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By Frank C. Greene

Drilling in Missouri in 1943 continued at a lower rate than in 1942, only 28 wells being completed. Following the completion of the Cities Service Oil Company's No. I Jim Cook near Tarkio, in the northwest corner, NW. 'fi sec. 32, T. 65 N., R. 39, W., Atchison County, four dry holes were drilled by other parties, all a mile or more from the Cook well. Later the Cities Service Oil Co, completed No. 2 Cook for 60 bbl. Table I gives a summary of activities by counties. The total footage drilled was 23,83134 ft., of which 12,802 1/2 ft. was by cable tools and 11,029 by rotary. Four of the dry holes were drilled into Mississippian or older beds.

Jan 1, 1944

By E. C. Reed

Drilling operations in Nebraska during 1943 were reduced to approximately two thirds of the 1942 number. Twenty-seven wells were completed during 1943 and five wells were drilling at the close of the year. Eight of the completions, in provcn fields, were producers. The operations were distributed throughout the state as follows: eleven in Richardson County, four each in Buffalo and Harlan Counties, three in Furnas County, and single operations in Antelope, Butler, Dakota, Dawes, Gage, Nemaha, Otoe, Pawnee, Scotts Bluff and Sherman Counties. Thc principal feature of exploration drilling in the state during the year was the more extensive testing in the central Nebraska Basin region, principally in Buffalo and Harlan Counties, where

Jan 1, 1944

By John M. Kelly

New Mexico produced 38,882,342 bbl. of oil in 1943, and regained seventh place among the oil-producing states. This production was an increase of 6,968,526 bbl., or 21.8 per cent, over the figure for 1942. The maximum per-well allowable on Jan. I, 1943, was 38 bbl. daily and at the end of the year this figure had been increased to 48 bbl. Allocations as set by the New Mexico Oil Conservation Commission closely followed recommendations by the Petroleum Administrator for War and the average daily pipe-line runs were 106,476 bbl., being within 2.2 per cent of these allocations. Production for Lea County was 33,043,925 bbl.; Eddy County, 5,405,-967 bbl.; northwestern New Mexico, 432,070 bbl., and Chaves County, 380 barrels. Drilling activity for New Mexico in 1943 was only 75 per cent of that in 1942, with 255 completions. Of these completions 180 were oil wells, 10 gas wells and 65 dry holes. The ratio of dry holes to producers, more than I to 3, was the greatest in recent years. Of these dry holes, 46 were drilled within the boundaries of proven . areas while 19 were wildcats. Wildcat drilling during 1943 was responsible for the discovery of four new oil fields and one new gas field, as well as three extensions to existing proration areas. At the close of the year the New Mexico Oil Conservation Commission had designated 64 areas as proven for oil and/or gas. The Monument area was again New Mexico's largest producing oil field, with an annual production of 7,228,855 bbl. Next was Eunice, with 6,461,044 bbl., followed by Vacuum with 4,946,110 bbl. IIobbs, ranking fourth, with 3,799,114 bbl., was the leader in total recovery with an accumulated production of 104,180,53I bbl., or more than 10,000 bbl. per acre to date. Drilling activity in Lea County accounted for completion of 67 oil wells, 2 gas wells and 24 dry holes. One of these oil wells was the discovery well of a new area and three extended proven areas. The most active drilling campaign in the county was again in the Maljamar area, where 18 oil wells were completed. The Maljamar Cooperative Repressuring Agreement affected 141 producing wells, and operations were a decided success, more than 85 per cent of the gas produced being returned to formation. The new oil field for Lea County was designated as the San Simon area although boundaries have not been established to date. Discovery well for this area was the Skelly Oil Company's State U. No. I, in theNE. NE. K of sec. 5, T.22 S.,R.ssE. This well was drilled to a total depth of 4183 ft. and plugged back to 4138 ft. after encountering bottom-hole water. Initial production was 124 bbl. per day on the pump. This oil is 37.4' gravity and has a sulphur content of I per cent. Productian is from Yates sand of Permian age. The Lynn area of southern Lea cbunty was extended 145 miles to the northwest

Jan 1, 1944

By Kenneth Cottingham

The number of wells drilled in Ohio in 1943 was slightly in excess of the number drilled in 1942. Compared with the average annual completions for the five years preceding, the year 1943 was short 11 per cent, hut the average initial volume of gas wells was considerably improved. In 1942 the average initial open flow per gas well was 668 M cu. ft., whereas in 1943 the average was 913 M cu. ft. Although no large gas-producing areas were discovered during the year under review, some 30 small pools were found in 17 of the counties of eastern Ohio. These new pools averaged about 300 acres each, and most of them were not extensions but were separate pools adjacent to older production. The Clinton sand furnished most of these discoveries, although six were from the Berea, one was Newburg, and three were shallow sands. No discoveries were made outside former producing counties, and there was no new development the Trenton area of western Ohio. The number of oil wells decreased from 181 drilled in 1942, to 170 in the year 1943. The production of Pennsylvania-grade oil increased 7644 bbl. The total Corning production, however, decreased 91,325 bbl. The present price of Corning-grade oil, $1.31 per bbl., is too low, in the opinion of the operator, to justify exploration. Until something is done in correcting the price level of Corning grade, the production probably will continue to decline. The oil industry in Ohio is making a concentrated effort toward increased production and improved methods of recovering Pennsylvania-grade oil, and a.s this report is written a research and engineering program is being formulated for the benefit and information of the various producers of that grade in Ohio.

Jan 1, 1944

By C. A. Hartnagel

The year 1944 marks the eightieth anniversary of the discovery of petroleum by drilling in New York State. It was in 1864 that a half dozen shallow wells were drilled at Limestone in Cattaraugus County, in a region that now forms the northern extension of the 82,000-acre Bradford pool. These early wells found oil, but not in paying quantities. They did, however, attract attention to the district and were a factor in the development of the still active Bradford pool of Pennsylvania and New York. During 1943, the production of petroleum in New York amounted to 5,029,000 bbl. This represents a decrease over the previous year, in which 5,421,000 bbl. was produced. The flush production for the New York fields occurred in the early eighties shortly after the discovery of oil in the Richburg pool of Allegany County. During the flush period, production was in excess of five million barrels annually. By 1887, however, the output had decreased to an amount only slightly more than two million barrels, and through the early years of the present century the annual total was often less than one million barrels. Flooding of the oil sands for increasing productioil was made legal in 1919, and in 1927 the output once more reached the two million mark. Two years later it had increased to over three million barrels. In Table r is shown production since 1935, in which year for the first time the output under flooding methods was in excess of four million barrels. From this table, it is evident that oil production in New 'I'ork is rather well stabilized, and since most of the oil is obtained by the flooding, or water-drive, method, with little or no prospect of discovery of new oil territory, rapid changes in yield from year to year are not to be expected. In thickness, the oil sands have a maximum of about 50 ft., and by means oi flooding may produce 10 to 12 thousand barrels an acre and proportional amounts for thinner sands. In some cases, floods have been developed in sands only 12 ft. thick. Under good flooding conditions a yield of 2000 bbl. an acre is about the lower limit at which oil can bc produced at the present price of $3.00 a barrel. The average cost for the physical development ol a lease, not including the cost ol the lease itself, is $5000 an acre. Since several months must intervene before the flood begins to act on the oil wells, and a year or more is required to bring thc wells to maximum daily production, it is evident that a considerable interval occurs before maximum returns are realized. Once a flood is developed and the wells

Jan 1, 1944

By Raymond D. Sloan

Dropping from third position among the oil-producing states of the nation in 1942, Oklahoma ranked fourth in 1943 with a total output of 121,431,ooo bbl., a decline of 11.9 per cent from the previous year's total of 137,792,000 bbl. Production ranged from a maximum of 346,900 bbl. daily in February to a low of 322,800 bbl. daily in October, and at the close of the year was averaging 330,000 bbl. daily from 52,096 wells, or an average of 6.3 bbl. per well. The state's well, average at the close of 1942 amounted to 6.7 bbl. At the turn of the year, it appeared reasonable to assume that Oklahoma's producing rate would continue its downward trend during 1944 unless reversed by greater than normal discoveries. To Jan. I, 1944, Oklahoma has produced 5,188,466,-ooo bbl. of crude oil. Development and Exploration A total of 1287 wells was drilled in 1943, representing an increase of 77 wells, or 6.4 per cent over the preceding year's total of 1210. Of the wells completed, 587 (45.6 per cent) were oil wells with an average initial production of 319 bbl.; 127 (9.9 per cent) were gas wells with an average initial of 8,639,000 cu. ft.; and 573 (44.5 per cent) were dry. A total of 333 wildcats was drilled (25.9 per cent of all wells), an increase of 13 (4.1 per cent) over the 1942 total of 320. Of the*wildcats drilled, 46 (13.8 per cent) were oil wells with an average initial production of 235 bbl.; 27 (8.1 per cent) were gas wells with an average initial of 8,249,-ooo cu. ft.; and 260 (78.1 per cent) were recorded as failures. Reconditioning of wells throughout the state led to a total recompletion of 230 wells. Of these, 131 were oil wells with a combined initial production of 8360 bbl., 31 were gas wells with a total initial of 211,950,000 cu. ft., and 68 were abandoned. The 46 successful wildcats opened 33 new producing areas, one of which produced from three separate horizons, and led to the development of production in new horizons in 11 old pools. While none of the 1943 discoveries have as yet developed into what might be termed major pools, the West Moore pool, in Cleveland County, and the West Edmond pool, in Oklahoma County, are the two outstanding new areas opened to production. The West Moore pool, sec. 29, 10 N., 3 W., discovered in December 1943, was completed for an initial production of 248 bbl. of oil in 3 hr. through small tubing chokes in the second Wilcox sand from 8787 to 8800 ft. One well was drilling in this area at the close of the year. The West Edmond pool, an April discovery in sec. 32, 14 N 4 W., is producing from the Hunton lime at a depth of approximately 6950 ft., the world's deepest Hunton lime pool. To the end of the year, 15 oil wells had been completed, with no gas wells and no failures. Accumulated production to Jan. I, 1944, amounted to 474,300 bbl. of 41" gravity oil. There were 29 active operations in the field at the end of the year. The West Edmond and West Moore pool discoveries established the first commercial production west of the Granite Ridge,

Jan 1, 1944

By Arthur C. Simmons

The area producing Pennsylvania-grade crude oil declined sharply in 1943, with a daily average production in the entire area of 71,056 bbl. as against a daily average in 1942 of 77,786. The total decline in the Pennsylvania-grade area amounted to 2,456,311 bbl., and 1,g81,z71 bbl. of this occurrcd within the state of Pennsylvania. The principal decline occurred in the Bradford field, where it was caused primarily by a drastic reduction in well completions. All of the zones in the Pennsylvania-grade producing area showed a decline except the part of Ohio that produces that grade, where production increased very slightly over 1942. Table I shows the average daily production by months for the several districts of the area. Table z is a comparison of the production in the two districts within the state of Pennsylvania. It is interesting to note that the Bradford field produced approximately half the total quantity of Pennsylvania grade but accounted for nearly three-fourths of the decline in production from the previous year. It is believed that this decline is ocasioned by restrictive price ceilings and a lack of adequate manpower to drill the necessary wells to maintain production. Stocks of Pennsylvania Grade At the beginning of 1942, stocks of Pennsylvania-grade crude totaled 3,196,000 bbl. and at the beginning of 1943 they totaled 2,626,000 bbl. At the end of 1943 the stocks of Pennsylvania-grade crude had declined to 1,95z,000 bbl. The available crude stocks have been almost completely consumed, as nearly all of the present crude stocks are "unavailable" and required for

Jan 1, 1944

By John T. Galey

A combination of two factors in addition to the current Federal drilling and price regulations reduced by 120 from I942 the number of new wells completed in southwestern Pennsylvania during the year. No new prospective area was found comparable to the Armbrust gas pool, Westmoreland Co., which accounted for a seventh of the last year's drilling, and it is considered doubtful whether, even if such a field had been discovered, the drilling contractors, who have been seriously affected by the manpower shortage, could have drilled many more wells than they did during the year. New wells totaling 445 were completed for a combined footage of over 1,250,000 Dry holes numbered 131 and had a footage of nearly 400,000. Old wells drilled deeper total 55, of which 17 were found nonproductive. Shallow Development Oil Oil completions yielded an initial of only slightly over one hundred barrels from 21 wells for about the same per well average as that of a year ago. However, 65 bbl. of this total came from two wells in two new strikes. The footage drilled of nearly 33,000 gives an average of nearly I00 ft. less per well than a year ago. Two old wells drilled deeper had a combined initial of only 4 bbl. The largest oil well of the year, 40 bbl., was found in the Speechley (U. Dev.) sand at a depth of 3492 ft. in German township, Fayette County. The location is several miles east of the nearest oil production hut as the area that could be occupied by a pool is fairly well delimited by drilling, the extent of this production would not appear to be large. The other notable oil production was found in the Dunkard (Penna.) sand, Cumberland township, Greene County, at a depth of 1065 ft. Here the first well had an initial of g bbl. and the second 25 bbl. However, a third proved dry, and as this area is also delimited by drilling, the pool doubtless will be of small area. Gas Gas completions yielded an initial of slightly over one hundred million cubic feet per day and new wells, totaling 303, account for all but four million of this volume. Old wells drilled deeper, numbering 35, found gas. The per well average in new drilling of approximately 320 M cu. ft. is nearly 165 M cu. ft. less than a year ago and the total footage is slightly over 830,000, which is about a quarter of a million feet less than in 1942. Average rock pressure of new completions is approximately 365 lb. per sq. in. The entire volume of new production is from the Upper Devonian or higher stratigraphic horizons. In Allegheny County, the grestest activity was in Forward and Plum townships. Wells there account for more than one half the completions. One large well was drilled in Forward township and an open flow of 3.623 million cubic feet was found in an old Gantz (U. Dev.) sand area. The top of the sand was encountered

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 Charles S. Barrett

This paper is a progress report covering metallographic applications of the electron microscope that have been made during the past year at Carnegie Institute of Technology. An account is presented of the techniques that have been most satisfactory, the difficulties encountered, the resolution obtained, and the peculiarities that have been noted in the microstruc-tures. About 1200 exposures have been made during the year on the instrument, which is an RCA type B2 transmission microscope,' and a number of these have been selected to illustrate the results obtained. prints are also included showing the common types of falsities—to borrow a term from the biological field, the "artifacts." ln brief, the paper is a record of our attempt to determine the value of the electron microscope in the study of the structure of metals and alloys. In addition to comments on techniques and the quality of photomicrographs obtainable with them, the paper discusses the nature of the etch attack on a few metals, and the possible relation between the fine structure revealed by etching and the mosaic block structure of the grains, since numerous papers and reviews are available on the subject of imperfection in crystals, the comments here may be very brief; in fact, are restricted almost entirely to points having to do with recent theories relating the strength of metals to imperfections and to spacings of slip lines. Specimen Preparation and Photographs Mechanical polishing by hand was used throughout this work. Precautions that must be taken in microscopy at high magnification, which have been well explained by Vilella in his book on Metallographic Technique for Steel, are likewise important with the electron microscope. This applies particularly to the need for these polishing and etching (each successive polish becoming less severe and each etch lighter), since the fina1 etch should in general be no heavier than is used for oil-immersion optical microscopy and in many instances should be much lighter (compare Figs. 6a and 7a, 6d and 7b). An extremely light etch, of course, is incapable of cutting through a flowed layer of appreciable thickness. Unquestionably it would be very advantageous in each instance to compare the structures obtained by electrolytic polishing with those obtained by mechanical polishing, but difficulties with the electrolytic method have prevented this in the following collection of prints. The choice of etchant is important, of course; for example, picral proved superior to nital for tempered martensite. With the exception of Figs. Ib and 16, the replicas used were of silica, deposited upon polystyrene and floated from the polystyrene in ethyl bromide according to the method of Heidenreich and Peck.2 The samples were mounted in Bakelite, polished and etched, then the polished Bakelite

Jan 1, 1944

By I. R. Kramer

[The final paper in the diffusion symposium was given by I. R. Kramer. The author called attention to the diffusion characteristics of chromium deposited on the surface of steel by treatment with chromium chloride and alloyed with the surface layer of the steel by thermal treatment. As the data cited were previously published in the paper " Chromizing of Steel," by I. R. Kramer and Robert H. Hafner (Metals Technology, October 1942, and in the Transactions, volume 154, 1943, pages 415-420), it is unnecessary to reproduce these data here. The following paragraphs are taken from the author's presentation.— Editor.] Aside from the well-known practical application of the diffusion phenomena to carburizing and calorizing, -diffusion also finds application in adding alloying elements to the surfaces of steel parts. The chromizing of steels is a process by which the surface of a low-alloy steel may be enriched with chromium to form a highly corrosion-resistant case; This chromized case differs from an electroplated coat in that it is a diffused layer integral with the base metal and has all of the properties of a high-chromium steel. Recently a method of chromizing has been developed in Germany by Daeves, Becker and Steinberg in which gaseous chromium chloride and hydrogen are passed over the steel at temperatures of 1650° to 1800°F. The chromium chloride reacts with the iron to give chromium and iron chloride. The chromium atoms are deposited on the surface and diffuse in as the iron atoms diffuse out, forming a layer rich in chromium. The principal role of hydrogen is to remove the carbon from. the surface of the steel. Of the two mechanisms, chemical reaction and diffusion, the one operating at the slower rate will determine the rate of formation of the layer. In this case, diffusion is slower and therefore any factors influencing its rate will affect the process. The rate of diffusion is influenced by the temperature and crystal structure of the parent metal. Depth-concentration studies show that the concentration falls off gradually for a considerable distance and then drops sharply at about 13 per cent chromium, the point coincident with the boundary of the gamma loop. The influence of the composition of the base metal upon diffusion is quite important. The depth of penetration of the chromium decreases as the carbon content increases and, of more importance, the chromized layer becomes brittle and is likely to spa11 if the carbon content is too high. It appears that in order to chromize successfully the carbon must be fixed by strong carbide-forming elements such as chromium or molybdenum, which decrease the diffusion of carbon. If this is not done, the carbon will diffuse from the interior faster than the chromium can diffuse inward, thus forming a carbide barrier. The corrosion resistance of the chromized layer is high, and these steels offer some unique advantages over other corrosion-resisting coating or alloys. While chromizing is not meant to replace stainless steels, it may serve in the saving of alloying elements. The chromizing process uses soft or low alloyed steels that can be easily hot or cold formed and since the chromized layer is soft and firmly adherent, chromized parts can be subjected to cold deformation without spalling or chipping and without loss of corrosion resistance.

Jan 1, 1944

By A. A. Smith

The application of indium to bearings was first advocated by C. F. Smsrtl in 1938, for the purpose of inhibiting corrosion of certain bearing alloys. He found that a thin layer of indium plated on the bearing surface and subsequently diffused at elevated temperatures markedly decreased the rate of corrosion in lubricating oils containing organic? acids. Most of his work was done on cadmium-base alloys, although he showed that the treatment was also effective for copper-lead and other; alloys. Since their introduction, indium-treated bearings have found considerable use, particularly in connection with airplane motors.2 Undoubtedly the effectiveness of the indium plate in resisting corrosion depends upon its relative concentration on the bearing surface after the diffusion treatment and after prolonged use at operating temperatures. Some diffusion experiments were made on a number of base metals that had been indium plated, to determine the depth of penetration after heating for reasonably long periods of time. As only the practical aspects were desired, no attempt was made to determine actual diffusion constants. Method Two different series of experiments were carried out to study the diffusion of indium into several base metals. Cast cylinders about one-inch diameter were machined to 0.750-in. diameter, so as to remove all surface imperfections, and final finishing was done with oo sandpaper. The original diameters were very carefully measured with micrometers and then a layer of indium was electrolytically deposited on the cylinders from a sulphate bath.3 In the first series of experiments, about 0.002 in. of indium' was deposited and diffusion, was carried out at 150°C. for a period of 500 hr. in a thermostatically controlled electric oven. After the diffusion period, successive layers were machined from the specimens and analyzed spectro-graphically and chemically—the spectro-graphic examination serving as a guide to determine which layers should be chemically analyzed. Apparently there was some surface oxidation of the indium plate due to the long heat-treatment, which may have had some effect on the diffusion. A1so, the cadmium alloy showed some incipient melting, which probably was caused by the formation of a low-melting eutectic. To eliminate these factors, another series of experiments was carried out by heating in an electrically heated, automatically controlled, oil bath at lower temperature. The preparation of the specimens was the same as before except that a layer of indium 0.0001 in. thick, an amount commonly used commercially on bearings, was deposited on each of the cylinders. Diffusion was carried out at 120°C. for a period of 200

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 R. S. Dean

The commercial production of electrolytic manganese on a small scale commenced in 1939. The writer made a short report on the progress of production and utilization in Mining and Metallurgy for January 1941. Progress during the last two years, naturally, has been more rapid. In June 1940, Congressman (now Senator) Scrugham presented a proposal to Congress for an appropriation authorizing erection of a pilot plant for " the production of metallic manganese by electrolytic or other means." As a result of this, a pilot plant, having a capacity of a few hundred pounds per day was built at Boulder City, Nev. Subsequent appropriations permitted expansion of the plant to about a ton per day. Much has been learned in this plant about electrolytic manganese, and the product even in its small way has found war uses of considerable importance. Meanwhile, the Knoxville plant of the Electro Manganese Corporation, the sole commercial producer, was expanded to about 4 tons per day to supply needed material for the war program. Other proposals for commercial plants have not been favorably received by the War Production Board. The Bureau reported on one such proposal by the American Alloys and Chemical Corporation. Practice at BouldeR City The present practice, as carried out at Boulder City, which is being described in more detail in a current paper by the Bureau staff at Boulder City, starts with a manganese dioxide ore containing about 20 per cent manganese. Currently this ore comes from the Three Kids deposit near Las Vegas. The steps for the production of electrolytic manganese, in general, are as follows: 1. The manganese in the ore is reduced to MnO. 2. The MnO is dissolved from the ore in spent electrolyte, which contains about 38 to 47 grams per liter of free sulphuric acid, 135 grams per liter of ammonium sulphate, and 10 to 12 grams per liter of Mn as sulphate. In the leaching step the manganese is built back up to 32 to 36 grams per liter of Mn as sulphate; the pH is adjusted to neutral by means of gaseous ammonia and passed through thickeners. 3. The electrolyte is purified by adding H2S, which precipitates the heavy metals. After filtering, ferrous sulphate is added to the solution and oxidized with air and the solution is filtered and clarified on a precoat filter. 4. The purified catholyte is electrolyzed in a diaphragm cell using stainless-steel cathodes and lead-silver anodes. The current density is about 45 amp. per sq. ft. Current efficiencies of 60 to 65 per cent are regularly obtained.

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 E. A. Anderson, P. W. Ramsey, E. J. Boyle

Only a few zinc-rich alloys are in commercial use today, and these depend largely upon solid solution effects for their desirable properties. Typical examples are rolled alloys containing about 1 Per cent of copper, with Or without additions of elements such as magnesium, and die-casting alloys containing about 4 Per cent of aluminum with small amounts of magnesium and sometimes copper." A number of elements are capable of forming alloys with zinc, Which do not enter into solid solution except in limited degree. The Present Paper considers One such system, zinc-titanium, in which alloys having potentially useful properties in the rolled form were found. Zinc-titanium System The zinc-rich portion of the zinc-titanium diagram, as determined by standard methods in this laboratory,3 is shown in Fig. I. The portion of the diagram of significance in the present work extends from 0 to about 0.5 per cent titanium. Gebhardt4 places the eutectic at 0.45 per cent, but the evidence in favor 01 the composition given in Fig. I is considerable. The solid solubility of titanium in zinc is very low indeed and possibly places these alloys in a somewhat different category from the commercial alloys previously mentioned. Alloy Preparation All of the alloys used in this work were prepared with titanium metal of 98.9 per cent purity. In most cases high-purity zinc (99.99 per cent) was used but sufficient work was done later to show that zinc of about high-grade composition would yield approximately equal results. Best practice in alloy manufacture seemed to be to prepare a zinc-titanium hardener by adding about 4 per cent of titanium metal to molten zinc and holding under a boric acid cover, with frequent stirrings, at 750°C, until the titanium had dissolved. The desired titanium content could readily be obtained in the final alloy by adding the calculated amount 01 this hardener. The alloys proved to be quite stable in composition, unless overheated, and, with reasonable temperature control, required no cover or flux to prevent loss of titanium content by oxidatioll, Hot-rollig Tests Three alloys containing, by analysis, 0.05, 0.12, and 0.23 per cent titanium were selected for preliminary study. Slab cross sections a a marked grain refinement* (Fig. 2) in the two alloys of highest titanium content. Cast unalloyed zinc has a columnar grain structure similar to that shown for the alloy of lowest titanium content but without the scatter of small equiaxed grains at the center.

Jan 1, 1944