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By E. R. Parker, C. F. Riisness

That grain size has a great effect on the mechanical properties of metals has been recognized for a long time. Bassett and Davis1 in 1919 did excellent work in determining the effect of grain size on the hardness of brass. About the same time Jeffries2 and Sykes3 ascertained the effect of grain size on the strength and ductility of several metals at temperatures ranging from 80°K. to their melting points. When creep was recognized as an important property of metals, those engaged in the study of this property tried to determine the effect of grain size4-9 on creep rates. Unfortunately, most of the investigations were conducted on only two grain sizes, often designated simply as "fine" and "coarse." It is well known that at high temperatures coarse-grained test bars creep less than fine-grained bars. The relation between grain size and size of test bar, however, has been frequently overlooked. In his early work, Jeffries2 showed that the number of grains in the cross section has a more important influence on the properties of the material than the actual grain size. More recently Hanson and Sandfordl0 and Pell-Walpole,ll in their measurements of the creep and tensile properties of tin, tested a wide range of grain sizes and correlated the grain size with the strength. Hanson9 later established the relation between the number of grains in the cross section and the creep rate. At high temperatures, generally a coarsegrained structure is considered superior in creep to a fine-grained structure, but it is evident that for a given bar size continuously increasing the grain size will

Jan 1, 1944

By W. M. Rust, W. D, D. W. Mounce

The almost universal acceptance of electrical logging by the petroleum industry calls for a critical examination of the physical bases of the common methods. This is particularly needed for the natural potential log. The conventional explanations are based on the phenomena of electrofiltration and electro-osmosis. However, experimental data show that they fail to give a basis that is quantitatively sound. Moreover, they lead to interpretations of details of electrical logs that are erroneous. It was found experimentally that when a plug of shale is placed in a chain of dissimilar electrolytes, a current flow results. Experiments on oil-well cores and fluids similar to those existing in wells show that potentials are set up which are in reasonable agreement with those encountered in electrical logging. Doubtless other sources of potential are important but this explanation not only accounts for much of the potential but also clarifies some fairly familiar examples of misinterpretations. Introduction The extraordinary value of electrical well logging as a tool for petroleum engineers and geologists is now so uni- versally recognized that it is not necessary to point out the ways in which it can be useful. It is sufficient to mention only the saving that has resulted from the elimination of much coring that would have been necessary under former practices and the considerable additions to reserves resulting from the discovery of sands missed in coring. Paradoxically, the very remarkable success that has resulted from the application of electrical logging to correlation and completion problems has cost some of its most consistent users dearly.' The fact that some operators have placed unwarranted faith in erroneous interpretations of electrical logs does not reduce the value of the logs. It should, however, make one pause long enough to ask why experienced users should be misled. The answer to this question is not hard to find. In nearly every case, the fault has been oversimplification. This is illustrated very aptly by the familiar interpretation and theory of the natural potential log. Recording and Interpreting Logs The natural potential log is extremely simple to record precisely enough for all present-day uses. One needs only an electrode, a cable to lower the electrode through the drilling mud, a recording meter and a surface ground connection. The electrode can be elaborate but need not be. A simple brass rod 2 in, in diameter and 2 or 3 in. long is quite satisfactory. The cable need not be particularly well insulated, nor need it have a very low resistance. The recorder can be a vacuum-tube 1 References are at the end of the paper.

Jan 1, 1944

By H. H. Kaveler

A summary of the reservoir engineering and related geologic data on the Schuler field, Union County, Arkansas, is presented here in a manner intended to interest both technical and nontechnical readers. The Cotton Valley formation and the Reynolds oolite are oil-productive formations in the Schuler field, but the Jones sand pool, at a depth of 7500 ft., developed with 146 wells on zo-acre spacing, is the reservoir of principal interest. The Jones sand sandstone reservoir is an anticlinal trap typically gas-drive or depletion type in performance. The core analyses from 88 per cent of the wells drilled, together with drilling time and electric-log data, yield an accurate estimate of the "productive" sand thickness and its areal distribution over the pool. Accurate production statistics, monthly reservoir-pressure surveys, and bottom-hole sample analyses when correlated by the "material-balance equation" show unusually good agreement with that principle. Estimates of oil initially in place made by the material-balance method and the sand-volume method are in good agreement at 116 to rzo million barrels. The reservoir-pressure history of the pool reflects the reaction of a reservoir to production, proration and secondary-recovery practices. The cost of the extensive program of reservoir study in the Jones sand pool has been estimated, in order to emphasize the value derived from such an investment through better understanding of a reservoir's reaction to production practices. Unit operation of 140 of the 146 Jones sand wells made possible an effective unitized gas-injection pressure-maintenance program. Res-ervoir-pressure decline was arrested, natural flow was maintained, and pumping and lease equipment were conserved. An increased ultimate recovery of zo million barrels beyond the estimated 34 million barrels primary recovery is indicated at present. Extension of the Jones sand unit to include the undeveloped Cotton Valley formation will permit additional recovery of otherwise uneconomic reserves of oil through wells no longer required in the Jones sand operations. Introduction The Schuler field comprises approximately 4000 acres in and about sec. 18, T. 18 S., R. 17 W. in west central Union County, Arkansas. Three reservoirs are procluctive of oil and gas: the Cotton Valley formation, the Jones sand, and the Reynolds oolite section of the Smackover limestone. The Jones sand pool is the most important reservoir from an engineering viewpoint. It possesses the traditional and somewhat classic characteristics usually associated with an anticlinal trap. Development and operations have followed the dictates of advanced engineering practices. The pool has attracted attention because of the unusually detailed reservoir data obtained, its interesting production history, and the success of the unitized gas-injection pres-sure-maintenance operation now being carried out. The purpose of this paper is to present a summary of the engineering data relating to the field, with particular reference to the more interesting general applications of

Jan 1, 1944

By E. Brunner, G. L. Hassler, T. J. Deahl

The capillary effects in reservoir rock are discussed in terms of the pressures they cause in sandstones and dolomites. Data for the two-phase case (oil-gas or water-gas) and for the three-phase case (oil, water and gas in rock) are used to demonstrate that in one sense the wetting preference of a rock depends on its saturation. The nature of capillary hysteresis is described for partially stable conditions, and the concept is enlarged. Reproducibly measurable pressures include the "capillary pressure," which is the pressure difference between any two phases that are each interconnected; the "threshold pressure," necessary to force a nonwetting phase through partially saturated rock; the "displacement pressure," which is that special case of the threshold pressure in which both phases fully saturate separate portions of the rock. Displacement pressure is equal to the minimum value of the "capillary pressure." The theory of flow including capillary forces is developed at the producing surface of a well to reveal the presence there of a pressure discontinuity in the gas (or other nonwetting) phase that can be controlled to the end that more oil may be poduced from an oil field. Experiments with packed sand-flow tubes having artificial producing surfaces support the theory. Introduction The basic surface quantities acting in an oil field are two: namely, surface tensions and contact angles. These are the quantities, variously expressed, and particularized as spreading forces, adhesion tensions, heats of wetting, etc., which are measured in the laboratory by techniques mostly confined to flat or circularly cylindrical surfaces. Such measurements have not had the extensive engineering application they seem to deserve because in most practical cases they are unavoidably compounded with the complex and unapproached subject of the internal shape of the interstices of rock. In this paper it is intended that the pressure differences developed in rock by capillarity be examined, defined, and given some engineering use in terms of some new measurements that have been made. Such pressure differences—namely, the capillary pressure, the displacement pressure and the threshold pressure—seem to provide a proper contact between the basic molecular quantities and the oil field. While certain modifications of usage will be undertaken, the present effort rests upon the background of work by the U. S. Geological Survey,l by Versluys, and especially by W. 0. Smith, 3,4,5 which has been reviewed recently in papers by Leverett.=s7 The most important concept of pressure difference is the capillary pressure, a function of saturation that expresses the pressure difference between the interconnected phases in a rock. It is often measured when water and air are the fluids present, but it can be measured with other fluids. A number of curves of capillary pressure have recently been measured by a method which it is intended shall be published in a later paper. Since heretofore capillary-pressure measurements upon rock have not been

Jan 1, 1944

By Robert B. Bossler, Parke A. Dickey

The presence of connate water in oil sands is of far greater practical significance in secondary oil-recovery operations than it is in primary operations. The percentage saturations of oil, water, and gas in a depleted field determine whether it will be economically possible to recover oil by secondary methods, and whether water-flooding or gas-driving, or either, will be successful. It is suggested that economic recovery of oil by secondary water-flooding can occur only when a rich bank of oil is formed by the encroachingm water. If the sand has a greater effective permeability to water than it has to oil before flooding, a bank will not be formed, and water-flooding will not be successful, although gas-driving may be. Published results of laboratory work indicate that the effective permeability of a sand to oil and water depends primarily on the saturation of the sand by these phases. They also indicate that a small difference in relative saturation produces a large difference in effective permeability to the phase in question. There thus exists a critical range of saturations, wherein a small change in oil and water content of the sands will make water-flooding possible or impossible. In gas-drive operations the water saturation is less critical but no less important. The presence of connate water in a sand increases the proportion of the residual oil that may be recovered by gas drive. Sands containing oil saturations too low and water saturations too high to make water-flooding possible can often be subjected to gas drive with economic recovery of oil. The results of laboratory work on test samples that do not contain water cannot be applied to normal field operations. More tests on cores containing water as well as oil are desirable, and the improvement of coring technique is necessary. However, sufficient data are already available to enable an operator to use core data intelligently in estimating the chances of a secondary oil-recovery program. Introduction In recent years laboratory work has led to a much better understanding of the principles of oil-reservoir performance. The general principles of the expulsion of oil from sandstone by gas or water were developed by geologists of the Second Geological Survey of Pennsylvania in the 1870lsl but only recently has the mechanism of gas or water drive been intensively investigated. Most published articles have large the facts established in the labora tory to the primary production of oil from flush fields- This Paper is not based on any new observations, but is an attempt to apply some of the conclusions obtained in the laboratory and described in the literature to the recovery of oil from depleted pools by secondary methods. One of the most important factors that determine whether or not a secondary-recovery operation is economically successful is the ratio of injected fluid to oil recovered. This ratio may be expressed as the over-all or cumulative gas-oil ratio if gas is the driving medium, or water-oil ratio if water is the driving medium. Recent theoretical and experimental work has shown that the relative amounts of

Jan 1, 1944

By P. E. Fitzgerald, Dana G. Hefley

An apparatus has been developed which permits selective acidizing of producing formations and determination of the relative permeability of a formation by fluid injection. This apparatus, known as the "Electric Pilot," is an electrical fluid-interface locator, the electrical circuit of which is completed when the elec-tcodes in the well are in contact with a conductive fluid, but is not completed when immersed in a nonconductive fluid. Results are given for a number of typical acidizing applications in which the interface locator was used to control the acid. Description of the method used in making a permeability survey and the data obtained are also included. Introduction Early in the development of the acidizing industry it was recognized that one of the most important problems to be solved in the chemical treatment of any well was the determination of what part of the exposed section in the well should be treated and the selection of the technique that would insure treatment of the desired section. One of the first techniques adopted for assisting in proper placement of the acid, which is still widely used, is the method of confining the acid to the producing section by means of a column of oil, which is known as the Carr1 method of treatment, named for its inventor. In the Carr method it is not possible to selectively acidize a specific horizon in a multiple pay zone, so many improvements and modifications of the basic Carr technique were devised to accomplish this result. In order to overcome the possibility of the acid entering an undesirable section at the bottom of the well, organic gel plugs2 were introduced into the bottom of the well, which served to halt the entrance of the treating solution into these zones.3 These chemical gels later liquefied because of bacterial action and were removed from the well with the produced fluid. In fields where a gas cap existed, as in the Goldsmith field of Ector County, Texas) it was imperative that a treating technique be evolved that would confine the acid to the oil-producing zone below the gas cap. By so doing the oil-productive capacity of the wells could be improved without greatly increasing the gas production and this would lower the gas-oil ratio of the well. ~h, technique employed4 to achieve this effect utilized two pumps, one for pumping the chemicals down the tubing, the other to simultaneously force oil down the annular space to confine the acid to the oil pay, thus preventing the chemicals from entering the upper gas-bearing zones. Experience has indicated that gas wells and certain types of oil wells respond better to ''stage treating.'' This technique utilizes the introduction of a certain volume of acid and then allows the well to ''clean up99 before introduction of the next and usually successively larger stages. Where such methods are employed steps must be taken to keep a disproportionate share of the acid from entering the most permeable and previously treated Zones. A special tool

Jan 1, 1944

By L. S. Reid, R. L. Huntington, Chen Chun Ku

The simultaneous adsorption of water and hydrocarbon vapor from natural gas by three grades of alumina has been studied at atmospheric pressure and temperature. Results of this investigation reveal that the presence of water vapor in the gas inhibits the adsorption of hydrocarbon vapor, although the presence of the latter does not have a pronounced effect upon the adsorption of water vapor. Adsorption of water-hydrocarbon mixtures from gas is divided into three phases. In the first, both water and hydrocarbon vapor are adsorbed; in the second, adsorption of water vapor proceeds while desorption of hydrocarbon takes place; in the third phase, the adsorbyt approaches complete saturation with respect to both water and hydrocarbon vapors. Both theory and experimental data can be applied to design and operation of commercial dehydration plants, and an illustration is presented. Introduction Dehydration of natural gas becomes increasingly important as the operating pressures employed in gas processing and transmission are increased above 500 ib. per sq. in. Gas produced from high-pressure wells is saturated with water vapor when it leaves the reservoir and it continues into the processing plant or transmission system in a saturated condition because of the substantial decrease in temperature due to expansion at the wellhead. Usually this gas is accompanied by liquid water and hydrocarbons that have condensed with the change in temperature and pressure. Without dehydration, gas temperatures must be held at relatively high levels to prevent solidification of gas hydrates. According to Hammerschmidt's data8 on the relationship of pressure to the freezing point of natural-gas hydrates, the minimum safe operating temperatures range from 55' to go°F. for pressures ranging from 500 to 3000 lb. per sq. in., respectively. Often it is difficult to maintain gas temperatures above the hydrate-freezing temperature because of climatic conditions, unless flow-line heaters are installed. Also, in processing gas for its gasoline content at high pressures, it is desirable to employ operating temperatures lower than the hydrate-freezing point. In distributing high-pressure gas, the large pressure drop from line pressure to town-gate pressure often prbduces sufficient cooling to freeze the regulators and disrupt consumer service. Therefore, it is highly essential to dehydrate high-pressure natural gas if smooth and economical operation is to be maintained at all times. Few published data are available on the simultaneous adsorption of water and hydrocarbon vapors. The literature contains many mathematical expressions for rate of adsorption in various systems but a rational correlation of the existing rate

Jan 1, 1944

By Sidney A. Swensrud

The 24-in. crude-oil line. and- the 20-in. petroleum-products line, built as a war emergency by the United States Government and running from points in Texas to the New York-New Jersey-Philadelphia area, were constructed only because of the inability during the war to continue nor-inal ocean tanker movements from the Gulf Coast to the East Coast. The postwar disposition of these lines may be considered as one of the important problems of the postwar readjustments in the oil industry, if not the most important one. In the first place there appear to be many complications in keeping the lines in crude-oil or petroleum-products service. This conclusion was reached also in a study by T. E. Swigart, President of Shell Pipeline Corporation.' Since the lines are too largc for any one company to utilize, and since it appears likely that a surplus rather than a deficiency of tankers will exist after the war, most companies probably will feel that they can achieve lower costs and more satisfactoiy results from the resumption of tanker movements to the East Coast rather than by endeavoring to take over or utilize the capacity in the large pipe lines under some tariff-rate structure. As for using the lines for making deliveries to the middle west or central eastern areas, it would appear that when the war is over and normal transportation arrangements can be resumed, there will be no need of any extra capacity for such deliveries. Therefore, the War Emergency lines could be utilized for this purpose only if privately owned pipe lines and other transportation facilities were to be displaced. Against this rather unprepossessing prospect for use in petroleum or product service is the fact that at or near the source of the lines lie the greatest developed gas reserves in the world, for much of which there is at present no satisfactory market outlet; and at the other end of the lines lies one of the greatest concentrations of population in the world, which is not now served by natural gas. These who have been fortunate enough to use natural gas can have little doubt of its desirability as a domestic fuel. An analysis of the market potentialities and comparison with other areas where natural gas is being distributed, and where it has displaced manufactured gas, makes it seem clear beyond question that the full capacity of both of the large-diameter lines could be fully utilized in this service, and this without creating any undue drain upon the gas reserves of the nation. On the basis of an estimated capacity of roo to 120 billion cubic feet per year, the gas that might be marketed through these lines would amount to only 3 to 4 per cent of the total con-

Jan 1, 1944

By Winthrop P. Haynes

The symposium on production for the year 1943 contains few papers on the foreign situation. It has always been the policy of officers in charge of the symposium to refrain from publishing information that might possibly injure national or private interests. At the close of the war we hope again to publish full and accurate records of production abroad. A noteworthy feature of the reports on Texas this year is the map on page 469, which shows the districts covered by the statistics. Excerpts from Circular to Authors In order to facilitate interpretation of the data in this chapter, we print the following excerpts from the Circular to Authors. The field is the unit in this tabulation. In cases of fields extending across State boundaries, such as Rodessa, it is suggested that each State author treat the section of the field in his State as a unit, and by a footnote indicate that the field extends into an adjacent State. Each place in the table may represent one of three possibilities; either the proper entry is determinable and can be supplied by the author, or an approximate figure can be supplied which is the author's best guess and should be entered followed by an x, or it does not apply to the particular field and the space is left blank. Contributions of great value may be made by the author in many cases where entries are not subject to precise determina-tion. In such cases the author should use his good judgment and make the best entry possible under the circumstances. The entry of a zero is a positive declaration, and it is an important declaration where it is in order. It is thought that the nearest whole numbers are suficiently accurate for our purposes except as to percentage of sulphur in oil. If an author desires to report any other figures to tenths, he may do so. The quantity of gas produced should include, where possible, gas sold or otherwise marketed, and gas blown into the air, burned as flares or otherwise wasted. Segregation of these figures would be interesting if the authors can make such segregation. In any event, the figures should represent as nearly as possible the total quantity of gas removed from the reservoir. Under the columns on ''Depth," the average depth to the top of the productive zones and to the bottom of the productive wells, when subtracted, should give the approximate thickness of the productive zone. For fields where this is not true because of unusually high dip or for some other reasons, it is suggested that the authors indicate in their text the approximate average thickness of the productive zone. The net thickness of the producing formation should be the thickness of the producing zone, less the estimated amount to cover the portions of the zone that do not yield oil, such as dense shales, etc. It is recognized that for some fields the authors can only make rough guesses; in such cases, they should enter their best estimate followed by an x. Average production per acre-foot need not be reported as it can be calculated by those interested from the figures given. In classifying wells as to producing methods, enter all wells that are not "flowing" in the column headed "Artificial Lift." If possible, add footnotes to indicate whether the lift is "pumping," "gas lift" or "air lift."

Jan 1, 1944

By Max C. Eastman, V. H. Wilhelm

California had a record year in production and drilling activity, but the results have not been sufficient to keep up with the enormous increase in demand due to war activity. During the year, 164 dry wildcats were drilled, 80 dry wells in proved areas, 31 gas wells, and 1158 successful oil-well completions for a total of 1433 wells, compared with a total of 765 in 1942. With new discoveries of only 20,000,000 and production of 283,000,000 bbl. for the year, total reserves of California oil have decreased more than 250,000,000 bbl. However, revised estimates of the reserves of old fields indicate an increase in the state's reserves of I00,000,000 barrels. The completion of 1158 wells has served only to maintain the maximum efficient daily rate of production at 800,000 barrels. There is evidence in many fields that oil is being withdrawn too rapidly to obtain the maximum recovery, and more rapidly than is conducive to good production practice. Statistics for 1943 as compared with I942 are shown in the table in the next column, Supply and Demand Steadily mounting needs of the military forces and increased industrial consumption raised total demand for all petroleum products on the Pacific Coast to 914,000 bbl. daily in 1943. That all-time record demand was 149,ooo bbl. daily higher than in 1942 and 214,000 bbl. daily above 1941 demand. Despite restrictions due to shortages of critical material, crude-oil production was boosted from 680,000 bbl. daily in 1942 to 779,000 bbl. daily in 1943, the highest level in 15 years. However, the new crude supply plus natural gasoline production and imports from other states totaled only 840,000 bbl. daily, leaving a deficiency between supply and demand of 74,000 bbl. daily. That shortage had to be made up by withdrawals from inventories, which had been steadily depleted during the previous four years. Aboveground reserves, which totaled 159,574,000 bbl. on Jan. I, 1939, were down to ~8.000,000, bbl. at the end of 1943. Significantly enough, the greater part of that decrease occurred during the last six months of I9437 when more than 23,000,000 bbl. was taken from inventories of both crude and products. Although the size of total inventories on Dec. 31, 1943 might appear substantial, about 65 per

Jan 1, 1944

By Charles W. Carter, Alfred H. Bell

In 1943, Illinois produced 82,256,000 bbl. of oil, or 5.5 per cent of the total for the United States, and ranked sixth in the nation in oil production. This represents a decline of 23 per cent from 1942, when the total Illinois production was 106,ggo,o~~ bbl. and Illinois ranked fifth. The daily average production for 1943 was approximately 225,000 bbl. Daily averages by months were as follows: Jan......... 238,000 July......... 218,000 Feb......... 240,000 Aug......... 216,000 Mar......... 237,qoo Sept........ 220,ooo Apr......... 230,000 Oct......... 220,000 May....... 221,000 Nov......... 223,000 June......; . 222,000 Dec......... z18,ooo This shows that most of the decline during the year took place between March and May, and that for the last eight months of 1943 production has been essentially steady. This means that there has been enough production from new wells drilled to balance the natural decline of the Older wells. The trends of drilling and production are shown in Fig. I and Table 3.

Jan 1, 1944

By Theron Wasson

The oil and gas fields of Michigan that have been under development since 1925 are in an area that extends across the middle of the lower peninsula from northeast to southwest, a distance of about 200 miles, and with a width of about 80 miles. In 19 years 70 fields have been discovered. Most of these are relatively small when compared with other oil-producing areas. This is borne out by the fact that since the first wells were drilled these fields have produced a total of only 204,000,000 bbl. However, Michigan is still maintaining its production, for during the past five years the annual production has remained fairly constant at approximately 20,000,000 bbl. Production for 1943, as reported by the Bureau of Mines, was 20,682,000 barrels. Roughly, one third oi Michigan's production in 1943 came from the Reed City field, which was discovered in 1941. During the year, 237 oil wells were completed in Michigan in 1943. The decrease of 56 from the 1942 total is probably due to the continuance of Government regulations requiring a 40-acre spacing pattern over most of the state. Fig. I shows the principal oil and gas fields of Michigan, and the columnar section, Fig. 2, shows the principal producing horizons in relation to the section drilled. The data of Table I and Table 2 have been carefully checked with previous reports to eliminate errors. Six new producing areas were discovered during 1943 and five areas discovered in 1942 were developed during the year. Both the new discoveries and the 1942 discoveries that were developed appear to be small and relatively unimportant. Goodwell Field.—The best discovery of the year is the Goodwell field, T. 14 N., R. 11 W., Goodwell township, Newaygo County. This small structure was located by core testing done by The Pure Oil Co. in 1942 and early 1943. The first producing well, C. R. Harris No. I, was completed on July 5, 1943, ill the Traverse limestone at a total depth of 2742 ft., with ail estimated potential of 1100 bbl. per day. By the end of the year, 18 wells had been completed in this field and approximately 281,000 bbl. of oil produced. The field operated under proration of 262 bbl. per day per well from Oct. I to Dec. I; 150 bbl. per day per well after that date. Woodville Field.—The small Woodville pool, T. 15 N., R. 11 W., 3 miles north of the Goodwell field, was discovered by core testing by the Ohio Oil Co. The discovery well was completed on May 5, 1943, flowing 650 bbl. of fluid, including 18 per cent salt water the first 18 hr., from the Traverse limestone at a depth of 2810 to 2815 ft. Seven wells had been completed by the end of the year and 67,000 bbl. of oil had been produced. Development is now practically at a standstill because further drilling does not aDDear economically iustified.

Jan 1, 1944

By A. H. Geisler, F. Keller

Some of the important changes that take lace in the structure of aluminum alloys are largely submicroscopic in character. This is especially true of the changes that accompany age-hardening and recrys-tallization. Although improved metal-lographic practices have been helpful in indicating some of these changes indirectly, results are limited by the resolving power of optical microscope lenses. The electron microscope, however, provides a new and important means for investigating the fine structure of metals in a range not possible heretofore. It is anticipated that this microscope will yield new and useful information to metallurgists when suitable techniques are developed to utilize its very high resolving power. Several unique methods have been devised to permit the examination of the structure of opaque samples by the electron microscope. These are all based 011 the principle of producing a very thin film that represents the prepared surface of the opaque metal sample, which can be examined in the transmission microscope; however, the available methods fall into three categories, depending on the manner in which the film is obtained. With the oxide-film method developed by Mah13-l7 a very thin surface layer of the metallographic sample is converted into oxide by a thermal, chcmical or anodic treatment. .After removal from the metal sample by one of the special techniques described by Evans,l9 this oxide film is examined in the electron microscope, and is found to portray the structure of the original metal surface. Films formed on aluminum,8,l7 nicke1,7 iron3,8,9 and a nickel-beryllium alloyl1 by heating; films formed on iron8,9 by chemical action; and films formed on aluminum3-'" by anodic oxidation, have been examined. The other two are more recent methods developed principally in this country; they consist in making the thin film in the form of a mold or replica of the surface contour of an etched sample. With the negative replica method the thin film is made directly on the sample; with the positive replica method it is made on a negative reproduction of the sample. With both methods, variations in the contour of the metal sample, caused mainly by etching, produce variations in the thickness of the surface replica. Because of the direct dependence of the amount of scattering of the illuminating electrons upon the thickness of the film penetrated, only the variations in thickness of the replica are responsible for tones in the electron image. Negative replicas are made by forming a thin film of some suitable material directly on the polished and etched metal sample, and derive their name from the fact that after removal from the sample they have the high and low points in the sample reversed, as shown in Fig. I. Nega-

Jan 1, 1944

By R. H. Brown, F. Keller

Because of the extensive use of Alclad 24s alloy sheet in aircraft construction, there is much interest in the metallurgical changes caused by heat-treatment of this product.1, 2 One of these changes is the result of the diffusion of soluble elements from the core into the coating during treatment. This paper deals with the thermal treatments that may influence diffusion and with the practical effects of diffusion on the serviceability of the product. As is well known, Alclad 24s-T sheet has a core of high-strength alloy combined with surface layers of relatively pure aluminum. The microstructure of a cross section of this product is shown by Fig. I. Not only does the relatively high-purity coating have a high resistance to corrosion, and hence serves as a mechanical barrier between the core metal and the corroding environment, but in addition this coating exerts electrochemical protection over areas where the core may be exposed, such as cut edges. In addition, the coating affords electrochemical protection to projecting heads of A17s-T, 17s-T and 24s-T rivets, or attached members made from these alloys. Under some conditions of heat-treatment, however, diffusion of copper into the coating will alter the electrochemical relationship between the coating and the core to the extent that only partial protection will be obtained under some corrosive conditions. The reason for the electrochemical protection lies in the fact that the coating layers of pure aluminum are anodic to the alloy core. The addition of copper to aluminum produces alloys in which the potential is lower than that of the pure metal. Moreover, as the amount of copper in solid solution in 24s alloy is increased, the potential of the alloy becomes more cathodic. When heat-treated at 920°F. and quenched in cold water, 24s-T is about 0.16 volt cathodic to pure aluminum. However, copper will diffuse from the core into the coating, and if it reaches the surface the potential will be altered in a cathodic direction. Thus the potential difference between the core and coating may be less than 0.16 volt, depending uponIthe thickness of the coating, and the time and temperature of heat-treatment. Of the methods available for determining the extent of diffusion of copper from the core into the coating of Alclad 24s-T, two are generally used; namely, the metallo-graphic and the solution potential methods.3 Metallographic Methods Metallographic methods will reveal the progress of diffusion of copper into the coating. For instance, the diffusion zone in the coating intermediate between the coating surface and the core is shown in Fig. I. This photomicrograph is of a polished and etched cross section of 0.040-in. Alclad 24s-T sheet. Diffusion proceeds into the coating more rapidly along the grain boundaries than through the body of the grains. Consequently, the diffusion zone is not of uniform width

Jan 1, 1944

By Marie L. V. Gayler

Without diffusion taking place in liquid metals and alloys, no castings could be made; it is therefore the most important factor affecting the structure of metals. Diffusion involves the interchange of atoms, a process which takes place during the life history of an ingot. In the liquid, atoms are in a state of high thermal agitation, but this thermal vibration is reduced in amplitude with falling temperature. When solidification sets in, the atoms arrange themselves on an ordered space lattice and the changes in structure which take place in the solid are due to the interchange of atoms on this space lattice. The rate of atomic interchange—e.g., of diffusion—is most rapid at temperatures close to the melting point and decelerates as the temperature is lowered. At room temperature, the rate of diffusion is practically negligible in most alloys, and any change in structure can only be brought about by using methods which will accelerate the rate of diffusion. The rate of diffusion depends on three factors (I) temperature; (2) concentration gradient and (3) activation energy. The growth of grains and particles in the solid alloy also depend on these factors and are therefore intimately associated with diffusion. The rate of homogenization in a cast alloy depends on several factors, such as: (I) rate of solidification, which involves grain and particle size which, in their turn, depend on diffusion: (2) the nature of the constituents; (3) the temperature interval between the melting point of the metal or alloy and the temperature at which it is being heat-treated. It is well known that coarse, cast structures are extremely difficult—if possible— to homogenize, and the finer the grain size and particle size, the more readily solid solution will take place. The rate of diffusion depends, also, largely on the nature of the constituents; for instance, copper and magnesium form solid solutions with aluminum quite readily but nickel and iron do not; neither do certain intermetallic compounds, such as alpha and beta FeSi. Furthermore, the actual formation of intermetallic compounds may be a very slow process, particularly when they are formed in the solid state as equilibrium products. For example, BFeSi is formed in the solid as the result of the reaction aFeSi + A1 —+ PFeSi. The particles of aFeSi become surrounded with a reaction ring of PFeSi. This layer is formed as the result of diffusion of atoms taking place between the aluminum matrix and aFeSi. As the amount of aFeSi surrounding the core of aFeSi increases the concentration gradient becomes low and so the rate of diffusion of atoms also decreases until it practically ceases. This occurs after a comparatively thin layer of ßFeSi has been formed. It follows that when intermetallic compounds of this type are formed in the solid, as the result of diffusion, it is generally impossible ever to attain equilibrium, since the forma-

Jan 1, 1944

By A. L. Marshall, F. J Norton

The object of this investigation was to make a comprehensive study of the degassing of molybdenum in order to determine how rigorous a treatment was necessary to completely remove sorbed gases from molybdenum electrodes in vacuum tubes. Some work has also been done with tungsten, nickel, iron and carbon. As a logical development of this work it has been shown that the gas is present throughout the body of the metal and a study has been made of the solubility of nitrogen in molybdenum and tungsten and the rate, of diffusion of nitrogen through molybdenum has been calculated. Tests were made on molybdenum from all the commercial sources and no difference was discovered in the nature of the gases present, the amounts or the ease of removal. The reason for this was apparent when a study was made of the manner in which gases are absorbed by gas-free molybdenum. It is necessary to heat molybdenum to 1760°C. in a vacuum of the order of 0.001 micron for a time which varies lineally with the thickness, in order to obtain a condition in which no further gas is evolved by the sample. A sample so degassed can be handled and subsequently assembled in a tube and then degassed readily. The gases obtained from molybdenum are carbon monoxide and nitrogen, the nitrogen being the more difficult to remove. Apparatus and Technique The apparatus is shown in Figs. I and 2. It consisted of two units, a degassing system and an analytical system. Each had a bake-out oven, as shown surrounding the systems in the sketches. The system , will be traced, starting from the sample in the degassing system. A water-cooled quartz chamber surrounded the sample. The high-frequency coil, which heated the sample, extended only around this chamber and was cooled by an air blast. High-frequency power of 1800-meter wave length was obtained from a self-rectifying oscillator circuit with a maximum power input of 20 kw. A graded seal connected the quartz to the rest of the apparatus, which was of hard glass. The temperature of the molybdenum sample was observed by an optical pyrometer through an optical window about 40 cm. distant from the sample. Since the object viewed under these conditions was not a black body, true temperature was not observed, but the so-called "brightness temperature." The correction of this to true temperature is discussed in a later section. The apparatus was taken apart just above the graded seal; the quartz chamber was slipped off, washed with nitric acid, water and alcohol, and dried by an air stream. The old sample was removed by unscrewing the lower nut, and the new

Jan 1, 1944

By Frederick N. Rhines

Because of the nature of the environments in which metals are handled, it is natural that gases should be suspected of intruding into metallurgical operations, there to produce effects both beneficial and detrimental. The problem of tracing and controlling such effects is often made difficult by the complexity of the conditions surrounding their occurrellce, even though the fundamental mechanisms invalved may be simple and of familiar type. Many gas-metal reactions are known to be implemented by Processes of diffusion. These form a homogeneous group of phenomena which become more readily understandable when viewed together, in that the knowledge gained from one serves to interpiet the next. It is the purpose of the present Paper to present, by means of examples drawn from practice, a brief survey of the ways in which gas-metal diffusion serves and obstructs the Purposes of the metal-fabricating industries. The selection of the cases described was made by consulting more than thirty-six practicing experts whose combined experience provided an extensive coverage of the field and who were in a position to supply examples of occurrences of present day interest. The response was generous and it is regrettable that space permits the description of only a limited number of typical examples with ' but brief mention of parallel cases. The Nature of Gas-metal Diffusion The term ugas-metal diffusion," although commonly used, is ambiguous in so far as it implies that a definite group of " substances may be identified as gases and may be expected to behave in a manner distinct from other substances in association with metals. "Gases" such as oxygen and hydrogen when diffusing through a liquid or solid metal are properly components of the liquid or solid solution; they behave as alloying elements and are not to be distinguished in their diffusion characteristics from other elements, except that each has an individual rate of diffusion. On the other hand, a number of metals in certain.temperature ranges are volatile to the extent that they may appear in the form of vapor in metallurgical operations. For the sake of greater definiteness, therefore, it will be convenient to regard as "gas-metal diffusion" any process in which the result depends upon one or more of the diffusing elements appearing, at some stage, in the gaseous state, or as a compound gas. NO element, gaseous or otherwise, can diffuse through a liquid or solid metal unless it is at least slightly soluble in that metal. The elements of low atomic number

Jan 1, 1944

By Robert F. Mehl

Jan 1, 1944

By F. Keller, J. D. Edwards

The anodic treatment of aluminum presents problems of scientific as well as of commercial interest.l-3 Of particular interest is the fact that, during the anodic oxidation process, the oxide continues to form at the metal-oxide interface under any oxide previously formed. This has led to speculation as to the mechanism involved in the formation of the relatively thick oxide coatings that are used commercially for decorative or protective purposes. Furthermore, the ability of certain types of oxide coatings to adsorb dyes and other substances has stimulated research to determine the actual structure of these adsorptive coatings. It has been found that anodic oxide coatings on aluminum are composed essentially of aluminum oxide. They are formed by the action of oxygen ions penetrating to the metal surface during the electrolytic oxidation treatment. These coatings can be formed in a number of different electrolytes, as for example, those which contain sulphuric acid, chromic acid, oxalic acid, or boric acid. These are the commonest and most useful electrolytes employed commercially. Except for certain specific conditions of formation, the coatings in general have been found to be amorphous alumina, as far as can be determined by X-ray or electron-diffraction methods. Anodic oxidation processes can be arranged in three rather general classes if they are grouped in relation to the solvent action of the electrolyte on the coating.4 In the first class, the electrolyte has little or no solvent action on the coating that is formed. In general, coatings produced under such circumstances are nonporous and non-adsorptive. In the second class, the electrolyte exerts an appreciable solvent action on the coating. These coatings are porous and adsorptive. Finally, for the third class, the electrolyte tends to dissolve the coating about as rapidly as it is formed. This action produces electrolytic brightening or anodic polishing of the aluminum surface and at most leaves only a very thin film of oxide. The nonporous and nonadsorptive type of oxide film is represented by the coatings that are formed when solutions of boric acid are employed as the electrolyte. It is especially significant that these impervious films are formed in electrolytes that exert little or no solvent action on the coating. Where a boric acid electrolyte is used, the coating tends to form rapidly, with the result that the flow of current is soon reduced to substantially zero. This indicates that the growth of the coating has stopped. As a rule, the thickness of the coating is roughly proportional to the voltage employed for formation and the coatings of this type are exceedingly thin. In an electrolyte of this type, the coating has a high resistance when the aluminum is made anode; consequently, any current that may flow (leakage current) is very

Jan 1, 1944

By Gerald Edmunds

The liquidus line on the phase diagram for temperature versus composition of a binary alloy system, representing the boundary between the homogeneous melt and the heterogeneous melt plus solid, besides showing the minimum casting temperature, is useful in determining eutectic compositions and the presence of phase changes such as peritectic transformations and intermetallic compound formation. The liquidus often is determined by the cooling curves of thermal analysis, but supercooling frequently occurs, so that the temperature values are low. An alternative method, the one employed here, consists of determining the composition of samples of the melts from heterogeneous alloys that are at equilibrium. With meticulous attention to fundamentals, this method is capable of yielding values limited in precision only by the temperature control and measurement and analyses. Apparatus By starting, on the one hand, with a supersaturated solution and allowing the excess solute to precipitate, and on the other hand with an undersaturated solution and allowing more of the solute to be dissolved, both processes being carried out at the same temperature, equilibrium may be said to have been approached from both directions; that is, from above and from below. If the analyses show the solutions to contain the same fraction of solute when equilibrium has been approached from above and from below, one is assured that equilibrium has been reached in both determinations. In order to carry out such determinations, it is necessary to have equipment for obtaining and maintaining the proper temperatures; for holding the melt, measuring its temperature, and stirring, sampling and analyzing it. The present work required temperatures from 420° to 900°C. The equipment consisted of: A furnace, which was a vertical alundum tube, 13/4-in. diameter inside and 18 in. long, wound with Nichrome resistance wire, surrounded by a 3-in. i.d. alundum tube wound for 5 in. of length near each end, for compensation of end losses. This muffle was contained in an iron shell with Transite end plates, the intervening space being packed with Sil-O-Cel. The outside dimensions of the furnace were 12 in. in diameter by 181/2 in. in height. Heating current was supplied by three independent variable-voltage transformers (Variac), one connected to each end compensator winding and manually controlled, and one connected to the main winding through a series resistance of 5 ohms. This resistance was short-circuited for

Jan 1, 1944