Search Documents

By C. J. Sparks, J. C. Ogle, E. A. Starke

DEFORMATION of cold-rolled fcc metals and alloys produces one or the other of two types of rolling textures, usually referred to as the copper type or the brass type. The pure fcc metals, with the exception of silver, develop the copper-type texture when rolled at room temperature. Silver, brass, and many other alloys develop the brass-type texture. Transition from one texture type to another can also occur. Solute additions to pure copper cause a transition from the copper-type to the brass-type texture.' Varying the deformation temperature also produces texture transitions. Copper rolled at -196°C developed the brass-type texture2 and silver rolled at elevated temperatures, 200°C, developed the copper-type texture.374 The work of Haessner,' Smallman and Green,6 and Hu and coworkers3'4 seems to have established an apparent correlation between the type of rolling texture (and the texture transition) and the stacking-fault probability. Thus materials with low stacking-fault energies are thought to develop the brass-type texture while high stacking-fault energy materials develop the copper-type texture. Mikkola and cohen7 measured by X-ray diffraction techniques the stacking-fault probability, a, in the ordered and disordered fcc alloy Cu3Au. Unexpectedly, ordered specimens showed about twice the stacking-fault probability as the disordered ones. Marcinkowski and Zwe118 also found stacking faults in ordered Cu,Au, but not in the disordered CusAu. More recently, Camanzi and coworkers9 have shown that the intrinsic stacking-fault energy of Cu3Au undergoes a considerable decrease (approximately 100 ergs per sq cm) when passing from the disordered to the ordered phase. In general, deformation reduces order'' but some of our measurements showed that some long-range order still remains in Cu3Au after cold reduction by rolling 80 pct. From the above considerations Cu3Au offers the possibility of studying the texture transition in fcc alloys without varying either the temperature or the composition. If the stacking-fault energy correlation is correct, an initially ordered alloy should develop the brass-type texture during rolling while a disordered alloy should develop the copper-type texture. The present communication describes some initial results of experiments designed to investigate this possibility. The rolling textures of ordered and disordered Cu3Au samples were determined after various amounts of deformation. The ordered sample had an initial long-range-order parameter of S = 1, determined from X-ray diffraction. The grain size of both the ordered and disordered samples was the same, and the initial textures of both were also identical and approximately random. No obvious differences in the deformation textures of the ordered and disordered materials were detected up to 35 pct reduction and the (111) pole figures of Fig. 1 resemble that of pure copper. However, with reduction larger than 35 pct and less than 50 pct, a marked deviation from the copper texture was noted in the ordered material. The newly developed orientation was close to the (110)[i12] ideal orientations re-

Jan 1, 1970

By J. P. Hammond, C. J. McHargue

THERE have been no publications on the wire texture, on the cold-rolled sheet texture, nor on the recrystallized sheet texture of vanadium. Since it has a body-centered cubic structure, it would be expected to show strongly preferred orientations such as are found in iron' and molybdenum.' The wire textures of body-centered cubic iron,3 tungsten," molybdenum,5 antalum,6 iobium,6 and brass6 have been found to have [110] directions lying parallel to the wire axis. Wires of iron,' containing 1.95 pct V or 1.95 pct Si,7 and steel8 retain their texture upon recrystallization. Molybdenum9 and tungsttln' wires retain their texture after recrystallization at low temperatures. A [loo] recrystallization texture has been reported for mo1ybdenum9 and for a Fe-Ni alloy (53 atomic pct Ni).10 The cold-rolled sheet texture for iron,' mild steel," and molybdenum chiefly one in which the [110] directions lie parallel to the rolling direction and the (100) planes lie parallel to the rolling plane with a deviation from this position chiefly about the rolling direction as an axis. This paper presents the cold-rolled and the re-crystallized wire textures, and the cold-rolled and the recrystallized sheet textures for vanadium. The results show that the textures in vanadium are not significantly different from those reported for other body-centered cubic metals. The vanadium used in this investigation was the so-called "ductile" vanadium which has a nominal composition within the following limits:12 0, 0.05 to 0.12 pct; H, 0.001 to 0.004; N, 0.02 to 0.04; C, 0.03 to 0.07; and V, 99.8 to 99.9. The wires were formed by rolling annealed rods of 0.280 in. diam to 0.028 in., a reduction in diameter of 90 pct. The wires were then electrolytically etched to 0.005 in. diam and used as such for specimens. Annealed sheet was reduced 95 pct in thickness from 0.100 to 0.005 in. with a two-high, 4-in. diam mill using reductions no greater than 10 pct per pass. In order to avoid temperature effects, the sheet was allowed to cool between passes. X-ray specimens were made in the form of posts from the sheet. The sheet was mounted in a fixture and the edges were polished using metallographic technique. Each edge was alternately polished and etched during the last stages in order that all worked material would be removed. These post specimens were approximately square in cross-section. The specimens to be recrystallized were wrapped in tantalum foil, sealed in evacuated quartz tubes, and annealed at 1600°F. The X-ray data were obtained from transmission shots made with a 0.030 in. pinhole camera, and molybdenum radiation with a zirconium filter inserted between the specimen and film. The grain size was sufficiently small in both the cold-worked and recrystallized material to give satisfactory results with the specimens stationary. In order for the wire texture to be determined, transmission X-ray patterns were taken with the

Jan 1, 1953

By Y. H. Liu, R. Kiessling

The chromium, iron, and tungsten borides have been treated with ammonia at different temperatures. They are attacked, forming metal nitride and boron nitride, and the results are summarized in the tables. In the tungsten-nitrogen system a new phase has been observed, closely related to the known ß phase. THE present investigations were begun to determine whether any ternary phases exist in the transition metal-boron-nitrogen systems for the metals chromium, iron, and tungsten. Attempts to prepare such phases were made by using the borides of the metals as starting materials and ammonia as the nitriding agent. Although no new ternary phases have been found to exist, the results may be of some interest with regard to the technical use of the borides. General Procedure A steady stream of dry ammonia was passed through a silica reaction tube, the central part of which was kept at the reaction temperature while its ends were water-cooled. Weighed amounts of the borides were placed in a silica or porcelain boat and heated at different temperatures for a period of 10 to 24 hr. The boat was then rapidly removed from the reaction zone to the quenching zone, the water-cooled end of the tube, by means of a simple magnetic device. The nitrogen content of the products was determined by the increase in weight of the specimens, and the phase analysis was carried out by X-ray methods. For this analysis a Guinier-type camera, constructed at this Institute, was used with a bent, ground quartz crystal monochromator. The general reaction, which occurred in all the experiments, may be summarized as: metal boride + nitrogen -* boron nitride + metal nitride For the higher temperatures pure metal was formed instead of metal nitride. It is sometimes difficult to Discussi detect boron nitride among the reaction products by X-ray methods. Prolonged exposures of some specimens showed, however, that the strongest reflections of boron nitride were present. Additional evidence for its presence was given by the increase in weight of the specimens after nitriding. This increase was always greater than that corresponding to nitride formation only and was often in close agreement with the formula given above. Finally, a white powder, which was shown by X-ray methods to be boron nitride, was left if the reaction products after nitriding Fe,B at 448°C and FeB at 768°C were dissolved in diluted sulphuric acid. Ch rom iu m - Boron - N itrogen Five phases have been found to exist in the Cr-B system,' , and all were used as starting materials. Investigations on the Cr-N system have shown the existence of two nitrides with ideal composition Cr,N and CrN.".' * The results are summarized in Table I. All the borides are attacked and decomposed into chromium nitride and boron nitride, and the kind of nitride formed depends only on the temperature and not on the boride used as starting material. The lowest reaction temperature, however, is different for the different borides. Thus the 6 phase begins to react at about 735 "C, the r phase at about 800°, the S phase at about 900°, the 7, phase

Jan 1, 1952

By B. Post, D. Moskowitz, F. W. Glaser

Lattice parameters of various hafnium compounds, two borides, a carbide and a nitride were determined. Some physical properties were measured and comparisons with the properties of the corre-sponing zirconium compounds were drawn. A LTHOUGH borides of transition metals have A been extensively investigated in recent years, there are few references in the literature to borides of hafnium. This is not surprising, in view of the extreme scarcity and great cost of the purified metal. Becker' reported the existence of a boride, carbide, and nitride of hafnium; he listed the formulas as HfB, HfC, and HfN. However, in his work no mention was made of chemical analyses of the reaction products. In this paper results of a study of various hafnium compounds, including borides, carbides, and nitrides, are reported. It was expected, of course, that these compounds would closely resemble their zirconium analogues, which have previously been extensively investigated. Three borides of zirconium are known: ZrB,² ZrB,² and ZrB212.4 In addition, one carbide, ZrC,5 and one nitride, ZrN,5 have been reported. It should be noted that ZrB and ZrB12 are stable phases only in relatively high-temperature regions, unlike ZrB2, which is stable from room temperature to its melting point." It was felt that hafnium would yield corresponding borides, carbides, and nitrides with similar stability ranges. Experimental Procedures and Results A quantity of hafnium metal that was better than 97 pct pure, with zirconium as its major impurity, was furnished by the Argonne National Laboratories. The boron powder used was approximately 96.5 pct pure. In general, the procedure involved mixing the metal and boron powders in the desired proportions, and subsequently hot pressing them. The resulting specimens were analyzed chemically and phases present were identified by X-ray diffraction methods. A Philips Norelco Geiger counter spectrometer was used for identification of components and for measurement of lattice constants. Filtered copper radiation was used for all X-ray work. Electrical resistivity and density measurements were carried out at room temperature. The stable diboride, HfB2, will be described first. Stoichiometric quantities of boron and metal were heated to approximately 2000°C during hot pressing. The reaction product was shown by X-ray diffraction methods to be isomorphous with ZrB2 (space group Dlgh; P6/mm). Values of lattice constants of HfB2 compared with those of ZrB2 are shown in Table I. The calculated density of HfB2 is 11.2 g per cc, compared with a measured (pycnometric) value of 10.5 g per cc. HfB2 specimens prepared under a wide variety of conditions (including variations in initial Hf-B ratios) showed only insignificant variations in lattice constants, indicating a very narrow range of homogeneity. Like ZrB2,7 HfB2 is an excellent electrical conductor. The resistivity at room temperature of hot-pressed samples, approximately 85 pct dense, is 12 microhm-cm. This compares favorably with the electrical resistivity of 10 mi-

Jan 1, 1954

By William H. Spice

Exploratory drilling in South Central Texas for the year 1944 showed a marked increase over that of 1943 and resulted in a similar increase in new fields discovered. In this area, which comprises the 30 counties included in district No. I, Oil and Gas Division, Railroad Commission of Texas,? 61 exploratory wells were drilled during 1944 as compared with 29 exploratory wells drilled during 1943, or an increase of over 100 per cent. Three new oil fields, two new gas fields and one gas-distillate field were discovered during the year, as compared with one new oil field and one new gas field discovered during 1943. These new fields were the result of exploratory drilling throughout the district along the Wilcox trend and the deeper Edwards lime trend, which was started during the previous year. The Wilcox trend yielded the new Loma iilta-Wilcox oil field and the San Caja gas-* tlistillate field, both in McMullen County. The Charlotte field, in Atascosa County, was discovered along the deeper Edwards lime trend. These three discoveries were of considerable importance and subsequent development should indicate the desirability of continued exploration along these trends. The other three discoveries, United oil field in Guadalupe County, Pederson gas field in Milam County and Van Cleve gas field in Zavalla County, were of minor importance. Charlotte Field, Atascosa County, was discovered by the Humble Oil and Refining Company's No. 3 Pruitt, completcd on Aug. 9, 1944, flowing 176 bbl. per day, 3/16-in. choke, 710 lb. tubing, 475 lb. casing pressures, 37.7º A.P.I. gravity, from the top of the Edwards lime from 6917 to 6923 ft. Two oil wells were completed during the year in this field. This discovery is 14 miles southwest of the same company's Imogene field, also producing from the Edwards lime but with considerable difference in reservoir characteristics. The discovery of this field is the result of surface geology and subsequent seismograph survey of the area. Loma Alta-Wilcox Field, McMullen County, was discovered by the Atlantic Refining Company's No. I Atkinson, completed on June I, 1944, flowing 102 bbl. per day, 9/64-in. choke, 1900 lb. tubing pressure, 37º A.P.I. gravity, from Wilcox sand from 6866 to 6869 ft. after being drilled to a total depth of 7185 ft. This discovery is the result of subsurface geology and an extensive seismograph survey of the entire area. Sun Caja Field, McMullen County, was discovered by Edwin M. Jones No. 2-C Ezzell, completed on June 2, 1944 as a dual completion in the Wilcox sands, flowing 1,740,000 cu. ft. gas with 53 bbl. distillate, 1/4-in. choke, 2035 lb. tubing pressure, 53.2º A.P.I. gravity, from sand 6416 to 6453 ft. and flowing 2,000,000 cu. ft. of gas with 127 bbl. distillate, 1/4-in. choke, 2500 lb. tubing pressure, 50º A.P.I. gravity, from sand 6889 to 6916 ft., after being drilled to a total depth of 7264 ft. Three gas-distillate wells were completed during

Jan 1, 1945

By R. C. Hassinger, D. V. von Rosenberg

Transverse dispersion has received considerably less treatment in the literature than has longitudinal dispersion. Different methods for determining transverse dispersion coefficients have been used in different investigations, and the results obtained have not been consistent enough to permit accurate generalizations as to the effect of various physical parameters on the magnitude of these coefficients. A numerical solution to the differential equation describing transverse dispersion in the absence of longitudinal dispersion was obtained to enable one to calculate the dispersion coefficient from experimental results. The more general dispersion equation including longitudinal dispersion also was solved numerically to give quantitative limits of a dimensionless group within which the assumption of negligible longitudinal dispersion is justified. Possible experimental procedures were examined, and one utilizing a cylindrical packed column was chosen for the determination of transverse dispersion coefficients. Values of these coefficients were determined for a system of two miscible organic fluids of equal density and viscosity, for two sizes of packing material over a wide range of flow rates in the laminar regime. The dispersion coefficient was found to decrease, for a constant value of the product of packing size and interstitial velocity, as the size of the packing material particles increased. INTRODUCTION Longitudinal dispersion has received extensive treatment in the literature, and consequently is better understood than its orthogonal counterpart, transverse dispersion. Many mathematical models of dispersion processes assume that transverse dispersion is rapid enough to damp out any radial** concentration gradients and therefore may be neglected. Laboratory and production results, however, indicate that this is a poor assumption.l,2 Various experimental procedures for determining transverse dispersion coefficients have been used in previous investigations, but the results have generally been expressed by similar correlations. The transverse dispersion coefficients obtained, however, have often varied considerably for given values of the correlation parameters. We feel that further experimental determinations of transverse dispersion coefficients will help alleviate some of the inconsistencies in these empirical correlations. One assumption implicit in all previous investigations is that of negligible longitudinal dispersion in the experimental system. An attempt to justify this assumption often is made using intuitive reasoning, but it is apparent that this reasoning must break down as the condition of zero flow rate is approached. A mathematical examination of the equations describing the system yields physical limits outside of which the assumption of negligible longitudinal dispersion is invalid. BACKGROUND In a porous medium, the "effective molecular diffusivity" De is less than the molecular diffusivity D measured in the absence of a porous medium, due to the tortuous path which a diffusing molecule must travel. Various authors3-5 have reported values of the ratio De/D in the range of 0.6 to 0.7. When there is fluid flow within the porous medium, mass transfer occurs by convective dispersion as well as by molecular diffusion. These are separate phenomena and can be treated as such on a microscopic scale. However, the mathematical complexity is such that only extremely simple geometries could be considered, and the results hardly would be applicable to the complex geometries existent in actual porous media. A more

Jan 1, 1969

By D. C. Shelton

This paper discusses the metallurgical testing procedures and their applications at the laboratories and mills of Pima Mining Co. The author shows, using discussions and case histories, that routine sampling and evaluation of daily and monthly data can be as valuable as thorough laboratory investigations and mill test work. A great deal of valuable information can be made available this way. This paper discusses laboratory and mill metal-lurgical testing procedures and their applications at Pima Mining Co., located about 25 miles southwest of Tuscon, Ariz. The Company, incorporated in 1951 (the year the orebody was found) in California to operate the Pima mine, is jointly owned by Cyprus Mines Corp., Utah Contruction and Mining Co., and Union Oil Co. Milling started in December 1956. The main Pima orebody is a contact metamorphic vein of copper-bearing hornfels with an average dip of 45° to the south with an east-west strike. The hanging and footwalls are quartzitic pyroclastics (arkosite) containing some sulfides. Barren igneous intrusions are also present. Conglomerates and alluvial wash cover the deposit to a depth averaging about 200 ft. The principal copper mineral is chal-copyrite. Native copper, chalcocite, and minor amounts of chrysocolla and other copper minerals are also present, together with sphalerite and some molybdenite. Generally, it has been noted that the ratio of chalcocite to chalcopyrite is higher in the lower grade ores, while as the grade increases, there are only minor amounts of chalcocite. Open pit mining is employed at Pima, using both trucks and an inclined skiphoist system. A detailed description of Pima Mining Co. operations was presented by Spaulding et all. More recently another orebody to the north and east of the present pit has been discovered and will be placed in operation within a few years. This ore is of a porphyritic rather than a lode nature since values are disseminated in both igneous and metamor- phosed sedimentary rocks. The new orebody is expected to be harder and cleaner than the present deposit. The views expressed in this article are those of the author and do not necessarily reflect those of Pima Mining Co. nor of the profession in general. PlMA MILL The following outline of milling practice is presented to furnish a background for later chapters of this report wherein specific problems will be detailed and analyzed. Run of mine ore is crushed in three stages, using conventional equipment to 85% minus 1/2-in. for feed to two 10 x l6-ft rod mills operating in open circuit. Each rod mill discharge is split between two 10% x 13-ft ball mills in closed circuit with three 20-in. cyclones. In addition, a 7 x 12-ft ball mill with one 20-in. cyclone receives part of the discharge from one of the rod mills. This equipment was manufactured by Allis Chalmers and Equipment Engineers. The cyclone overflows are combined, sampled and, after joining the regrind cyclone overflow, are distributed into 12 10-cell Fagergren 66-in. flotation machines. The primary rougher concentrate produced

Jan 1, 1965

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 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 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 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 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 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