Search Documents

By A. Lubinski

In drilling operations, attention generally is given to hole angles rather than to changes of angle, in spite of the fact that the latter are responsible for drilling and production troubles. The paper presents means for specifying maximum permissible changes of hole angle to insure a trouble-free hole, using a minimum amount of surveys. It is expected that the paper will result in a decrease of drilling costs, not only by avoiding troubles, but also by removing the fear of such troubles. SUMMARY, CONCLUSIONS AND RECOMMENDATIONS Excessive dog-legs result in such troubles as fatigue failures of drill pipe, fatigue failures of drill-collar connections, worn tool joints and drill pipe, key seats, grooved casing, etc. Most of these detrimental effects greatly increase with the amount of tension to which drill pipe is subjected in the dog-leg. Therefore, the closer a dog-leg is to the total anticipated depth, the greater becomes its acceptable severity. Very large collar-to-hole clearances will cause fatigue of drill-collar connections and shorten their life, even in very mild dog-legs. Another finding regarding fatiguing of collar connections in dog-legs is that rotating with the bit off bottom sometimes may be worse than drilling with the full weight of drill collars on the bit, mainly in highly inclined holes when the inclination decreases with depth in the dog-leg. Means are given for specifying maximum dog-legs compatible with trouble-free holes. An inexpensive technique proposed is to take inclinometer or directional surveys far apart; then, if an excessive dog-leg is detected in some interval, intermediate close-spaced surveys are run in this interval. The application of the findings should result in a decrease of drilling costs, not only by avoiding troubles, but mainly by removing the fear of such troubles. The result would be much more frequent drilling with heavy weights on bit, regardless of hole deviation. Because of errors inherent to their use, presently available surveys are not very suitable for detecting dog-legs. There is a need for instruments especially adapted to dog-leg surveys. Crooked hole drilling rules should fall into two distinct categories—(1) those whose purpose is to bottom the hole as desired, and (2) those whose purpose is to insure a trouble-free hole. Three kinds of first-category rules in usage today are as follows. 1. A means to bottom the hole as desired is to prevent the bottom of the hole from being horizontally too far from the surface location; this may be achieved by keeping the hole inclination below some maximum permissible value such as, for instance, 5. 2. Another means to achieve the same goal is to limit the rate at which the inclination is allowed to increase with depth. A frequently used rate is 1/1,000 ft. In other words, a maximum deviation of l° is allowed at 1,000 ft, 2 at 2,000 ft, 3 at 3,000 ft, etc. 3. Whenever application of the first two means precludes carrying the full weight on bit required for most economical drilling, then the best course is to take advantage of the natural tendency of the hole to drift updip, displace the surface location accordingly and impose a target area within which the hole should be bottomed. This method has already been successfully applied,'.' and its usage probably will become more frequent in the future. Means for calculating the amount of necessary surface location displacement are avail-able.3'5'6 If in high-dip formations the full weight on bit should result in unreasonably great deviations, the situation could be remedied by increasing the size of collars and (if needed) the size of both hole and collars,351 or in some cases by using several stabilizers. Rules which would fall into the second category (i.e., rules whose purpose is to insure a trouble-free hole) are seldom specified today. It is vaguely believed that following Rules 1 and 2 of the first category will automatically prevent troubles. Actually, this is not true. If at some depth the only specified rule is that the hole inclination must be less than 4", the hole may be lost if the deviation suddenly drops from 4 to 2, or if the direction of the drift changes, etc. Rule 3 of the first category is generally used in conjunction with a rule belonging to the second category, namely, that the hole curvature' (dog-leg severity) must not exceed the arbitrarily chosen value of 1½ /100 ft. Moreover, when using this rule, the industry is not clear over what depth intervals the hole curvature should be measured. All this results in a frequent fear

K. T. Aust and J. W. Rutter (General Electric Research Laboratory)—We find it difficult to reconcile the activation energies determined by Gifkins with his general conclusion that "migration during both creep and grain growth can thus be treated on the basis of the same model" (that of Lucke and Detert). Gifkins finds the activation energy for grain boundary migration during creep to be 24.5 kcal per rnol and that for grain boundary migration during grain growth to be 7.5 kcal per mol. The calculation carried out by Gifkins of the activation energy for grain boundary migration during grain growth, using the Lucke and Detert model, gives a value of 20 to 24.5 kcal per mol, rather than his experimental value of 7.5 kcal per mol. The theory of Lucke and Detert was developed to account for the rates of migration of grain boundaries in the presence of impurities during grain growth. The theory does not take into account the effect on the boundary migration of another, simultaneous process such as creep deformation and would be expected, therefore, to be applicable only to migration during grain growth. The fact that Gifkins measured a different activation energy for boundary migration during grain growth (7.5 kcal per mol) from that during creep (24.5 kcal per mol), although the specimens were of the same composition, shows clearly that such an effect exists under his experimental conditions; the presence of a simultaneous creep deformation markedly affects the boundary migration process in comparison with what would be observed under the same conditions but without the creep deformation. The failure of McLean's equation (Eq. [4] of Gifkins' paper) to give a satisfactory dislocation density difference for boundary migration during creep is not surprising, since the activation energy which must be used in this equation refers only to the elementary atom transfer process of grain boundary migration. This activation energy value is approximately 6 kcal per mol for zone-refined lead, as determined in both the grain boundary migration experiments of Aust and Rutter31, 32 and the grain growth experiments of Bolling and Winegard.33 Using this activation energy value, McLean's equation gives reasonable agreement with observed migration rates for grain boundaries moving free of the influence of impurities.31, 32 The value of 24.5 kcal per mol is probably associated with the presence of impurity atoms, as Gifkins suggests. It should be noted, however, that this value was obtained using lead of only one composition and measurements at only two temperatures. The work of Aust and Rutter3"' on the effects of tin, silver, and gold on grain boundary migration in zone-refined lead in the temperature range from 320" to 200°C, as well as the work of Bolling and Winegard34 on the effect of silver and gold on grain growth in zone-refined lead, shows that the measured activation energy is markedly dependent upon the kind and amount of solute present. Gifkins' work does not permit evaluation of the effect of the 8 ppm of impurities other than oxygen present in his specimens. One incidental point: the symbols used to designate the experimental points of Fig. 6 appear to be in incorrect order in the figure caption. As the caption is printed, it would indicate that larger grain sizes were obtained after annealing at 47°C than at 100°C, which does not agree with the text (point M, p. 1019). Finally, it seems clear from Gifkins' results that any serious attempt to determine whether grain boundary migration and grain boundary sliding during creep occur with the same activation energy, as Gifkins suggests and McLean rejects, must take into account the effects of impurities on these two processes, Although the work of Weinberg35 indicated that adding small amounts of copper, iron and silicon to aluminum did not affect the grain boundary shear behavior, it should be noted that his starting material contained approximately 60 ppm of impurities. Gifkins' results indicate impurity effects at an impurity level of 8 ppm, suggesting strongly that the most significant impurity range to be investigated lies substantially below that value. R. C. Gifkins (author's reply) — As Drs. Aust and Rutter suggest, the results under discussion may have to be reinterpreted in the light of their own work on grain boundary migration, which was not available to me when the paper was written. Because of their work, Aust and Rutter attach more importance than I did to the activation energy for grain boundary migration during annealing (7.5 kcal per mol) obtained from a "direct" plot of log-rate against the reciprocal of absolute temperature. At the time it was obtained, this value seemed rather low, although it was similar to the value obtained by Bolling and Winegard.36 It was then, and still is, difficult to accept this value because of the low value of the index in the power law for grain growth, which seemed to indicate the influence of impurities. It was also concluded that the low value of the activation energy might have arisen from the manner of selecting rates of grain growth which were truly comparable at the two temperatures. There were many other indications in these experiments and those on recrystallization during creep3? that an impurity, probably oxygen, was of importance. The model for grain-boundary migration which Lucke and Detert had proposed was an obvious possibility and its use yielded an activation energy for boundary migration during annealing of 20 to 25 kcal per mol.

Jan 1, 1961

By W. W. Anderson, S. Razi

Electroluminescetrce of single crystals of terbium-(loped ZnS prepared by vapor-transport technique shows the sharp line specirum characteristic of the 4f— 4ft,ansitiotzs of the trivalent Tb3 rotz. V-I tt~easuverr~ents give evidence of space-ellarge-lirrlited curvent but the thrveshold for trap-filled law behavior is not iu agreement with Lampert&apos;s theory for. Single injection. Variations of &apos;brightness with applied voltage, the observation of double peaks its brightness because joms, and the spatial distribution oi electroLur?zir~escerrce indicate that the accelet~atiotz-collision mechanism involving the bst lattice and/ov shallow traps is most likely to be responsible fov excitation of&apos; electrolnminescence. Efficiency rtreusuver)~etits show the quantwn efficiency to be about 10 pct and powev efficiency about 0.05 pct. Effect of anr~eallng the crystal in sulfur vapor is to enluztzce llle rare-earth emission. It rs pvoposed tlzat sulfitv anr~ealing crreates acceptorr-lvpe defects with which the donor-type vare-eavtll ion can associate more readily vesulting in enhanced rare-earth emission. A&apos;o such e~zlznr~cerr~etrt is obserued when the crystal is atztrealetl in zinc vapor. Photolianinescence of ZnS doped nith a variety of rare earths also shows tile slurvp l~rze rwve-eavtlz erriission which in sorrretirr~es accompanied by broad band, stvuctureless lattice emission. Photo-atrd electrolutr~itzesce?~ce of ZIIS:Tb slw~rj do!rlit~unt rare-earth emission in the ~ticirzity of 54(3OA corre-sporrdit~g to the transition D* — Fj. Hoz~!el)er, the detailed line structuve of the luo spectvtr is cliffevet~t, irzdicutit~g that different sites are active in the two processes. Decay of rave-eartlr fluorescence in ZnS doped with any of sei!evul vuve eurtlzs car1 be described by a single exporleritial e.scepl joy ZrlS:lIo. Tl~is exceptiotr can be explaitred it~ tevrr~s of tlre closely spaced er~evgy 1e1:els Jov the HO~&apos; iorr. Decay lime measurertzekzts jov ZnS:Tb, using pulsed elect,-ical ar~d pulsed opticcll excitutiorzs, (11-e itz goor1 agrcetrier~t. LUMINESCENCE of rare-earth-doped materials has been a subject of interest for the past 20 years. Within the past few years there has been a considerable increase in rare-earth research motivated in search of new and more efficient laser materials and also due to the use of certain-rare-earth compounds in the preparation of color television screens. The purpose of this study has been to seek an understanding of some of the basic processes involved in exciting the rare-earth luminescence which is associated with transitions within the 4f shell of the trivalent rare-earth ion. Single crystals of ZnS doped with a variety of rare-earth ions have been prepared by vapor-transport technique described elsewhere.&apos; Photoluminescence was excited by a high-pressure short-arc mercury lamp together with suitable glass and chemical filters. For electroluminescence, sinusoidal and pulse excitations were used. 1) ELECTRICAL CHARACTERISTICS 1.1) V-I Measurements. Electroluminescence experiments were performed on crystals of terbium-doped ZnS. The samples were cleaned and etched and indium or In-Ga alloy contacts were alloyed on by heating in H2 atmosphere to 600°C for times ranging up to 10 min. Static voltage-current measurements were made on several samples. Fig. 1 shows the results for a typical sample. For voltage V < 20 v, the V-I relationship is linear giving a resistivity of 2.5 x 109 ohm-cm for this particular sample at room temperature. In the range of 20 to 250 v, I varies as V "3 and at still higher voltages (when electroluminescence is visible to the scotopic eye) current varies as Vs up to 600 v, all at room temperature. At 77"K, for V > 200 v, / I vge5 up to 1000 v. The V-I characteristics at room temperature follow reasonably well the behavior predicted by Lampert&apos; for one carrier space-charge-limited current in an insulator with traps although, as shown later, the expression derived by Lampert2 for the threshold for trap-filled law behavior Vtfl yields an unrealistically low value for trap density if we use the experimental value of 300 v for VtfL. Assuming the case for shallow trapping, the transition from Ohm&apos;s law behavior to space-charge-limited behavior occurs at voltage Vtr given by where no = thermally generated free carrier density, L = length of the sample, e = static dielectric constant, 6 = ratio of free to trapped electron densities, e = electron charge. For the ZnS:Tb crystal, L = 0.5 mm, E = 8.3 €0, Vtr - 20 v, and no = 5 x 10&apos; per cu cm, calculated from the ohmic behavior assuming electron mobility of 100 sq cm per v-sec. This results in 9 = 0= As more and more electrons are injected the Fermi level moves up in the forbidden gap toward the conduction band. If we assume a single-energy level for traps (which is not strictly correct, as we will show later), the current voltage characteristic is profoundly affected when the Fermi level crosses the trap level. The traps are now filled and injected carriers can no longer be immobilized in traps. Hence, current rises sharply with voltage. The transition from space-charge-limited behavior to the trap-filled behavior occurs at voltage VTFL given by

Jan 1, 1968

By R. D. West

Miscible displacenzent recovers all oil in the area contacted by the injected .fluid, whereas water or immiscible gas drives usually leave substantial amounts of oil as residual. However, the Door mobility ratios associated with a gas-driven miscible displacement cause the sweep pattern efficiency to be much lower than that obtained with water flooding. One way in which the sweep eficiency in a miscible displacement process can be increased is by decreasing the mobility behind the flooding front. This can be achieved by injecting water along with the gas which drives the miscible slug. This water reduces the relative permeability to gas in this area and thus lowers the total mobility. The main operating conditions for the simultaneous injection -vrocess are that a zone of gas exists between the miscible slug and the leading edge of the water and that a su,@cient amount of gas be injected with the water to form the pas volume which is being left in the water zone. Laboratory model studies have shown that the ultimate sweep pattern efficiency can be as high as 90 per cent for a five-spot flooding system. If gar alone is used as the driving medium an ultimate sweep-out efficiency of about 60 per cent would be obtained in the same system. I INTRODUCTION The miscible displacement processes are a step towards total oil recovery. Conventional gas or water drives usually leave 25 to 5.0 per cent of the oil as residual in the swept portion of the reservoir. This residual can be eliminated if the oil is driven by a fluid with which it is miscible. At some reservoir conditions natural gas will become miscible with the oil. This is the "high pressure gas process".&apos; More often, the oil does not contain enough light hydrocarbons to cause the gas to become miscible with the oil at reasonable pressures. In these cases a small band of fluid which is miscible both with the oil and gas must be kept between them2. Less than 2 per cent of the reservoir volume of the slug material is needed to keep the displacement miscible. Both processes work in the same manner, recovering all of the oil in the portion of the reservoir contacted by the injected fluids. The only difference is the manner in which the miscibility between the oil and the injected gas is obtained. Previous publications have contained detailed descriptions of these processes.1,2,3,4 However, total displacement of the oil in the swept region does not guarantee an efficient recovery process. The amount of oil to be recovered is also determined by the fraction of the reservoir contacted by the flood. This fraction is largely determined by the mobilities of the fluids. (The fluid mobility is the permeability of the rock to that fluid divided by the fluid&apos;s viscosity, k/p). This. dependence of the fraction swept on the mobility ratio has been shown in previous studies. Fig. 1 shows the ultimate fraction swept in a five-spot system as a function of the mobility ratio. The small drawings show the location of the areas left unswept for two different mobility ratios. The ultimate fraction of the reservoir swept is here considered to be attained when the producing stream contains less than 5 per cent oil at reservoir conditions. THE GAS-DRIVEN MISCIBLE DISPLACEMENT Since there is no oil left in the swept region after miscible displacement the mobility in this region is very high. It is often 50 times the mobility in the unswept regions. This means that the fraction of the reservoir contacted by the injected fluid will be less for a gas-driven miscible displacement than for a conventional water or gas drive. For a five-spot injection system, water would contact the entire reservoir volume, and the low pressure gas would contact about 90 per cent of this volume, while a gas-driven miscible displacement would only contact about 65 per cent of the reservoir. This poor sweep efficiency often offsets the benefits obtained through miscible displacement. Fig. 2 shows what the recovery curves for the three processes might look like for a five-spot system. The curves show the fraction of the in-place oil recovered as a function of reser-

By Raymond L. Orr

Calorimetric measurements have been made of the heats of solution of gold axd indium in a number of liquid tin-rich alloys at a temperature of 705°K. Relative partial molar enthalpies of gold were determined as a function of dilute solute concentrations in the binary Au-Sn system and in the ternary Ag-Au-Sn and Au-In-Sn systems. Relative partial molar enthalpies of indium were determined for dilute solute concentrations in the In-Sn, Ag-In-Sn, and Au-In-Sn systems. Through application of the interaction coefficient concept introduced by Wagner and more recently extended by Lupis and Elliott, ualues have been obtained for the Au-Au, Ag-Au, Au-In, and Ag-In enthalpy interaction coefficients in liquid tin. The results are inte@reted in terms of solute atom distributions through comparisons with the predictions of dilute solution models. INTEREST in the thermodynamic behavior of dilute liquid alloys stems from two primary sources. From a practical viewpoint, it is often of importance to know or to be able to predict the effect that one solute will have on the thermodynamic properties of the other solutes in a multicomponent system. Studies of dilute solutions may also be rewarding from the theoretical point of view. Some of the difficulties arising from the more complex interactions possible in concentrated solutions are avoided, leading to easier interpretations in terms of solutibn models and bonding energies. For example, in a binary alloy the limiting values of the partial molar properties of the solute represent the case for which each solute atom is completely surrounded by atoms of the solvent, and no other interactions are possible. Solute - solute interactions in dilute solutions are conveniently treated by the interaction coefficient concept of ~agner.&apos; Using a Taylor series expansion for the logarithm of the activity coefficient, In yi, of a component, i, in a solution consisting of dilute solutes with atomic fractions xi, xj, xk, and so forth, in a solvent, s, and neglecting the second- and higher-order terms, Wagner obtained the expression: Where Wheyz is the limiting value of yi in the pure solvent, s. The interaction coefficients, e:, e:, and so forth, are defined by: Since yi is related to the excess partial molar Gibbs energy of component i by GfS = RT In yi, E: is re- ferred to as the "Gibbs energy interaction coefficient". Lupis and Elliott~ extended Wagner&apos;s treatment to the relative partial molar enthalpy, aHi, and the excess partial molar entropy, qS. They defined the enthalpy interaction coefficient as: and the excess entropy interaction coefficient as: leading to expressions similar to Eq. [I]: The three interaction coefficients are related by? The self-interaction coefficients, E:,qf,and at, represent the effects of interactions between atoms of component i in solvent s; €3, q{, and 03 represent the effects of interactions between i and j atoms in solvent s; and so forth. From the Maxwell-type relationships between partial molar quantities, it may be shown1&apos;2 that e{ = ej, r}\ =tj), and ai - crj. Experimental determination of the interaction coefficients requires extremely precise measurements of the appropriate properties as functions of solute concentrations in very dilute regions. Few such data exist for intermetallic alloys, even for binary systems, because of experimental difficulties. This is especially true with respect to enthalpy data for dilute alloys. Examination of the compilation of data for binary alloys by Hultgren, Orr, Anderson, and ~elle~~ reveals that determination of limiting values of &fii(Xi =0) often requires extrapolations to infinite dilution from xi = 0.05 to 0.10. Direct measurements of the enthalpy interaction coefficient, qi, for multicomponent systems are virtually nonexistent. This quantity is of course subject to direct calorimetric measurement, but its determination must be limited to cases where high experimental precision is possible. The heats of solution of gold and indium in liquid tin can be measured with relatively high precision, which makes determinations of 73 involving these metals as the measured solutes experimentally attractive. This paper presents the results of such determinations of the Au-Au, Ag-Au, Au-In, and Ag-In enthalpy interaction coefficients in liquid tin. MODELS FOR DILUTE-SOLUTION BEHAVIOR Random-Solution Behavior. In the quasi-chemical treatment of solutions, only nearest-neighbor bonds are considered, and a composition independent value

Jan 1, 1967

By Gerhard Bockstiegel

Kuczynski&apos;s formula has been derived for the case of nonspherical particles. TWO formulae of Kuczynski&apos;s type have been derived, one describing the increase in tensile strength, the other describing the progress of shrinkage of a powder compact. It has been strength,shown that the exponents of all three formulae each contain two magnitudes of different physical characters, viz, the geometrical factor a and the kinetic factor ß. The interrelationships between the three exponents are stated. SOME years ago Kuczynski1 experimentally showed that the radius, x, of the area of contact between very small spherical metal particles and a metallic block is related to the time of sintering, t, by the following equation x = constant tk [11 where k has the value 1/5 or 1/7. Assuming that the metal particles were perfect spheres and the metallic block was perfectly flat, he derived the foregoing equation from theoretical considerations of the process of material transport in metals, and he showed that exponent k is different for different mechanisms of transport, e.g., k = 1/2 for viscous flow (according to Frenkel2), k = 1/3 for evaporation and condensation, k = 1/5 for volume diffusion, and k = 1/7 for surface diffusion. From this Kuczynski concluded that the mechanism of transport was either volume diffusion or surface diffusion, depending on whether the value of k, as found in his experiments, was 1/5 or 1/7. Subsequently. Cabrera8 corrected Kuczynski&apos;s calculations with regard to surface diffusion, showing that the theoretical value of exponent k is 1/5 for both volume and surface diffusion. He supposed that the different experimental values of k were due to slight differences in the shape of the metal particles. An exponential relationship similar to the aforementioned was found by Okamura, Masuda, and Kikuta,4 Masuda and Kikuta, and Takasaki8 when studying the rate of shrinkage on powder compacts during sintering. The authors measured the shrinkage by means of the fraction w = Vp — V./Vp — V,,,, where V,, is the volume of the green compact, V, is the volume of the sintered compact, and V,,, is the volume of the compact in its densest state. This fraction, w, they found, is related to the time of sintering, t, by the equation w == constant tm. [21 Further, Bockstiegel, Masing, and Zapf7 observed that the tensile strength, s, of sintering iron powder compacts can also be related to the time of sintering, t, by an equation of the foregoing type, i.e., s = constant tn. [3] For exponent n the values 0.28 (S=2/7) and 0.35 ( 2/5) were obtained, and the authors pointed out that there might exist a simple interrelation between exponent n as found in their experiments and exponent k in Kuczynski&apos;s equation. The authors supposed that 2k = n, since the strength of adhesion between a metal sphere and a block (as in Kuczyn-ski&apos;s experiments) must approximately be proportional to their contact area, p. x2. Theoretical Considerations This paper is an attempt to correlate the fundamental experiments of Kuczynski&apos;s type with the results obtained with powder compacts as represented by Egs. 2 and 3. In particular, the paper is to show how the rate of sintering is influenced by the geometry of the sintering particles and by the type of material transport. As the geometry of particles conglomerating in a powder compact is very complex, some simplifying assumption has to be made, of course, in order to adapt the problem to mathematical treatment. In the following paragraph a suitable simplification is introduced, and Kuczynski&apos;s formula is derived for the case of nonsphcrical particles. Relation Between Area of Contact and Sintering Time—As the face of contact between two particles in a sintering powder compact is not necessarily a circle (as in the case of spheres sintering to a block), Kuczynski&apos;s formula is modified as follows: Let the perimeter of the face of contact be described by means of polar coordinates R, 4, as shown in Fig. la, so the area of contact, f, is determined by f= 1/2 . S112p[R(Æ) ]2 dÆ [4] Then, let the two particles be intersected by a plane perpendicular to area f. The intersection is shown in Fig. lb. According to the nomenclature in this figure, the distance, h, between the surfaces of the two particles is a function of T and Æ: h = h(r,Æ). For the particular case of spherical particles, as in Kuczynski&apos;s theory, this function becomes: h = constant r2. It shall be assumed here that in the close neighborhood of their

Jan 1, 1957

By G. Horvay, J. G. Henzel

Nomograms and charts are provided which permit rapid determination of the mold-casting interFace temperature and the speed of solidification when a semiinfinite ingot is cast into a semiinfinite mold. The physical properties of the mold, the frozen metal, and the liquid metal are not assumed to be equal, but they are assumed to be temperature independent. The results are correlated with charts prepared by Paschkis and Hlinka—using Columbia University&apos;s Analog Computer—for the freezing of finite ingot slabs when a constant surface temperature is impressed, and with experimental cooling curves obtained by Pellini in sand and iron molds for 7 in.-sq steel castings. x = coordinate directed to right of zero (freezing direction) y = coordinate directed to left of zero (melting direction) e = position of freezing front (in x direction) ? = position of melting front (in y direction) $ = temperature (function of position and time) ? = fixed temperature 2L = width of finite slab Y = a fixed position in the semiinfinite mold, or the width of a finite mold (see Section 7) Properties y = density, lb per cu ft c = specific heat, Btu per lb deg F k = conductivity, Btu per ft hr deg F X = heat of fusion, Btu per lb k = k/Yc = temperature diffusivity, sq ft per hr* b - = = - heat diffusivity, Btu per sq ft deg F Vhr Subscripts 2 = pertaining to the still-liquid metal (case of freezing), or the medium which furnishes the heat (case of melting) 1 = pertaining to solidified metal (case of freezing), or to molten metal (case of melting)* 0 = pertaining to mold (case of freezing), or to the still-solid metal (case of melting) f = pertaining to fusion condition (eg.,?f - fusion temperature) i = pertaining to the location x = 0 (the mold-ingot "interface")

Jan 1, 1960

By L. D. Jaffe, F. W. Cotter, E. Cordon

The hardenability of titanium-base alloys was studied by metallographic examination and hardness survey of Jominy specimens end-quenched from the B range. Analyses of the data led to the equation log J = -0.57 + 0.25 @ct Fe + pct Mn + pct Mo) + 0.19 @ct Cr) +0.16 @ct V) + 0.03 @ct Zr). Here J is the distance, in sixteenths of an inch, from the quenched end of a Jominy hardenability specimen in the position of peak hardness, for material quenched from the B range. This equation fitted the experimental data with a standard deviation of approximately 0.29. The effects of the elements Al, Sn, W, Cu, Ni, B, C, N, 0, and H, and of pain size, were not statistically significant or not practically significant. A check against hardenability measurements in the literature showed agreement within the stated standard deviation. The equation should be useful in estimating hardenability of new or modified titanium alloys. HARDENABILITY in a titanium-base alloy is the ability of the alloy to retain the B structure on quenching. An alloy with high hardenability will retain the /3 structure even when cooled relatively slowly from a temperature at which B or P plus a is stable. A low hardenability material will retain P only if quenched extremely rapidly from the range of p or 0-plus-a stability, or will not retain it at all, at room temperature. High hardenability is desirable in titanium alloys to be heat-treated to high-strength levels. Its value is by no means limited to large section sizes. With high hardenability, a material can be solution-treated and cooled at a variety of rates, either to give high strength directly or, more generally, to give a soft ductile condition from which high strength can be obtained by subsequent aging. With low hardenability, high strength can be obtained, if at all, only by very rapid quenching, and there will generally be little increase in hardness on subsequent aging; an alloy of this type is limited in its applicability. On the other hand, alloys of very low hardenability have some advantages in weldability; essentially, they are always in the annealed condition, after welding as well as before. For commercial alloys, hardenability data are usually available, in the form either of property data after cooling from the solution temperature at various rates, with or without subsequent aging, or of results of a standard hardenability test, such as that originally developed for steels by Jominy and Boegehold.&apos; When modifications of an available alloy are considered, or preparation of new alloy compositions, it would be Very convenient to be able to estimate the hardenability of the new material without having to make and test it. A method of estimating hardenability of titanium alloys from their composition was suggested by one of the authors some time ago, on a preliminary basis, utilizing scattered data found in the literature.&apos; It seemed worthwhile to carry out a systematic experimental study of the effect of composition upon hardenability. EXPERIMENTAL PROCEDURE Approximately fifty heats of various compositions, weighing 8 to 10 Ib apiece, were melted in a small inert-gas tungsten-arc furnace with water-cooled copper walls. The starting material was 110 Brine11 titanium sponge, with high-purity metals added for alloying. Each heat was bottom-poured under vacuum through a molybdenum burnout strip into a cold graphite mold, to form an ingot approximately 4-1/2 by 3-1/2 by 3 in.* From each ingot were cut *The material was melted and cast by Pitman-Dunn Laboratory, Frankford Arsenal, to whom the authors must express their thanks. two pieces 4-1/2 by 1-1/2 by 1-1/2 in. These were forged, at temperatures adjusted to the composition, into 1-1/4-in. rounds, from which standard 1-in.-diam hardenability specimens3 were machined. A number of small samples were also prepared from forged materials of each heat, annealed, quenched from various temperatures, and examined metallographically. The P-transus temperature was determined by observation of the degree of resolution of primary a in these pieces. samples for chemical analyses were also taken from the forgings. One hardenability specimen of each heat was solution-treated for 1 hr approximately 50°F above the measured transus temperature, and the other for 1 hr approximately 250°F above the transus. (An additional hour was allowed for the specimens to reach furnace temperature.) These are not necessarily the temperatures that would be selected for

Jan 1, 1964

By P. Gordon

An isothermal jacket microcalorimeter, supplemented by metallographic, microhardness, and X-ray measurements has been used to study the isothermal annealing of high purity copper after room temperature tensile deformation. The amount of stored energy released during annealing has been measured as a function of deformation in the range 10.8 to 39.5 pct elongation. The data have shown the major heat effect to be associated with recrystallization and have allowed an analysis of the recrystal-lization kinetics and the calculation of activation energies of recrystallization. WHEN a metal is deformed plastically, some of the energy expended is dissipated as heat during the working process, while the remainder is stored within the metal in the form of lattice distortions and imperfections. During subsequent heating of the metal, the distortions and imperfections can be largely annealed out and the associated stored energy released as heat. It is apparent that measurements of the evolution of stored energy during such annealing may produce important information concerning the nature of the annealing mechanisms and the imperfections involved. Some excellent studies of this type have been made in the past, notably those of Taylor and Quinney,&apos; Suzuki,2 Bever and Ticknor,3 Borelius, Berglund, and Sjöberg,4 and Clarebrough et al.5,6 None of this work, however, employed isothermal techniques, with the exception of the Borelius studies&apos; in which only the early annealing stages were investigated. Since isothermal measurements, as compared with heating or cooling curve, have the merits that 1—they reveal the kinetics of a process more clearly, 2—the results obtained are more easily applied to theory, and 3—most fundamental investigations of annealing using techniques other than calorimetry have been carried out isothermally, it was considered important to apply calorimetry to the study of the isothermal annealing of metals. Accordingly, an isothermal jacket calorimeter of the Borelius type,&apos; supplemented by metallographic, hardness, and X-ray measurements, has been used to study the annealing of high purity copper after room temperature tensile deformation. Experimental The microcalorimeter has been described fully elsewhere." Briefly, the specimen to be studied is placed in a constant temperature environment of virtually infinite heat capacity achieved, as shown in the drawing of Fig. 1, by means of a vapor thermostat. A high thermal resistance is provided between the sample and the environment and a sensitive differential thermopile (see Figs. 2 and 3) arranged with half its junctions in contact with, and thus at the constant temperature of, the environment, and the other half in contact with the sample. A reaction in the sample develops a small difference in temperature, AT, across the thermopile, which is followed by a recorder-galvanometer set-up as a function of time, t, and is converted to reaction heat per unit time, P, by the use of the equation AT P=a?T + b AT dt The constants, a and b, in Eq. 1 are determined by a simple calibration, making use of the Peltier heat developed by a small current run through the junction of a thermocouple located in an axial hole in the specimen (Fig. 2). In its present form, the limit of sensitivity of the calorimeter is a heat flow of 0.003 cal per hr. The copper used was the spectroscopically pure metal supplied by the American Smelting and Refining Co. in the form of 3/8 in. diam continuously cast rod, reported to be 99.999+ pct Cu. A small amount of the copper was available at the start of this work and is referred to hereafter as lot A. A second batch, lot B, was obtained later, most of the results described subsequently being for this lot. As will be seen, there is some indication that lot A was somewhat purer than lot B, but it is not known whether this difference was present in the as-received metal or arose during subsequent handling. The two lots of copper were remelted and cast into two 1½ in. diam ingots in vacuo, using high purity graphite crucibles and molds. The ingots were upset several times to break up the large cast grains, and then rolled and swaged to rods 0.391 in. in diameter, using several intermediate anneals with about 40 pct reduction in area between anneals. The penultimate anneal was 2 hr at 350°C. X-ray examination showed no marked general preferred orientation in the resulting rods. The grain structure typical of the two rods is shown in the micrograph of Fig. 4." It was found to be virtually im- possible to get an unambiguous measure of the absolute grain size in the two annealed rods because of the profusion of annealing twins and the lack of regularity of the grain boundaries. However, counts of the number of boundaries intersected per unit length along a random line on a polished section, making a correction for the proportion of boundaries (about half) estimated to be twin boundaries, gave a figure of about 0.015 mm for the average grain diameter. The grain size of the rod from lot A was about 5 pct smaller than that from lot B. The rods were cut into 1 ft long bars and these deformed in tension at room temperature to various total elongations in the range 10.8 to 39.5 pct. A strain rate of 1 pct per min was used. The deformed bars were then stored in a dry ice chest until such time as samples were to be cut from them. Five bars deformed as indicated in Table I were used for the subsequent tests. In all cases, all the calorimeter.

Jan 1, 1956

By H. R. Ogden, E. S. Bartlett, A. G. Imgram

Unmodified disilicide coatirigs were applied to sheet-tensile specimens ofCb-Dg3 and Mo-TZM veJractovy- metal alloys. Coating thickness, degree of coating-substrate interdiffusion, and specimen geonzetry (notched and plain were included in the variables studied. Tensile tests were made to determine the ductile-lo-brittle transition temperature. The disilicide coating modestly increased the transition temperatlre of TZM, but had no effect on 043. Neither material condition (recrystallized or stress-velieved) nor specimen geometry (notched or unnotched) significantly altered the effects of coatings on the transilion temperatures of. the alloys. Cracks in the brittle coatings did not propagate into the substrate, and fracture modes appeared to be the same for both un-coated and coated specimens. MOST potential structural applications for refractory metals and alloys involve exposures to oxidizing environments at elevated temperatures. The general lack of oxidation resistance of these metals will require protective coatings to allow fulfillment of their potential. Currently preferred coatings for the oxidation protection of refractory metals are brittle intermetallic aluminides or silicides. These are typically formed on the surface of the refractory-metal substrate by a diffusion reaction between the substrate and a gaseous or liquid medium that is rich in aluminum or silicon. Because of the brittleness of these coatings, they will sustain no plastic deformation at low temperatures. They are frequently cracked by cooling from the coating temperature because of the thermal-expansion mismatch with the substrate alloy. Even if they survive cooling intact, they crack rather than sustain deformation under load at low temperatures. Thus, when a coated refractory metal is strained beyond the elastic limit of the coating at low temperatures, the mechanical environment of the substrate would include both static and dynamic cracks. These might be expected to influence the flow and fracture behavior of the substrate. This could be manifested in an altered fracture mode and/or an increase in the normal ductile-to-brittle transition temperature of the refractory-metal substrate. This paper presents the results of a research program that was conducted to determine the influence of the presence of a brittle surface coating on the low-strain-rate tensile behavior of typical refractory metals at low temperatures. EXPERIMENTAL PROCEDURES Material Preparation. Thirty-mil-thick sheets of molybdenum TZM alloy (Mo-0.5Ti-O.1Zr) and colum-bium D43 alloy (Cb-IOW-1Zr-O.1C) were obtained commercially. These alloys were selected as substrate materials representing two classes of materials important in current refractory-metal technology. The TZM was in the stress-relieved condition, and exhibited a heavily fibered grain structure. The D43 had been processed by the duPont "optimum" fabrication schedule,&apos; and exhibited slightly elongated grains typical of this process. Tensile specimens of two geometries were prepared from these materials: 1) plain specimens with 0.2-in.-wide 1.0-in.-long gage sections; 2) specimens similar to above, but with a 0.06-in.-diam hole drilled in the center of the gage section, providing a stress concentration factor, Kt, of 2.5. The "notch" geometry was selected to represent a typical condition of a rivet hole or other geometric discontinuities as might be encountered in various applications. Machined specimens were degreased, with a final rinse in acetone, prior to the application of coatings. Specimens of each substrate and configuration were pack-siliconizedin a particulate mixture of 80 pct A1203, 17 pct Si, and 3 pct NaF. Specimens were embedded in this mix (contained in graphite retorts) and coated in an electrically heated argon-atmosphere furnace under time-temperature conditions to effect nominal 1- and 3-mil-thick silicide coatings: Coating Thickness, mils Thermal Treatment 0.6 to 1.4 24 hr at 982°C 2.4 to 3.2 48 hr at 1093°C Coating kinetics were similar for both the TZM and D43 substrates. These treatments had little or no visible effect on the substrate microstructure as determined by optical metallography. The coatings on TZM were essentially single-phase unmodified disilicides, while those on D43 showed substantial evidence of modification by proportionate reaction with the respective substrate elements or phases, as shown in Fig. 1. It was recognized that these coatings might not be particularly desirable regarding protective capability. However, it was desired to circumvent possible inter -ferring chemical interaction with the substrate by pack additives such as chromium, titanium, boron, aluminum, and other elements that typify the better protective coatings for these materials.&apos; Thus, the results presented apply specifically to the simple silicide coatings investigated. They may not be rep-

Jan 1, 1967

By J. H. Waxweiler, L. C. Ikenberry, R. J. Bendure

Carbon which is present as insoluble carbides in austenitic stainless steels can be measured quantitatively by dissolving the steel in iodine-methanol and analyzing the residue for carbon. Severe sen-sitization was observed in Type 302 due to precipitation of only 0.003 pet carbon. Both cold work and the presence of delta ferrite caused a marked acceleration in rate of carbide precipitation. Carbide precipitation rates in 17-7 PH were stzulied for the austenite conditioning and also the aging heat treatment. CARBON and its compounds exercise a major influence on the properties of stainless steels and their response to thermal treatment. Sensitization in 18-8 type stainless steels has been the subject of numerous investigations throughout the years. Bain, Aborn, and utherford," and Binder, Brown, Frankss all studied the effects of heating austenitic stainless steels in the temperature range of 1000° to 1500°F. The primary purpose of most of these studies was the investigation of susceptibility to in-tergranular attack in acids due to these sensitizing heat treatments. Intergranular precipitation of carbides was always associated with intergranular attack but it was recognized2 that severe attack could occur with but minute quantities of precipitated carbide. Mahla and ielsen utilized the electron microscope to make a significant contribution in illustrating the appearance and method of growth of chromium carbides during sensitizing heat treatments. However, as they stated, their studies of residues could not be used to obtain a quantitative measurement of the amount of carbon which was actually precipitated. The aim of the present investigation was to devise a relatively fast, simple method for the quantitative measurement of carbides in stainless steel. EXPERIMENTAL WORK The initial investigations were made to determine the best means of separating carbides from the matrix. A number of dissolving media were tried using both chemical and electrolytic attack. Qualitative examination of the extracted residues by X-ray diffraction indicated that solution in iodine-methanol would furnish a good means of separation. Consequently, further work was pursued along this line. The method is quite simple. The sample in the form of millings or nibblings is dissolved in iodine-methanol solution at room temperature (6-g iodine, 25-ml methanol per g of sample). The insoluble residue containing the carbides is separated by suction filtration through an ultra-fine glass filter disc. This is a very fine filter medium that will retain particles as small as 0.1 to 0.2 p in diameter. After washing with methanol and drying, the filter disc and residue are placed in a conventional combustion carbon-tube furnace and the carbon determined gravimetrically. Using this technique it was found that reproducible insoluble carbon values were obtained. However, since such small amounts of insoluble carbon were obtained on Type 302 after sensitizatipn at 1250°F and 1500°F, the values were confirmed by a second method. In the second method the sample was dissolved with copper potassium chloride and filtered through a millipore paper. This treatment dissolves the matrix but leaves undissolved practically all of the carbon irrespective of how it is present in the steel. The amount of insoluble carbon present as chromium carbide is determined by calculation from the analysis of the residue for chromium and iron. The derivation of the formula used for this calculation is discussed later. The values obtained by the indirect copper-potassium-chloride method were in agreement with those obtained by the iodine-methano1 method. See Table I. It should be pointed out that the sensitivity of the direct combustion method is not too high when the amount of carbide present is small. This is due primarily to inherent blanks and to analytical errors such as weighing. For this reason it cannot be stated with any degree of certainty that there is a significant difference between values of 0.002 and 0.005 pct. Having confirmed that the iodine-methanol extraction gave a quantitative measurement of the precipitated carbides in Type 302, exploratory tests were conducted on Armco 17-7 PH stainless steel. Samples from commercial Heat 54807 were solution annealed at 2000°F, water quenched and heated at 1250" and 1500°F, and water quenched. The analysis of Heat 54808 is as follows:

Jan 1, 1962

By R. J. Burgess, A. R. Ramey, A. R. Adams

During interpretation of pressure buildup tests on gas wells in a tight dolomite gas reservoir, peculiar behavior was noticed. Two straight lines were apparent. Effective permeability to gas taken from either straight line was about the same, and the Miller-Dyes-Hutchinson dimensionless time check for the straight line was proper for both straight lines. Geological data indicated the likelihood of scattered trending fractures in the reservoirs. Since the first straight Iine yielded permeability values close to the geometric mean permeability from core analyses, it was postulated that the reservoir model was that of an acidized well completed in the tight dolomite, but that widely scattered hairline fractures caused the mean permeability of the reservoir distant from the well to be higher than the matrix permeability. Because all other studies of fractured reservoirs to the authors&apos; knowledge assumed that the fracture matrix was dense enough to communicate directly with the well, no interpretative methods were available. The Hurst line-source solution for a radial change in permeability for interference between oil reservoirs was adapted to pressure buildup testing. The result indicated that the first straight line should yield the proper matrix permeability and wellbore skin effect. The second straight line may be extrapolated to obtain static pressure. The time of bend between the straight lines was used to estimate distance to a fracture. Application to field test data is shown. It is believed that the methods developed and the case history presented will add to present tools available for pressure buildup interpretation. Introduction Since the pioneer studies by Miller, Dyes, and Hutchin-son1 and Horner&apos; in 1950 and 1951, well test analysis has become recognized as one of the most powerful tools available to both production and reservoir engineers. Well test analysis serves as a logical basis for well stimulation and completion analysis, and for long-term reservoir engineering. Since the early 19501s, much effort has been placed on the development of well-test analytical methods. Reservoir and well conditions of increasing complexity have been considered systematically to provide the analyst with a catalog of causes and effects. Matthews and Russella state that some 200 papers dealing with this subject have been published in the last 35 years. Developments in well test analysis appear to have originated in one of two ways. Either a physically realistic field condition was anticipated and analytical solutions for the condition achieved, or anomalous field test behavior was recognized and interpretative methods sought for the anomaly. In recent years, it has appeared that the latter has inspired an increasing number of studies. The analyst today finds an increasing number of known cause and effect studies available for well test analysis, the classic of which is that of finding the specific flow problem that generated the answer — the well behavior. Although it may be impossible to achieve this goal uniquely, the analyst often is able to select a useful interpretation that combines all known performance and geologic data — or to show that various logical alternatives would not significantly affect the interpretation. During a recent reservoir study, we observed gas well test behavior that did not appear to fit behavior described previously. Although it cannot be said that we have found a unique interpretation, we shall present in this paper the peculiar behavior observed, and describe the reservoir and interpretative methods developed. Reservoir Description The subject gas reservoir is a 9-mile-long, narrow dolomite reservoir lying within a limestone of Ordovician age. (See Fig. 1.) The dolomitized rock in the field consists of dark brown to buff, dense to coarsely crystalline, vugular dolomite containing numerous hairline fractures, many of which may have been closed in the reservoir and parted when cores were brought to the surface. Larger fractures are also apparent in core, but usually are filled and sealed with euhedral dolomite crystals. Portions of the north flank of the reservoir are known to be cut by a sealing fault downthrown to the north. Gas wells located near the fault have higher open flow potentials than those more distant from the fault. This is believed to be a result of higher permeability near the fault due to more extensive and open fractures. Detailed coring and core analysis have been performed on several of the wells in this reservoir. Fig. 2 presents permeability variation&apos; plots for both horizontal and vertical

Jan 1, 1969

By R. D. Schoone, J. T. Michalak

Recovery, recrystallization, and texture development of a cold-rolled aluminum-killed steel have been studied during simulated box annealing. Two different initial conditions existed prior to cold rolling: 1) essentially all of the nitrogen in solid solution and 2) most of the nitrogen precipitated as AlN. The combined effect of nitrogen and aluminum in solid solution before annealing was to inhibit recovery and sub-grain growth at temperatures above about 1000°F and to raise the recrystallization temperature range on continuous heating at 40°F per hr from 1000"-1050°F to 1065"-1085°F. For the material with nitrogen and aluminum initially in solution there was an inhibition in the nucleation of the (001) [110] texture component and an enhancement of the (111) [110] texture component. The differences in annealing behavior mzd texture development are attributed to preprecipitation clustering of aluminum and nitrogen at subboundary sites developed by prior cold working. THE annealing of cold-worked aluminum-killed steels has been the subject of numerous investigations.&apos;-&apos;2 These studies have been concerned with kinetics of recrystallization, with microstructure and texture development, and with the individual and combined effects of composition, thermal history prior to cold rolling, and heating rates during subsequent annealing. It has been shown that the inhibition of recrystallization, and the development of the pancake-shaped grain and recrystallization texture characteristic of aluminum-killed steels, can be associated with the precipitation of A1N particles during a recrystallization anneal involving heating rates in the range 20" to 80°F per hr. If the AIN is precipitated before cold rolling or if more rapid heating rates are employed, the cold-rolled steels recrystallize more rapidly to an equiaxed grain structure and texture comparable to that of rimmed low-carbon steel. The retardation of recrystallization, the development of the elongated grain structure, and the pronounced (111) texture have been attributed to: 1) precipitation of A1N at prior cold-worked grain boundaries to form a mechanical barrier to grain boundary migration;&apos; 2) precipitation on the boundaries of the growing recrystal-lizing grains as well as on cold-worked grain boundaries;&apos;" and 3) preprecipitation clustering or precipitation on subboundaries to retard recovery, nucleation, and growth. The present study was undertaken to study in more detail recrystallization and texture development during commercial box annealing of cold-rolled aluminum-killed steels. Comparison of the annealing be- havior after cold rolling, for two different conditions prior to cold rolling, was made in an attempt to define more clearly the role of aluminum and nitrogen in forming the recrystallization texture. A) MATERIAL AND PROCEDURE The material used in this investigation was a commercial low-carbon aluminum-killed steel which was hot-rolled with a finishing temperature of about 1565"F, then coiled at about 1020°F. The composition, in wt pct, was: 0.050 C, 0.30 Mn, 0.007 P, 0.019 Si, 0.03 Cu, 0.02 Ni, 0.02 Cr, 0.045 Al, and 0.004 N. Two 4.5 by 13 by 0.078 in. sections were cut from the center section of a hot-rolled panel and one of these was reheated to provide two different conditions prior to cold rolling: low AlN: as commercially hot-rolled, with aluminum and nitrogen in solid solution; and high AlN: as commercially hot-rolled, then reheated at 1300°F for 3.5 hr to precipitate most of the nitrogen as AlN. ~etallc&a~hic examination indicated that the reheating did not change grain size nor carbide distribution (some spheroidization of pearlite was noted). Texture analysis at half-thickness level showed that both sections had the same substantially random as-hot-rolled texture. The results of check chemical analysis of each sample are given in Table I. Both sections were cold-reduced 65 pct on a laboratory rolling mill to a final thickness of 0.027 in. Cold rolling, in one direction only, was in the direction of the prior hot rolling. Specimens 1.0 by 1.25 in. were cut from the cold-rolled sheets and given a simulated box anneal in an atmosphere of 2 pct HZ-98 pct He. Specimens were heated at a constant rate of 40°F per hr from room temperature to various temperatures in the range 750" to 1300°F and cooled immediately by withdrawal to the water-cooled end of a tube furnace. The temperature in the 6-in. uniform hot zone of the furnace was controlled within 3"F. Selection of the individual specimens was made to give a random distribution of annealing temperatures with respect to location in the cold-rolled sheet. At least two specimens of each condition were annealed to the same temperature and smaller specimens for light microscopy, transmission electron microscopy, and X-ray studies were prepared from each of these. Rolling-plane sections for each of these studies were taken at half thickness. Light microscopy and transmission electron micro-

Jan 1, 1969

By B. C. Burgess

IN the first edition of this volume,44 feldspar was introduced as "the I commonest mineral of the crystalline rocks," usually in small grains associated with other minerals and commercially produced only from pegrnatites. Now other crystalline rocks, such as alaskites and granites, have become present or potential sources of feldspar. In addition, feldspar has encountered very vigorous competition from such substitutes as nepheline syenite and aplite. COMPOSITION AND PROPERTIES The feldspars form a group of which the principal species are orthoclase, microcline, albite, and anorthite. These are aluminum silicates of potassium, sodium and calcium. There are also a barium feldspar, celsian, and barium orthoclase feldspar, hyalophane, rarely found and of no commercial importance. None of the minerals in the feldspar group are found pure or nearly pure. The potash feldspars, orthoclase and microcline, nearly always contain some albite (soda microcline, an- orthoclase); the soda feldspars usually contain some anorthite (lime feldspar). There is a series of soda-lime feldspars known as plagioclase in which the albite and anorthite molecules replace each other in varying proportions from albite through oligoclase, andesine, labradorite, and bytownite to anorthite. Theoretical chemical composition of the principal feldspars is given in Table 1. The Whiteware Division of the American Ceramic Society sub- mitted a list of definitions of ceramic terms, in April 1947, for use in technical literature. For feldspar it gives: "A group of igneous minerals consisting chiefly of the aluminum silicates of potash, soda and lime, in which one base generally predominates." Commercial feldspars are intergrowths of at least two species of feldspar, which occur associated with one or more accessory minerals such as quartz, muscovite, biotite, garnet and tourmaline as well as with small but varying proportions of the decomposition product, kaolinite. An intergrowth of quartz and feldspar frequently contains

Jan 1, 1949

By R. Silverman, H. Blumenthal

It was found that despite the similarity of chemical analyses of different titanium carbides used as base materials for cermets, the physical properties, especially transverse-rupture strengths, of test bars were different. Hence this metallographic study attempts to link physical properties to micro-structures. It is shown that microstructure, grain shape, and grain growth are functions of three interrelated factors: 1—powder production procedure, 2—surface conditioning of the particles, and 3—impurities either contained in the original powder or acquired during ball milling. An explanation is offered for the "coring effect," long observed, but heretofore of unknown origin. The explanation is based on assumption of an oxide film and on chemical analyses which substantiate these findings. TITANIUM carbide has become in recent years a material of great interest in the high temperature field. Consequently, many manufacturers in the United States and Europe are producing titanium carbide for cermet applications as well as for additions to the well known tungsten carbide tools. All present commercial processes of titanium carbide production utilize the chemical reaction of titanium dioxide and carbon to form as nearly as possible stoichiometric Tic. This reaction is carried out in three ways: 1—in a menstruum of molten metal,&apos; 2—in the solid state, either in a protective atmosphere2 or in vacuum;" or 3—in an are-melting operation. In spite of the fact that the pure carbides obtained in these operations are almost identical chemically, the physical properties vary considerably when they are combined with a binder (Ni, Co) to form cermets. This fact led the authors to examine metal-lographically nickel-bonded titanium carbide in order to find the possible reasons for this behavior. Materials and Methods Five different titanium carbides were used in this investigation. They are identified in Table I. The first four materials were used in the as-received condition. Material E, received in lumps, was crushed to —100 mesh and carried through a flotation process in order to bring its graphite content in line with the other products. A Galagher flotation cell was used with pine oil as frothing agent. The chemical analyses of the investigated materials are given in Table 11. The binder used was carbonyl nickel of 9 to 14 microns particle size, supplied by A. D. Mackay. The materials were ball milled at a ball to charge ratio of 6:1 using procedures described under "Experiments and Results." All particle sizes mentioned are averages determined with a Fisher Sub-sieve Sizer. Test bars (lx0.40x0.16 in.) were prepared by 1—hot pressing to 85 to 95 pct of theoretical density at pressures between 1 and 1½ tsi and temperatures from 1600" to 1800°C, 2-—-cold presssing after 3 pct camphor had been added, or 3—wet pressing, both 2 and 3 at pressures between 5 and 10 tsi. All pressed bars were sintered in a vacuum of 105 to 10-6 mm Hg for 2 hr at 1350 °C. Transverse-rupture strengths were determined by breaking on a Baldwin Universal Testing Machine over a 9/16 in. span. Densities were measured by water displacement. The preparation of the specimens for micrographs was done according to Silverman and Doshna Luscz." All magnifications are at X1000. A sodium picrate electrolytic etch was used. Experiments and Results The influence of ball-milling procedure, ball-milling medium, pressing procedure, and sintering procedure on the microstructure of 80/20 — TiC/Ni were investigated. Ball Milling of Materials A, B, and C in a Steel Mill: Figs. 1 and 2 show microstructures of hot-pressed and vacuum-sintered test bars of materials A and B after the respective materials had been ball milled to 2.1 microns particle size in a steel mill and mixed with 20 pct Ni binder. Material A (Fig. 1) shows considerable grain growth. Also evident is a tendency of the carbide grains to coalesce. The density is 98 pct and the low transverse-rupture strength of 111,000 psi is probably caused by many large grains and an unfavorable packing factor. Almost all grains show a slight indication of "coring." Material B (Fig. 2), although showing grain growth, still has many small particles and a better distribution of binder and carbide due to the relative absence of the coalescing tendency. "Coring" can be observed in almost all grains. The high transverse-rupture strength of 179,000 psi and the density of 100 pct are believed to be due to the many small grains completely surrounded by the binder phase. There is also a preference to form spherical grains with material A, while most grains of material B preserve their angular shapes. Material C, of which no picture is given, stays between A and B in every respect. Rounding of some grains can be observed as well as coring, but the latter to a lesser degree than with material B. Its densification is good and the transverse-rupture strength obtained is 142,000 psi. Ball Milling of Materials A, B, C, and E in a WC Mill: When the Tic powders were ball milled to 2 microns particle size in a we mill, then ball-mill mixed with 20 pct Ni binder, hot pressed, and vacuum

Jan 1, 1956

By H. G. Doll

A new electrical logging method. called MicroLaterology is described. whereby the resistivity R of the invaded zone close to the wall of the bore hole is measured. This method essentially utilizes a system of concentric circular electrodes iml,edded in an insulating support which is applied to the wall of the hole. A beam of current of very small diameter is focused horizontally into the formations by means of an automatic control device. and then opens widely at short distance from the wall. with this method, R most often can be recorded directly. except when the mud cake is very thick. in which case a correction is easily provided. The basic role of factor R in the quantitative analysis of electrical logs in terms of fluid saturation and of porosity is explained. The paper is illustrated with field examples. INTRODUCTION In electrical logging. the resistivity of that part of the penneable and porous formations which is invaded by mud filtrate is an important factor in the interpretation. Measurements made with the conventional devices — normal. lateral — and also with improved systems as the Laterolog and induction logging&apos; — are very often more or less affected by the presence of the invaded zone. and the knowledge of the resistivity of this zone is useful in the evaluation of the true resistivity of the beds. which itself is a basic element for the determination of fluid saturation. Moreover. the comparison of the resistivity of the invaded zone with the resistivity of the mud filtrate gives valuable indications on the magnitude of the formation resistivity factor — which in turn is necessary for the quantitative interpretation of the logs. both in terms of fluid saturation and of porosity. On the other hand. it is generally admitted that the invaded zone is not a homogeneous medium separated from the uncon-tamirlated part of the bed hy a well defined cylindrical boundary. but that the fluid distribution—filtrate. connate water. hydrocarbon — and hence. the resistivity. in the invaded zone varies progressively with the distance from the wall of the hole. The term "resistivity of the invaded zone" therefore corre-sponds to an average value which is a function of the distribution of the fluids Inasmuch as the law of this distribution is not exactly known, the resistivity of the invaded zone is not a well defined factor. A much better definition is obtained if the medium under consideration is limited to that part of the formation which is within a short distance from the wall of the hole. It seems likely a within a distance of at least two or three in., most of the fluids in in the pores of tile formation have been displaced by the mud filtrate. The connate water has almost certainly been flushed out. and the oil. if any has generally been reduced to a comparatively small amount. The resistivity witliir~ the radial limit of two to three in. is. therefore. prac.tically constant at an). given level: its value. at least when the proportion of conductive solids in the formation is negligible. is chiefly dependent on the resistivity of the filtrate and on the porosity of the formation, and is affected only to a relatively small degree by the presence of the small amount of residual oil. This part of the formation close to the wall of the hole will he designated in the following as the "flushed zone." a-distinguished from the more general term of "invaded zone&apos;. which relates to the part of the formation extending from the wall out to the distance where the formation is completely uncontaminated. The symbol R,, will he used for the resistivity of the flushed zone. (The notation R is related to the radial distance from the hole. If x designates this distance. xo is the initial value of x, i.e., the value corresponding to the region very close to the wall.) The determination of R is difficult, if not impossible. from logs made with the conventional devices. The long normal and the long lateral are. of course. not suited for this purpose because their radii of investigation are by far too large. The short normal. and the limestone sonde—-after correction for the effect of the hole hole — give resistivity values which corre. spond to materials situated within a comparatively short distance from the hole, but this distance is still several time. as great as the thickness of tire flushed zone. The only value which can be obtained with these devices corresponds to an average resistivity of the invaded zone- — and this only provided the invasion is deep enough, since otherwise the meas "red values would also be affected by the uncontaminated region beyond the invaded zone. It should nevertheless be recalled that despite these limitations. the measurements given by the short normal and or the limestone sonde are always very useful for qualitative interpretation. and also in favorable cases for the qantitative analysis of the logs in terms of saturation and porosity. The MicroLog. which was primarily developed for the detection of permeable beds and for an accurate determination of their boundaries. provides a good approach towards the evaluation of R. In the case of hard formation.. however. The

Jan 1, 1953

By E. E. Underwood, L. L. Marsh

Aluminum single crystals, alloyed with 0.042 atomic pet Cu and 0.11 and 1.1 atomic pct Mg, were subjected to constant stress creep tests, tensile tests, and hot hardness measurements within a temperature range of 300° to 866OK. Calculations based on Dorn&apos;s temperature-compensated time parameter, 6, gave a value of DH, = 27,000 cal per mol for the activation energy of early creep in aluminum single crystals. Correlations have been obtained for aluminum alloy single crystals with the parameter E for solid solution strengthening, as well as with the parameter F for solid solution hardening, by using a valence of three for aluminum. Limited measurements on tensile specimens show that the slip band density tends to decrease with increasing temperature and with decreasing solute concentration. INCREASING interest is being shown in the mechanisms of plastic deformation in single crystals during tensile and creep testing. The complexity of deformational processes in polycrystalline materials has led to a search for simpler experimental conditions. Numerous creep and tensile investigations have been conducted with pure, metallic single crystals. To a lesser degree, the effects of alloying elements on the tensile properties of single crystals have been determined. However: the literature dealing with the effects of alloying additions in single crystals under creep conditions is vanishingly small. This paper represents an attempt to narrow this gap in the knowledge of the subject. Previous investigations of creep behavior at the Battelle Memorial Institute1-1 have been of great value in the analysis of the present single crystal data. It is equally desirable, however, to ascertain the extent of correspondence between the behavior of single crystal and polycrystalline materials. For this purpose, correlations, similar to those developed for polycrystalline aluminum alloys by Dorn and co-workers, have been made with the single crystal data. The results from this study have tended to confirm and extend those correlations to the case of alloyed single crystals. Materials and Procedures Three dilute binary aluminum alloys were prepared for this investigation from 99.99 + wt pct Al, 99.8 wt pct Mg, and 99.92 wt pct (electrolytic) Cu. The nominal compositions of the alloys were 0.042 atomic pct Cu, and 0.11 and 1.1 atomic pet Mg. Precautions were taken to avoid contamination of the stock during melting and casting of the alloys. After a heat treatment of 8 hr at 925°F the alloys were extruded, then machined into) threaded tensile specimens with a 3 in. reduced section and a 0.505 in. diam. Spectrographic examination showed less than 47 ppm metallic impurities in each alloy. The single crystals were grown by the strain-anneal method, with a critical strain of about 11/4 pet giving the optimum results. In general, 3 in. crystals were obtained with the Al-Cu alloy, but smaller crystals in the magnesium alloys necessitated the use of 2 in. and 1 in. gage lengths with the low and high magnesium alloy specimens, respectively. After an electrolytic polish, the orientation of that portion of the specimen containing the largest single crystal was determined from Laue back-reflection photographs. Tensile tests were conducted at a constant load rate of about 2 lb per min. Creep runs were made in a constant temperature room, under constant stress at the higher creep temperatures, and constant load at the lower temperatures. The eloneation was measured to within ±5 microin. by a specially designed capacitance extensometer. The ex-tensometer arms were attached to the 3 in. specimens at the shoulders of the test piece or, where the crystals were smaller than 3 in., by knife-edge grips.

Jan 1, 1957

By H. Groeneveld, C. A. Connally, P. J. Hoenmans, J. J. Justen, W. L. Mason

A miscible displacement pilot using a slug of LPG driven by separator gas was conducted in the Cardiurn reservoir of the Pembina field. The injection pattern was a 10-acre, inverted, isolated five-spot. Upon completion of the LPG-gar phase, an experiment was conducted using a slug of water followed by gas. Calculated performance of the pilot is compared with actual performance. Equations are developed to calculate the distribution of LPG into zones of varying permeability, to estimate the progress of the flood at different times in the various zones and to estimate gas rates after breakthrough. The analysis indicates that permeability stratification was a dominant factor in controlling oil recovery and that oil was completely displaced from the swept pore volume. The results of the pilot indicated that miscible flooding is a practical means of pressure maintenance in this reservoir. The total recovery from the pilot area was good in spite of the early breakthrough of LPG. The effects of stratification were reduced by injecting a slug of water into the partially swept reservoir. INTRODUCTION The Pembina field,&apos; located in Alberta, is the largest oil field in Canada and one of the largest in the North American continent. The reservoir is a stratigraphic trap producing from the Cardium sand. Neither bottom water nor free gas has been found. The recovery of oil by the natural depletion mechanism has been estimated at 12.5 per cent. Pressure maintenance studies of various areas have indicated that the recovery can be increased 21/2 times by water flooding, and a large area of the field is presently under water flood. However, reservoir studies of the North Pembina area indicated that miscible flooding might be competitive with water flooding. A pilot test was conducted to evaluate the performance of a miscible flood. A 10-acre, inverted, isolated, five-spot pattern was selected for the pilot. The pattern area was large enough to minimize wellbore fracturing effects and contained sufficient oil to provide significant working numbers. The performance of each of the four producers could be evaluated individually and compared. In the event of breakthrough in one direction, the effect would be isolated from the other producers. The use of a single injector minimized the volume of LPG required, and, because of the high mobility of gas, one well was sufficient to inject the necessary daily volume to replace the high rate of production. With four producers, the test could be completed in time for results to be evaluated, additional engineering studies to be made and a unit to be formed before the reservoir pressure in the North Pembina area declined below the bubble point. The pilot was located in an area developed on staggered, 80-acre spacing. The injection well was drilled at a regular location, while the four producers were drilled 467-ft north, east, south and west of the injector. Each quadrant and its associated producer were identified according to their direction from the injector— that is, north, east, south or west. The eight surrounding producers on 80-acre spacing were shut in to isolate the pilot area and provide for reservoir pressure observation. The pilot wells were completed using permanent-type completion techniques. After coring, casing was run through the pay section and cemented. Inside 51/2-in. casing, 2 1/2-in. tubing was hung. The wells were perforated opposite the Upper Cardium sand and lightly fractured. Fracturing volumes, rates and pressures were low to minimize the extent of the fractures. The fracturing treatments average 1,000 lb of 20-40 mesh sand in 700 gal of a low fluid-loss sand-carrying agent. Feed rates and wellhead fracturing pressures averaged 5.5 bbl/min at 2,535 psig, respectively. After fracturing, the productivity index was measured in each of the five pilot wells. The average PI of the four producers was 0.41 BOPD/psig drawdown. The measured PI&apos;S were approximately the same as PI&apos;S calculated from core analysis data, indicating that the fracturing treatments were just sufficient to overcome

By J. F. Abel

It can be concluded that rock mechanics instrumentation, geologic mapping, and operations research in combination will produce an accurate estimate of tunnel support requirements for establishing a steel-set load prediction model. This estimate can be used to increase safety and to reduce tunneling costs. Unnecessary supports can be eliminated; overloaded or insufficient supports can be replaced on a more scientific basis than previously possible. Only a limited number of measurements are required to develop a steel set load prediction model. The results of this study can be applied generally; but, every tunnel must be considered as a separate problem. The construction and geologic variables which were found to be significant in the prediction of rock loads in this tunnel were: steel section modulus, set blocking points, percentage of alteration, relative degree of faulting, relative water condition, distance to the nearest fault, and average joint spacing. INTRODUCTION A combined engineering geology and rock mechanics program was performed throughout the Straight Creek tunnel pilot bore in Colorado in order to develop a technique for estimation of steel tunnel support loads. The technique involves the construction of a statistical model from measured steel set loads, geologic and construction factors. The aim of the investigation was to produce a set of charts, based on these factors, which could be used by a trained man equipped with a hand lens and measuring tape, to specify a safe and economical steel size and set spacing. In order to be of practical value the measured parameters had to be rapidly measurable and capable of quantification. It was apparent from the beginning that quantitative values for many of the geologic factors would have to be arbitrary. It was impossible to ascertain in advance which of the readily determi-nable geologic and construction factors significantly affect steel set loading. As the investigation progressed the number of observations was systematically reduced in order to determine the minimum amount of data which would be necessary for a significant mathematical model. This paper presents an analysis of all the variables measured at each instrumented steel set. The statistical significance of the measured variables was determined. On the basis of this determination, a mathematical model was constructed and charts were prepared to select and space the steel tunnel supports at any given point in the tunnel. Once the effect of geologic and construction factors on set loading is sufficiently established, it is possible to exert close control over the selection of steel tunnel support size and spacing. The magnitude of this rock mechanics program can be appreciated when it is known that there were 44 instrumentation stations for which steel set loads were measured. For each of these sets there were three construction variables recorded, and nine geologic parameters determined (Table I). A rough approximation of the cost for both the collection and reduction of the data would be $50,000. This is in addition to the cost of geologic mapping.

Jan 1, 1967

By J. S. Kirkaldy, D. H. Weichert, G. R. Purdy

Two-phase diffusion couples have been used to simulate the growth of proeutectoid ferrite in ternary Fe-C-Mn austenites. It has been shown, theoretically and expermentally, that the results fall into two classes: a high-super saturation class in which the major role of manganese additions is to influence the boundary conditions for carbon diffusion; and a low-supersaturation class in which the partition of manganese is required. In the latter case, a drastic inhibition of the reaction rate is to be expected. As an aid to the kinetic analysis, a portion of the iron-rich comer of the Fe-C-Mn constitution diagvam has been determined. The conclusions drawn from this work have a direct bearing on the kinetics of the grain boundary ferrite precipitation reaction and thus yield insight into the manner in which alloying elements can influence the rate of austenite-decomposition reactions. THE role of alloying elements in the austenite-decomposition reactions has provoked considerable interest, since it is apparent that an understanding of this phenomenon will yield insight into the harden-ability problem. In the present investigation, attention is focused upon the proeutectoid-ferrite transformation in the system Fe-C-Mn, and upon the manner in which manganese additions affect the growth rate of ferrite. When hypoeutectoid austenite is supersaturated, the ferrite first formed usually exhibits two distinct types of morphology. At low super saturations, grain boundary layers grow into the austenite grains with an approximately planar interface, and usually possess at least one incoherent phase boundary. At high supersaturations, Widmanstiitten plates appear, which bear an orientation relationship&apos; to the parent austenite. In this case, there is a chance of partial lattice matching along the sides of the plates and an attendant semicoherent interface structure. Purdy and Kirkaldy2 have used a two-phase binary Fe-C diffusion couple to demonstrate that carbon volume diffusion controls the incoherent reaction, while Rouze and rube,&apos; using thermionic-emission microscopy, have shown that the thickening of Widmanstatten ferrite plates is appreciably slower than expected for carbon-diffusion control. This suggests that the plates are bounded by partially coherent, low-mobility interfaces. The redistribution of alloying elements during transformation has been the object of studies by Aaronson4 and owmman,5 who have shown that no alloy partition occurs during ferrite precipitation in the systems Fe-C-Cr and Fe-C-Mo, respectively. More recently, Aaronson et al.6 have shown that some manganese partition occurs at low super-saturations in the system Fe-C-Mn, but that no partition occurs at higher super saturations. Pickle-simer et al.7 observed that no manganese partition occurred during the early stages of the pearlite transformation in a manganese steel, and concluded that volume diffusion of the alloying element is not the rate-deter mining factor. The diffusion coefficients pertinent to this investigation have been measured by Wells, Batz, and Mehl8 (carbon in austenite), R. P. smith9 (carbon in ferrite), Wells and Mehl 10 (manganese in austenite), and Kirkaldy and Purdy11 (diffusion of carbon on a manganese gradient in austenite). Kurdjumov 12 has shown that the diffusivity of substitutional elements in ternary austenites up-quenched from martensite may be greatly enhanced, due, apparently, to the presence of a persistent defect structure. The recent work of Krauss 19 showing high densities of tangled dislocations in reversed Fe-Ni martensite is in agreement with this conception. THEORETICAL Diffusion in ternary or higher-order systems may be described with the aid of Onsager&apos;s extenbion of Fick&apos;s first law,14 in which the flux of each of the n components is assumed to be a linear function of all concentration gradients:

Jan 1, 1964