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By E. T. Turkdogan, P. Grieveson

Molten silver is equilibrated with silicon nitride at 1400°C in nitrogen + hydrogen gas mixtures, and from the solubility data the activity coefficient of silicon is found to be 1.76 at silicon concentrations below 1 pct. Using this value, and that available from the silicon cmbide solubility measurements, together with those derived from the phase equilibrium diagvam, the activities of silver and silicon are estimated for the entire composition range. The main feature of the activity data is that there is a pronounced positive deviation from ideality. The activity of silver in molten silver containing up to 5 pct Si was determined by Schadel, Derge, and Birchenall1 by measuring the vapor pressure of pure silver and of the alloy over a temperature range of 850º to 1050°C. They deduced from their results that there is a positive deviation from Raoult's law and that the activity coefficient of silver increases with decreasing temperature. However, as pointed out by Kubaschewski and Catterall,2 their activity coefficients are much too high, giving silver activities greater than unity. At a later date McCabe and Birchenal13 showed that the previous vapor pressure data on silver4 were high by a factor of about 1.3; presumably a similar error must have occurred with the vapor pressure measurements on the Ag-Si alloys. The activities of silicon and silver calculated by tager' from the phase diagram and by Gibbs-Duhem integration, respectively, show a positive deviation from Raoult's law for silicon activity and positive and negative deviations for the silver activity. According to these computations, at infinite dilution of silicon ygi = 1.12 at 1420°C. d'Entremont and chipman6 measured the solubility of silicon carbide in molten silver at unit carbon activity; the equilibrium silicon content is found to be Nsi = 0.017 ± 0.002 atom fraction for 1420°C. Using the data of Grieveson and Alcock7 for the free energy of formation of silicon carbide from pure silicon and graphite, the activity of silicon for unit activity of carbon and of silicon carbide is asi = 0.0308 at 1420°c; therefore for the above solubility data on silver, YSi = 1.81, which is somewhat higher than that given by Hager. Use is often made of silver alloys in the measurements of activities of solutes in metals where silver has a very low solubility; in fact, Ag-Si and Ag-A1 alloys have been used in the past for such purposes. In an attempt to gain more thermodynamic data on molten Ag-Si alloys, measurements have been made in the present study on the solubility of silicon nitride in molten silver; the results on these solubilities are given in this paper together with a detailed discussion of activities of silver and silicon. SOLUBILITY OF SILICON NITRIDE The standard free energy of formation of silicon nitride is known with a reasonably high degree of accuracy. According to the measurements made by Hincke and Brantle8 and by Pehlke and Elliott,' the following are the free energy data for the standard states of solid Si3N4, liquid silicon, and Nz at 1 atm pressure:

Jan 1, 1963

By D. A. Stevenson, T. Alden, J. Wulff

A portion of the liquidus curve has been determined for the binary alloy systems Ni-Pb and Cr-Pb. The solubility of nickel is 0.53 atomic pet at 372° and 18.63 atomic pet at 1200°C. Chromium shows low solubility, 0.634 atomic pet at 1210°C. Molybdenum and tungsten were also studied and found insoluble in lead, less than 0.005 atomic pet at 1200°C. INCREASED use of liquid metals of low melting X point for heat transfer, coating, joining, and other purposes has renewed interest in the solubility of structural metals in these liquids. A study of Hansen1 and current literature indicates that few liquidus curves at the low melting end of the binary diagrams have been accurately delineated. This statement applies particularly to the binaries of lead. The present paper is limited to nickel, chromium, tungsten, and molybdenum in lead. In early studies2, 3 of the lead end of the Pb-Ni system, a monotectic at 1340°C was established. Tammann and Oelsen' determined the solid solubility of nickel in lead at 20°C to be 0.023 wt pet. Recently Pelzel5 determined the liquidus curve from the eutectic temperature of 327° up to 727°C using a segregation method. In the present paper this part of the curve has been checked and extended to 1244°C. The Pb-Cr system was first studied by Hindrichs.6 He pointed out the existence of a monotectic at 1470°C and indicated a tentative liquidus. Recent corrosion studies of Fe-Cr alloys in lead suggest that chromium is more soluble than iron in lead.7-8 The solubility of tungsten in lead according to Inouye8 is about 30 wt pet at 1200°C. Appreciable solubility of molybdenum in lead might therefore be expected. Experimental Various experimental techniques have been employed in the determination of solubility in liquid metals. For low solubility, thermal analysis is unsatisfactory. A segregation method was used by Pelzel3 in his study of the Pb-Ni system. In this procedure separation of liquid and solid is possible due to difference in density. In the technique of Kleppa10 a single piece of material is maintained in contact with the liquid metal in evacuated Vycor vials. After equilibration, solid and liquid are separated by tilting. Keck and Broder" measured the weight of a piece of the solid solute before and after immersion in a pure solvent bath; the weight loss was a measure of the solubility. All of the above procedures are time-consuming since they permit only one determination per run. Numerous samples for analysis may be taken from the melt in the method described by Gurinsky and CO-workers.10 The rate of extraction of samples is limited only by the time required for equilibration. In the present work, a modification of this method was employed. A 150-g charge of analytical reagent grade lead and the added metal* were contained in an Alun- dum crucible. It rested on firiely divided silica at the closed end of a 45 mm Vycor tube, 500 mm long. The top of the tube was provided with an inlet and

Jan 1, 1959

By A. G. Guy

Zinc vapor from a reservoir of liquid zinc maintained at lower temperatures was diffused into sets of copper-zinc alloys at 759° and 870° C and into sets of silver-zinc alloys at 650° and 700° C. Each set of ,four copper-zinc alloys consisted of pure copper and 90/10, 80/20, and 70/30 brass. Similarly the set of silver-base alloys consisted of specimens containing 0, 7, 15, and 20 pct Zn. Natural markers at the initial surfaces of the specimens ware "trapped" under a thin electroplate and their depth of burying was measured after diffusion. The ratio of diffusivities of the two components determined from these data and the chemical diffusion coefficient calculated by the Matano method agreed with previously reported results. The line of markers was irregular and was often discontinuous when a grain boundary was crossed. TECHNIQUES involving the vapor phase have been widely employed in studying diffusion phenomena in metals. Many investigators have evaporated the more volatile component from an alloy, but it is generally believed that the porosity created under these conditions interferes with adequate interpretation of the experimental results. The extensive work of Gertsriken6 has been criticized on this score. Accary1 found that the diffusion coefficient for de-zincification of brass is larger by a factor of five than that for zincification, although he attributed the difference to a higher vacancy concentration under conditions of dezincification. Balluffi and siegle2 thoroughly investigated the technique of adding a more volatile component to a less volatile base metal as a means for studying diffusion. They verified that no porosity forms in a brass under these conditions and that the diffusivities of the two components can be determined from observations of the motion of markers originally placed on the surface of the specimen. The mathematical analysis that they developed for treating the experimental data was modified in a later note, but essentially it involved using the graphical Boltzmann-Matano method that is customarily applied to solid-solid diffusion couples. The experimental method used in the present research was similar to that employed by Balluffi and Siegle except for two modifications. Balluffi and Siegle used alloy chips as the source of metal vapor. This procedure has the disadvantage that the concentration of solute at the surface of the specimen changes during the diffusion experiment as the alloy content of the chips is gradually decreased. This disadvantage was overcome by employing liquid zinc as the source of zinc vapor in a manner similar to that described by Herasymenko.9 There was then no limitation on the amount of solute usefully available, and several relatively large specimens could be diffused in a given experiment. The second modification was the use of natural markers on the surface of the specimen rather than larger, artificial markers, such as the alumina powder employed by Balluffi and Siegle. It was expected that the fine, natural markers would permit more precise measurement of the buried interface as in the case of ordinary sandwich specimens.10 EXPERIMENTAL The experiments were designed so that zinc from the vapor phase would maintain a constant zinc content at the surface of pure copper (or silver) and

Jan 1, 1960

By W. Rostoker, D. W. Levinson, A. Yamamoto

The influence of carbon on tensile strength, tensile ductility, transformation kinetics, and grain growth characteristics of selected Ti-Mo base alloys was studied. No systematic influence of carbon in tensile strength or significant deleterious effect on tensile ductility was observed. There was a marked increase in transformation rate due to carbon. Dispersed carbides exert a marked inhibiting effect on grain boundary migration, and thus effectively prevent grain coarsening during solution treatment in the ß phase field. AS part of a research program directed toward the illumination of factors governing modes of transformation, transformation kinetics, and mechanical properties obtainable through these transformations by heat treatment, Ti-Mo base alloys were selected for study. The binary system is a characteristic phase diagram type which has been studied in some detail', ' in relation to transformation kinetics and mechanical properties. Although carbon bearing alloys have acquired a bad reputation, the possibilities of melting titanium under conditions which occasion some carbon pickup are very attractive. It is therefore of considerable importance to know whether carbon, present as a dispersed carbide phase, is actually deleterious when all other detrimental factors are minimized. Basic alloy compositions containing nominally 3, 5, 7, and 11 pet Mo were prepared with systematic carbon addition up to 1 pet by weight. Various of these alloys were subjected to a series of critical and definitive experiments to delineate the effect of carbon on the transformation behavior and associated mechanical properties. Experimental Procedure Alloys were prepared from 115 Bhn magnesium-reduced sponge titanium. This sponge analyzed ap- proximately 0.05 pet C. Ti-Mo and Ti-C master alloys were made by arc-melting the sponge with high purity (99.9 + pet) molybdenum and spectro-scopic grade graphite, respectively. Alloys were then prepared from the master alloys and sponge by double are-melting. One kg ingots were prepared by melting in a nonconsumable electrode furnace. These ingots were forged at 1000°C to '/z in. rods, and cleaned and processed into electrodes for the second melting operation. The final ingots were ground to remove surface defects, then forged again to 1/2 in. or 3/8 in. diam rods for processing to test samples. It is significant that all of the alloys at all carbon levels forged satisfactorily. For convenience, the alloys will be referred to throughout the text by their nominal analyses. Samples for the study of transformation rates were prepared from 1/2 in. diam round stock. They were then solution treated in a helium filled tube furnace at 1000°C for 30 min prior to the isothermal transformation treatments in lead bath furnaces. Temperature control in both cases was within ±3oC. Following the isothermal transformation treatments the samples were water quenched. These experiments were carried out before the general adoption of the resistometric procedure for kinetic studies. The data were therefore obtained entirely by metal-lographic analysis. M, temperature was also determined by the metallographic method. Shoulder-type tensile test pieces were machined from heat treated, 1/2 in. diam slugs to provide a 0.252 in. test diam and a 1 in. gage length. The isothermal-type heat treatments were chosen from previous data' to provide three levels of strength and ductility.

Jan 1, 1957

By M. C. Flemings, P. J. Ahearn

Dendvite morphology of unidirectionally solidified Sn-12 pct Bi alloy was determined with the aid of X-ray and macroetch techniques. Columnar growth direction (growth direction of primary arms) in this alloy is [110]; secondary arms grow in the [lii], [111), and [112] directions. Interstices between [112] dendrite arms fill in during early stages of solidification so that well-defined (110) planes are seen in the final structure (parallel to the heat-flozo direction). Similarly, interslices betweex the [111] secondary arrlls fill in to form (112) planes, and interstices between [1111 ] arms fill in to form (112) planes. DENDRITE morphology in alloys is conveniently studied in unidirectionally solidified castings. In this type of solidification, heat is extracted from a single chill surface of the casting while other surfaces are insulated. Solidification progresses from the chill and results in cast grains that are columnar with the long axis of the grain perpendicular to the chill. Dendrite morphology is conveniently studied by examination of etched surfaces parallel and perpendicular to the chill, as previously described.'" Experimental studies on the growth direction for tin are in general agreement. The major growth direction is [110]:-' although this is altered somewhat by supercooling. In one study, tin dendrites pulled from a supercooled melt had a growth orientation 12 deg away from the [110] direction toward the [002] direction.' This orientation could be changed back to the [110] or close to the [110] direction by changing the tempera- ture gradient in the melt. In a study using autoradio-graphic techniques, (111) directions were shown to be directions of preferred growth in addition to the [110) direction.7 PROCEDURE The samples employed in this study were cut from 12 pct Bi-88 pct Sn castings, 1.5 in. in diam and 3.5 in. tall. The casting procedure consisted of heating the charge to 390°C and then pouring the molten alloy directly into a gypsum sleeve mounted on a massive copper chill. Specimens were cut from the ingot, mounted, polished, and etched with Taffs reagent [FeC13 .6H2O, 2 g; HC1, 5 cu cm;H20, 30 cu cm; CzHaOH (95 pct), 60 cu cm].' The dendritic pattern was clearly visible after etching. Photomicrographs at about 8 and 35 times were taken on surfaces parallel and perpendicular to the chill. Laue back-reflection patterns were obtained from three different columnar grains in a singIe polished face 2 in. from the chill. The cut face was polished and positioned in the beam of a Laue camera, so that diffraction occurred from a single dendritic grain. The resulting diffraction pattern was interpreted to determine crystal log raphic orientation in relation to the heat-flow direction and in relation to microstruc-ture of the given grain. RESULTS Fig. 1 shows a horizontal and vertical section of the columnar structure, at low magnification. Light regions are rich in tin, and darker regions tin-poor; the primary phase is tin-rich a phase. The two sections shown were taken orthogonally from the same metallographic specimen. It is readily seen from Fig. 1 that the dendrites have

Jan 1, 1968

By Kenneth Cottingham

The number of wells completed in Ohio during I940 was about 20 per cent more than during the preceding year, the comparative totals being 1020 and 1228. Of the 1940 completions, 327 were oil wells, 491 gas wells, and 410 dry. The completions for the past five years, divided into oil wells, gas wells, and dry holes, are shown in Table 2. Wells drilled deeper and input wells in water-flood areas are not included in the tabulation. The annual production of oil has decreased steadily in Ohio from the maximum of 23,941,000 bbl. produced in 1896. Table 3 shows the quantities of oil produced in the last five years. In 1940, the total was 3,052,000 bbl., produced by about 25,500 wells. The number of wells and the approximate quantities by grades are shown in Table I. Table i ,—Tabulation by Grade Grade 1 2 Barrels __________________________________________________________________________________________ Pennsylvania ............. . 1,198,000 Lima.................... . 325,000 Corning................... 3,730 1,159,000 Lodi...................... T,040 350,000 Cleveland................. 30 1:1,000 Total................... 25,500 3,052,000 The prices paid for Ohio crude oil in 1940, together with dates of changes in posting, are shown in Table 4. The production of natural gas in 0hio has declined from a maximum of 79,510,032 M cu. ft. in I9I5 S to 36,469,000 M cu. ft. in 1939, the most recent year for which a figure is available. Consumption reached its peak in Ohio in the year 1916, when it was 169,480,01r M cu. ft., declining to 114,720,ooo M CU. ft. in 1939. The produc-tion and consumption of natural gas in Ohio for the past five years are shown in Table 5. TAble 2.—Completions in Ohio during Past Five Years Numbs of Wells Drilled during Year YearI, ] Oil Gas Dry Total 1936............. 263 570 324 1,157 1937............. 317 503 45I 1,271 1938............. 189 433 288 gro 1939............. I70 501 349 1,020 19391940............. 327 491 410 1,228 Total.......... 1,266 2,498 1,822 5,586 Table 6 shows the number of oil wells and the number of gas wells completed by sands during 1940, with the average initial production per well for each sand. Table 7 shows the total number of wells drilled—oil, gas and dry—by sands. Development during 1940 Szth-Trenton.—For several years, considerahle interest has been shown in a horizon lying some 500 to 700 ft. below the top of the Trenton, known to the driller in western Ohio as the "green sand," and in eastern Ohio as the St. Peter. In 1939, ten 'lgreen sand" tests were drilled, all in western Ohio and all dry- In 19401 eight wells were drilled to this horizon, one of which was a small oil well (one barrel) in Men county- Of the remaining seven—all of which were dry-—one in Franklin County, in central Ohio, was drilled to a depth of 2903 ft. .Another was in Medina

Jan 1, 1941

By Kenneth Cottingham

The number of wells completed in Ohio during I940 was about 20 per cent more than during the preceding year, the comparative totals being 1020 and 1228. Of the 1940 completions, 327 were oil wells, 491 gas wells, and 410 dry. The completions for the past five years, divided into oil wells, gas wells, and dry holes, are shown in Table 2. Wells drilled deeper and input wells in water-flood areas are not included in the tabulation. The annual production of oil has decreased steadily in Ohio from the maximum of 23,941,000 bbl. produced in 1896. Table 3 shows the quantities of oil produced in the last five years. In 1940, the total was 3,052,000 bbl., produced by about 25,500 wells. The number of wells and the approximate quantities by grades are shown in Table I. Table i ,—Tabulation by Grade Grade 1 2 Barrels __________________________________________________________________________________________ Pennsylvania ............. . 1,198,000 Lima.................... . 325,000 Corning................... 3,730 1,159,000 Lodi...................... T,040 350,000 Cleveland................. 30 1:1,000 Total................... 25,500 3,052,000 The prices paid for Ohio crude oil in 1940, together with dates of changes in posting, are shown in Table 4. The production of natural gas in 0hio has declined from a maximum of 79,510,032 M cu. ft. in I9I5 S to 36,469,000 M cu. ft. in 1939, the most recent year for which a figure is available. Consumption reached its peak in Ohio in the year 1916, when it was 169,480,01r M cu. ft., declining to 114,720,ooo M CU. ft. in 1939. The produc-tion and consumption of natural gas in Ohio for the past five years are shown in Table 5. TAble 2.—Completions in Ohio during Past Five Years Numbs of Wells Drilled during Year YearI, ] Oil Gas Dry Total 1936............. 263 570 324 1,157 1937............. 317 503 45I 1,271 1938............. 189 433 288 gro 1939............. I70 501 349 1,020 19391940............. 327 491 410 1,228 Total.......... 1,266 2,498 1,822 5,586 Table 6 shows the number of oil wells and the number of gas wells completed by sands during 1940, with the average initial production per well for each sand. Table 7 shows the total number of wells drilled—oil, gas and dry—by sands. Development during 1940 Szth-Trenton.—For several years, considerahle interest has been shown in a horizon lying some 500 to 700 ft. below the top of the Trenton, known to the driller in western Ohio as the "green sand," and in eastern Ohio as the St. Peter. In 1939, ten 'lgreen sand" tests were drilled, all in western Ohio and all dry- In 19401 eight wells were drilled to this horizon, one of which was a small oil well (one barrel) in Men county- Of the remaining seven—all of which were dry-—one in Franklin County, in central Ohio, was drilled to a depth of 2903 ft. .Another was in Medina

Jan 1, 1941

By John T. Galey

Production of crude oil for 1940 in southwestern Pennsylvania was off nearly 70,000 bbl., largely as a result of the great number oi abandonments, together with the lack of extension of the Washington and Green County pools. Oil wells completed numbered 51, which is 26 more than last year, but the total initial production of 259 bbl. is only 18 bbl. greater than in 1939. There was an increase of 72 over last year for a total of 209f gas wells. However, 68 7 dry holes were drilled, which is 40 more than a year ago. Thus, 328f wells were drilled during the year, and rigs are erected or drilling is progressing on 59 t more. Shallow Development Oil.—Butler County led in number of oil wells completed, with a total of 27 for an initial production of only 69 bbl. Washington County, with 12 new oil wells, one of which made 40 bbl. from the Fifth sand in S. Franklin township, has 95 bbl., while in Allegheny County 9 wells gave an initial of 86 bbl. for the highest Per well average in the area. This initial was given a considerable boost by one 35-bbl and another 2;-bbl. well in West Deer township, where the Fourth sand produced at 1840 feet. Greene County had only one oil well completed during 1940, and Washington County had 12. The subnormal totals for these counties may be explained by the higher cost of completions and the declining price of crude. The first price change in crude during the year occurred on May 22, when a 25 cut was made. A second 25 cut was made July 12, and was followed by a 156 cut on .Aug. 28. This price held until Nov. 12, when there was a restoration of 156. On Dec. 17 a second 156 increase was put into effect, bringing the price to $I.So per barrel. Gas The large increase in the number of gas wells completed may be attributed to three factors; namely, the recently discovered production possibilities of moderately deep, hitherto little tested horizons, together with increased demand and price. The latter has been made possible by a recent decision of the court, which ruled restraining the public service Commision's prohibition of a raise in the minimum monthly charge to small consumers by one of the major gas companies. A portion of the revenue derived in this manner is being passed along to the producer in the form of higher prices in the field. This higher field rate will remain in effect until a new ruling is made, when it will be reduced in proportion to the reduction of the monthly minimum charge. In an effort to extend the chambers Dam Fifth sand oil pool southwest from Amwell township, Washington County, several wells have been drilled. One of these, in Morris township, washington County, had an initial of 3.2 million cu. ft. open flow from the Big Injun sand. This indicates an entirely new productive area for the latter horizon. Allegheny County had one spectacular well in South Fayette township-—at a depth of about 2500 ft. a 4-million-CU. ft.

Jan 1, 1941

By Arch J. Alexander

COAL is produced, in commercial quantities, in thirty-five of the sty-five counties of West Virginia. Oil and gas are produced, commercially, in forty-two counties. So, you may readily see that coal, oil and gas are closely related as to production areas. Many of the West Virginia coal mines are studded with oil and gas wells, as drilling has been done in thirty-two of the coal bearing counties. When the drilling of oil and gas wells was placed under the regulatory control of the Department of Mines on June I, 1929, it was estimated, by the State Geological Survey, that 64,000 wells had been drilled in West Virginia and that 34,mo wells were then being operated as oil and gas producers. No records of many of these remaining 30,000 abandoned wells exist and some of them remain a standing menace to safety as our coal extraction continues. Of a total of 13,100 new wells drilled since June 1929, approximately 5,200 have been drilled through coal measures. Approximately 7,000 wells, which were drilled through coal measures, have been abandoned in the same period of time. Many of these wells were drilled prior to the enactment of the oil and gas laws. Prior to the enactment of the Oil and Gas Law, which established the Oil and Gas Division of the Department of Mines in 1929, there had been several mine explosions attributable to cutting into un- charted wells and the improper plugging of other wells. The most serious explosion was that of Mines No. 47 and No. 49 of the Consolidation Coal Co. in Marion Co., when one of the so-called plugged wells leaked or seeped through some 80 ft of strata to the coal bed elevation, filling the mine with gas, the gas being ignited, killing a good many men and wrecking two coal mines. Legislation, to combat well hazards to coal mines, was slow in coming. In 1928, R. M. Lambie, then Chief of the Dept. of Mines, got sufficient support from coal, oil and gas interests to get the legislature to pass our present oil and gas laws. These statutes not only protected the coal industry but went a long way toward conserving the oil and gas resources of our state. Before drilling for oil or gas on any tract of land, known to be underlaid with one or more workable seams of coal, the well operator is required to submit a map of the area showing the location of the proposed well, and to send a copy to the Dept. of Mines and a copy to the coal operator. If no objections to the location of the proposed well are made by the coal operator within ten days, a drilling permit and a number for the well are then issued and work may proceed. If, however, the location of the proposed well is objected to by the coal operator, on the grounds that the location of the well will interfere with present mine operations, projected workings, or other- wise Cause a dangerous condition, the operator may file a written objection with the Dept. of Mines.

Jan 1, 1948

By John T. Galey

Production of crude oil for 1940 in southwestern Pennsylvania was off nearly 70,000 bbl., largely as a result of the great number oi abandonments, together with the lack of extension of the Washington and Green County pools. Oil wells completed numbered 51, which is 26 more than last year, but the total initial production of 259 bbl. is only 18 bbl. greater than in 1939. There was an increase of 72 over last year for a total of 209f gas wells. However, 68 7 dry holes were drilled, which is 40 more than a year ago. Thus, 328f wells were drilled during the year, and rigs are erected or drilling is progressing on 59 t more. Shallow Development Oil.—Butler County led in number of oil wells completed, with a total of 27 for an initial production of only 69 bbl. Washington County, with 12 new oil wells, one of which made 40 bbl. from the Fifth sand in S. Franklin township, has 95 bbl., while in Allegheny County 9 wells gave an initial of 86 bbl. for the highest Per well average in the area. This initial was given a considerable boost by one 35-bbl and another 2;-bbl. well in West Deer township, where the Fourth sand produced at 1840 feet. Greene County had only one oil well completed during 1940, and Washington County had 12. The subnormal totals for these counties may be explained by the higher cost of completions and the declining price of crude. The first price change in crude during the year occurred on May 22, when a 25 cut was made. A second 25 cut was made July 12, and was followed by a 156 cut on .Aug. 28. This price held until Nov. 12, when there was a restoration of 156. On Dec. 17 a second 156 increase was put into effect, bringing the price to $I.So per barrel. Gas The large increase in the number of gas wells completed may be attributed to three factors; namely, the recently discovered production possibilities of moderately deep, hitherto little tested horizons, together with increased demand and price. The latter has been made possible by a recent decision of the court, which ruled restraining the public service Commision's prohibition of a raise in the minimum monthly charge to small consumers by one of the major gas companies. A portion of the revenue derived in this manner is being passed along to the producer in the form of higher prices in the field. This higher field rate will remain in effect until a new ruling is made, when it will be reduced in proportion to the reduction of the monthly minimum charge. In an effort to extend the chambers Dam Fifth sand oil pool southwest from Amwell township, Washington County, several wells have been drilled. One of these, in Morris township, washington County, had an initial of 3.2 million cu. ft. open flow from the Big Injun sand. This indicates an entirely new productive area for the latter horizon. Allegheny County had one spectacular well in South Fayette township-—at a depth of about 2500 ft. a 4-million-CU. ft.

Jan 1, 1941

By Alec M. Crowell, J. W. Sanders

While the production of crude oil and condensate in South Arkansas increased only 1.7 per cent over the 1940 figure, complete utilization of gas produced with the oil and condensate, and heretofore wasted, was beginning to be evidenced. There were 26,229,264 bbl. of oil and condensate produced in South Arkansas during 1941, as against 25,790,380 bbl. for the year 1940. (Fig. I.) Since 1936, deep producing sands have been discovered in 18 fields and during that period only 40 per cent of the total state production has come from Upper Cretaceous formations while 60 per cent came from the Lower Cretaceous and Jurassic formations. The gas produced with crude oil and condensate from the latter formation contains large quantities of hydrogen sulphide, the maximum being 6900 grains per 100 cu. ft. in the Patton pool of Lafayette County. Gas Utilization During the latter part of 1940 and the early part of 1941, pilot plants were placed in operation to determine whether the hydrogen sulphide and deleterious material in South Arkansas gases could be removed economically. The Federal Government desired to build a large aluminum plant in the Ouachita Valley and was seeking cheap fuel for the generation of electricity. The fact that the gases were produced with appreciable quantities of crude oil and condensate made it available at a very low price, since the state's conservation law prohibits the flaring of any gas. As a result of these experiments the first large-scale unit for the processing of gases containing hydrogen sulphide was placed in operation on Sept. I, 1941. The plant is in the Magnolia oil field, Columbia County. It processes residue gas from the Shell Oil Company's gasoline plant in that field and also raw gas from the Village field, 6 miles east of the Magnolia field. The gas entering the desulphuri-zation unit is laden with approximately 1400 grains of hydrogen sulphide per 100 cu. ft. and is stripped to a content of 4 grains per 100 cu. ft. The capacity of the plant is 15 million cu. ft. of gas treated daily under a pressure of 160 lb. per sq. in. The cost of treatment, exclusive of depreciation, is appreciably less than I per 1000 cubic feet. Two other plants of much greater capacity have been announced and priorities have been granted, which should bring the total amount of gas treated to 150 million cu. ft. daily. The gas to be treated will have a maximum hydrogen sulphide content of 4500 grains per 100 cu. ft. and will be processed under a pressure of 600 lb. per sq. in. These developments are something entirely new in field practice for the industry. The fact that this heretofore wasted gas is available at very low cost has led to the location of some eight war industries within the state, in addition to the alu-minum plant. Recovery OF Sulphur The Susearch Corporation and the Southern Acid and Sulphur Co. placed in operation during 1941 pilot plants to de-

Jan 1, 1942

By Alec M. Crowell, J. W. Sanders

While the production of crude oil and condensate in South Arkansas increased only 1.7 per cent over the 1940 figure, complete utilization of gas produced with the oil and condensate, and heretofore wasted, was beginning to be evidenced. There were 26,229,264 bbl. of oil and condensate produced in South Arkansas during 1941, as against 25,790,380 bbl. for the year 1940. (Fig. I.) Since 1936, deep producing sands have been discovered in 18 fields and during that period only 40 per cent of the total state production has come from Upper Cretaceous formations while 60 per cent came from the Lower Cretaceous and Jurassic formations. The gas produced with crude oil and condensate from the latter formation contains large quantities of hydrogen sulphide, the maximum being 6900 grains per 100 cu. ft. in the Patton pool of Lafayette County. Gas Utilization During the latter part of 1940 and the early part of 1941, pilot plants were placed in operation to determine whether the hydrogen sulphide and deleterious material in South Arkansas gases could be removed economically. The Federal Government desired to build a large aluminum plant in the Ouachita Valley and was seeking cheap fuel for the generation of electricity. The fact that the gases were produced with appreciable quantities of crude oil and condensate made it available at a very low price, since the state's conservation law prohibits the flaring of any gas. As a result of these experiments the first large-scale unit for the processing of gases containing hydrogen sulphide was placed in operation on Sept. I, 1941. The plant is in the Magnolia oil field, Columbia County. It processes residue gas from the Shell Oil Company's gasoline plant in that field and also raw gas from the Village field, 6 miles east of the Magnolia field. The gas entering the desulphuri-zation unit is laden with approximately 1400 grains of hydrogen sulphide per 100 cu. ft. and is stripped to a content of 4 grains per 100 cu. ft. The capacity of the plant is 15 million cu. ft. of gas treated daily under a pressure of 160 lb. per sq. in. The cost of treatment, exclusive of depreciation, is appreciably less than I per 1000 cubic feet. Two other plants of much greater capacity have been announced and priorities have been granted, which should bring the total amount of gas treated to 150 million cu. ft. daily. The gas to be treated will have a maximum hydrogen sulphide content of 4500 grains per 100 cu. ft. and will be processed under a pressure of 600 lb. per sq. in. These developments are something entirely new in field practice for the industry. The fact that this heretofore wasted gas is available at very low cost has led to the location of some eight war industries within the state, in addition to the alu-minum plant. Recovery OF Sulphur The Susearch Corporation and the Southern Acid and Sulphur Co. placed in operation during 1941 pilot plants to de-

Jan 1, 1942

By O. D. Gonzalez

ThIS communication presents the results of a determination of the permeabilities of hydrogen and deuterium in a iron from 360° to 560°C. Recently Heu-mann and primas' have given values of the diffusivity and solubility in a iron of the two isotopes from which the permeability can be calculated. The work reported in the present communication, however, is a direct measurement of the rate of permeation of the isotopes through an identical iron specimen under the same conditions, so that systematic errors can be minimized in the calculation of the ratio of the permeabilities—the value which is usually of main importance in establishing limits for isotopic differences in diffusive processes. Experimentally the procedure used was the usual one: a steady-state flow of gas produced by a pressure difference across an iron membrane was observed as the pressure rise with time in a previously evacuated, calibrated volume connected to the outlet side of the membrane, while a constant pressure of gas was maintained on the opposite inlet side. The membrane was a cylindrical tube 9.38 cm long, 0.730 cm inside diam, 0.187 cm wall thickness, fabricated of 99.95 pct vacuum-melted National Research Corp. iron (less than 0.003 pct C). One end was sealed by a heliarc-welded iron (99.95 pctj lid of 0.147 cm thickness; the other end of the tube was welded to a 304 stainless-steel tube (0.318 cm ID and 0.318 cm wall) which connects to a vacuum system and to the calibrated volume including a dibutylphthalate manometer. The temperature of the iron membrane was maintained constant to ±0.l°C and was measured with an iron-constantan thermocouple which was calibrated against a standard Pt/Pt-Rh thermocouple: the temperature variation along the length of the membrane did not exceed ±0.5°C. Hydrogen was allowed to pass through the membrane assembly for 72 hr at 615°C before permeability measurements were begun. The system was tested at temperature before and after the experiments by a substitution of helium for hydrogen in the inlet side; under these conditions the pressure rise observed in the outlet side was negligible at all times. The gases used for the permeability measurements were 99.95 pct Matheson prepurified H2 and 99.7 pct D2 (0.3 pct HD) from the Isomet Corp. The gases were dried with liquid N2 before use. In Fig. 1 the logarithms of observed flows, jt, for a pressure difference of 73.4 cm Hg are plotted against T-1 Each point in Fig. 1 represents the slope determined by a least-square evaluation of a plot of the pressure in the outlet side of the membrane against time, including at least two separate sets of observations. Each point in the figure has an uncertainty of ±0.6 pct arising from the experimental uncertainty in the pressure and time measurements. The standard deviation of the observed pressures from the straight lines in all cases is less than the experimental precision of the measurements. The observed flow, jt, includes a small but not negligible flow through the stainless-steel connection.

Jan 1, 1968

By H. Papazian, Robert A. Lad

SINCE it can be shown both theoretically'' : and experimentally that disordered Cu3Au has a greater internal energy than the ordered alloy, it might be expected that its chemical reactivity would be greater. Experiments were initiated' to test this hypothesis. This note will describe some recent results obtained in the study of the rates of corrosion of ordered and disordered polycrystalline Cu3Au by aqueous FeCl., The work of Robertson' has indicated that the attack by such solutions is intergran-ular and highly orientation dependent. It was of interest to see whether the order-disorder effect was great enough to overcome the variations from specimen to specimen which would arise from this type of attack. The polycrystalline alloy specimens (0.020 in. wire, 1¾ in. long) were preannealed in ½ atm H, at 700°C for 2 hr. The subsequent heat treatments to produce order and disorder were performed in M atm He. Disordered specimens were obtained by heating at 450°C for 2 hr and quenching in water. Ordered specimens were produced by heating for 2 hr at 450°, furnace cooling to 380°, and soaking at 380°C for 80 to 90 hr. Room temperature was reached by cooling to 150" at a rate never exceeding 7" per hr, and water quenching from 150°C. The specimens so produced exhibited electrical resistivities characteristic of the two states; of the order of 11.27x10 ohm-cm for the disordered, and 4.28x10 ohm-cm for the ordered specimens. The corrosion rates were studied at 30°C in ferric chloride solutions of several concentrations (?,¼, 1.5, and 1 molar). The specimens were attached to a stirrer during the tests. Tests were interrupted at intervals, and the specimen weight change was determined after washing and drying. Analysis of the solutions showed that the attack was limited to the copper. The higher corrosion rate for the disordered alloy, as illustrated in Fig. l, is typical of the results obtained. The effect of variation in ferric chloride concentrations is indicated in Table I for typical specimens. The variations in the ratio of reactivity for disordered and ordered specimens at the different concentrations are within experimental error, and the best value is estimated to be near 1.4. The experimental variation was due in part to the mode of attack, as mentioned, and in part to the fact that films were formed on the specimens under some conditions. Electron diffraction patterns of the films were very complex and indicated the presence of metallic iron, as did chemical analysis. In an attempt to eliminate the difficulties arising from the mechanism of attack, single crystal specimens were used. A greater reaction rate was again measured for the disordered specimens, but the reproduci-bility was no better than that for the polycrystalline metal. This would indicate that film formation was primarily responsible. It was concluded that the reaction with aqueous ferric chloride served to demonstrate that the reactivity of disordered Cu3Au is greater than that of the ordered alloy. However, the difficulties with film formation did not permit determinations of a precision great enough to warrant extension of the study to partially ordered alloy systems.

Jan 1, 1957

By A. A. Burr, D. G. Ebeling

The effects of casting texture, grain orientation and grain size upon the performance of Alnico permanent magnets is described. Single-crystal specimens were produced by special sintering and grain coarsening techniques to study the effect of crystal orientation. In addition to texture and orientation effects, an analysis of the results indicates that the permanent magnet performance is impaired by a refinement of the grain size. AN excellent historical review of the development of Alnico permanent magnets has been prepared by Bozorth.1 The desirable permanent magnet characteristics of Fe-Ni-A1 alloys were discovered in 1932 by Mishima.2,3 The work of Ruder' showed that the alloys were age-hardenable, and Betteridge5 defined the best composition and heat treatment for the magnetically isotropic alloy known as "Alnico 3." Horsburgh and Tetley0 increased the energy product by the addition of cobalt and copper, "Alnico 2," and Oliver and Sheddon7 demonstrated that cooling in a magnetic field improved the residual induction of this alloy. Jonas8,9 then disclosed the great practical benefits of heat treating an alloy of higher cobalt content in a magnetic field and the resulting alloy, "Alnico 5," has become the standard of the industry. This paper describes the fundamental aspects of a procedure which can be used to further improve the properties of these anisotropic permanent magnet alloys. A study of the casting techniques used in the production of anisotropic Alnico permanent magnets indicated that the magnetic quality was affected by the as-cast macrostructure. Improved performance was observed in magnets containing a high percentage of columnar grains whose long axes were parallel to the magnetic axis of the casting. McCaig10 studied the effect of such columnar grain structures upon the magnetostriction characteristics of similar alloys, however no data was presented showing the effects on other magnetic properties. The following paragraphs describe two experiments which were conducted to determine the effect of various grain orientations upon the energy product. Special composite molds were prepared of highly conductive and highly refractive components to remove the heat of solidification from the casting in a controlled manner. Representative macrostructures produced by these techniques are shown in Fig. 1, along with the relative volumes of favorably oriented columnar grains. The alloy, Alnico 5, has the highest permanent magnet performance of any commercial magnet material. It has the nominal weight composition of 8 pct Al, 14 pct Ni, 24 pct Co, 3 pct Cu, and 51 pct Fe. A heat of this material was cast into molds producing the type A and B grain structures shown in Fig. 1 and pairs of the resulting magnets were placed in heat-treating boats so as to eliminate any biasing effects of boat position. After a standard heat treatment the type A magnets, with 16 pct of the volume composed of favorably aligned grains, had a maximum energy value of 3,940,000 gauss-oersteds, while the type B magnets with 73 pct aligned grains averaged 5,090,000. This large im-

Jan 1, 1954

By M. G. Cheney

Careful estimates indicate that during 1942 new discoveries and extensions in West Central Texas added oil reserves slightly in excess of the eight million barrels produced. Drilling activity fell 40 per cent below 1941 and 82 per cent below the normal drilling activity of the late 1920's. Total production for the district continued its downward trend, now being less than % of the 42.7 million barrels peak in 1921. Rapid revival of activity is not probable under existing conditions, as costs of discovery, development and operations on the average probably now exceed current market price for the oil, the latter having remained constant since the spring of I941. Costs have advanced materially since the third quarter of 1941, when reports to the Tariff Commission indicated a margin of profit of 13.3 per barrel. Physical as well as economic conditions are holding back the amount of drilling in this district. The lenticular sands are not suited to 40-acre spacing regulations. There is no surplus of experienced oil-field labor. To reduce costs, much second-hand material is used for all except the deeper wells.. Price controls have retarded movement of used equipment by prescribing maximum prices that arc too low for the better grade materizl, thus making , owners reluctant to sell. On the other hand, buyers are unwilling to pay ceiling prices asked by sellers for poor material. Seventeen new oil fields and five new gas fields were found during 1942. Extensions and deeper 'drilling brought favorable results in eight older fields. The most significant new developments appear to have been in Coleman, Jones, Shackelford and Taylor Counties. A 5800-ft. completion in Wise County brought this county into the producing column for the first time. None of these new discoveries can he rated above one million barrel reserve on the basis of present development. Probably the most important development was discovery of a deeper pay (Gunsight lime) in the Wimberly field of Jones County, which shows promise of producing over an area of about 1000 acres. Jones and Shackelford Counties still lead the district in total annual production. Discovery of the Reddin pool, north central Taylor County, is credited to geochemical methods, making one success out of five or more wildcats based on such methods. Geophysical surveying increased decidedly during 1942 and returns from these studies are expected during coming years. Most of the wildcatting in the district is still based on surface and subsurface geological structural mapping, study of log data as to distribution of prospective producing reservoirs, and drilling in proximity to previous showings of oil and gas. Geological debate continues as to the proper correlation of the 100 to 300 ft. of gray lime that has produced more than 100 million barrels in the Parks, Brecken-ridge, Curry, Eliasville, Ibex, Pioneer and other important fields of this district. Fossils indicate that this limestone is younger than the Atoka beds of Oklahoma. On a structural basis most geologists include this formation with the Bend but a number of paleontologists believe it is more properly classified with the Strawn.

Jan 1, 1943

By John B. Campbell, George G. Binder, Loren H. Jenks

Conventional methods of producing crude oil generally leave in the depleted reservoir 1 to 3 bbl of oil for every barrel brought to the surface. This paper describes a field test which explores the possibility of using gas-driven liquid propane to improve oil recovery efficiency. Laboratory theoretical and experimental studies leading to the field test indicated that low residual oil values could be obtained using limited amounts of propane driven by gas. The field test involved (I) repressuring the reservoir to the vapor pressure of liquid propane, (2) injecting the liquid propane, and (3) injecting dry natural gas to drive the propane and oil to the producing wells. Considerable preliminary work, including new drilling, work-overs, and a pressure survey was necessary. During the test, oil production rates have averaged about nine times the final primary rates. The field average GOR is still below the pre-test value. Oil recovery to date is 112,000 STB. About one-third of the 143,-000 bbl of propane injected has been produced to date. Results of the C-2 block test are encouraging and larger, more definitive field projects ore indicated. INTRODUCTION The cost of finding new crude oil reservoirs continues to increase. Today the oil industry is drilling more and deeper wells and making fewer big discoveries. Nevertheless, the demand for oil and oil products increases each year. It is natural that oil companies, faced with this situation, concentrate on recovering more of the oil existing in our known crude oil reservoirs. There is room for much improvement. For every barrel of oil brought to the surface by present day methods of producing crude oil, generally 1 to 3 bbl are left behind in the depleted reservoirs. The "unrecoverable" oil in petroleum reservoirs is largely "trapped" by capillarity. Since flushing with a solvent is exceedingly effective in combatting oil loss due to capillarity, much effort in this direction has been made in recent years1,2,3,4,5. Liquefied petroleum gas (LPG) has been suggested as a relatively inexpensive. abundant, easily recoverable solvent for crude. Some operators have observed striking responses in oil recovery at production wells offsetting input wells in LPG storage reservoirs6,7,8. In spite of the low unit cost of LPG, however, it is uneconomic in general to inject a volume of LPG into a reservoir to remove a like volume of oil. A modification of solvent flushing in which a limited quantity of liquid propane is gas driven through a reservoir appears capable of recovering much more than 1 bbl of oil per barrel of propane injected. Also, most of the propane injected should be recoverable for sale or re-use. Since such a process could well have widespread and profitable application, The Carter Oil Co. is making an extensive evaluation of the technique's possibilities. Laboratory development of the gas-driven propane recovery technique was sufficiently encouraging to justify testing in the field. Since 1952, the Production and Research Departments of The Carter Oil Co. have cooperated in a field test in the C-2 Block leases of the

Jan 1, 1958

By M. G. Cheney

Careful estimates indicate that during 1942 new discoveries and extensions in West Central Texas added oil reserves slightly in excess of the eight million barrels produced. Drilling activity fell 40 per cent below 1941 and 82 per cent below the normal drilling activity of the late 1920's. Total production for the district continued its downward trend, now being less than % of the 42.7 million barrels peak in 1921. Rapid revival of activity is not probable under existing conditions, as costs of discovery, development and operations on the average probably now exceed current market price for the oil, the latter having remained constant since the spring of I941. Costs have advanced materially since the third quarter of 1941, when reports to the Tariff Commission indicated a margin of profit of 13.3 per barrel. Physical as well as economic conditions are holding back the amount of drilling in this district. The lenticular sands are not suited to 40-acre spacing regulations. There is no surplus of experienced oil-field labor. To reduce costs, much second-hand material is used for all except the deeper wells.. Price controls have retarded movement of used equipment by prescribing maximum prices that arc too low for the better grade materizl, thus making , owners reluctant to sell. On the other hand, buyers are unwilling to pay ceiling prices asked by sellers for poor material. Seventeen new oil fields and five new gas fields were found during 1942. Extensions and deeper 'drilling brought favorable results in eight older fields. The most significant new developments appear to have been in Coleman, Jones, Shackelford and Taylor Counties. A 5800-ft. completion in Wise County brought this county into the producing column for the first time. None of these new discoveries can he rated above one million barrel reserve on the basis of present development. Probably the most important development was discovery of a deeper pay (Gunsight lime) in the Wimberly field of Jones County, which shows promise of producing over an area of about 1000 acres. Jones and Shackelford Counties still lead the district in total annual production. Discovery of the Reddin pool, north central Taylor County, is credited to geochemical methods, making one success out of five or more wildcats based on such methods. Geophysical surveying increased decidedly during 1942 and returns from these studies are expected during coming years. Most of the wildcatting in the district is still based on surface and subsurface geological structural mapping, study of log data as to distribution of prospective producing reservoirs, and drilling in proximity to previous showings of oil and gas. Geological debate continues as to the proper correlation of the 100 to 300 ft. of gray lime that has produced more than 100 million barrels in the Parks, Brecken-ridge, Curry, Eliasville, Ibex, Pioneer and other important fields of this district. Fossils indicate that this limestone is younger than the Atoka beds of Oklahoma. On a structural basis most geologists include this formation with the Bend but a number of paleontologists believe it is more properly classified with the Strawn.

Jan 1, 1943

By P. Marier, T. R. Ingraham

When anhydrous cupric sulfate is heated in a stream of nonreactive gas, cupric oxysulfate is formed. When this reaction is complete, the cupric oxysulfate then decomposes to cupric oxide, which is the normal end product of reaction. The kinetics of each of these reactions has been studied using pellets prepared from finely divided cupric sulfate and from finely divided cupric oxysulfate. In each case, the reactant-product interface within the pellet is well-defined, and by normalizing the decrease in inter facial area with the weight fraction of the pellet decomposed it has been shown that the interface migrates into the pellet at a uniform rate at constant temperature. The activation energy estirnated for the decomposition of cupric sulfate is 57 ± 7 kcal per mole and that for cupric oxysulfate is 67 ± 8 kcal per mole. The rate of interfacial reaction is flow-sensitive, increasing with increasing flow of a sweep gas in the range from 50 to 2000 cu cm per min. The rate of decomposition is retarded by sulphur trioxide in the sweep gas. The relationship between sulfur trioxide Partial pressure and rate is consistent with the Langmuir Adsorption Isotherm governing the retention of sulfur trioxide in the interfacial layer. MOST of the work reported on the thermal decomposition of cupric sulfate and of cupric oxysulfate is related to the thermodynamics of the individual decompositions.'-4 No information is available on the rates of the individual reactions, on their activation energies, or on the effects of gas flow or of partial pressure of sulfur trioxide on the reaction rates. Some dubious conclusions based on relative reaction rates have been drawn from studies on the oxidation of sulfides. For example, on the basis of the products observed in a quenched system, it has been suggested5" that, when copper sulfide is roasted, the cupric oxide which is formed arises from the decomposition of either cupric sulfate or cupric oxysulfate. This is very difficult to reconcile with the thermodynamics of the C-S-O System,3 which support the probability that both cuprous oxide and cupric oxide precede cupric oxysulfate and cupric sulfate in the sequence of products formed during the oxidation of cuprous sulfide. In this paper the individual sulfate decomposition reactions will be examined and suggestions will be advanced for the mechanism of reaction. This will be based on the effects on reaction rate of changes in interfacial area, flow rate, and back-pressure of sulfur trioxide. EXPERIMENTAL Materials. The copper source material used in all experiments was Fisher Certified Reagent Grade anhydrous cupric sulfate, for which the following analysis was supplied by the manufacturer: chloride, 0.002 pct; alkalies and earths, 0.2 pct; insoluble, 0.002 pct; iron, 0.020 pct. Cupric oxysulfate was prepared by roasting cupric sulfate for 48 hr, with frequent rabbling, in an open tray in a muffle furnace maintained at 725°C. At this temperature, cupric sulfate develops about 0.16 atm pressure of combined sulfur trioxide, sulfur dioxide, and oxygen. Cupric oxysulfate develops only about 0.05 atm pressure, and is stable until

Jan 1, 1965

By H. J. Beach, W. C. Goins

The laboratory development and field use of oil well cement compositions* with high resistance to drilling mud contamination are described. Resistance is obtained by adding a I-lb mixture composed of three parts paraformaldehyde to two parts sodium chromate tetra-hydrate for each sack of cement. This mixture neutralizes the cement-retarding properties of quebracho and other tannins, starch, sodium carboxymethylcellu-lose, Ignite, and monovalent salts of lignosulfonic acid. The retarding properties of calcium lignosulfonate are unaffected. The decontaminating mixture may be used in common cement (designated Type I by ASTM specifica-tions,' Class A by API Std. 10A2) or in a slow set slurry prepared from common cement by addition of calcium lignosulfonate. No changes in slurry viscosities or thickening times are caused by the protecting reagents. The method has been used in 185 field jobs where an improved success ratio has been obtained in plug setting. INTRODUCTION Field experience and laboratory investigations have established contamination by drilling mud as a major factor in oil well cement failures. During 1955, 12 attempts were required to set six open-hole cement plugs in the Timbalier Bay field, La. Eighteen to 30 hours elapsed between placing and testing the plugs in preparation for sidetracking operations. Considerations of rig time expense required immediate resetting where soft cement was drilled after a reasonable waiting period. Sea water drilling mud was used in each well and daily additions of thinners, usually lignites, had been required. Sodium carboxymethylcellulose had been added regularly to control fluid loss. The 50 per cent plug failures were attributed primarily to contamination by the mud. Similar experiences can be found in other fields along the Texas and Louisiana coasts where drilling muds normally contain large quantities of organic treating materials. Cement contamination was the subject of a survey by the Mid-Continent District Study Committee on Cementing Practices and Testing of Oil-Well Cements of the API.3 Data collected from member laboratories and released in Sept., 1951, reported the effects of a number of drilling mud treating chemicals on cement. The study revealed that many of the additives, notably the organic materials in relatively small quantities, had marked effects on the properties of cements tested. Severe losses in strength and erratic thickening time resulted from small additions of mud treating chemicals such as quebracho, starch, sodium carboxymethylcellulose, and lignite. The report included no recommendations of methods for overcoming the problem. One investigation of the contamination problem reported the successful use of activated charcoal in setting cement plugs after conventional slurries had failed.4,5 The investigation indicated that an optimum concentration of 5 per cent activated charcoal was effective in combating contamination from 16.7 volume per cent of treated mud. Laboratory and field muds were included in tests and contained varied quantities of ode or more of the following: quebracho, caustic, starch, lime, and calcium lignosulfonate. The function of the charcoal appears to be physical, removing the organic materials by adsorption. The method may be employed in API Class A or Class D (unretarded slow set) cements. The chemical approach presented here is based on

Jan 1, 1958