agreement with a silicon effect. Briefly, the idea here involves the use of more precisely defined textures to obtain if possible better control of important variables that affect the recrystallization process. PROCEDURE A (110) oriented crystal of Ferrovac "E" iron (99.9 pct pure) was prepared in sheet form 0.080 in. thick with the [001] direction parallel to the long dimension of the specimen.&apos;&apos; This crystal was etched to 0.073 in. thickness (to remove some small included grains) and then was cold rolled in a 6-in.-diam mill to a final thickness of 0.022 in. The rolling was unidirectional except for an inadvertent reversal at 0.061 in. thickness. At this thickness, and also at 0.040 in., the rolling was interrupted for transmission Laue photographs. Molybdenum Ka-radiation filtered with zirconium was used in a transmission method1&apos; to obtain the cold-rolled (110) pole figure. The sample was a 0.002-in.-thick section taken from the central region of the 0.022-in.-thick cold-rolled crystal. For the primary recrystallization study, cold-rolled samples were etched from 0.022 to 0.021 in. thick and annealed in hydrogen at 850°C. Primary recrystallization to a fine-grained structure, Fig. 1, was obtained in a 5-min anneal. Eleven sheets after

Jan 1, 1963

By M. Nicholas, D. M. Poole

The diameters of sessile drops have been found to increase linearly with time in five reacting binary metal systems. The spreading rates of the drops are markedly dependent on temperature and on prior alloying of the solid with the lower melting point metal, hut are independent of the drop volume, wetting atruosphere , solid-surface roughness, and prior alloying of the drop with the substrate metal. A mechanism has been suggested that relates the linear-spreading rate to lateral diffusion of the liquid-metal atoms into the solid at the drop edge. An Arrhenius- type equation has been derived that describes the temperature dependence 0) the spreading rate, and although the agreement between the actual and the predicted pre-exponen-tial terms is poor that between the activation energies is excellent and the variation in the spreading rate of copper on Ni-Cu alloys produced by different extents of alloying can be predicted with considerable accuracy. CHEMICAL interactions frequently change the wetting behavior of solid-liquid systems causing, for example, "secondary spreading1 of sessile drops beyond the size defined by the surface and interfacial tensions of the unreacted components. The kinetics of the contact-angle decreases associated with this spreading are similar for many systems, but few studies have been made with the objective of determining whether the similarities are a reflection of a common mechanism. Some workers2,3 have assumed the secondary spreading is controlled by changes in the liquid surface and liquid-solid interfacial tensions and hence by the composition of the liquid, and contact-angle changes measured by the vertical-plate technique have been used to follow the course of liquid-solid chemical reactions.4 Other processes that have been invoked to explain these time-dependent changes in specific systems include the removal of adsorbed gas from the liquid-solid interface.5 penetration of containment layers on the solid Surface,6 interdiffusion,1,7 reori-entation of the solid surface into a wettable configuration: vapor-phase transport of the liquid onto the solid in advance of the drop,9 and, from vertical-plate studies. capillary flow between oxide layers and the solid surface.10 One of the reasons for the profuseness of these suggestions may be the complexity of the contact-angle change kinetics. However, in an analysis of secondary spreading gold and copper on UC,11 it was found that the diameter of the contact area between the sessile drop and the solid surface showed a simple linear increase with time although contact-angle changes were more complex. To check whether the linearity was merely fortuitous! additional exploratory work was conducted with four reacting metal-metal systems: Au on Ni. Cu on Ni, Cu on Fe, and Ag on Au. Linear spreading was observed in every case even though the kinetics of the contact-angle changes were complex. A further detailed study of the kinetics of linear spreading of five reacting metal-metal systems has been made with the object of determining the mechanism involved. The influence of variables such as temperature, drop volume. and the initial composition of the drop on the linear-spreading rate has been measured and compared with those predicted by a number of possible mechanisms. The systems employed in this study (Cu and Au on Ni and Pt, and Ag on Au) were selected because of the availability of potentially relevant chemical and physical property data. the simplicity of their phase diagrams at the wetting temperatures, and the ease of experimentation. EXPERIMENTAL TECHNIQUES The purities of the metals used in the study were: copper, 99.9 pct; gold. 99.96 pct; nickel, 99.2 pct; platinum 99.99 pct; and silver, 99.999 pct. The wetting tests were performed in a split tantalum tube vacuum resistance furnace of a conventional design. The furnace element was held vertically and was 1 $ in. in diam and 6 in, long. Viewing ports were provided in the water-cooled chamber to enable the specimens to be observed in both the horizontal and vertical planes. The temperature in the hot zone of the furnace could be held at 1500" i 5°C for an indefinite time. The surfaces of the solid-plaque metals were ground flat on Microcut paper and both the sessile drop and substrate metals were ultrasonically cleaned in methyl alcohol prior to their insertion in the furnace. After loading, the furnace was pumped down to a pressure of 2 x 10-5 mm of mercury and degassed for 30 min at 900° to 950°C. The temperature was then increased at more than 100°C per min to that used in the wetting test. The vacuum at the wetting temperature was better than 5 x 10-5 mm of mercury. Dewetting and retraction of the drop on cooling did not occur and the contact-area diameters, therefore, were measured after solidification with a vernier traveling microscope. The diameters quoted later are arithmetic means of ten measurements. The standard error of the mean never exceeded 3 pct and was often less than 1 pct.

Jan 1, 1967

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

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

Jan 1, 1970