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By Herbert R. Mosley, Paul M. Tyler

Strategically situated in almost the heart of the leading fertilizer-consuming area of the United States, Tennessee long has ranked second only to Florida as a phosphate-producing state. Since 1932 its share of the national output of phosphate rock has increased steadily, and in 1937 its production mounted to an all-time record. More significant even than the increase in tonnage are the forward strides in technology. The Tennessee Valley Authority's research program has led to quasicommer-cia1 operations using hydroelectric power to manufacture concentrated phosphatic fertilizer that is used to further the farmer education program designed to streamline the fertilizer business and halt the appalling waste of farm land by soil erosion. Even more stimulating to chemically minded imaginations is the production of elemental phosphorus by a private company that not only has succeeded in extracting it from the phosphate rock in electric furnaces but actually has contrived to capture it and to transport it safely in tank cars. New values have been created for low-grade phosphate deposits, and the economic life of reserves has been lengthened while the waste of former years goes back into the mills for recovery of its values by modernized methods. Tennessee's phosphate-mining industry dates from the discovery of blue rock in Lewis County in December 1893. Its known reserves are of the order of 101,500,000 tons, which compares with the production of 825,099 tons in 1937; that is, 21 per cent of the phosphate-rock output of the whole nation. The total output reported from 1894 until July 1. 1938, was approximately 19,000,000 tons. Offcial estimates of reserves are overly conservative and evidence submitted before a joint Congressional committee in November 1938 places "probable" reserves at more than 6,000,000,000 tons.

Jan 1, 1942

By John J. McKetta. Jr., Louis B. Lesem, George H. Fancher

The proration of oil produced in the field frequently is based partially or entirely upon the gas-oil ratio of wells. The measurement of the gas-oil ratio is one of the more important field tests in regulatory and pro-ration work, and the test always should be conducted according to standardized methods and procedure. Obviously, the gas-oil ratio and the volume of gas produced by a well depend upon many factors but should be independent of the method of measurement and of the devices used to measure gas and oil. Consequently, the volume of gas accompanying a barrel of oil produced by a well may be measured by any reliable and accurate device or instrument. Frequently either a critical flow prover or an orifice well tester is used for this purpose, and for a particular well the same rate of flow of gas should be obtained regardless of whether a critical flow prover or an orifice well tester is employed in the test. In Texas, when using either instrument, either Capacity Table 1 or 5' is employed in making the necessary computations. If the tables are used, a discrepancy always is found whenever the two instruments are compared by extrapolation to the same conditions of flow. Clearly, Tables 1 and 5 must be at fault in some respects. The orifice well tester and the Bureau of Mines type of critical flow prover are essentially the same instrument; both devices utilize a square-edged orifice 1/8 in. in di-ameter as the primary element, and both freely discharge gas to the atmosphere. Tables for the orifice well tester' have been published in the ranges of 0 to 15 in, of water and 0 to 40 in. of mercury (Hg) differential in pressure. Coefficients for the critical flow prover have been published for differentials in pressure greater than 75 psia. An extrapolation of either differs from the other set of data as much as 18 per cent at some points. No immediately obvious reasons for the discrepancy was found, and data available from the literature were insufficient to effect reconciliation. Consequently, a series of experiments was performed to check the available data and to determine discharge coefficients for the two devices in an overlapping range of differential pressure. The correlating equation used in preparation of tables such as Tables 1 and 5' is the so-called hydraulic equation, Q = C1 vh .....(1) The tables cover orifice sizes from 1/8 through 1 1/4 in. A second set of tables, for use with greater differentials in pressure, apply only to the 3/4, 1, and 1 1/4-in. orifice plates over a pressure range of 0 to 40 in. of Hg. The correlating equation used in preparation of the tables is Q = C2 vH(29.32 + 0.3H)/G . (2) Each of these equations is valid only for the range to which it has been applied, and neither equation is valid for extrapolation. Theoretical equations for flow through an orifice are based upon assumptions of fractionless flow and an emergent jet the size of the orifice. A multiplier, C,, called the discharge coefficient, is inserted into the theoretical expression to compensate for both frictional losses and the contraction of the jet experienced in the plane of the orifice. Buckingham3 shows that C, should vary with the ratio of upstream to downstream pressure for flow of a compressible fluid at any average linear velocity through the orifice less than the velocity of sound. Work published by the National Advisory Committee for Aeronautics4 indicates that the variation continues into the so-called critical flow region until the vena contracta coincides with the plane of the orifice. The NACA work, however, does not indicate a leveling off of the coefficient. The work of the Bureau of Mines5 for the critical flow prover was based on differential pressures greater than 75 psi and indicates that the discharge coefficient, Cd, is constant in this region at a value of about 0.86.

Jan 1, 1958

By J. F. Radavich

Many heats of steel of low carbon value have been known to produce brittle pieces of steel. The brittleness is believed to be due to the impurities located within the grain boundaries. Such brittle steels have been examined with an optical microscope to ascertain the nature and the amount of the impurities present at the grain boundaries. Due to the relatively low resolving power of the optical microscope, the impurities are not visible in fine detail. The writer obtained some sheet steel and proceeded to determine the location of the impurities and to show the application of the electron microscope to the study of grain boundaries. One sample was known to be capable of becoming embrittled, whereas another sample was believed to be much less susceptible to embrittlement. Treatment of Specimens The specimens were embrittled by annealing above the A3 point under mildly oxidizing conditions. One piece of ingot iron could not withstand a 90" bend, whereas another piece of ingot iron was not affected and could withstand a 90" bend. The brittle piece was then annealed at a high temperature in a hydrogen atmosphere. The annealed ingot iron was termed cured and could withstand a 90" bend very easily. The three specimens examined will be designated as brittle, good. and cured in the discussion that follows. Procedure The sizes of the specimens were as follows: one piece of brittle ingot iron-3/8 by 35 in.; one piece of good ingot iron-96 by 1/8 in.; one piece of cured ingot iron-36 by 54 in. The specimens were too small to be polished by hand and therefore were mounted in bakelite. The polishing procedure was carried out in the conventional manner with the use of 1/0 through 3/0 papers, and the final polish was done with alumina on a billiard cloth. The specimens were then etched in a 4 pct solution of picral in alcohol, and then they were examined through an optical microscope. An area was chosen that showed distinct grain boundaries, and an effort was made to keep near this area when pulling the replicas REPLICA TECHNIQIJE The replica technique used in the preparation of the replicas for examination under the electron microscope is described in Electron Metallography.' It consists essentially of the following steps: 1. Obtaining a suitably etched specimen. 2. Applying a swab of ethylene di-chloride on the surface. 3. Applying a formvar solution on the surface. 4. Placing a screen on any desired spot. 5. Breathing on the fornivar layer. 6. Applying scotch tape on the screen and film. 7. Pulling the film and the screen up with the Scotch tape. 8. Separating the screen from the Scotch tape. This replica technique is very similar to the one described by Harker and Shaefer. However, with the added step, the percentage of replicas removed is very much higher regardless of the length of the time from the etching of the specimen to the actual pulling of the replica. The replicas were then shadow cast with manganese at a filament height to replica distance ratio of 1 1/2:7. This produced a very high contrast replica for use in the electron microscope. One of the dificulties encountered with this study was the restricted area of the specimen. The width of the specimens was the same as that of the 200 mesh nickel supporting screen. In order to increase the effective area, the screens were cut down as shown in Fig 1. The arrow indicates the direction in which the replica was pulled. This operation made it possible to obtain a large percentage of good replicas. Fig 3 shows an electron micrograph of a brittle piece of ingot iron and a grain boundary that was polished mechanically. The surface is very rough probably due to the incomplete removal of the flowed layer by the picral etchant. The grain boundary does show evidence of impurities. It was decided to electropolish the specimens to obtain a much smoother surface than the one obtained by mechanical polishing. ELECTROPOLISHING The specimens were cut in half to expose the metal on the back side. The exposed metal had sufficient area to make good electrical contact and electropolishing was carried out easily. The conditions for electropolishing were 0.9 amp, 35 volts, and 25 sec. in an electrolyte composed of 850 cc of ethyl alcohol, 100 cc distilled water, and 50 cc of perchloric acid. The polished specimens were then etched in the 4 pct picral solution for a shorter time than was necessary for

Jan 1, 1950

By John T. Norton

FoR many years the copper-bearing steels have been of considerable interest to the metallurgist because of their corrosion-resistant properties. More recently the discovery of their definite age-hardening characteristics has focused attention on them again. In a recent paper, Smith and Palmer(l)† have given an admirable description of the behavior of a considerable number of steels of this type and a study of their results suggests two questions of a more or less fundamental sort. In the first place, it has been plainly shown that the hardening effect of added copper does not increase up to the maximum solubility of copper in iron as given by earlier investigators, but reaches its greatest value considerably below this point. This fact suggests that either the solubility is not so great as previous investigators have stated, or that the age-hardening mechanism is not the simple precipitation phenomenon that has been postulated. In the second place, the nature of the aging mechanism in this particular system should be determined. Recent developments in the study of age-hardening processes have shown that the increase of hardness is often, but not always, accompanied by precipitation and the action of a particular system is not predictable on the basis of its components or type of phase diagram. It would be of considerable interest to study the aging of the iron-rich iron-copper alloys in detail. One would like to know whether the aging mechanism is different at high and low aging temperatures, and whether the extreme sluggishness of the system may perhaps represent some new type of aging process. The experiments to be described were carried out in an endeavor to answer these questions. Obviously, in such experiments it is important to confine the hardening effect to the single element, copper, so that iron and copper of high purity must be used in the preparation of specimens. An observation of lattice changes during the aging process, correlated with the hardness changes, seems to be the best available method of

Jan 1, 1935

By John T. Norton

FoR many years the copper-bearing steels have been of considerable interest to the metallurgist because of their corrosion-resistant properties. More recently the discovery of their definite age-hardening characteristics has focused attention on them again. In a recent paper, Smith and Palmer(l)† have given an admirable description of the behavior of a considerable number of steels of this type and a study of their results suggests two questions of a more or less fundamental sort. In the first place, it has been plainly shown that the hardening effect of added copper does not increase up to the maximum solubility of copper in iron as given by earlier investigators, but reaches its greatest value considerably below this point. This fact suggests that either the solubility is not so great as previous investigators have stated, or that the age-hardening mechanism is not the simple precipitation phenomenon that has been postulated. In the second place, the nature of the aging mechanism in this particular system should be determined. Recent developments in the study of age-hardening processes have shown that the increase of hardness is often, but not always, accompanied by precipitation and the action of a particular system is not predictable on the basis of its components or type of phase diagram. It would be of considerable interest to study the aging of the iron-rich iron-copper alloys in detail. One would like to know whether the aging mechanism is different at high and low aging temperatures, and whether the extreme sluggishness of the system may perhaps represent some new type of aging process. The experiments to be described were carried out in an endeavor to answer these questions. Obviously, in such experiments it is important to confine the hardening effect to the single element, copper, so that iron and copper of high purity must be used in the preparation of specimens. An observation of lattice changes during the aging process, correlated with the hardness changes, seems to be the best available method of

Jan 1, 1935

By Alexander B. Morris

In a recent paper on the intermittent injection of gas in gas-lift operations as opposed to continuous injection, Morgan Walker presented a comparative table showing the effect on oil and gas production from the same wells under the two methods of operation.' This table carried a column showing the formational gas-oil ratios under each method, computed by deducting the volume of input gas from the volume of trap gas. During the entire spring and summer of 1928, the present writer had been engaged on some extensive test car tests of rich gas in Glenpool, seeking, primarily, for an explanation of the apparent loss of gasoline during the summer season between the field meters and the plant master meter. Tests at several of the field meters where the richest gas was obtained regularly failed to check with other tests on the same gas made farther along the line, and the difference was not made up by the quantity of drip gasoline collected between the points. In the course of these tests, the final outcome of which is immaterial to the present purpose, an attempt was made to construct a curve representing the relationship between gasoline content of the gas in gallons per thousand cubic feet and the shrinkage in the volume of gas treated as a result of removing the condensible fractions. Such a curve was made, expressed in units of gallons per thousand cubic feet on the abcissa and the ratio vapor volume to liquid volume on the ordinate. This curve is a rectangular hyperbola and shows that 3 gal. of gasoline taken from 1000 cu. ft. of raw gas as a vapor occupied much less space, per gallon, than did 1 gal. of gasoline taken from 1000 cu. ft. of another sample of gas. This is, in general, corroborated by converting to the same units the residue settlement curves prepared by the Tidal Oil Co. and by the Natural Gasoline Manufacturers Assn., though the three curves, when plotted together, occupy entirely different positions on the paper, as shown in Fig. 1. The bearing of all this on Mr. Walker's discussion of gas-lift is this: if the formational gas is to be computed by deducting the input gas from the trap gas, some correction must be made for the vapor volume

Jan 1, 1930

By George M. Enos, Robert J. Anderson

This paper gives a summary of tests made on the accelerated electrolytic corrosion of the tin brass, 70:29:1 copper-zinc-tin (admiralty metal), of different grain sixes in various electrolytes. There has been great difference of opinion as to the effect of grain size on the corrosion rate of brass, particularly in condenser-tube practice, but so far as is known no information has been published on the subject. It has been assumed, on the basis of the amorphous-cement theory, that fine-grained brass would corrode more rapidly than coarse-grained because the amorphous phase is more soluble than the crystalline and there is more cement per unit area exposed in the fine-grained material. In previous work on the corrosion of metals and alloys in acid mine waters from coal mines,1,2 it was found that the grain size, within a restricted range, had practically no effect on the corrosion of the brass 70:29:1 copper-zinc-tin: In the tests made, samples of three grain sizes were included; viz., 0.025, 0.035, and 0.075 mm. diameter (1600, 817, and 177 gr. per sq. mm., respectively), and the average losses on exposure to the most acid of three waters were 7.07, 6.80, and 6.72 mg. per sq. cm. per day (24 hr.), respectively. No distinguishing features were observed on microscopic examination of the corroded samples. In two other mine waters, the corrosion losses were substantially the same for the respective samples. These tests were -incidental to other tests and were not sufficiently comprehensive to warrant drawing definite conclusions. In further work with the accelerated electrolytic corrosion test, as developed recently in the Bureau of Mines, tests were made

Jan 1, 1924

By J. T. Burwell

As is well known, the alloys of iron containing 18 ± per cent chromium, 8 ± per cent nickel and less than 1.2 per cent carbon exhibit the same allotropic modifications as iron. The face-centered cubic or gamma phase is stable at high temperatures and the body-centered cubic or alpha ferrite is presumably stable at room temperature. The transformation from the gamma phase to the alpha phase in alloys of the above composi-tion (18-8 or stainless steel) is sluggish; even moderately rapid cooling permits the retention of the gamma phase. Cold-work, however, causes the transformation from gamma to alpha to occur at room temperatures. It is difficult, nevertheless, to induce complete transformation regardless of the method of cold-working. Since metallographic polishing is very effective in transforming the surface austenite to ferrite, as indicated by the magnetic studies of Buehl and Wulff, 1 it was decided to investigate the phenomenon by electron diffraction methods.

Jan 1, 1939

By E. W. Edson, F. W. Hertal

In some fields the problem of mud fluid is simple and easy of solution. But in the Ventura Avenue field the acquisition and disposal of good drilling mud is not the least of the problems that confront the operator. In fact, mud fluid in the Ventura Avenue field is a very important factor in the drilling of the wells. It is quite probable that many of the factors affecting mud in this field will not be found in most of the fields with which the reader is familiar. However, in the fields where the mud fluid causes no apparent problem it is probable that some of the points brought out in this paper could be used to economic advantage. In fields where caving and squeezing formations and high gas pressures are present, as in the Ventura Avenue field, it is believed that application of methods outlined will be of great assistance in drilling wells. On account of the sandy nature of the formation and the lack of suitable shale bodies in the strata drilled through in the Ventura Avenue field, the wells make practically no mud during drilling. It is necessary therefore to supply drilling mud to the wells that will carry the drill cuttings to the surface, and also will " wall up" the drill hole and prevent the sandy formations from caving. Mixing and Handling Mud Fluid The clay used to make the mud fluid is obtained from a shale stratum in the upper Pico (Plioccne) formation found about a mile on either side of the field. Since high gas pressures and caving formations were first encountered in the Ventura Avenue field and mud fluid was needed to combat them, the mixing of this mud fluid has gone through a process of evolution. First, the clay was mined and hauled to the derrick, where it was shoveled into the well and left for the churning action of the bit to mix into a mud in the hole. The next move was the construction of a mixer to mix the clay to a mud fluid which was pumped into the well. These mixing

Jan 1, 1930

The stabilization of a gravel road with soil is a method of treatment developed in recent years by the United States Bureau of Public Roads for the purpose of binding the constituents together better, and maintaining a more durable surface. The process consists in adding to the gravel or crushed stone and sand, a soil mortar, so-called, of fine sand, silt and clay, mixed in the proper proportions. The coarse gravel and sand supply structural strength and hardness; the fine sand adds embedment support to the coarse sand; the silt acts as a filler to prevent the granular particles from rocking; while the clay serves not only as a binder but also provides pores minute enough to cause connecting moisture films which are supposed to have high cohesive properties'. It will be recognized that the clay is an important ingredient both when wet and dry, and should not show excessive expansion when wet, nor correspondingly high shrinkage in drying, as otherwise there is danger of unseating the nonplastie particles. Such a stabilized road, although an improvement on one with a floating surface, will in course of time be subject to wear, and become dusty when the clay dries out and breaks up. It has been found that if some salts are added to the road mixture they tend to maintain the soil moisture and prevent dustiness of the road or raveling of the road surface. In addition to this, it is claimed that these dissolved salts cause a thinning of the moisture films on the particles, thus permitting greater compaction of the road mixture, and thereby increasing its density. This fact can be proved by noting the increased compaction which a road mixture shows when certain salts are added to the soil water. Since certain chemical substances such as sodium chloride are electrolytes, the question arises whether they cannot have wine effect on the qualities of the clay in the soil mortar, and perhaps improve them. In view of the fact that certain salts seem to exert a favorable effeet on the road mixture it is desirable that they he held in the road soil as long a time as possible.

Jan 1, 1938

The stabilization of a gravel road with soil is a method of treatment developed in recent years by the United States Bureau of Public Roads for the purpose of binding the constituents together better, and maintaining a more durable surface. The process consists in adding to the gravel or crushed stone and sand, a soil mortar, so-called, of fine sand, silt and clay, mixed in the proper proportions. The coarse gravel and sand supply structural strength and hardness; the fine sand adds embedment support to the coarse sand; the silt acts as a filler to prevent the granular particles from rocking; while the clay serves not only as a binder but also provides pores minute enough to cause connecting moisture films which are supposed to have high cohesive properties'. It will be recognized that the clay is an important ingredient both when wet and dry, and should not show excessive expansion when wet, nor correspondingly high shrinkage in drying, as otherwise there is danger of unseating the nonplastie particles. Such a stabilized road, although an improvement on one with a floating surface, will in course of time be subject to wear, and become dusty when the clay dries out and breaks up. It has been found that if some salts are added to the road mixture they tend to maintain the soil moisture and prevent dustiness of the road or raveling of the road surface. In addition to this, it is claimed that these dissolved salts cause a thinning of the moisture films on the particles, thus permitting greater compaction of the road mixture, and thereby increasing its density. This fact can be proved by noting the increased compaction which a road mixture shows when certain salts are added to the soil water. Since certain chemical substances such as sodium chloride are electrolytes, the question arises whether they cannot have wine effect on the qualities of the clay in the soil mortar, and perhaps improve them. In view of the fact that certain salts seem to exert a favorable effeet on the road mixture it is desirable that they he held in the road soil as long a time as possible.

Jan 1, 1938

By F. H. Froes, D. H. Warrington

Electron microscope evidence which indicates that TaC may precipitate at random sites in the matrix is presented. Initially the particles are almost spherical and coherent with the matrix. However, as they grow in conditions in which there are insufficient vacancies to relieve lattice strain, the particles rapidly lose coherency in two directions and continue to grow as plates with approximately the full lattice mismatch strain present perpendicular to the plane of the plate. The necessary relief of strain comes from dislocations loops which do not become visible until the later stages of aging. The rapid decrease of apparent strain to low values of appoximately 1 pct at small particle sizes arises not from a complete incoherency but from applying a model wrong for the particle shape and strain distribution. PREVIOUS work has shown that MC-type carbides may precipitate intragranularly in austenitic stainless steel on dislocations,1&apos;2 in association with stacking faults,3&apos;4 and randomly through the matrix,5-7 In investigations of the matrix precipitate by thin-foil electron microscopy, considerable lattice strain has been found to occur around the precipitating phase.7&apos;8 Attempts have been made to evaluate the amount of lattice strain by using the methods developed by Ashby and brown.9,10 Values of the linear strain, much less than the 17 pct theoretical mismatch (for TaC), have been reported; it has been suggested that this is due to either a loss of coherency1&apos; or vacancy absorption which occurs during either the initial nucleation or growth of the precipitate." This report is an extension of earlier work7 that dealt with the precipitation of TaC from an 18Cr/12Ni/ 2Ta/O.lC alloy after it had been quenched from 1300°C and aged between 600" and 840°C. In particular, the shape of the precipitate particles and the amount of strain in the matrix, due to the precipitate, have been studied. The work described here is part of a wider investigation of factors that affect carbide precipitation in austenitic stainless steel," details of which are to appear elsewhere. RESULTS The present investigation can be conveniently split into two aspects of the strain-fields surrounding the matrix particles: 1) information derived from the strain-field which indicates the shape and habit plane of the precipitate particles and 2) the magnitude and sign of the strain-field. The Shape and Habit Plane of the TaC Precipitate. In the early stages of aging twin lobes (normally black F. H. FROES, formerly at the University of Sheffield, Sheffield, England, is Staff Scientist, Colt Industries, Crucible Materials Research Center, Pittsburgh, Pa. D. H. WARRINGTON is Lecturer, Department of Metallurgy, University of Sheffield. Manuscript submitted November 1, 1968. IMD on white background, i.e., for the deviation parameter, S > 0) that indicate the strained region of the matrix define the position of the particles by bright field transmission electron microscopy. The actual particles were not detected until they were approximately 120Å diam; below this size they were too small to be imaged in the electron microscope. This meant that particle growth that had occurred before this stage had to be inferred from the matrix strain-field contrast. In all cases when diffraction effects were observed from the precipitate particles, a cube-cube orientation relationship (i.e., (llO)ppt Il<llO>matrix and {1ll }ppt {III} matrix) existed between the precipitate and the matrix. From the matrix precipitate particles lying along edge-on {111} planes (e.g., at A, Fig. I), the precipitates are seen to be plate-like with their diameter being roughly 18 times their thickness after 5000 hr at 650°C. However, the exact shape of the particles cannot be determined because of the masking effect of the strain-field contrast. If a dark-field micrograph, using a precipitate reflection, is studied, Fig. 2, a number of the projected images of the TaC particles [on the (110) foil surface] apear to have straight edges parallel to projected f111) planes. Thus, it appears that in the later stages of aging the TaC particles are plate-like with some tendency for the edges of the plate to be bounded by the matrix close-packed {ill} planes (though the general shape of the particles in the plane of the plate is circular and thus the "diameter" of the particles has a real physical significance). It should be noted that the bands of fine discrete particles observed in Figs. 1 and 2 are not the matrix precipitate discussed in this paper but are precipitates associated with extrinsic stacking faults3j4 occurring on (111) matrix planes. **£** ****** \ *x 23 Fig. 1—18/12/2~a/0.1~ alloy. Solution treated at 1300°C for 1 hr, water quenched, and aged 5000 hr at 650°C. The (112) directions shown are the traces of the e&e-on (111) planes. Foil normal [110]; operating reflection (331); bright field micrograph.

Jan 1, 1970

By J. M. Lovejoy

Various estimates have been made as 60 the percentage of oil left in a field after the wells have become so small that it is no longer practical to produce them. Engineers have given the matter much study and can substantiate their figures by data taken from fields from the Appalachians to California. The average oil sand has a porosity of about 20 per cent., which gives a capacity per acre-foot of approximately 1500 bbl. The sand thickness in Oklahoma pools averages 20 ft. With 20 per cent, porosity and a 20-ft. sand thickness, the capacity per acre is 30,000 bbl., yet these pools will seldom yield more than 5000 bbl. to the acre. These figures gupport the theory that at least 50 per cent. of the oil remains in a sand after all known methods to recover it have been used. Certainly we can never recover all the oil, unless in years to come oil becomes so rare and yet so necessary that the price will justify sinking shafts into the abandoned fields and regular mining methods of drifting and stoping. However, with improved methods of production and conservation of the natural agencies of expulsion, we should be able to increase recovery. It is with this in mind that this paper, relating to the effect of back pressure on wells, is presented. Except in the fields where production is caused by hydrostatic pressure, the chief agency for getting oil out of the sand into the hole is the gas that occurs with the oil. After the pressure has declined, probably gravity also is a factor, but not an important one. With a given amount of oil in a sand and a given amount of gas occurring with the oil, the ratio of gas volume per barrel of oil is the key to the ultimate recovery from that sand. Our efforts should be along lines that will lower this ratio and make the gas, the agency given us by nature, do its work better and yield more of the oil, of which it is a part. T. E. Swigart,&apos; of the U. S. Bureau of Mines, has published an extract of the paper he is preparing under the title "The Effect of Back Pressures. on Wells." The experiments described were made on two

Jan 1, 1924

By W. J. Reagan

A survey of the literature on bottom-cast practice gives but Scant information as to some of the real facts concerning this most int&apos;eresting method of steel manufacture, and some of the information available is very misleading. An exceptionally good description of this met,hod of pouring or teeming is to be found in an English publication2 on the heterogeneity of steel ingots. Quoting from this paper: (a) With bottom teeming, the metal rises steadily and progressively in the mold with the minimum possible agitation, the main force of the stream coming from the ladle being broken down or retarded by the down gate or runner. Further, the stream of metal from the ladle, under these conditions of casting, is invariably maintained at a much more continuous rate and is steadier than with top teeming. (b) In view of the facts referred to in (a) it follows that with bottom teeming the metal is not exposed to atmospheric oxidation to anything like the same degree as with top teeming. In this paper it is intended to detail briefly some of the advantages of bottom-cast practice and to discuss the possibilities of iron-oxide control in the basic open-hearth furnace. A description of the type of charge, ingot rnold set-up, etc., is found in detail in an earlier paper.3 Design of Ingot Molds In any kind of steel manufacture, ingot-mold design is important. L. H. Nelson4 lists in the order of their probable importance the following factors as influencing most the solidification of the ingot:

Jan 1, 1934

By L. S. Castleman, R. K. Hotzler

We are currently studying the effects on recrys-tallization of impurities diffused into dispersion-hardened alloys. Our interest in this phenomenon was originally aroused by the observation that the recrystallization temperature range of tungsten "doped" with alumina and silica, or with thoria, is lowered drastically if nickel is plated onto the tungsten prior to heat treatment.&apos; In this note, we report a similar effect that sulfur has on the recrystallization behavior of thoriated nickel. The experimental procedure for this exploratory phase of the investigation has consisted simply in heating commercially obtained stress-relieved samples of thoriated nickel for varying temperatures and times in sealed capsules containing air and small quantities of sulfur. The samples contain 2.4 vol pct thoria and initially less than 18 ppm S by weight; they are prepared either from 0.5-in.-ciiam rod stock or from 0.092-in. sheet and are in the "as-received" (stress-relieved) condition prior to exposure. In an atmosphere free of sulfur, such samples do not show evidence of recrystallization after being annealed for 1 hr at a temperature of 2500°F (1372C).2 The photomicrograph in Fig. 1 shows the microstructure of one of our samples annealed for 75 hr at 1000° C (1832°F) in a sulfur-free capsule. The grain structure is hardly evident (if at all) at 465 times magnification. In contrast, the photomicrograph of Fig. 2 shows the recrystallization that has taken place in a sample exposed to sulfur for 5 hr at 1000°C (1832°F). A nickel sulfide phase is visible at the grain boundaries of the light-appearing grains. We have also observed recrystallization to occur in a sample annealed at 600°C (1112°F) for 25 hr. This temperature is below the 637°C (1178°F) eutectic in the Ni-S system. In the latter case, no nickel sulfide phase is evident in the microstructure. Moreover, we have noticed the occur-

Jan 1, 1969

By L. W. Saperstein

Public Law (PL) 95-87 contains explicit demands for land use planning in its reclamation and designation sections. Both sections require recognition of local land use plans; however, they are not well integrated. Accommodation to these planning requirements affords an opportunity to create better links among local land use planners, the state&apos;s permitting authority and designation office, and mine designers. Mining companies should take a more positive interest in local land use plans and in resource inventories. States should coder handing down to local government the responsibility for accepting mine permit applications and designation of unsuitability petitions.

Jan 1, 1984

By Charles J. Deegan

The purpose of this paper is to point out some features of the position of fuel oil and it&apos;s relationship to the economic balance and price structure of the petroleum industry. The term "fuel oil" as used in this paper includes crude used as fuel as well as refined gas oil and fuel oil. The period covered, from 1922 to date, may be characterized as the new normal era after the post-war inflation and deflation. In order to establish a proper perspective, the figures on consumption of the principal products of petroleum are shown in Table 1. This table shows that fuel oil and gasoline made up the bulk of the total demand in 1928 just as they did in 1922. There has been so much comment about the enormous increase in gasoline consumption that it may come as a surprise to some people to find that fuel oil is still at the head of the consumption list, in point of volume at least, and seems likely to hold that place for at least another year. Having established the fact that gasoline and fuel oil are by far the most important products, the remainder of this paper will deal almost entirely with these two items.

Jan 1, 1929

By John Chipman

THE equilibrium between titanium in liquid iron and titanium oxides has been studied by Hadley and Derge.&apos; They have shown that a minimum occurs in the oxygen content of the metal between 0.1 and 1.0 pct Ti, but its exact level was not fixed. The oxide phase in this minimum range was principally TiO, containing some iron oxide. On the other hand, for concentrations above 5 pct Ti the oxide phase was TiO and the oxygen content of the metal increased rapidly with increasing titanium content. From their observations and the free energy of Ti0 and TiOz reported by Kelley and ah,&apos; it is possible to derive approximate values for the activity coefficients of titanium and oxygen in liquid iron-titanium alloys and the conditions for equilibrium in steel deoxidation. Neglecting possible departures from the stoichio-metric composition, the condition of equilibrium with Ti0 may be expressed as follows: TiO= Ti_ + C) log K = log NTl + log [% O] + log yTi + log fQ Here as a matter of convenience the titanium concentration is expressed in mol fraction while that of oxygen is in weight percent. The activity coefficients are yTi and fo. The value of log fo approaches zero as the concentration of titanium approaches zero, while that of log yTi approaches a limiting value of In Fig. 1 the sum of log NTi + log [% 0] is plotted for mol fractions of titanium between 0.05 and 0.50. The smooth extrapolation gives a value of —4.15 which corresponds to log K — log y:i . We therefore have the equation: According to the data of Kelley and Mah,&apos; the free energy of formation of Ti0 at 1900°K is -82,400 cal. The free energy of solution of half a mol of oxygen in iron, taking 1 pct 0 as the standard state, is -29,300 cal. From these we write: From these equations the activity coefficient of titanium at infinite dilution in iron is found to have a value of 0.011 or log y°. = -1.96. This is only an approximate value but is certainly better than the estimated 0.05 in Basic Open Hearth Steelmaking To obtain approximate values for the activity coefficient at intermediate concentrations, it is as- sumed that log yTi(l is constant and equal to -1.96. This corresponds to a value of E;: = 3 In yTi/aNTi = 9.0 which is not unreasonable We now have the value for the activity of titanium and the percentage of oxygen in equilibrium with TiO. It is therefore a simple matter to calculate the activity coefficient of oxygen which is shown in Fig. 2. The effect of titanium is rather large, being comparable to that of vanadium, but not so large as has been reported for aluminum. The slope of the line at low concentrations corresponds to E: = aln yo/ aNTi=-0.37. At concentrations below 1 pct Ti the deoxidation constant and oxygen content for equilibrium with TiO, can be calculated from the foregoing data and the free energy of formation of TiO,, which according to Kelley and Mah is -144,600 cal at 1900°K. The free energy of solution of oxygen has been given; that of Ti to form a dilute solution with 1 pct Ti as the standard state is RT ln (0.5585 y:i/47.9) = -34,800 cal. From these data we find (for concentrations in wt pct): TiO, = Ti + 2 -0; hFTgO0= + 51,200 cal log if =-5.89 The interaction coefficients, concentrations being expressed as wt pct, are e;: = alogfTi/a[% Ti] = +0.048 and e:&apos; = a logfo,/a[ojTi] = -0.187. The calculation gives the following results which, in view of the impurity of the oxide phase, must be regarded as approximate:

Jan 1, 1961

By J. W. Hickman

INTRODUCTION MOST of the electron diffraction studies of oxide films which form on metals and alloys have been carried out by oxidizing the specimens in an auxiliary furnace, cooling down to room temperature and then inserting the sample in the camera and taking a diffraction photograph. Prior to the investigations at the Westinghouse Research Laboratories, no systematic study of the oxidation of any metal or alloy had been made over a wide temperature range with photographs taken at elevated temperatures except the investigation of iron by Jackson and Quarrell.1 In order to interpret the electron diffraction patterns of the oxides which may form on alloys, it seemed advisable to make a comprehensive study of the oxidation of the purest metals available in the bulk form. Thus far studies have been completed on iron,2 cobalt,2 nickel,2 chromium ,2 Copper2, tungsten,3 molybdenum,3 beryllium ,4 uranium,4 thorium4 titanium5 and zirconium5 while investigations are in progress on tantalum and columbium, The next step in the study is concerned with the investigation of the oxides which form on binary alloys. Some of the alloys consist of a single, phase while others contain more than one phase. The identification of the oxides on the surface of a binary alloy may be more difficult than on the metals since oxides containing both metals as well as those of each metal separately may form. Furthermore, it is possible that solid solutions of the various oxides may occur. In these cases the electron diffraction method may not be able to identify the oxidation products unequivocally, Examples of solid solutions which may present difficulties are MoO2 and W02, Fe3O4 and FeO-Cr2O3 since the diffraction patterns are so similar. Since electron diffraction can determine only the structure of the oxide, the chemical composition must be inferred from the diffraction data based upon X ray diffraction investigations of specimens of known composition. It is possible in some cases to decide whether a given solid phase reaction can occur on the surface of an alloy by a study of available thermodynamic data. Table I lists the equations for the formation of most of the oxides from the elements together with values of log10 KR for the several temperatures. [OF°R = -RT In KR 0 and-~75T = logi°KR] [?F°R] and KR are the free energy and equilibrium constant of the reaction. Calculations may be made using the values given in Table I to determine whether a given solid phase reaction is possible thermodynamically. For example, a solid phase reaction should occur between aluminum and chromium&apos; oxide to form

Jan 1, 1948

By F. J. Dunkerlery, V. Damiano, J. Fulton, F. Pledger

Grain-growth and recrystallization characteristics of a commercially pure zirconium prepared by the iodide process are reported. Grain growth from 640° to 800°C was continuous once initiated and obeyed D = kt". Recrystallization of zirconium occurred at temperatures of 450° to 550°C after deformations of 20 and 50 pct. Hardening from partially soluble inclusions prevented determination of the absolute rates of recrystallization, but the relative rates of recrystallization obtained are useful as a guide in fabrication practice. BASIC information needed as a guide in the hot and cold working and annealing of metals includes recrystallization and grain-growth data. A search of the literature revealed no such information for pure zirconium. This is a report of practical grain-growth and recrystallization results obtained for a commercial grade of pure zirconium on a project sponsored by the Office of Naval Research. In this work, isothermal grain-growth curves were obtained at five temperatures from 640" to 800°C inclusively; while recrystallization curves have been determined at 450°, 500°, and 550°C for the metal at the deformation levels of 20 and 50 pct. In addition to the usual variables of temperature, time, and deformation, distribution of the second phase found in all commercial grades of iodide zirconium is also treated as an important factor in these grain-growth and recrystallization studies. In conducting this work, two properties of zirconium were particularly pertinent in dictating experimental conditions. First, since zirconium undergoes a transformation from the a close-packed hexagonal form to the ß body-centered cubic form at 862°C, no recrystallization or grain-growth studies were made above 800°C. Second, because dissolved gases (oxygen, nitrogen and/or hydrogen) increase the hardness and lower the ductility of the solid metal, all annealing treatments in this investigation were carried out in vacuum or in a helium atmosphere. Materials and Methods The zirconium used in this investigation was prepared by the Foote Mineral Co. by deposition from its iodide. A spectrochemical analysis of the metal showed the following composition in weight pct: Hf, 2.1; Mg, 0.012; Fe, 0.035; Si, 0.095; Ti, 0.023; Al, 0.037; Mo, trace; Ni, trace; Cr, trace; Ca, 0.006. Conventional metallographic procedures involving hand polishing on wet metallographic papers, followed by final polishing on fine, levigated alumina on gamal cloth and a medium speed wheel were used throughout this investigation. Grain boundaries were revealed with modified Tucker&apos;s etch containing 20 parts glycerine, 2 parts hydrofluoric acid, and one part nitric acid. Grain-Growth Procedure: Three lots of zirconium, designated here as series A, B, and C were prepared for the grain-growth studies as follows: Series A was prepared by cold swaging the % in. as-deposited rod to a 3/16 in. final diameter, followed

Jan 1, 1952