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By M. F. Fogler

An attempt to duplicate Rawdon and Mutchler's experiments showing a reversal of hardness with continued rolling gave negative results, indicating that the phenomenon is not general but depends, probably, on local conditions of rolling. IN A recent paper, Rawdon and Mutchler1 gave some exceptionally interesting results on the Brinell and scratch hardness of severely cold-worked metals. In their work, they found that, on continued cold rolling, the metal hardened up to a particular point and then reversed and became softer; this was true for both Brinell and scratch hardness values. The generally reported behavior2 of metals, with respect to Brinell tests on cold-worked material, is that the metals harden up to a certain point and then, on further cold rolling, no change in Brinell hardness occurs. Jeffries and Archer3 state that there is little difference between the scratch hardness of annealed and cold-worked metals; the work of Faust and Tammann4 also indicated no difference between-the hardness of annealed and cold-worked copper. Rawdon and Mutchler found, when they plotted the reduction ratio (initial thickness divided by thickness after rolling) against the hardness value for the cold-rolled material, that the hardness number increased up to a reduction ratio of about 3 and then decreased and became even smaller than that for the annealed metal. This behavior was reported for both scratch and Brinell hardness; Figs. 1 and 2 show their results for Brinell hardness on the metals for which they published data. This is an exceptionally interesting phenomenon, if it occurs under all conditions of rolling, and would have an important bearing on the practice of cold

Jan 1, 1925

By John Wellington Finch

In August, 1927, the writer examined certain copper deposits in New Mexico1 which occur in beds of sandstones and shale, and in connection therewith reviewed the literature upon deposits of this type. Such deposits are known and have been reported upon at various points in Texas, Oklahoma, Arizona, Colorado, Wyoming and Utah, but in New Mexico they have been given more development than elsewhere and apparently occur there more conspicuously than in the other states. Some 25 years ago the writer examined deposits of similar origin in northern Arizona and more recently other deposits in western and southwestern Colorado, and these examinations have led him to realize how widely scattered are the deposits and how generally noncommercial they are. On superficial development, to one without a comprehension of their geologic nature, they are alluring on account of occasional small amounts of high-grade ore and much misplaced capital has been expended upon them. This paper, therefore, aims to present briefly certain theories of genesis, some details of which may possibly be new, and to lead up to practical conclusions which may be useful to other geologists and engineers. A bibliography of the more important literature upon such deposits is given below.2 Coffin's Bulletin upon the Radium, Uranium and Vanadium Deposits of Colorado, published in 1921, is a particularly clear discussion. The most comprehensive recent statement is Butler's.

Jan 1, 1928

By William P. Lohden

INTRODUCTION It is recognized that, for a variety of reasons, some companies in the mineral industry today are by no means cash-rich and, in fact, are reporting a growing proportion of long-term debt in their capital structures. A review of recent balance sheets of small, medium-size, and some larger companies, indicates that a fair number still have substantial positions in cash equivalents such as U.S. government issues and other short-term money market instruments. In part, this paper concerns itself with companies which have sufficient cash and equivalents and/or cash generation to internally finance mining projects or expansions but which, for some reason, choose to borrow funds. Misconceptions which appear to frequently underlie so-called "leveraging" decisions are explored in this paper. Also considered arc' those circumstances under which any company, including one that is cash rich, should consider borrowing for a project in an amount beyond what would otherwise be necessary based upon its internal financing ability. I do not attempt to cover the raising of equity capital in public markets in this paper. OVERALL RETURN ON INVESTABLE CASH If you approach an individual with an investment which can be financed from savings, or by borrowing at a rate higher than one is earning on savings, that individual will quickly tell you that to pay interest at a rate higher than is being earned on savings would reduce overall income. Assuming that additional investment opportunities are not currently being considered, the individual concludes that a draw-down on savings, leaving a cushion for contingencies suited to individual circumstances, is the correct financial decision. For reasons discussed later, the simple mathematical logic leading to this conclusion tends to become obscured at the corporate level. When Leveraged Studies Are Inappropriate or Premature Surprisingly, I have heard of a number of companies that could afford to finance an investment solely with internal funds, which have made DCFROR (i.e. discounted-cash-flow rate-of-return) studies not only on a 100% equity basis but also on a leveraged basis. Certainly, a leveraged study would be appropriate if additional projects were competing for more capital than was available internally. Often, however, other projects are not far enough along to warrant a leveraged study and there is some danger that a project may be undertaken because it has an estimated acceptable rate of return, on a leveraged basis, that is not ultimately earned because some of the other projects are postponed or abandoned and borrowing is less than expected. For the above reasons, until it has been determined that (1) borrowing is a reasonable certainty for a particular project and (2) the timing and amount to be borrowed has been determined within a reasonable range of accuracy, I believe it is inappropriate and misleading to calculate DCFROR for a project other than on a 100% equity basis. Even when there are several projects currently competing for funds and borrowing will be required to finance one or more of them, using the common yardstick of calculating DCFROR on a 100% equity basis is a safer method to initially evaluate and compare the attractiveness of the projects. Many companies, whether they would have to borrow or not, will reject projects that on a 100% equity basis do not meet their minimum rate of return standards. Some companies which have to borrow will undertake a project provided the project's DCFROR on a leveraged basis meets its minimum return standards. The danger of this approach is that even moderate shrinkages of estimated cash flows could plunge return below

Jan 1, 1985

By G. S. Phipps, E. E. Schumacher, G. M. Bouton

THE seriousness of the present tin scarcity has stimulated large consumers of this vital metal to develop drastic conservation measures in order to extend the available supplies to cover the emergency period. By devising new soldering methods and alloys the Bell System has contributed a substantial share in the tin conservation effort, Fortunately, the changes, as far as can be determined now, have not introduced weakness into the soldered joints. Some of the new procedures were already in the process of development at the onset of the emergency, while others were devised under its stress. In some instances, the newly developed solders were found to be more difficult to use than the alloys previously available, and would not have been introduced under normal conditions. One major change made that previously had been under consideration will result in large savings of tin. Unless service difficulties are encountered, this modification gives promise of remaining after the emergency has passed. The change involves a reduction in the amount of solder placed on a wiped joint between the cable sheath and the sleeve. Instead of the customary full sized wiped joint, a wipe of fillet proportions is formed. Through this change, a solder saving of more than 60 per cent per joint can be realized. Plumbers and cable splicers for many years have joined lead pipes and cable sheath by a soldering process called "wiping." The name is an apt description of the operation. For a wiped joint, the sections to be united' are heated by molten solder poured over their surfaces, and the resulting semiliquid mass is manipulated by wiping with cloth pads to a well rounded symmetrical form like the one shown in Fig. I, The operation requires considerable skill on the part of the splicer and close control of the composition of the solder. At first consideration, the problem of tightness in such joints seems simple but experience shows that even under the best conditions the fissures frequently found in the solder occasionally link and form a path that allows leakage to occur. In telephone cables not maintained under gas pressure, such leaks permit the entrance of water, which wets the paper-covered conductors and thereby impairs the insulation value and causes service interruptions. By going to an extreme and wiping off all the solder in excess. of a fillet, it has been found that many causes of porosity are eliminated. Figs. 2 and 3 show cross sections of joints wiped in the old and the new ways. The saving in solder, and consequently in strategic tin, is evident. The field splicing forces find that joints are easier to make by the new method and are less likely to be porous. The metallurgical considerations that are responsible for the success of the fillet wipe are of interest. Much has been written about the wiping process of soldering cable joints and the many requirements of a good wiping solder have frequently been listed. The success of the procedure described

Jan 1, 1943

By Roswell P. Angier, Herbert S. Kalish, Henry H. Hausner

POWDER metallurgical methods as applied to zirconium are of great interest because they permit not only the fabrication of parts directly to shape with a minimum loss of material but also the utilization of scrap, and the metal may be processed at temperatures well below the melting point. There are two difficulties involved in the melting of zirconium: 1—High vacuum is necessary for melting, and 2—zirconium reduces nearly all oxides so that it is difficult to find a suitable crucible material. The purest material, zirconium crystal bar, is expensive, and the methods of subsequent fabrication are limited. Cold rolling or extrusion of zirconium crystal bar is suitable for making certain shaped parts, but where melting is involved, the purity of the metal is invariably decreased, and a method of casting to a definite shape does not seem to be feasible. Where it is necessary to hot roll, zirconium must be covered with a steel or copper jacket to protect it from the air. This is necessarily a costly operation. Where annealing of zirconium is necessary it must be conducted in a high vacuum. In an investigation of powder metallurgical methods for zirconium, the zirconium powder used should be characterized by the following properties: 1— Highest degree of purity, 2—uniformity in particle shape and particle size distribution, 3—low compression ratio, and 4—satisfactory strength of the compacted powder (green strength). Zirconium powders have been made by two methods: By the reduction of zirconium tetrachloride (ZrC1,) with sodium,2' *•B "nd by the reduction of zirconium oxide with calcium and calcium chloride." The first method represents one of the earliest attempts to make pure zirconium metal, and the sintered product from this powder is extremely brittle. The second method of making zirconium powder is far more successful, but the powder made in this way has an extremely low apparent density and, therefore, a high compression ratio which makes it difficult to use it for powder metallurgical purposes. For these reasons the above-mentioned zirconium powders were not used in this investigation. To obtain sintered zirconium compacts of highest 'purity and good ductility, it was first necessary to produce a suitable powder. Pure zirconium has been made chiefly by two methods. The iodide method, from which the product is "crystal bar" zirconium, was developed first.'." By this purification process very soft, pure, and ductile zirconium metal can be produced. The second method, developed by the U. S. Bureau of Mines, is the reduction of zirconium chloride with magnesium." The sponge zirconium thus produced is also soft, pure, and ductile.

Jan 1, 1952

By H. A. Wahl

This paper presents methods of designing hydraulic fracture treatments in formations saturated with slightly compressible liquids. Howard and Fast describe the fluid-loss control resulting from the viscosity and compressibility effects of the reservoir fluid in terms of a fracturing fluid coefficient. However, for horizontal fractures, this coefficient is applicable to infinitely thick reservoirs. These methods of evaluating fluid loss from horizontal fractures during treatment differ from previous methods in that: (I) formation thickness is incorporated in the velocity function describing the rate of fluid loss to the formation; and (2) for a given thickness the relative position of the fracture to the horizontal boundaries of the reservoir or any interrnediate permeability barrier is incorporated in the design procedure. This theory is applied to several actual and hypothetical field cases. The results of these calculations demonstrate that the eflect of formation thickness on fluid loss from horizontal fractures may result in fractures several times larger than predicted by other methods. INTRODUCTION Hydraulic fracturing has been the dominating well-stimulation technique during the last decade. From the time it was commercially available, fracturing has had a very favorable success ratio compared to other stimulation methods. However, numerous wells that were successfully stimulated remained economic failures. Only in the last few years has the oil industry recognized the importance of designing treatments for each well which will yield the maximum profit. This implies that for a given set of treatment conditions the size and general physical characteristics of the fracture can be determined. One of the outstanding contributions in the field of fracture design was presented by Howard and Fast.' In their paper, three flow mechanisms that control fluid loss from the fracture to the formation are defined: (1) viscosity effects of the fracturing fluid, (2) viscosity and compressibility effects of the reservoir fluid, and (3) wall-building effects of a treated fracturing fluid. The rate of fluid loss to the formation adjacent to a fracture is shown to be a function of time. For each flow mechanism the velocity function v(t) is expressed as a constant or fracturing fluid coefficient divided by the square root of time. This form of v(t) can be used in the Carter equation, as developed in the Howard and Fasc paper, to estimate the areal extent of fractures. This equation may be written as In the following sections the effect of formation thickness on fluid loss from horizontal fractures is evaluated when the controlling flow mechanism is the viscosity and compressibility of the reservoir fluids. The major assumptions inherent in the Carter equation are brought out in subsequent mathematical developments. THE EFFECT OF RESERVOIR FLUIDS ON FRACTURE EXTENSION When a fracture treatment is performed using a fracturing fluid identical to the reservoir fluid, the only flow mechanism controlling fluid loss is the viscosity and compressibility effects of the reservoir fluids. In developing a fracturing fluid coefficient for this mechanism, Howard and Fast considered a segment of the formation bounded by a unit area on the fracture face and extending to infinity in the direction of leak-off as shown in Fig. 1(a). The direction of leak-off z is normal to the fracture face. The equation governing the linear isothermal flow of fluid into this segment is where a = Eq. 2 is a form of the diffusivity equation. It is derived from the equation of continuity, Darcy's law and Eq. 3

By K. M. Busen, J. Lindmayer

A heterojunction model is suggested for descrihzng the electronic conditions at oxide -semiconductor interfaces. Detailed study of the silicon oxide-silicon interface shows that the heterojunction model explains many experimental facts; however, it is necessary to assume that a transition layer exists at the interface. It will he demonstrated that ionic contrbution way also he present. Extended low-temperature heating stabilizes the oxide to a charge carrier density in the order of 10' cln-: determined by the heterojuncton model. OXIDIZED semiconductor surfaces are widely used, since they offer technological advantages and "passivate" the surfaces of semiconductor devices. However, it has been recognized that there are always n-type inversion layers formed in the silicon oxide-silicon system, which must be regarded as a definite disadvantage. An added complication is the "instability" of these inversion layers;' the inversion layer appears to vary with the processing and they change at temperatures as low as 100" to 200°C This paper will point out that the inversion layer is a result of the dissimilarity of the contacting materials and therefore must always be present. The dissimilarity is the essence of the heterojunction or electronic model and involves directly the structure of the materials involved. In addition, one finds the contribution from ions; this disturbance, however. can be eliminated for the case of silicon oxide-silicon interface. The strength of the inversion layer or channel will be expressed in terms of the density of elementary charges per square centimeter, N*, maintaining the channel. The next section contains the formulation of the heterojunction model by assuming a contact between two homogeneous materials. This calculation should not imply that silicon oxide is homogeneous; it serves only to point out the general properties of the electronic model. Following the electronic model, the practical case of the silicon oxide-silicon interface will be discussed. I) THE HETEROJUNCTION MODEL Contacting an oxide with a semiconductor, a work-function difference must be accommodated. Fig. 1 represents the oxide and the semiconductor before and after contact. When the contact has been made, one finds that qVi + qV, = A@; i.e., the work-function difference is distributed between the oxide and the semiconductor. Normally, the work-function difference appears on the wide-bandgap material, but in the present case the oxide is thin and far from being a single crystal. Accordingly, a significant fraction of the work-function difference must appear on the semiconductor. The work function of silicon2 is about 4.8 ev, but we shall not assign any particular work function for the oxide as it may vary. However, oxides usually have lower work functions and therefore the potentials must build up in the manner shown in Fig. 1. Such an argument predicts that the inversion layer must be n type, as opposed to the clean surface which is p type. Another important factor to be considered is that the oxide is disorderly and therefore contains many trapping levels. As a result, the charges in the oxide arise primarily from the change in trap occupation, while on the semiconductor side the space charge is composed of mobile free electrons. The consequence of this fact is that a change to another thermal equilibrium will require some time, dictated by the traps in the oxide. The conditions can easily be calculated on the semiconductor side. Assuming an intrinsic semiconductor, Poisson's equation is

Jan 1, 1965

By L. Burris, G. A. Bennett, P. A. Nelson

Staznless steels ave rrzuch less seuel-ely attacketl by zinc lapov than by molten zinc systems. To determine the applicubility of stainless steels fov equipment items which would be exposed only to zinc vapor, the corvosion resistance of several stainless steels to zinc vapor was investigated in 500-hr- exposuves at 900° C. Two austenilic stainless steels, Types 304 and 3-17, suffered severe intergranular attack. Loss of nickel from these steels and micro-probe crnalyses indicated the probable formation of low-melting zinc-rich phases. Good vesistance to attack by zinc vapor, as determined by metallo-9-rpaphic excr)rtination and physical testing, Loas exhibited by Type 405 stainless steel, a jevvitic steel. Type 440C stainless steel, a tnartensitic steel, although suffering considevable loss in weight, was not structurally weakened. At Argonne National Laboratory liquid zinc and zinc-rich alloys are being employed as solvent media in pyrometallurgical processes under development for recovering and purifying discharged reactor-fuel materials.' Because of the high solubility of most metals in liquid zinc,' there are few metals which can serve as container materials for liquid zinc at temperatures much above the melting point. The poor corrosion resistance of the common metals and alloys to molten zinc has been discussed by Eldred.3 DeKany, Lavendel, and Burris4 tested some of the less-common alloys of the nonrefractory metals and found that they also have poor resistance to attack by liquid zinc and Zn-Mg solutions. Of the metallic materials, only some of the refractory metals such as tantalum, tungsten, and molybdenum and their alloys have shown resistance to attack by liquid zinc.4-7 In the process-development work at Argonne National Laboratory, tantalum and tungsten vessels have been used to hold liquid-zinc alloys. These vessels are housed in stainless-steel equipment, principally to permit maintenance of an inert atmosphere and operation at various pressures. In this experimental work, it has often been observed that Type 304 stainless steel suffers little attack by zinc vapor at temperatures up to about 800 °C. In contrast, severe attack occurs in areas where zinc condenses as a liquid. The extent of attack by zinc vapor on several stainless steels was investigated because there are possible useful applications of stainless steel for equipment items which would be exposed only to attack by zinc vapor. These applications include, for example, housings around processing equipment as indicated above and vapor lines leading from zinc stillpots or retorts to condensers. EXPERIMENTAL EQUIPMENT AND PROCEDURE The experimental procedure consisted in exposing stainless-steel test coupons to static zinc vapor for 500 hr at a temperature of about 900°C. The apparatus, shown in Fig. 1, consisted of a 12-in.-long closed tantalum tube jacketed in Type 304 stainless steel to prevent oxidation of the tantalum. A Zn-10 wtpct Mg* alloy charge of 293 g in the bottom of the

Jan 1, 1965

By W. Hurst, R. E. Leeser, W. C. Goodson

Three aspects of gas deliverability are presented in this paper. The first treats with the gas deliverability or availability of a normal depletion-type dry gas field. Such encompasses not only the period of stabilized constant rate, but more so, the "tailings" when a fixed abandonment pressure is reached and the rate by necessity must decline. A comprehensive work plot is offered, developed from mathematics herein included, that removes the triai-and-errnr computations that attended such undertakings in the past. The second part treats with the discount factor of the open flow potential constant from what is observed initially in testing a gas well to what is evidenced when stabilization is reached. This prevails in tight formations, such as the Kansas Hugoton field which is offered as the example. The means of establishing this factor are pressure build-up curves which, as sustained by analytical deductions, reproduce this entire period of transient flow under conditions of a constant rate influx. Finally, what is offered in this paper is the deliverability performance of an exceedingly rich gas condensate field producing from a tight formation. The example shown is the Knox Bromide field in Oklahoma, producing from the Bromide formations. The results are ominous, showing early reduction in permeability to gas pow, due to the retrograde condensate forming in the pore space, with the attending early logging-up of these wells. The analytics of lowered permeability are incorporated in the gas deliverability formula along with the PVT data that gives the increased condensate liquid saturation as the gas flows to the well bore. This paper would not be complete without a critique oflered at the end. With the many gas wells now in production and those that have completed their life, there has been no factual information collected by any source as to what constitutes that permeability range where a gas well would be unimpaired in its gas deliverability by the presence of rich condensate content, and the lowered range where such would be harmful. This question confronts all producers. INTRODUCTION Various aspects of gas deliverability are presented in this paper that includes depletion-type reservoirs, deteriora- tion factor of the gas deliverability constant, and the performance of a rich gas condensate reservoir producing from a tight sand. With respect to the presentation of gas deliverability and its tailings for depletion-type gas reservoirs, one notes that this is essentially the information offered by every gas transmission company and producer appearing before the Federal Power Commission for Letters of Conveyance in the dedication of reserves. In the ordinary procedure, as many engage upon this study, trial-and-error calculations are included, particularly as apply to the tailings. For many years one of the writers has employed mathematical analyses to perform this step and avoid the complexities so associated. In the preparation of this paper these analyses have been amplified to include any slope n for the open flow potential relationship for which the tailings can be determined from Fig. 1. With reference to the deterioration or discount factor of the open flow potential constant as such occurs in the gas deliverability formula, this for the most part has been an unexplored subject. Although the issue first appeared in the Kansas Hugoton field, where such was surmised but only recently resolved, this situation of a deterioration of the gas deliverability constant can occur wherever dry gas production from a tight sand is encountered. The first concerted attacks upon this problem were the presentations of Hurst' and Goodson' before the Kansas Corporation Commission to show that transient fluid flow and unsteady-state flow formulas prevailed. This was amplified later before the Federal Power Commission3 to show that this deterioration factor could be identified from pressure build-up curves. This has been reported by McMahon.4 Its importance to the industry merits the review of these essential features in completing the program on the aspects of gas deliverability. Finally, as illustrated here, for a low permeability formation such as the Knox Bromide field where the gas is rich, representing some 165 bbl of condensate per MMcf of effluent gas, the gas deliverability can be of limited extent in the life of the field, leaving substantial amounts of condensate and gas unrecovered. In cases such as this, gas cycling is mandatory. This is particularly revealed by the fluid mechanics introduced here, employing factual field as well as laboratory data, to show this-restriction upon gas deliverability. PRESSURE DEPLETION What will now be offered is the study of gas deliver-

By John C. Sawyer

The mechanism of catastrophic oxidation of chromium and 446 stainless steel is examined. Data are presented to show that accelerated oxidation of these two materials, as caused by lead oxide, can occur in the absence of a liquid layer contrary to presently accepted theory. An alternate theory is proposed in which the rate of accelerated oxidation is a function of the rate at which lead oxide destroys the protective oxide formed on the base metal. An example of the application of the theory is given for the catastrophic oxidation of chromium in the presence of lead oxide. WHEN stainless iron-, nickel-, or cobalt-base alloys are heated in air to moderate temperatures in the presence of certain metallic oxides, oxidation will proceed at an accelerated rate. This phenomenon, often called "catastrophic oxidation", is most pronounced for the stainless steels. With these alloys the condition is so severe that large masses of oxide will form on the surface of the alloy in 1 hr or less at temperatures of 1200o to 1700oF. While a number of oxides are known to cause this effect, PbO, V2O5, and Moo3 are the most familiar, having been the subject of one or more investigations which have appeared in the literature.1-7 In presenting the results of these investigations, many of the authors have offered possible explanations to account for the more rapid rate of oxidation observed; however, the liquid layer theory as proposed by Rathenau and Meijering 2 has been the most commonly accepted mechanism. The liquid layer theory proposes that a low-melting oxide layer is formed on the surface of the alloy as the result of the interaction of the alloy oxide and the contaminating oxide. When the temperature of oxidation is above the melting point of the oxide on the surface, a liquid layer will form and oxidation will proceed at an accelerated rate. At temperatures below the melting point of the surface oxide, oxidation will proceed more slowly in the normal manner. It is argued that the rates of diffusion of oxygen and metal ions through the liquid layer are extremely rapid thereby accounting for the high rate of oxidation. Various experimental data have been presented to show that the temperature at which accelerated oxidation first becomes apparent coincides with the melting point of the eutectic oxide which would be present on the surface. Some exceptions have been observed, e.g., silver will oxidize in the presence of Moo3 at temperatures below the lowest melting eutectic; on the other hand, stainless steel will not be catastrophically oxidized at 1500oF in a molten bath of PbO and SiO2. In reviewing the various theories which have been used to explain catastrophic oxidation, Kubaschewski and Hopkins 8 favor the liquid layer theory, but note that, ".. .as experimental observations are not altogether in agreement with this theory (liquid layer theory), one should consider it a necessary but not a sufficient condition." In contemplating the liquid layer theory, it appears that sufficient evidence has not been presented to establish the theory beyond question. As a means of further clarification, a program of research was undertaken to determine in greater detail the mechanism of accelerated oxidation as caused by lead oxide. The first part of the program deals with a comparison of the oxidation of both AISI 446 stainless steel and chromium metal in the presence of lead oxide, vs the oxidation of these two materials in air alone. These comparisons are made at a number of different temperatures, most of which are below the melting point of the surface oxides. The second part of the program is concerned with a presentation of an alternate theory of accelerated oxidation exemplified by the system Cr-PbO-Air. PROCEDURE AND RESULTS Several experimental methods are commonly used to follow the progress of oxidation. One of these, the weight-gain method, was chosen for this work. This procedure requires that a specimen of the alloy be weighed, oxidized for a given period of time at an elevated temperature, and reweighed—the difference between the two weights being noted. The weight gain of the specimen represents the amount of oxygen acquired from the atmosphere to transform a portion of the specimen to oxide. In those cases where there is a tendency for the specimen or oxide to volatilize at the testing temperature, additional data must be collected so that a correction factor can be determined. This factor must be applied to the weight change in order to ascertain the actual amount of oxidation which has taken place. The specimens used for this work were 1 1/2 in.

Jan 1, 1963

By L. R. Raymond, G. G. Binder

One primary purpose of hydraulic fracturing as a well stimulation technique is to overcome formation damage. The literature provides ways of designing fracture treatments and evaluating their results but not of incorporating formation damage in vertically fractured wells. Results of an investigation of this problem are presented in this paper. Prediction of stimulation ratios in vertically fractured, damaged wells is accomplished with a mathematical model relating stimulation ratio to relative conductivity of fractures whose lengths are not more than about half the drainage radius of the well. Comparison of results from the new model to results in published predictions verify its utility; these results also show that the range of stimulation ratios that can be predicted for undamaged wells is extended to include relative conductivities of less than 300. This extension is important when using fracturing to stimulate wells with high production rates and high native formation permeabilities. For example, large increases in daily oil production rate can be obtained with stimulation ratio increases as low as 1.25. The importance of complete fracture fill-up (uniform proppant packing) is shown through use of the mathematical model. If, at the mouth of a fracture, only a small fraction (1/2 percent) of the total fracture length is not packed with proppant, nearly all the polential stimulation increase is lost. Proppant crushing, compaction and embedment have been shown in laboratory studies to be responsible for low fracture conductivities in wells producing from highly stressed formations. Equipment and methods for testing the effect of stress (overburden) on conductivity of fructures in consolidated and unconsolidated sands are discussed in this paper. Laboratory tests with simlilated fractures in cores from both types of formations showed that crushing, compaction and embedment seriously affect conductivity. Results indicate that similar laboratory tests should be made when accurate knowledge of fracture conductivity is needed to assure good stimulation results for important wells. The chief factor in stimulation ratio reduction was found to be overburden pressure, but the size and type of proppant and the hardness of the formation have significant effects. Fracture conductivity reductions of up to 50 percent were observed with sand propping fractures in consolidated cores; a reduction of 83 percent was measured for an unconsolidated core. The range of effective overburden pressures for which conductivities were measured was from 100 to 5,000 psi. An example fracture design and evaluation problem indicates the usefulness of considering formation damage in planning well stimulation jobs. When damage exists, but its extent and the degree of permeability reduction are not estimated from diagnostic tests, the formation permeability used in planning the job may lead to under-designing. As the example shows, too low a target stimulation ratio can lead to much lower production rates (by half) than could be attained otherwise. Solutions of equations representing several special cases of the mathematical model are presented in graphical form and details of the derivations of the equations are given in the Appendix. INTRODUCTION Since its inception in 1947, hydraulic fracturing has proven to be an effective and widely accepted stimulation technique. In the past 18 years the ability to execute a successful hydraulic fracturing treatment has been substantially increased. The development of design and evaluation procedures1,2 has been one of the major contributions to this increased skill. However, as the art of hydraulic fracturing has moved closer to a science, new problems concerning the design and evaluation of the optimal hydraulic fracturing treatment have arisen. Three questions are pertinent to these problems. I. How is a fracturing job evaluated in a damaged well? 2. What is the effect on the stimulation ratio of not filling the fracture in the vicinity of the wellbore? 3. What is the effect of overburden pressure on fracture conductivity and, consequently, the stimulation ratio? A primary objective of fracturing a well is to stimulate production by overcoming wellbore damage. Presently. however, there is no rational basis for designing or evaluating the optimal fracturing treatment in a damaged well. All present fracture design and evaluation techniques assume that proppants can be uniformly placed in fractures. This assumption may be in serious error, particularly for the portion of a fracture directly adjacent to the wellbore. In this area, turbulence of the injected fluid can cause the proppant to be swept farther into the fracture. Also, loss of fluid from the fracture to the

By K. A. Slagle

Hydraulic analysis of the wellbore has become increasingly inzportant for designing cementing operations and selecting equipment, materials and techniques to complenzent modern well-c-ompletion practices. Non-Newtonian fluid technology has advanced beyond the point where former empirical methods of analysis adequately define the hydraulic system and fluid properties. In view of these factors, this paper describes a series of rheological calculations which have been found practical, through field usage, for assistance in selecting a cementing program. A relatively simple laboratory method using standard viscometric equipment is suggested for determination of the rheological properties of slurries, and clrrta are presented on some of the more common cementitrg conzposition.A. A criterion for divergence from laminar-flow characteristics has been proposed. Usefulness of the calculations is indicated by examples of cementing operations where they have been used. INTRODUCTION With the changing aspects of well-completion practices during the past few years, it has been increasingly important to have a relatively simple method of analyzing the flow conditions existing in the well during cementing operations. This is particularly true in view of the improved economics toward which most of the changes have been directed. Rheological characteristics of slurries used for cementing should be a major consideration in the trend toward smaller casing sizes, either single or multiple strings. Receiving increased attention is the practice advocated in 1948 by Howard and Clark' of attaining turbulent flow with the fluids circulated during a primary cementing operation. While there may still be a difference of opinion concerning this technique, most available information indicates that superior primary-cementing results are generally obtained when high displacement rates are employed. Fluid properties of the slurry to be used must be available, as well as calculation methods, to determine what flow rates should be attained and the probable consequences in terms of frictional pressure and horsepower utilization. It would certainly be inappropriate to attempt high displacement velocities if sufficient pressure might be developed to create lost circulation. Since cementing slurries are non-Newtonian fluids, it is not possible to define their rheological or fluid properties by the single factor of viscosity and then make calculations for the quantities just described. Because the shear stress-shear rate ratio is not constant: it becomes necessary to establish at least two parameters for adequate fluid-flow calculations. It is not the purpose of this paper to delve into the mathematical development of non-Newtonian technology, nor to discuss the arbitrary classification system under which a single fluid may resemble two or three different classes depending upon experimental conditions. Rather, the intention is to present a useful series of calculations based on a concept applicable to both Newtonian fluids and to the preponderance of non-Newtonian fluids encountered in the oil-producing industry. Development of this approach was begun some 32 years ago,' and has most recently been brought to fruition by Metzner and his co-workers at the U. of Deleware. Some non-Newtonian fluids encountered in the petroleum industry, other than cementing slurries, have also had the benefit of this method of analysis."' The two parameters required to define the fluid are usually denoted by the symbols n' and K' and, for the purposes of this discussion, are called "flow behavior index" and "consistency index", respectively. These two slurry properties permit calculation of the Reynolds' number and the "critical" velocity, or the velocity at which departure from laminar flow begins. EXPERIMENTAL DETERMINATIONS The two principal instruments used for rheological studies are the pipeline (capillary-tube) viscometer and the rotational viscometer. When conveniently possible, a capillary-tube viscometer (where the pressure drop and flow rate of the material can be measured) is the better method for rigorous determination of the flow behavior index and consistency index for non-Newtonian fluids. With pressure-drop data at various flow rates, it is then possible to prepare a logarithmic plot of shear rate as the abscissa-shear stress as the ordinate. For fluids which do not exhibit time-dependency, these data will usually produce a straight line. The flow behavior index n' represents the slope of this line, while the consistency index K' becomes the intercept of this line at unity shear rate in accordance with the mathematical derivations associated with this concept of rheology. Due to the difficulties anticipated in maintaining a uniform, pumpable cement slurry for the time interval required to obtain measurements from the pipe viscometer, the n' and K' data reported herein were obtained using a direct-indicating rotational viscometer (Fig. 2). The

By D. M. Kehn

A method has been devloped for chromatographic analysis Of the vapor and liquid phases Of a a system containing methane to components having 20 or more carbon atoms. The method uses a windowed equilibrium cell in which volumetric phase behavior of the system can be observed accurately and from which small samples of gas or liquid can be withdrawn for analysis. Analyses are made using two chromatographs, one for the lighter and one for the heavier components in a sample. Combination of the two analyses yields a detailed analysis of the gas or liquid sample. The complexity of the condensate heavy ends is evident from the chromatograms of these fractions, and the predominance of the paraffin hydrocarborn serves as a useful marker in interpreting the chromatograms. The K-values obtained in this analytical method are presented for a high-pressure condensate system and predict closely the observed volumetric behavior of the system. INTRODUCTION Quantitative analysis of hydrocarbons from natural gas reservoirs is necessary for several reasons—to calculate the amount of sales gas produced, to calculate the amount of natural gasoline produced, to plan a liquid recovery system, or to calculate the potential economic value of a reservoir produced under one or more of several different conditions. Analysis of natural gas fluids produced to the surface consists of identifying and computing the mol fraction of each component of the mixture. Although methane is the predominant component, varying amounts of ethane, propane, butane, pentanes and heavier components are also present. Materials containing up to 30 carbon atoms occur in amounts which decrease with increasing molecular weight. However, the quantities of components in the 20 to 30 carbon atom range are usually so small that their importance is negligible, and they are undetect-able in natural gas by ordinary analytical methods. All the components up to those having 20 carbon atoms may sigsficantly affect phase behavior, however. Commonly, only the methane-through-pentane fraction is analyzed quantitatively for each component, while components heavier than Pentane are lumped and repored as "hexane- plus". Expensive, tedious techniques are required for analysis of this fraction. Consequently the detailed analyses needed for prediction of reservoir behavior are usually undertaken only when major gas fields are being developed. The need for complete analyses of condensate systems is apparent when it is recalled that most gas fields are produced by pressure depletion. As the pressure declines, some of the heavier hydrocarbons are lost as liquids which are in the reservoir. In many instances the amount of liquid in equilibrium with the gas phase at high pressure constitutes only 1 or 2 mol per cent of the total system. Flash calculations generally must predict the actual amount of liquid with an accuracy of a few per cent in order to be useful. This retrograde condensation has been understood for years, but accurate correlation methods to permit quantitative prediction of phase behavior in the retrograde region are not presently available. The increasing importance of natural gas has made accurate prediction of phase behavior and composition of produced natural gas streams an economic necessity. The work reported here was undertaken to provide a rapid, economical method for obtaining the vapor-liquid equilibrium information needed to predict accurately the composition of the fluids produced from a gas reservoir throughout its life. TO develop this method, a pressure cell equipped with windows was designed and built for observing the volumes of liquid and gas present at reservoir pressures and temperatures. Use was made of established chromatographic methods for rapid and detailed analysis of both phases. This paper describes the equipment and techniques developed for obtaining vapor-liquid equilibrium data, presents the results of analyses of a condensate system, and indicates the usefulness of these data in predicting hydrocarbon phase behavior. DESCRIPTION OF EQUIPMENT USED The equipment used in obtaining the required information on phase behavior and the complete analysis of hydrocarbon mixtures through C, will be described first, followed by a discussion of the operation of the equipment. It will be helpful, however, to consider first a brief outline of the technique used. A sample of separator gas and liquid is charged to the windowed cell (see Figs. 1 and 2) where volumetric equilibrium phase behavior at reservoir pressures and temperatures can be determined. Then samples of the coexisting phases are withdrawn. The methane-through-pentane fraction is analyzed with a chromatograph equipped with a hot-wire detector, and the pentane-plus fraction is analyzed with a second chromatograph equipped

Jan 1, 1965

By J. H. Swisher

Two recent papers in this journal1,2 contain experimental evidence for an anomaly in the concentration gradient for tracer diffusion. In both papers, the authors suggest that this anomaly is due to a Gibbs' absorption effect. Their hypothesis is that surface active tracer elements tend to remain in or near the surface adsorption layer, thereby altering the diffusion flux and concentration gradient. It is not clear how the anomaly can be explained in terms of an adsorption effect. Surface tension forces act parallel rather than perpendicular to a surface and therefore should affect only the rate of spreading of surface active agents tangentially across a surface. Frenkel3 has given a short treatment of surface tension as a driving force for surface diffusion. While the equilibrium concentration of a surface active agent at the surface of a solution is known to be higher than in the bulk, its chemical potential is necessarily the same. It is difficult to see how adsorption can result in an anomaly in the chemical potential gradient, which is the driving force for diffusion. A more detailed explanation by the authors of the adsorption mechanism is in order. A similar anomaly does not seem to arise where

Jan 1, 1970

By A. J. R. Curtis

THE Portland Cement Association was organized more than a third of a century ago by a group of cement manufacturers, to do cooperatively the educational and research work needed to ensure proper use of their product. Specifically, the Association has a threefold purpose: (1) to search out facts to ensure the best possible service from concrete; (2) to give the widest possible circulation to facts affecting the use of concrete; (3) to urge practical application of those facts on actual building projects. An organization of technically trained men conducts many research projects in the Association laboratories, interprets their findings and applies them practically in the field. The net effect of this work has been to improve the design and prolong the life of roads, bridges, industrial, commercial and public buildings, homes, farm structures and concrete products. The results of this technical research and experimentation are made available to the entire construction industry through bulletins and reports. Information is also released to the general public through newspapers, magazines and Association publications. In addition to a1 technical staff in the general office in Chicago, the Association has district offices in 22 cities. Field engineers cover 37 states, the District of Colum-bia and British Columbia, to give service to users of Portland cement.

Jan 1, 1937

By C. L. Colburn

Discovery is the first step in the location of the claim. The provision of the Revised Statutes (2320) is, " No location of a mining claim shall be made until the discovery of the vein or lode within the limits of the claim located." Strictly speaking, discovery may be defined as the finding of ore or metalliferous rock in place in a well-defined vein. This definition was too strict, so discovery extended later to cover such indications of the pregence of ore, within rock in place, as would justify an experienced miner in spending his time and money with a reasonable expectation of finding ore in paying quantities. According to Colorado statutes a discovery must show a well-defined crevice; in Arizona, a lode, deposit, or mineral in place; in Montana, a well-defined crevice or valuable depositi; in Nevada, a lode or deposit of mineral in place. It is wrong to require a discovery. An honest prospector, wishing to obey the law, finds himself compelled, in most cases, to evade this point. In Clear Creek district, Colorado, a quartz seam will constitute a discovery; in Butte, a red capping; in Leadville or Ely, it is any place where a man can find a piece of vacant ground big enough upon which to sink a . 10-ft. hole. If the vein or deposit outcrops a man can show a discovery, but if it does not outcrop it is foolish to compel him to show one; and this point has been gently side-stepped. Any hole 10 ft. deep now constitutes a discovery. It is no use having laws that the people cannot consistently ob_ey. No sane man will dig unless he expects to find mineral, and he should be protected while digging. He should be required to show that he has mineral ground only when he comes to patent.

Jan 1, 1915

By J. H. Wiggins

This paper first pictures the economic phase of evaporation losses and the actual evaporative conditions in handling and storing crude and gasoline in the United States; then follows a discussion of some of the theories of physics involved in evaporation loss and lastly an application of these theories to handling oil and gas on producing properties. GRANTING that about 600,000,000 bbl. of light oil will be produced in the United States this year and taking the Bureau of Mines' statement that 7 1/2 per cent. of the total crude production will be lost before the finished gasoline is shipped from the refinery, the volumetric evaporation will be 45,000,000 bbl. of the cream of the gasoline. This is a conservative figure and is equivalent to 1,890,000,000 gal. The real value of this liquid is at least 150 per cent. of the value of an equal volume of motor fuel. At only 10 c. per gal., the value lost is $189,000,000; at 15 c. per gal. the loss is $283,000,000. If 750,000,000 bbl. of light and heavy oil are produced here this year and the average price per barrel is $1.333, the gross return to producers will be $1,000,000,000 and the net returns about $200,000,000, if the cost of production is only $1 per barrel. Thus, the evaporation bill is about 20 per cent. of the gross income and is equal to the net income of the crude-oil producers. Two other comparisons with popular phases of the petroleum industry will help give an adequate conception of the evaporation problem. These are: cost of preventing evaporation compared to cost of cracked gasoline and volume of gasoline evaporated compared to volume of gasoline manufactured from natural gas.

Jan 7, 1924

By J. B. Umpleby

The subject of reservoir energy and its efficient utilization has been well explored in many papers. The present effort, therefore, is limited to a summary of existing information combined with an emphasis of the probability that the relative importance of controlling factors will change with advancing knowledge. Consequently the necessity for flexibility in laws and regulations, inherent in the problem, is emphasized. Definitions Many terms have been widely used in the literature without having been specifically defined. For example, confusion exists in the use of ((reservoir energy" and "gas energy." The latter is much more limited in meaning than the former. Other terms have been variously used. Consequently, I shall preface my remarks with definitions of a few of the more pertinent terms. Reservoir energy is that force or forces, active or potential, that is native to the reservoir and has the power to move oil through the reservoir rock. The energy may result from expanding gas, from hydrostatic head, from the weight of overburden, or from any other source. Gas energy is the expansive power of gas when pressure is reduced. It is one type of reservoir energy. An oil reservoir is that part of a geologic formation or formations in which oil occurs in commercial quantities wholly surrounded by nonproductive rock. The essence of this definition is effective separation rather than remoteness and under it oil reservoirs may be superimposed in the same oil pool. Conservation of reservoir energy means primarily its maximum use in the production of oil. Unit operation is a plan of development and production, which embraces an entire oil reservoir under a unity of engineering control. It is distinct from unitization, which has to do with arrangements of organization and equities to make unit operation possible in areas of divided ownership.

Jan 1, 1934

By E. A. Beck

(New York Meeting. February, 1913.) For a number of years many attempts have been made to use thermit in order to do away with piping in ingots. Some of these attempts were successful, while others did not give the expected results. Nearly every plant had its own method of using the thermit, and no special care was taken to study, the results or to find the causes for lack of success. Formerly the principle of the process was to decrease the piping by introducing a can filled with thermit, attached to an iron rod, into the head of the ingot directly after it bad been poured. In this case the thermit reaction took place in the upper part of the ingot, and it was thought that through the heat produced the head would keep liquid longer and piping thus be reduced. In other words, the aim was to keep the head of the ingot open by making use of the heat of the thermit reaction, which would thereby give the gases in the steel sufficient time to escape. This result can be attained by the application of a large enough quantity of thermit, but it would not be economical in general practice, and could only be used for high-grade material. Many steel-makers abroad and in this country have had this experience. The Th. Goldschmidt A. G., Germany, has, therefore, made a special study of this question with the co-operation of a well-known steel company, and has worked out a new method for. the application of thermit for this purpose. The results obtained have been most satisfactory and reliable, and this- process is now used in Germany on a large scale in many prominent steel-works.

Jan 4, 1913

By J. S. Miller

THIS paper describes the method of mining a steeply pitching anthracite seam on a heavy pitch in the Orchard vein in No. 1 Tunnel of the Lehigh Coal and Navigation Co. The Orchard vein in the Nesquehoning district has a thickness of about 15 ft. on the level of the gangway, which is sufficient thickness for the gangway to be driven full width in coal. Above the gangway, the vein becomes thinner and near the surface is about 8 ft. thick. The coal is of good hard quality and carries a fairly good roof. The pitch of the vein is between 65° and 70°. Usually the breast-and-pillar method has been employed in the mining of the steeply pitching veins in this section. This method produced good results as far as the mining of the breast was concerned but the recovery of the pillar was difficult as to full extraction and expensive as regards costs. To recover these pillars after the breasts were driven, three methods were commonly employed; they were known as the pillar-breast method, pillar-skipping method, and pillar-chute method. The pillar-breast method consisted in putting a battery in one corner of the pillar (Fig. 1), coupling the manways A and B of the two adjacent breasts for two or three lengths ahead of the working face of the pillar being cut, and working the pillar as a breast. This method was used by the more skilled miners of the earlier days but has practically been abandoned. A slight variation of this method is used to some extent. In this case, the pillars are left wider than ordinarily and of sufficient width for the full-width breast to be driven in and a small pillar left on each side of the pillar breast between it and the regular breasts. With the completion of the "pillar breast," the ribs are drilled full of holes, loaded, and fired.

Jan 3, 1925