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By R. F. Krueger, L. C. Vogel, P. W. Fischer

Previous studies have shown that the permeabilities of sandstone cores are markedly reduced following exposure to drilling fluid and subsequent clean-up with oil at high-pressure gradients. Laboratory experiments reported in this paper indicate that permeability damage from drilling mud or water can be substantially avoided through use of an initial low-pressure gradient followed by gradually increasing gradients during clean-up by reverse oil flow. On the other hand, attempts to improve the permeability of damaged Berea and oil formation cores with high-rate oil backflush (simulated well stimulation) and low-rate clean-up gave erratic results. Essentfully complete permeability repair was achieved in most of the fresh water-damaged cores from Miocene and Pliocene oil-producing formations; only minor improvement was noted generally in tests with both water-and mud-damaged Berea sandstone. Field well stimulation treatments using high-rate back-flush resulted in long-term productivity improvement when production was brought in at gradually increasing production rates and then restricted to a steady value less than the maximum possible rate. Wellbore plugging at high production rates correlated with increasing solids content in the produced oil. Observations and results from these tests agree with current concepts that formation damage in water-sensitive rocks results from movement and bridging of formation fines, rather than from clay swelling alone. INTRODUCTION Many laboratory studies1-g have shown that the permeabilities of sandstone cores are often markedly reduced following exposure to fresh water or water-base drilling mud filtrate. However, work with cores in the restored state has demonstrated that, although permeabilities to water may be very low for sandstones containing hy-dratable clays, flow of oil can often restore a substantial portion of the effective permeabilities to oi1.Neverthe- less, water invasion into water-sensitive sandstone cores results in varying degrees of permanent reduction in permeability to oil.24' Based on field data, Wade's statistical study" of well completion effectiveness also indicated a correlation between productivity damage and water invasion during completion. Similar damage can result from fluid invasion during workover. Nowak and Krueger' and Bertness4 observed in their early work (1951-53) that formation damage in water-sensitive sandstones was associated not only with swelling of expandable clays but also with movement of dispersed particles. Subsequent work by Monaghan et al." (1959), Atwood'' (19641, Mungan" (1965) and Gray and Rex'" (1965) has led to general acceptance of the hypothesis that permeability damage in water-sensitive formations is caused by migration of finely dispersed minerals and bridging in "brush heap" arrangements at pore constructions. In laboratory studies, Monaghan et al.' found the use of chemicals to be of only minor value for repairing formation damage. Atwood? however, was successful in substantially repairing damage in a number of low-permeability cores using an n-hexanol flush. In the field, except for treatments with acids, the use of chemical washes to reduce wellbore damage has had limited and sporadic success and generally is unpredictable. A statistical analysis of stimulation treatments in silt-blocked wells has shown that physical manipulation of wash materials is more important than chemical composition." The recent work reported on formation damage in water-sensitive sands brings to mind the results of some unpublished exploratory work done in 1954 in connection with drilling fluid studies.' This laboratory work and subsequent field stimulation treatments indicated a beneficial effect of controlled pressure drawdown and the associated production rate on formation clean-up. This paper reports the results of this work and more recent supplemental experiments on the clean-up of water-sensitive sandstones damaged by water or filtrate invasion. PERMEABILITY RECOVERY AFTER DAMAGE BY DRILLING MUD APPARATUS AND TEST SAMPLES A drilling mud circulating system was used to expose cores to simulated wellbore conditions. The mud flow system is the same as that described by Krueger and Voge17 except that no provision was made for scraping

By Pol Duwez

The effect of the rate of cooling on titanium, zirconium, and thallium has been measured. For titanium-molybdenum alloys, it has been shown that for molybdenum concentration up to 8 pct the rate of cooling has no effect on the transformation temperature, but this temperature decreases progressively with increasing molybdenum content. HIGH strength to weight ratio and remarkable corrosion resistance have often been advanced as the main reasons for the present widespread interest in titanium. For the physical metallurgist, the existence of an allotropic transformation in titanium is another important factor. As in the case of iron, an allotropic transformation may be the fundamental property upon which the response of Ti-base alloys to heat treatment will depend. It is therefore important to study the mechanism of the allotropic transformation in pure titanium and the effect of alloying elements on this transformation. The existence of an allotropic transformation in titanium was reported in 1931 by Schulze.' Later, De Boer et al.' determined the transformation temperature from a discontinuity in the electrical resistivity at 882"42O°C. According to recent work," the transformation temperature is 882.5"&1°C. The crystal structure of the room temperature a phase is hexagonal close-packed and the high temperature fi phase is body-centered cubic.' It is well known that the high temperature /3 phase of pure titanium cannot be retained by quenching to room temperature. Several investigators'-' have shown that in alloys of titanium with metals which are soluble in the @ phase (for example, nickel, molybdenum, chromium, or manganese), the /3 structure can be retained, providing the concentration of the alloying element is greater than a certain critical value. Below this critical value, the alloys transform during quenching, at least partially, into a supersaturated solid solution having the a. structure. This behavior is very similar to that found in some iron binary alloys (Fe-Ni and Fe-Mh, for example) and is an indication that the transformation might occur by means of a shear mechanism analogous to that observed in the austenite-martensite reaction. The present investigation is mostly concerned with the effect of the rate of cooling on the /3 to a transformation. In the first portion of this paper, the results obtained on pure titanium are described. Two other pure metals, zirconium and thallium, were also investigated, because they both have an allotropic transformation like titanium, from an hexagonal close-packed to a body-centered cubic structure. For purposes of comparison, the effect of rate of cooling of the y to a transformation of iron was included in the experimental program. The second part of this paper deals with Ti-Mo alloys. The equilibrium phase boundaries involving the solid state reactions on the Ti-rich side of the system were determined and a study was made of the effect of the rate of cooling on the transformation of the high temperature /3 solid solution. Experimental Procedure Since the main object of the present investigation was the determination of the effect of the rate of cooling on a transformation temperature, the best technique available was that used by Greninger" in his study of the martensite arrest in carbon steels. This method consists of heating a very small sample of metal to which fine thermocouple wires are .attached, cooling the sample rapidly by means of a blast of helium, and recording the temperature vs. time curve on an oscillograph. The apparatus used in the present experiments was very similar to that described by Greninger, except that the heating coil was made of molybdenum wire (0.040 in. in diam) and the assembly was placed in a bell jar under vacuum of 10" mm Hg or less. The specimen con-

Jan 1, 1952

By V. J. Berry, J. D. Pendergrass

Well pressure transient tests provide a means for directly obtaining information about formation pressure and reservoir flow capacity. Such tests have also been proposed for determining presence and location of faults or other reservoir closures and for measuring oil in place. For mathematical convenience, most theoretical studies have considered the reservoirs to be homogeneous. Definitive information is not yet available to show whether the actual presence of nonuniformities will make pressure transient behavior different from that of a uniform reservoir. The conclusions reached from actual transient tests are questionable, therefore, insofar as they rely on the original assumption of homogeneity. One type of nonuniformity commonly assumed to exist is that of stratification. In most reservoirs the strata are thought to be in vertical communication. Equations for the transient flow of a single-phase, compressible fluid in a one-well, bounded, circular reservoir have been solved for several situations involving crossflow between multiple strata of various thicknesses and permeabilities. The results show that except for the very early flow period, which usually is too short to be analyzed, the transient performance observed at the well is substantially identical with that of a homogeneous reservoir having the same dimensions and having the same steady-state flow capacity. Thus, stratification does not adversely affect interpretation of well transient tests. This conclusion holds for all commonly encountered combinations of reservoir thickness and external radius. Deviations are observed for unusually thick reservoirs whose outer radii are relatively small. The results of these studies also show that the presence and the amount of stratification cannot be simply diagnosed from reservoir pressure transient data when there is crossflow between strata. INTRODUCTION The last decade has brought wide acceptance of the transient well pressure test for determining reservoir parameters. Following the original work of Hurst and van Everdingen,1 the mathematical theory was thoroughly explored. Numerous authors have suggested how to determine static reservoir pressure, permeability-thickness product, original oil in place and reservoir limits for different reservoir geometry. The same mathematical techniques have been used to predict the transient performance of a reservoir over a long period of time. Most of the theoretical work has been for homogeneous, isotropic systems. Some results have also been presented for a homogeneous, anisotropic reservoir.2 Petroleum reservoirs are not homogeneous. The deposition process seems to favor creation of a stratified formation. This concept is sufficiently well accepted so that the most natural extension of the transient flow theory beyond the homogeneous case is to a stratified formation. Results for a stratified reservoir with no vertical communication between layers can be obtained from the results for a homogeneous reservoir. Lefkovitz, et a1,3 have given a thorough treatment of the two-layer case. Two recent papers4,5 have treated the case of a two-layered reservoir with vertical communication or crossflow, between layers. Russell and Prats4 find that, after a relatively short time, the two-layered reservoir with crossflow exhibits a simple exponential pressure decline. From this time forward, the behavior is not distinguishable from the behavior of a homogeneous reservoir having the same steady-state flow capacity. The results of Katz and Tek 5 are equivalent. Russell and Prats4 also speculate that a multi-layered reservoir with crossflow will behave as a homogeneous system after long enough production time "... providing the contrast in kh between layers is not too great". They also suggest that, at intermediate times, "... the relative positions of the layers with respect to each other will have a great influence on the production behavior and on the time at which the previously mentioned large-time approximation might be valid". Katz and Tek5 remark upon the mathematical difficulty of treating a reservoir having many layers or strata. If relative position of the layers is also

By J. Washburn

Two simple types of dislocation distribution were introduced into zinc crystal specimens and the effect of each on the stress-strain curve was investigated. Quantitative results were obtained for simple edge dislocation arrays and for an array of screw dislocations lying in the slip plane. A CCORDING to present knowledge, the disloca-tions present in large annealed metal crystals can be divided into two somewhat arbitrary groups: 1—single dislocation lines distributed more or less at random or forming elements of a three-dimensional network in which the distance between adjacent dislocations is of the order of 10 2 to lo-' cm and 2— widely separated planar arrays of edge dislocations forming dislocation walls or small angle boundaries within which adjacent dislocation lines are spaced at much smaller distances (lo-' to 10- hm). The former can be considered as a dislocation interpretation of the mosaic crystal proposed by Darwin and Ewaldl, ' 40 years ago to account for anomalously high integrated intensities of X-ray diffraction maxima. Small angle boundaries, although now known to be present in most single crystals used for mechanical testing, were not generally recognized by the early workers. This was partly due to the fact that only recently have improved X-ray and metal-lographic techniques been available for checking the macroscopic perfection of crystals."" It has long been known that changes in growth conditions and in annealing procedure, which might logically be expected to cause variations in the structural details of both the dislocation network and of dislocation boundaries, produce marked variations in some mechanical properties such as yield strength." However, no quantitative experimental correlations between changes in dislocation distribution and changes in mechanical properties have yet been made. Such a correlation has been difficult to obtain because, even when great care is exercised to keep the histories of a number of single crystal specimens identical, it usually has not been possible to avoid considerable variation in macroscopic per- fection.' The number and orientation of dislocation boundaries vary from specimen to specimen. This has probably been an important contributing factor to the large scatter in the results of most mechanical measurements on pure single crystals. Some recent experiments"% ith single crystals of zinc have shown that the presence of dislocation boundaries in a specimen can increase its resistance to deformation by slip. With polycrystalline aluminum and nickel, there is also evidence that dislocation boundaries within the individual grains of the aggregate can increase the resistance of the material to plastic deformation, either as measured by tension tests at room temperature or by creep tests at higher temperatures.'" " Although the foregoing observations seem to have established the fact that substructure can have a strengthening effect, the test conditions were too complex to give much information concerning the mechanism. In the foregoing cases, a network of intersecting boundaries having various orientations and boundary angles were present. Before their apparent strengthening effect can be understood, it will be necessary to isolate and study separately the effect of a number of variables: 1—boundary angle, 2—boundary orientation with respect to the active slip direction, 3—number of boundaries, 4—intersections of boundaries, 5—detailed structure of the boundaries, and 6—interaction of impurity atoms with dislocations in boundaries. The object of the present work was to study the effect of dislocation boundaries on flow stress under the following simple experimental conditions: 1— substantially pure shear deformation and 2—boundaries of controlled angle, orientation, and number. In this way, it might be possible to distinguish the important variables from the relatively unimportant ones. Experimental Procedure Stress-strain curves of hexagonal metals are generally nearly linear even out to very large strains."

Jan 1, 1956

By A. Schild

The effect of heating a producing well on the rate of oil recovery has been analyzed in the simple case of a well producing oil by a radial drive and in the steady state. Differences of production rates with and without borehole heating have been calculated and plotted; these measure some of the benefits of the thermal recovery process. A striking feature is that the production increase tends rapidly to a constant value for large production rates. Some concrete examples, including a rough comparison with field data. are discussed. Heating requirements have been calculated and plotted on the assumption that the heaters used are 100 per cent efficient. Heating has been thought of as applying only to low volume wells producing heavy oils. However, the calculations suggest that the thermal process considered might be profitable even for some wells producing large quantities of light oil, especially in unconsolidated formations where fracturing is not possible. In the case of wells producing other fluids with the oil or of wells producing partly or wholly by gravity drainage, the theory developed does not apply in detail. It can be expected, however, that any general qualitative be-havior will remain valid. Under normal temperature conditions, high viscosity emulsions sometimes form around the wellbore, lowering the permeability in the vicinity of the well and impeding the production of oil. Borehole heating often prevents such emulsification. This important effect is not easily amenable to mathematical analysis and has not been included in the theory presented here. It should therefore be kept in mind that the benefits due to borehole heating may in fact exceed the values given by the following calculations. INTRODUCTION The recovery of viscous, low gravity oils can often be stimulated by applying heat to the production zone. The higher temperature lowers the viscosity of the oil, increasing its mobility, and therefore its rate of production. One thermal method of recovery 1,2,3,4. consists in operating a heater inside a producing well and, at the same time, producing oil from the well. In this paper a simple theoretical model is analyzed to study the effect of such heating on the recovery of oil. The reservoir mechanics of the process is the only aspect of the problem which is considered here. The details of the heating system are ignored, and it is simply assumed that the heater raises the temperature in the immediate vicinity of the producing well to a pre-assigned temperature T w. Although heating requirements are calculated, these refer only to the heat supplied to the formation and to the oil being produced; they do not include heat losses due to the inefficiency of the heater. A short outline of the theory follows: The heat supplied to the producing well flows out into the formation by means of thermal conduction. At the same time, the flow of oil carries heat by convection from the formation towards the producing well. After sufficient time has elapsed, a steady-state is reached where the temperature, the velocity of the oil, etc., no longer vary with time but are functions of position only. In the steady state the temperature decays like an inverse power from the high value Tw at the wellbore to the original reservoir temperature T. at some distance away from the well. The effect of the high temperature and low oil viscosity near the producing well is the same as if the oil were produced at reservoir temperature To but through a producing well of a larger radius. From this point of view, the energy and money being expended to provide heat

Jan 1, 1958

By J. T. McGrath, R. C. A. Thurston

Poly crystalline specimens of copper, and copper with various additions of zinc, were tested in plane-bending fatigue. In tests performed at a constant stress, the fatigue life of copper increased slightly with the addition of up to fifteen per cent zinc. There was a sharp increase in fatigue life as further additions of zinc of up to 35 pct were made. Surface observations showed that the coarse slip bands that are characteristic of fatigue became narrower as the concentration of zinc increased. The rate of crack propagation also decreased with increasing zinc content. It is suggested that the fatigue behavior is controlled by cross slip processes. CROSS slip occurs when dislocations move from one primary slip plane to another along a connecting or cross slip plane. The primary and cross slip planes have a common slip direction. Wide stacking faults, having low energy, tend to make cross slip more difficult. According to recent theories, the ability of a material to cross slip is important to the formation and propagation of fatigue cracks. McEvily and Machlin2 have examined this concept experimentally by fatiguing single crys tals of lithium fluoride, sodium chloride, silver chloride, and KRS-5.* The latter two materials ex- hibit easy cross slip, while the former two do not. Normal rapid fatigue failure was obtained in the silver chloride and KRS-5 specimens, whereas it was much more difficult to achieve in sodium chloride and lithium fluoride crystals. Furthermore, numerous slip band extrusions and intrusions were found in silver chloride and KRS-5 crystals, whereas only one isolated extrusion was found in lithium fluoride and none was found in sodium chloride. McEvily and Machlin also consider that there is no clear-cut demarcation between crack initiation and propagation. The intrusion-extrusion process, which initiates crack formation, continues ahead of the cracks to allow propagation of these cracks along slip bands. The process of cross slip is therefore important not only to crack initiation, but also to crack propagation. Holden4 postulates that fatigue crack growth is dependent upon cross slip and thus upon stacking-fault energy. Using an X-ray microbeam technique, he found a cyclic subgrain structure in fatigued aluminum and a-iron. Holden suggests that micro-cracks develop in the densely-packed sub-boundaries ahead of the main crack front, and when sufficiently numerous join up to promote crack growth. The ease with which a subgrain structure could form would depend upon the ability of the dislocations to cross slip, and thus upon the stacking-fault energy. Hence in aluminum, which has a high stack-ing-fault energy and in which cross slip is easy, Holden found that the relative rate of fatigue crack propagation was considerably greater than in stainless steel, a low stacking-fault energy material. It has been shown by a number of investigators that the probability of forming deformation stacking faults in copper increases as zinc is added.5-7 Cross slip should, therefore, become more difficult as the zinc concentration is increased. In order to check the validity of the foregoing theories, it was decided to test copper and copper with various additions of zinc in plane bending fatigue, and determine to what extent their fatigue properties are dependent upon their ability to cross slip. EXPERIMENTAL PROCEDURE Fatigue tests were carried out on polycrystalline OFHC copper and various copper-zinc alloys with 5, 15, 20, 30, and 35 wt pct Zn. The Cu-Zn alloys were obtained commercially in sheet form. Test specimens, as shown in Fig. 1, were machined from sheet that had been reduced to an approximate grain size of 0.040 mm, the heat-treatment procedure being similar to that of Feltham anc copley.8

Jan 1, 1963

By W. E. Bearce

The recent concern for the recovery of even the finest fractions of coal preparation plant feeds has created needs for new equipment. Thermal dryers currently available have difficulty reducing the filter cake moisture on down to the desired point. This difficulty involves 1) the physical problem of handling this wet, sticky material and making each particle accessible to the hot gases, and 2) removing the extremely fine dried particles from the cooled gases. The dryer described in this paper handles the first of these problems, and eliminates the second by the substitution of steel balls for air as the heat transfer medium. As a general statement, the cost of preparing coal for market is inversely proportional to the size of the lumps or particles. In the not too distant past the finer sizes were discarded as being uneconomical to treat and this practice might be still continuing if it were not for the insistence of the public that this material be kept out of our streams. This being the only cost-free outlet, the disposal of fine refuse became a significant item of expense in every preparation plant. When this happened it was only reasonable to look to the recovery of the values in this material, not only to defray this expense, but to reduce the tonnage which had to be wasted. There seemed to be no device available suited to reducing the moisture in this material to what the market requires. All of the fine coal dryers commonly employed make use of air to bring the heat of combustion into contact with the coal particles. Any device employing air as a heat transfer medium, has the following two strikes against it in attempting to handle 28 mesh by 0 filter cake: 1) It is practically impossible to bring the hot air into intimate contact with the enormous number of fine particles stuck together in the cake. 2) Even if this can be effected, it is impossible to remove the dried coal from the air. A wet scrubber must be employed, the discharge of which must go back to the filter and dryer as a circulating load of the most objectionable sort, being the extreme fines. Various compromises have been used to cope with the problem of drying this relatively small tonnage of high moisture coal. Often some of the dried coal is mixed back with the feed to the dryer in an attempt to make the mixture more handleable and more available to contact with the hot air than the filter cake alone would be. This may help to some extent with the first problem but it does nothing about the second and a dryer operated in this way has to be oversized. Sometimes the filter cake is mixed with a coarser fraction for the same reason. Here again, while this may make a mixture (the particles of which are more readily brought into contact with the hot air), the problem of getting the fine coal out of the air remains and a larger percentage of the total coal to be dried is handled by the most expensive means. Mechanical dewatering has accounted for more and more of total coal drying lately and in many cases would satisfactorily handle the whole load, down to 28 mesh, if there were a means available for doing a good job on the —28 mesh by itself. The dryer which is the subject of this paper was designed expressly for doing this job — drying fine material by itself regardless of how wet it may be to start with, how fine it may be, or how gummy and sticky these properties in combination may make it. The essential features are depicted in Fig. 1. A rotating cylinder is supported on a frame in such a way that one end may be raised or lowered by hy-

Jan 1, 1968

By G. W. White

Over the past several years, the steady progress of gas lift from a mysterious art into a developing science has been traceable through the many fine papers that have appeared in Journal of Petroleum Technology. Consequently, this magazine has rightly become a standard for the serious students of gas lift all over the world. The following discussion is offered in a sincere attempt to accurately present certain topics covered in the subject paper in the light of acknowledged state of the art procedures. INSTALLATION DESIGN The first point to be questioned is the author's installation design, beginning with Eq. 6. The use of 1,200 psi in the spacing equation instead of the 1,275 psi noted as available seems, at first glance, to be a simple arithmetic error. Upon further examination, it appears evident that both this 75 psi plus the 100-psi safety factor must be subtracted from available kickoff pressure because of conditions imposed by the characteristics of the ASC valve (see Fig. B-1). Pressure-charged valve design is incorrectly penalized by spacing the first valve using only 1,100 psi. The use of such a high back-pressure makes it appear that a typical ASC installation would require no more valves than a comparable conventional valve installation. Using a value of 100-psi tree pressure, the well could be valved to 11,000 ft very conservatively with seven pressure-operated valves, but would still require 11 ASC valves. The use of 400-B/D spacing gradient for a 140-B/D rate is not an accepted practice using precharged valves. The author would have done well to note the advantages to be gained by reducing the 500-psi tree pressure, which is clearly explained by Beadle, Harlan and Brown.' In Step 1 of Part III of the continuous flow discussion, the author incorrectly applies the Poettmann and Carpenter curves.2 Item 2 is an incorrect statement. An excellent reference on this point is the paper by Baxen-dell and Thomas.' VALVE MECHANICS The next topic relates to the mechanics of precharged valves. Eq. 2 for the ASC valve can be used to describe the condition of equilibrium, wherein the valve is closed with opening pending. When this equation is used to determine relative values of casing, dome and tubing pressure with conditions approaching the transition value, some strange results are obtained. The following uses the author's symbols and values given on page 689. Fig. B-1 shows the condition that exists at the moment an ASC valve has been uncovered during the unloading process (Condition I). The obvious result is a locked condition. The basis for the curve is shown on the figure which includes 1,000 psig casing pressure to uncover the valve. If injection gas is not bled off the casing until the pressure is decreased by an amount exceeding the stabilizer discharging valve pressure, upward adjustment of the casing pressure is mandatory for the valve to open and unloading operations to continue. In Condition I the dome pressure exceeds the casing pressure by 20 psi, and the tubing pressure required to open the valve is 1,212 psig. This tubing pressure would not exist under the assumed conditions. In Condition I1 the casing pressure is increased to the dome pressure, and the tubing pressure required to open the valve is 1,102 psig. It is apparent that the casing pressure must be increased to a value exceeding the dome pressure before unloading operations could continue. In Condition I11 a maximum casing pressure of 100 psi (stabilizer charging valve set pressure) above the dome pressure is reached, and the tubing pressure required to open the valve is 549 psig. The author's statement after Eq. 5 that "the minimum tubing pressure required to open an ASC valve is equal to the casing pressure at depth less the transition pressure of the valve" is incorrect except for Condition I11 only. Otherwise, the equation is invalid.

Jan 1, 1965

By J. Fageant, W. C. Ellis

All major regions in a progressively solidified germanium ingot were related through successive orders of octahedral twinning. The occurrence of lineage structure and the generation and survival of orientations are discussed. WHEN metals solidify in a temperature gradient a preferred orientation, or casting texture, usually develops. For example, in face-centered and body-centered cubic metals, most of the solidifying crystals have a cube axis, <loo>, aligned approximately in the freezing direction.&apos; In the solidification of diamond cubic metals this is not the case, since there is a natural tendency to form twin orientations.&apos; . In this paper, twinning relationships in cast germanium are described; some conclusions with respect to nucleation and survival of new orientations are discussed. In the first experiment, an ingot of high purity germanium, % in. in diameter and 1 % in. in length, was formed by progressive solidification4 from the bottom. The ingot was cut into 21 slices, each circular and about 0.030 in. thick. The top surface of each slice was polished and etched to reveal the regions of different orientations. Orientations were determined by the Laue X-ray back-reflection method. The uncertainty in the determined orientation relationships was l" or 2" when separate slices and films were involved. Frequently, however, advantage was taken of illuminating across a boundary when the patterns of the two orientations were recorded on the same film. The uncertainty then was less than 1". Often the twin relation was evident from common zones or individual reflections. Twin relationships were recognized through comparison of the values of the nine angles between cube poles of the two orientations with those calculated for successive orders of octahedral twinning. The birth and survival of each region can be reconstructed by visual examination of the etched slices shown in Fig. 1. In slice 21, where solidification began, many regions are present; these regions were found to be twin-related. Solidification appears to have started from one nucleus formed probably at the wall of the crucible.* Subsequent ori- entations were developed by nucleation on existing solid surfaces, and only in the twin relationship. This is an example of a general process of nucleation on a surface of existing solid and may be descriptively termed oriented nuc1eation.t In germanium, and other diamond cubic substances, the orienting habit is that of twinning on an octahedral plane.&apos; " The prevalence of straight traces in the polished surfaces of succeeding slices (Fig. 1) suggests that the twinning observed in the first slice persisted throughout solidification. This was confirmed by X-ray determinations. The schematic diagram of Fig. 2 shows the twinning relationships of the major regions throughout the ingot. Since all observed relationships are describable as twinning, it is reasonable to conclude that no random nucleation occurred in the freezing of the ingot. An alternative possibility would be that nucleation of a random nature occurred, but only those nuclei in twin orientations survived in subsequent growth. This is unlikely for there would be as good a reason for the growth of randomly oriented nuclei as for the growth of the many different orientations present after several orders of twinning. The many twin components contain a wide distribution of orientations, and did grow. In fact, they are the only ones found in the solid. The conditions of solidification of this ingot were such as to discourage nucleation of crystals wholly in the liquid. The rate of solidification was 0.125 in. per min. This slow rate of heat removal afforded but small opportunity for supercooling within the liquid —a condition needed to provide enough decrease in free energy for such nucleation. When nucleation occurs on an existing solid surface, the interfacial energy between the existing and forming regions is important in determining the new stable orientation. The new orientation is expected to be one which minimizes this energy. In the diamond cubic structure, the interface for the

Jan 1, 1955

By Strathmore R. B. Cooke, Thomas E. Ban

MUCH experimental work has been performed on the mechanism of agglomeration and pelletizing of moist ore and concentrates and on the process of firing agglomerates, but except for the work of Tigerschiöld and Ilmoni1 much of the published information is empirical, and the literature contains no information concerning the structure of fired pellets. Results of a preliminary study of the microstructures occurring in pellets produced both in the laboratory and on a pilot-plant scale are presented in this paper. Most of the results were obtained from pellets prepared from Mesabi magnetic taconite, but through the courtesy of the staffs of the Minnesota Mines Experiment Station and the Bethlehem Steel Co., fired pellets produced from limonite and hematite ores and from Lebanon magnetite have also been examined. The work has been restricted almost entirely to pellets produced without additives, the exceptions being those in which coal was. added to the filter cake before rolling. Schwartz has described the microstructures occurring in ore sinters produced under reducing conditions.2 Many of the structures and constituents he describes are common to fired pellets, but the constituents normally occur in markedly different proportions. His statement that "in all satisfactory sinter the amount of hematite is small, perhaps not over 2 or 3 per cent" is inapplicable to pellets produced by pilot plant operation or by any process in which air is not deliberately excluded. Pilot plant pellets contain over 90 pct by weight of hematite, and those produced in the smaller furnaces of the Minnesota Mines Experiment Station contain more than 80 pct of that constituent. Preparation of Specimens It is difficult to examine unfired pellets microscopically because of their insufficient coherency to withstand sectioning and polishing. Fired pellets sometimes lack coherency and frequently contain holes which are troublesome during polishing. Impregnation of both air-dried and fired pellets is readily accomplished by the use of methyl methacrylate monomer.3 The dry pellets are covered in a test tube with excess monomer, to which a small amount of accelerator has been added. When the test tube is placed in a cooling bath and evacuated with an aspirator, most of the entrapped air is removed, and disruption of weak pellets by boiling of the monomer is reduced to a minimum. Polymerization is then effected by immersion of the test tube in a water-bath at about 45°C, this temperature being held for 4 or 5 days. The test tube may then be broken away from the solidified mass and the pellets sectioned by a carborundum wheel or a diamond saw. Where time is important, impregnation is carried out at a higher temperature by Meyer&apos;s method.4 Air-dried pellets must be impregnated with especial care; otherwise swelling occurs and the solids are displaced. It is more important to be certain that the monomer forms a reasonably complete network throughout the specimen than that all entrained air is removed, and for this reason the vacuum technique may be omitted. Impregnated agglomerated products and pellets are extremely coherent, section well, and may be polished either by hand or by machine. Hand polishing is not satisfactory for the examination of conditions existing at the boundaries of grains, and for this machine polishing must be used. The Graton-Vanderwilt machine gives excellent results, provided that pressure on the specimen is considerably in excess of that recommended by the manufacturer. Mineralogy of Fired Pellets Only two opaque iron minerals, magnetite and hematite, have been recognized in pellets. The complete identity of these artificial minerals with their corresponding natural counterparts is shown by their mineralographic characteristics and their X-ray structures. Wüstite has not been found. Slag is the most common transparent constituent of fired pellets. Occasionally conditions have been appropriate for the crystallization of fayalite from the slag, and at other times another crystalline sil-

Jan 1, 1952

By Matti J. Saarivirta

The relative machinabilities of the precipitation-hardenable Cu-0.9 pct Cr, Cu-0.25 pct Zr, and Cu-0.9 pct Cr-0.25 pct Zr alloys are improved from 18 to 80 pct by 0.75 to 1.25 pct Pb. The Lead also improves the tensile strength, hardness, ad resistance to softening of the Cu-Cr and Cu-Cr-Zr alloys. When the alloy containing 0.7 to 2.2 pct Cr, 0.10 to 0.25 pct Zr, 0.75 to 1.25 pct Pb, and balance copper is solution-annealed at 1000°C (1830°F) and then aged at 525°C (Y75°F), tensile strength of 65,000 psi, 16 pct elongation, 62Rb hardness, and 84 to 87pct IACS electrical conductivity are obtained. The copper base Cu-Cr, Cu-Zr, and Cu-Cr-Zr alloys have high electrical and thermal conductivities, high strength and resistance to softening at elevated temperatures, but their machinability is poor, i.e., close to that of the pure copper. In the manufacture of various components such as welding electrodes or electrical and thermal conductors it is ofter desirable that the alloy have good machinability for high production rates and long tool life. Thus, alloys that combine these properties may be used not only for existing applications, but for new ones where good machinability is a requirement. This investigation was undertaken to improve machinability without impairing other desirable characteristics of the Cu-Cr, Cu-Zr, and Cu-Cr-Zr alloys. These commercial alloys contain about 0.4 to 1.2 pct Cr, 0.10 to 0.25 pct Zr, and balance copper. Lead was selected as an element that should improve the machinability and possibly other characteristics of the alloy. WORK PROCEDURE This investigation began with a study of the effect of lead on the hardness, tensile strength, electrical conductivity, and machinability of the binary alloy containing 0.10 to 1.30 pct Cr and balance copper. This was followed by an investigation of the effect of lead on the Cu-0.1 to 0.4 pct Zr and Cu-Cr-Zr alloys. The alloys were made from initially oxygen-free copper and for comparison some castings were made from phosphorus-deoxidized Lake Copper. Commercially pure chromium, zirconium, and lead were used for alloying. In melting the chromium was added to molten copper at 1400°C (2550°F), the heat held for 15 min at temperature, and the temperature then lowered to 1350°C (2460°F) when the other elements were added. The alloys were held for 15 min at this temperature and cast into a cast-iron mold. One-kilogram, 3-in.-diam castings were made. An argon cover was maintained during melting and casting to prevent oxidation. The chemical compositions of the alloys are shown in Table I. The micro structure and properties of the alloys were studied in the cast and wrought conditions prior to and after various solution-annealing and heat-treating cycles. The relative machinability was determined as a function of the lead content and compared with the free-machining Cu-lpct Pb alloy. To determine the machinability, 13/16-in.-diam cast specimens were cut by a machine hack saw using a constant cutting speed of 50 fpm, a fixed feed force, and a new blade for each alloy specimen. Molybdenum highspeed steel saw blades, 0.032 in. thick with 14 teeth per in., were used in all tests. No cutting fluid was used. Five tests were made on each specimen and the average elapsed time per test was taken as a measure of the relative machinability for that alloy. The variation of cutting time for each alloy was less than 110 pct.

Jan 1, 1969

By H. D. Kessler, R. J. Van Thyne

Phase diagrams of the titanium-rich portion of the ternary systems from 0 to 10 wt pct Al and 0 to 1 wt pct 0, N, and C were determined. Micrographic analysis of annealed high purity arc melted alloys was the principal method of investigation and was supplemented by X-ray diffraction. TITANIUM-ALUMINUM alloys exhibit excellent properties, particularly for elevated temperature use. For this reason, the Materials Laboratory, Wright Air Development Center, sponsored an investigation of the effect of the interstitially soluble contaminants, oxygen! nitrogen, and carbon, on the Ti-A1 system. Using high purity arc melted alloys and micrographic analysis of annealed samples as the chief method of investigation, titanium-rich partial phase diagrams were determined for the ternary systems. Experimental Procedure Materials: The titanium used in the preparation of the alloys was iodide crystal bar (99.9+ pct pure) produced by the New Jersey Zinc Co. and Foote Mineral Co. The aluminum was obtained from the Aluminum Co. of America in the form of sheet. The given analysis was: Si, 0.0006 pct; Fe, 0.0005; Cu, 0.0022; Mg, 0.0003; Ca, <0.0006; Na, <0.0005; and Al, 99.99. High purity titanium dioxide purchased from the National Lead Co. was used in the preparation of the oxygen-bearing alloys. The spectrographic analysis of this material was as follows: SiO,, 0.07 pct; Fe,O,,, 0.002; A1,0,, <0.001; Sb,O,, <0.002; SnO,,, <0.001; Mg, <::0.001; Cb, <0.01; Cu, 0.0004; Pb, 0.002; Mn, <0.00005; W, <0.01; V, <0.002; Cr, <0.002; Ni, <0.001; and Mo, <0.002. Special spectroscopic graphite rod purchased from the National Carbon Co. was used in the preparation of the Ti-A1-C alloys. Alloy Preparation: Alloy ingots weighing 10 grams were melted in a nonconsumable tungsten electrode arc melting furnace using water-cooled copper hearths and a helium atmosphere. The arc was struck on a tungsten stud in the copper block to minimize contamination from the electrode. Details of the techniques have been reported.&apos;, &apos; Each ingot was inverted and remelted a minimum of four times to insure homogeneity, without opening the furnace. Remelting small control ingots of iodide titanium under similar conditions resulted in no measurable hardness increase, indicating contamination-free melting conditions were used. The alloy charges and resultant ingots were weighed to the nearest milligram. Only small weight losses were obtained upon melting, indicating that the actual compositions were very close to the nominal compositions. Check analyses substantiated this. Oxygen and nitrogen were added during ingot preparation as master alloys. An oxygen master alloy containing 25 wt pct 0 was prepared by melting iodide titanium and pressed titanium dioxide (40 pct 0) powder. The Ti-25 pct 0 alloy is more easily handled during weighing and charging than the pressed TiO, powder. Chemical analysis indicated that titanium-nitride received from an outside source contained large amounts of impurities (2.7 pct Ca). Therefore, a master alloy containing approximately 12 pct N was prepared by melting nitrided sponge titanium. As the sponge melted with difficulty, the alloy was diluted by addition of titanium to lower the melting point. The chemical analysis of the final alloy was 6.69 pct N. Both master alloys are friable and were used as —8 +16 mesh lumps resulting from crushing the ingots. NIelting the Ti-A1-0 and Ti-A1-N compositions five times produced homogeneous ingots. The preparation of homogeneous carbon-bearing alloys caused considerable difficulty. Alloys containing less than 1 pct C were prepared using spectrographic graphite rod, 1/8 in. diameter by 1/8 in. long. However, the graphite did not dissolve even with long melting times and many remelts. The ?/s in. pieces of graphite were used rather than powder because the low density powder is troublesome in arc melting.

Jan 1, 1955

By R. G. Schaal

The Magma Mine at Superior, Arizona had an unimpressive beginning as a. worked out silver mine that was purchased in 1910 for $130,000 and then incorporated into the Magma Copper Company which has been continuously mining the deposit since 1915. Copper is the principal metal produced. However, zinc, gold, silver and iron have also contributed to the total metal product. Prior to 1973, the production rate of 1500 tons per day was maintained by hoisting 4 and 5 ton pay-loads at speeds up to 1100 FPM through four small hoisting shafts. The hoists used included 8&apos; and 7&apos; diameter double drum, double clutched doc. and a.c. motor driven geared units built as early as 1917. One old timer that did yoeman&apos;s service for many years was an 8&apos; Bollen Pulley with a.c. geared drive that utilized an endless rope system with mechanical grip and release mechanism built into the pulley&apos;s throat. Primary power for all of these old production hoists was 25 Hertz. Exploration that was completed in 1967 developed a reserve of 10 Million tons of 5 per cent copper which was sufficient to justify new capital expenditures for enlargement of productive facilities to 3300 tons per day. To reach the new reserves a 22&apos; I.D. concrete lined vertical shaft was sunk to an initial depth of 48431. A 12 ½ diameter adit was bored from the mill side of the mountain to intercept the shaft at a point about 1100&apos; below the collar. This 9200&apos; long adit provides the right-of-way for the mine to mill railway and egress for heavy supplies from rail head as well as a conduit for potable water, electric power, compressed air and mine drainage. Mine operating levels begin 3582&apos; below collar and thereafter have been cut at 100&apos; vertical intervals. Skip loading stations have been installed 4282&apos; and 46821 below collar with an in-shaft skip dump station located 800&apos; below collar. This provides for 4500 tons of storage above the mine to mill train loading station located 1100&apos; below collar. Ore and waste are moved horizontally from stope chutes and drift headings by rail haulage to transfer raises which channel all material to the two mentioned skip loading stations. The 22&apos; diameter shaft crossection is arranged with the two skip compartments on the south side separated from the manway and utility compartments by the cage compartment. The cage counterweight operates in a portion of the southwest quadrant of the shaft. The hoisting plant consists of two conventional Nordberg double drum, single clutch, geared, d.c. motor driven units that are identical except for the drives and automatic controls. The drums are 15&apos; diameter x 105" face with LeBus grooving for 2-1/8" diameter wire rope wound in three layers. Mechanical design emp1o::ed is the same as has been used for the past twenty- five years. One drum is attached to the main shaft by 2 large bolted integral shaft flenge. The loose drum is engaged by a 4-arm positive tooth clutch meshing with radially cut teeth of the clutch ring which is bolted to the drum. The drums are one-piece steel plate weldments having a finished weight of 60 tons each and are mounted upon a 36" diameter shaft that also weighs 60 tons. With the addition of brake rings, clutch, bull gear and rope, the total dead weight adds up to nearly 250 tons that is supported by just three double row spherical roller pillow block bearings. There is no bearing between the drums. All pinion shafts as veil as all head sheave journals are supported in the same type of antifriction bearings.

Jan 1, 1975

By Donald L. Johnson

REVIEWS on the applications of optical ellipsometry to the study of polycrystalline metal surfaces and oxidation-corrosion processes have been presented by Kruger and Hayfield, and white.&apos; In view of the ability of this method to measure differences in film thicknesses to below 10A, ellipsometry was used to study nitrogen chromium surface reactions during the early stages of growth. Chromium specimens in the form of a vapor-deposited film on glass substrate were exposed to purified nitrogen for selected time increments at 700°F. This temperature was selected because it gave the best combination of exposure time and thickness change. Ellipsometer readings were taken immediately after exposure to determine polarizer and analyzer angles using monochromatic light at 5000A.2 After each set of readings was obtained, the specimens were exposed for an additional increment of time in nitrogen and a new set of readings taken. Film thickness was computed from LUCy&apos;s3 equation for nonabsorbing thin films. In Lucy&apos;s derivation, two equations for computing thickness were obtained. Peterson and Bashara4 have discussed the validity for using one of these equations when an independent value of the refractive index is used. The film was assumed to be Cr2N (Ref. 5) and was determined to be optically isotropic. Optical isotropy was determined by rotating the films about the surface normal and noting that the azimuth and phase difference did not change. Since Cr2N is reported to be hexagonal, it is assumed that optical isotropy results from randomly oriented grains of very small size. The thickness was computed using refractive indexes varying from 1.6 to 2.0. The maximum variation in computed thickness over this range for a given exposure was 20 pct. The data reported are based on a refractive index of 1.8. Reference readings on the metal surface were taken just prior to nitrogen exposure. No attempt was made to deoxidize or denitride the metal surface after vapor deposition, although specimens were observed to gain approximately 2A per day in air at room temperature. Twelve experimental exposures were made on a single sample over a total accumulative time of 132 min. Additional experiments over longer time intervals were made to determine the effect of heat up and cool down during and after exposure. As a result of these experiments, the thickness computed for each exposure was increased by 4A. Time profiles based on the linear law are similar to the oxidation profiles for many metals.&apos; The rate of accumulation of the nitride film is rapid at first and slows down as the film thickness increases. The parabolic law x2 =k1t +k2 [11 gives a straight line in Fig. 1; therefore, it is concluded that the kinetic behavior is parabolic. Sey-bolt and Haman5 reported similar results for CrlN on chromium at 1000°C although the order of the thickness was much greater (10-3 cm). Analysis of thickness data based on other values of refractive index shows that the curves are shifted vertically but retain the same shape. According to Mott,7 it is expected that for thin films k2 is zero in Eq. [I]. Since the plot in Fig. 1 is linear through the origin, k2 is zero and the parabolic nature of the film growth is further indicated. The parabolic rate constant, calculated from the slope in Fig. 1, is 4.4 x 10-16 sq cm per sec. The corresponding work (+) required to bring an electron from the metal into the oxide is estimated to be 1.5 ev.7 The author thanks professor N. M. Bashara and D. W. Peterson, Electrical Materials Laboratory, University of Nebraska, for making the ellipsometer available and providing technical assistance. The Electrical Materials Laboratory is supported by the office of Naval Research, NONR 3718 (01). This work was partially supported by the Engineering Experiment Station and the Mechanical Engineering Department, University of Nebraska.

Jan 1, 1967

By E. J. Koval

Practical miscible displacement processes will be characterized by lingering of the solvent into the oil. The lingering process is brought on by viscosity differences, and can be accentuated by channeling and longitudinal dispersion. The effects of these factors on the efficiency of unstable completely miscible displacements are combined in what is called the K-factor method. This method, analogous to the Buckley-Leverett method, predicts recovery and solvent cut as a function of pore volumes of solvent injected. Experimental data are included and show excellent agreement with theory for a wide variety of sandstone cores and viscosity ratios. INTRODUCTION Theoretical considerations,1 laboratory experiments,2 and pilot tests3 lead to the conclusion that miscible displacements in the field will be unstable In an unstable miscible displacement, the solvent fingers through the oil. This fingering leads to early breakthrough of the solvent and an extended period during which both oil and solvent are produced. For such a system, there appear to be four principal factors which bring about or accentuate the effects of instability: longitudinal dispersion (including geometrical effects), channeling, viscosity differences and gravity differences. Other factors, such as diffusion and flooding rate, can also influence the effects of instability, but at the flooding rates considered in this report, circa 15 ft/D, they are unimportant. Longitudinal dispersion can be thought of as a spreading of the solvent front caused by the presence of microscopic inhomogeneities. Channeling of the solvent occurs when a porous medium has macroscopic inhomogeneities; i.e., gross permeability variations. Viscosity differences lead to fingering of the less viscous solvent. This difference in viscosity accelerates the growth of fingers along paths previously developed because of permeability variations. Gravity differences lead to overriding by the usually less dense solvent. Al- though gravity effects are generally small at a flooding rate of 15 ft/D, they would, nevertheless, unnecessarily complicate the interpretation of flooding experiments. For this reason, all the experiments reported herein were done with matched density fluids. Fingering and the resultant poor areal sweep were recognized early as the dominant influences on the efficiency and the economics of miscible displacement processes. Much research effort has been spent on ways to minimize fingering and increase areal sweep such as the use of graded viscosity slugs4 or water slugs. Some researchers attempted to work out ways to prevent fingering completely; i.e., to achieve a stable displacement through gravity or latitudinal dispersion stabilization. l Others did not attempt to control fingering but obtained an economic process by merely recycling the solvent and sweeping pattern by pattern.6 During this period, all aspects of fingering came under close scrutiny. Some researchers reported on how fingering looks2 and how it is affected by viscosity ratio,7 geometry,7 and slug size.2,* Peaceman and Rachfordg suggested a mathematical approach to the prediction of unstable miscible displacements in relatively homogeneous sand packs, but their work cannot be extended conveniently to heterogeneous systems. Hence for a heterogeneous system, no method is presently available for predicting solvent cut and recovery as functions of pore volumes of solvent injected. The purpose of this investigation was to attempt to fill in the gap in our knowledge concerning the prediction of performance of unstable miscible dis placements. Necessarily, the system selected for study was a relatively simple one. The restrictions placed on the system were: (1) The system was linear; (2) The solvent was miscible in all proportions with the oil in place; (3) The solvent was continuously injected into the porous medium; (4) Gravitational effects were eliminated by matching densities and (5) All the flood rates were high and constant at 15 ft/D to avoid any small rate effect and to minimize any diffusion effects. To simplify and to indicate that both longitudinal dispersion and channeling arise from permeability variations, the effects which they cause or influence have been termed heterogeneity effects. The use of

By B. R. Berger

The Getchell area in the northern Osgood Range, Humboldt County, Nevada, was first prospected in the late 1800s for silver, copper, and gold; the first recorded mention of mining activity concerned a silver discovery. The September 17, 1874 edition of the Winnemucca Silver State notes that the Crystal Mining District was newly organized in the Fremont Range (as the Osgood Range was then called) to include discoveries of silver, lead, and antimony made on the Louisa claim. The name Crystal was derived from the plentiful quartz crystals found in-cavities near the prospects. This same area, occurring on the northwestern margin of the Osgood granodiorite stock, was later mined as the Richmond tungsten property, and crystals may still be found there in cavities in a massive garnet tactite. By 1878, how-ever, the name Crystal had been abandoned in favor of Potosi. The next flurry of activity in the Osgood Range was reported in 1899 when a copper strike on Granite Creek in the southern portion of the range received attention. The copper occukences were in a granite contact zone on the southeastern edge of the Osgood stock and, in 1916, the first tungsten in the district was discovered in the same deposit. During the last part of the nineteenth century, cattle and sheep were brought into the Kelly Creek Valley east of the Osgood Mountains by various ranchers. Alphonso and Adrian Bernard were among these ranchers, and in the first decade of the twentieth century, one of them recognized the altered rock where the Getchell Center it is now located. A 3-m (10-ft) deep prospect pit was dug on the outcrop, but the highest assay ran about $11/t ($10 per st). No further work was done on the gold-bearing rock. In 1934, Emmet Chase of Battle Mountain and Ed Knight of Golconda prospected in the area of the Bernard prospect pit and located several lode claims. At this time, Noble H. Getchell, a state senator, was looking for new mining opportunities to develop. He held interests in the Gold Circle Consolidated at Midas, which was becoming a losing venture. Chase and Knight brought their discovery to his attention, and he grubstaked them to prospect further in the area. In need of financial backing, Getchell solicited the help of George Wingfield, Sr., who held a minor interest in the Gold Circle. Wingfield was a successful banker and mine operator during the heyday of Tonopah and Goldfield, and he had become good friends with Henry C. Frick and Bernard Baruch. Wingfield let Baruch in on several very successful mining ventures in Goldfield, and Baruch returned the favor by underwriting the financing of the Getchell mine. Eleanor Roosevelt and Jack Dempsey were early stockholders in the Getchell operation. George Wingfield brought his brother-in-law, Roy A. Hardy, a consulting engineer who had constructed the American Flat mill near Virginia City, to look at the property. Upon inspecting the Chase-Knight claims, Hardy declared the whole area to be mineralized. A crosscut was driven to check the extent of the ore, and the results were better than anticipated. The locators were reportedly given $50,000 for the claims. The Getchell Mine, Inc., was organized on November 5, 1936. A small railroad that ran from Battle Mountain to Austin was purchased, and the ties and rails were moved to Getchell to be used in underground exploration. Enough reserves were found in the Center and South pit areas to construct a 40 t/d (44 stpd) mill. The financial and engineering help for the mill was provided by the Newmont Mining Co. for a 17 1/2% interest in the corporation. Newmont set about trying to solve the metallurgical problems with the sulfide ore, and also directed the early development work. Newmont wanted to grind the sulfide ore underground and oxidize it in the atmosphere by spreading salt on it. Detrital Flat in Arizona was purchased to provide salt for

Jan 1, 1985

By R. I. Jaffee, C. M. Craighead, G. A. Lenning

THERE has been considerable discussion among A metallurgists and others interested in the development of titanium alloys as to the nature of the fine line markings which appear in the microstruc-tures of unalloyed titanium and a titanium alloys. These markings have been variously called x phase, etching pits, and twins. Figs. 1 to 3 show typical examples of the line markings as they appear, respectively, in high purity iodide titanium, commercial purity titanium rod, and a high purity a alloy containing 0.2 pct N. The commercial purity titanium sample, shown in Fig. 2, contains both line markings and some spheroidal retained-ß phase. The ß phase seen in this micrograph should not be confused with the line marking, since it originates from the iron present as an impurity in the sponge metal. It will be noted that the line markings seem to have a definite orientation pattern with respect to the grains and in titanium noticeably resemble the precipitation occurring in artificially aged high purity Al-Cu alloys. This similarity led to the hypothesis that the line markings observed in titanium and a titanium alloys resulted from precipitation of some unknown phase. With the work of Hägg1 and McQuillan2 as background, there was little reason to suspect hydrogen of being responsible for the line markings. Hagg reported that up to 33 atomic pct H was soluble in a titanium, and McQuillan reported an a solubility of up to 8 atomic pct. Furthermore, McQuillan examined metallographically a 5.1 atomic pct H alloy quenched from 300°C and stated that the structure appeared to be a single-phase a solid solution. Line markings have been observed frequently and were first noted by Jaffee and Campbell3 in 1949. They did not observe them in vacuum-annealed titanium and a Ti-O and Ti-N alloys, but did observe them in Ti-H alloys containing 0.25, 0.5, and 1 atomic pct H. They stated that it was doubtful that the markings were a second phase based on hydrogen, because 1 atomic pct was far from the accepted solid solubility of hydrogen in titanium. Finlay, Resketo, and Vordahl,4 in 1950, concluded that the markings were a true second phase as a result of observations on their etching characteristics. Anderson5 Commenting on these markings in titanium was inclined to associate them with hydrogen, but was loath to call them titanium hydride, because of the reported high solubility of hydrogen. Work at Battelle Memorial Institute for the Navy Bureau of Aeronautics," done concurrently with the work described in this paper, provided information on the experiment converse to that described by Jaffee and Campbell in 1949. This work showed that the amount of line markings in unalloyed titanium could be decreased by vacuum annealing at elevated temperature. It was suggested that this was the result of removal of hydrogen; previously, the data of Jaffee and Campbell9 howed that the markings appeared when hydrogen was added. Recent work at Battelle for the Ordnance Corps, Department of the Army, which is described here, now establishes the identity of the markings as a titanium hydride phase. A sample of high-purity titanium rod 1/4 in. diam, 0.009±0.001 wt pct H (0.43 atomic pct), Fig. 1, was resistance heated in a 0.05 micron vacuum for 41/2 hr at 1500°C. During the early states of heating, the pressure increased to 150 microns, indicating that gases were being evolved. After cooling in vacuum, the iodide titanium rod was analyzed for hydrogen. Vacuum-fusion analysis showed 0.0006 ±0.0003 wt pct H (0.03 atomic pct) to be present.* Metallographic examination of the vacuum-annealed rod showed only a transformed ß structure. There was no evidence of fine line markings, Fig. 4. A section of this vacuum-annealed rod was cold rolled to 0.040 in. thick sheet and annealed for 1 hr

Jan 1, 1953

By E. S. Bumps, H. D. Kessler, M. Hansen

The titanium-rich end of the Ti-AI phase diagram has been determined to the compound TiAI3 (62.7 pct Al), thus joining the aluminum-rich portion previously investigated by others and completing the diagram. Micrographic analysis and X-ray diffraction were the chief methods used to determine the phase relationships. THE Ti-Al phase diagram has been investigated as part of a program on titanium phase diagrams for the Wright Air Development Center. Included in the available information concerning the phase relationships in titanium-rich Ti-A1 alloys is a brief statement by Brown&apos; that: "aluminum raises the transformation temperature to 1000°C (183Z°F)." This observation is interesting in that it is the first example of a metallic alloying component raising the transformation temperature of titanium, and consequently widening the field of the a solid solution. Busch and Freyer&apos; presented resistivity data which indicated the formation of titanium-rich solid solutions of 1 and 3 pct A1 alloys prepared by powder metallurgy methods. Duweza found that there is only one other intermediate phase other than the known compound TiA1, (62.7 pct Al). This phase, designated as y, is of variable composition; its crystal structure is of the AuCu type and is therefore based on the composition TiAl (36.02 pct Al). Earlier work on the constitution of the aluminum-rich alloys has been reviewed by Hansen, and need not be discussed here. The tetragonal crystal lattice of TiAl,, as found by Fink, Van Horn, and Budge," was confirmed by Brauer." Recently, Schubert7 has reported that TiA1, is homogeneous within a limited composition range; however, the solubility limits were not given. The Ti-A1 phase diagram as presented in. this paper was determined by micrographic analysis of alloys containing from 1 to 62 pct Al, annealed at and quenched from temperatures between 700" and 1400°C. The phases and phase ranges investigated extend to the compound TiA1, (62.7 pct Al) to join the aluminum-rich end of the system determined by other investigators, thus completing the diagram. Methods of Investigation Preparation of Alloys: Iodide titanium, 99.9+ pct pure, obtained from the New Jersey Zinc Co., and high-purity (99.99+ pct) aluminum sheet from the Aluminum Co. of America were used to make up alloy ingots weighing 10 to 20 g. Detailed descriptions of melting techniques have been presented previously for work on the Ti-Mo and Ti-Cb> nd Ti-Si" phase diagrams. Briefly, the melting practice consisted of arc melting an accurately weighed charge in a copper block crucible insert in a non-consumable tungsten electrode furnace, under helium at atmospheric pressure. All ingots were carefully weighed after melting to detect possible losses. Comparison of weight before and after melting showed no appreciable weight changes. Also, chemical analyses were in close agreement with nominal compositions, Table I. The diagram as presented is, therefore, based on nominal compositions. Alloys were prepared having the following nominal aluminum contents: 1 ... 36 (1 pct increments), 38, 40, 41, 42.5, 44, 45, 46, 47.5, 49 . . . 64 (1 pct increments), 67, 70, 80, and 90. Ingots with up to 14 pct A1 were cold-pressed various amounts in order to increase the rate of attaining equilibrium structures on heat treatment. The amount of cold deformation that could be applied decreased with increasing aluminum content, until alloys containing 12 pct A1 or more cracked after only a few percent deformation. Annealing Treatments: Samples annealed at temperatures of 700" to 1000°C were sealed in

Jan 1, 1953

By T. D. Mueller, F. C. Miller, Jr. Earlougher R. C.

In analyzing pressure buildup tests for field wells producing both oil and gas, the common practice is to use a modification of single-phase flow theory. Validity of such an approximation has been demonstrated for single-well solution-gas-drive systems. This paper indicates that such approximations are also valid for two-well solution-gas&apos;-drive systems. From this it is inferred that the technique can be used for multiple-well systems. A computer was used to simulate the behavior of a two-well solution-gas-drive reservoir to test the validity of the above type of analysis. Simulation results indicate that pressure buildup tests in such a system can be analyzed within engineering accuracy for formation permeability and pressure. A rule of thumb is given for estimating the length of time a well must be shut in for the pressure in a nearby producing well to increase significantly. To observe such an increase, the shut-in well would have to be left shut in much longer than normal. INTRODUCTION An important technique for obtaining data concerning a producing petroleum reservoir is the pressure buildup test. Such a test, when properly conducted and analyzed, provides information on the average reservoir pressure and the permeability in the major drainage area of a well. The theory upon which the analysis of a pressure buildup test is based assumes that the behavior of the fluid in the reservoir is adequately described by the diffusivity equation.1 Use of the diffusivity equation implies that a single fluid of small and constant compressibility is flowing. To analyze a pressure buildup test in situations which involve more than one fluid phase, the single-fluid analysis is extended. This paper verifies the extension of pressure buildup analyses to two-phase, two-well systems. Miller, Dyes and Hutchinson1 have presented a technique for analyzing pressure buildup tests in circular bounded reservoirs. Their method requires that the reservoir be producing at pseudo-steady state (constant pressure gradients) prior to shut-in. An alternate reservoir model, presented by Horner,2 assumes that the reservoir is infinite. The Homer model does not assume a Pseudo-steady state prior to shut-in, but the assumption that the reservoir is infinite implies that the average pressure can be determined only if the total production prior to shut-in is small compared to the total fluid originally present. Limitations imposed by the pseudo-steady state and infinite reservoir assumptions are avoided by the technique proposed by Matthews, Brons and Hazebroek.3 Their method can be used to calculate both the Permeability and the average pressure in bounded single-well systems which are not necessarily at steady state. They also suggested determining the average pressure of a multi-well reservoir producing from pseudo-steady state by volumetrically averaging the static pressures of the individual wells. Matthews and Lefkovits4 used numerical simulation techniques to verify that this method does produce adequate results for single-phase, multiple-well systems. Perrine5 proposed modifications to the single-phase theory so that pressure buildup tests in multiple-phase systems could be analyzed. He suggested replacing the single-phase mobility (k/µ) by the sum of the mobilities of the individual phases, and replacing the fluid compressibility by an average compressibility weighted by the saturations of the separate phases. By using numerical techniques to solve the two-phase flow problem for a single-well system, he concluded that this approximation gives results within engineering accuracy. More recently, Weller6 has shown that, for a gas-oil system with a single well at the center of a circular reservoir, pressure buildup tests can be analyzed adequately by using the modification proposed by Perrine. Feller&apos;s results also indicate that, as the gas saturation increases, this analysis becomes less accurate. To date, no evidence is available to show that the Perrine approximations can be combined with the Matthews-Brons-Hazebroek technique to calculate the average pressure of a multi-well,

By R. A. Graham, R. W. Rohde, J. R. Holland

In a shock wave compression study of a martensitic Fe-30 pct Ni alloy, Graham, Anderson, and Holland&apos; found a region of unusual compressibility extending from a few kilobars up to about 20 kbars. This region was characterized by a continuously decreasing shock wave velocity with increasing stress. In this note, we report the results of a study initiated to determine the source of this unusual compressibility. In earlier shock-loading experiments on martensitic Fe-30 pct Ni, Loree et a1.&apos; determined that a phase change occurred at about 80 kbars. Subsequently, Bowden and elly found that samples of a similar material shock-loaded at about 100 kbars experienced a martensite-to-austenite transition. Their crystal-lographic analysis showed the transition was a direct reversal of the established martensite system to the austenite phase. The shock loading in the present experiments was accomplished by precisely controlled plane impact between two discs of the sample material. This configuration created a state of uniaxial strain in the two the front of a projectile which was accelerated to various velocities. Planarity between the impacting discs was controlled to 5 x 10-4 rad, and impact velocities were measured to 0.5 pct. From a knowledge of the Hugoniot relationships of the material and the impact velocity, the shock-wave stress can be calculated. Samples were shocked at 18, 50, 70, and 100 kbars. The specimen discs shocked at 18 and 50 kbars were instrumented with quartz gages to observe the stress time profile. A more detailed description of the experiment has been given previously.4 The shock-loaded specimens were recovered intact by decelerating them in a catcher filled with soft wood. Discs of Fe-30 pct Ni nominally 12.7 mm thick and 64 mm in diam were cut from bar stock. Chemical analysis of the material provided the following composition in weight percents: 29.5 Ni, 0.50 Mn, 0.21 Si, and 0.10 C, with traces of Cr, Cu, Mo, Al, and Co. The discs were austenitized at 650° C for 2 hr at a pressure of less than l0-&apos; torr, and furnace-cooled. Martensite was then produced by quenching the discs at -196" and holding 168 hr. The initial martensitic structure formed is shown in Fig. l(a). Typical microstructures of samples shock-loaded at 18 and 100 kbars are shown in Figs. l(b) and l(c). The banded structure with the austenite regions running parallel to the shock propagation direction was characteristic of samples shock-loaded at all stresses. No such banding was found in samples that were not shock-loaded. Comparison of Figs. l(b) and l(c) shows that, although under the optical microscope the two microstructures are quite similar, the martensite plates of the specimen shocked at 100 kbars etched in a distinctly different manner. This unique etching behavior of martensite in samples shock-loaded above the 80 kbar transition point has also been observed by Leslie el al.&apos; These investigators determined from X-ray and electron microscope studies that fcc martensite, similar in appearance to normal bcc martensite, had been formed under shock loading. A quantitative determination of the amount of austenite present after shock loading was made by X-ray techniques. Both the methods of Lindren&apos; and Miller&apos; were utilized. The results are shown in Table I. The error limits are those experimentally observed from two independent analyses of each sample and represent the precision of the experiment. The absolute error, which should be similar for each sample, is believed to be about 10 pct. It is seen that as the shock stress increases the amount of austenite present also increases. On the basis of the X-ray and microscopic observations, we conclude that shock loading below the 80 kbar ersal will initiate a martensitic reversal: the amount of reversal that occurs increases with in-

Jan 1, 1969