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By R. A. David, D. J. Vink, D. L. Katz

A phase diagram showing boundary curve and quantity of liquid in the two-phase region was determined for a mixture of natural gas and natural gasoline in the region of its critical conditions. The temperatures and pressures of phase measurements were in the range of 85 to 212 F. and 1300 to 2600 Ib. per sq. in., respectively, with the critical conditions at 169.5 F. and 2615 Ib. per sq. in. abs. Color phenomena were observed in the region of the boundary curve from 102' to 192 F. Approximate densities of the single-phase and two-phase regions and analysis of the system are included. Boundary curves between the single-phase and the two-phase regions have been determined for several binary mixtures containing hydrocarbons. 2,3,4.6,7,10,11,12,14 These investigators did not report the relative amounts of liquid and vapor within the two-phase region. The equilibrium values obtained from the dew-point and bubble-point data can be used to compute the lines showing percentage of liquid on the pressure-temperature phase diagram8 but the positions of the lines near the critical temperature and pressure are uncertain. Relative amounts of vapor and liquid were obtained for a gasoline and a naphtha1 within the two-phase area but not in the region of the critical temperature and pressure. The bubble-point and dew-point lines, as well as the percentage liquid lines within the two-phase region, were determined by visual observations in glass apparatus. Apparatus An arrangement of the apparatus is given in Fig. 1, showing the Jerguson gauge A with glass windows B. Pressure was supplied by the

Jan 1, 1940

By R. A. David, D. L. Katz, D. J. Vink

A phase diagram showing boundary curve and quantity of liquid in the two-phase region was determined for a mixture of natural gas and natural gasoline in the region of its critical conditions. The temperatures and pressures of phase measurements were in the range of 85 to 212 F. and 1300 to 2600 Ib. per sq. in., respectively, with the critical conditions at 169.5 F. and 2615 Ib. per sq. in. abs. Color phenomena were observed in the region of the boundary curve from 102' to 192 F. Approximate densities of the single-phase and two-phase regions and analysis of the system are included. Boundary curves between the single-phase and the two-phase regions have been determined for several binary mixtures containing hydrocarbons. 2,3,4.6,7,10,11,12,14 These investigators did not report the relative amounts of liquid and vapor within the two-phase region. The equilibrium values obtained from the dew-point and bubble-point data can be used to compute the lines showing percentage of liquid on the pressure-temperature phase diagram8 but the positions of the lines near the critical temperature and pressure are uncertain. Relative amounts of vapor and liquid were obtained for a gasoline and a naphtha1 within the two-phase area but not in the region of the critical temperature and pressure. The bubble-point and dew-point lines, as well as the percentage liquid lines within the two-phase region, were determined by visual observations in glass apparatus. Apparatus An arrangement of the apparatus is given in Fig. 1, showing the Jerguson gauge A with glass windows B. Pressure was supplied by the

Jan 1, 1940

By F. M. Waring

produced when zinc is substituted for a certain amount of tin are decidedly unsatisfactory. The substitution of aluminum for tin is entirely impractical, and such castings are worthless. This does not, however, exhaust all the possibilities of substituting other metals for tin in the copper-tin-lead alloys, but it is my opinion that the substitution of any other metals, in those alloys, can be made only by sacrificing the quality of the alloy. The possibility of substituting alloys of an entirely different type presents an attractive field for research. The copper-tin-lead alloy has attained its position as the most desirable bronze bearing alloy, but this does not mean that some other alloy may not be found which may give equally good or better results. In the search for such a substitute alloy it should be borne in mind that a bearing metal should possess the following properties: (1) It should be sufficiently rigid to support the load or resist the impact, but yet not so brittle that it will easily crack. (2) It should have as great a yielding or plastic nature as is consistent with its ability to support the load or resist the impact without deformation of the bearing as a whole. (3) The ideal structure combines a hard matrix to support the load and a softer metal or alloy contained within such matrix, to permit the bearing surface to adjust itself to irregularities of service. (4) It should be easy to handle in the foundry and machine shop. (5) It should be capable of being remelted without deterioration. (6) For use in babbitt-lined bearings, it should be capable of being tinned, so that the babbitt can be applied thereto. (7) It should have good heat conductivity in order to dissipate the heat generated by friction. Pennsylvania Railroad Anti-friction and Bell Metals F. M. Waring," Altoona, Pa.—Thc necessity for conserving tin has recently been very forcibly brought to the attention of all consumers, and efforts are now being made to reduce the tin content in certain alloys or to substitute other alloys not containing tin. The approximate composition of the non-ferrous alloys in general use on the Pennsylvania Railroad are given in the accompanying table. Phosphor bronze is used principally for rod bushings, main-rod brasses, and crosshead shoes. Ex. B bronze is used to a small extent for backs of car and coach bearings, but the majority of these are now made of the car-journal bronze, which contains, on the average, about 5 per cent. tin.

Jan 1, 1919

By Alan R. Grant

The Cascade Range of Washington can be considered metallogenetically to be primarily a copper province. Structural and chemical data compiled from examination of numerous copper occurrences in the Cascades indicate a marked parallel of physical conditions for sulfide deposition. In probable order of significance, the environmental criteria are as follows: 1) adjacent or subjacent, postregional metamorphism high-level intrusive activity, most commonly in the time range from 15 million years to 30 million years; 2) transverse northeast trending structural belts which obliquely cut the northwest regional trend of the range; 3) potassium-silica wall rock alteration; most important of the alteration suite of silicates are orthoclase secondary biotite and quartz; 4) the intersection of northwest trending and northeast trending structures. The varying geologic environments in the Washington Cascades present a complex setting for the sulfide deposits. The North Cascades are comprised of predominantly pre-Tertiary metamorphic rocks invaded by Tertiary calcalkaline intrustive rocks. The Central Cascades, lying south of the North Cascades, exhibit a younger, higher level geologic environment comprised of predominantly early to middle Tertiary volcanic rocks and subordinate sedimentary rocks which are intruded by Tertiary calc-alkaline igneous rocks. Although the Tertiary Cascade intrusions are dominantly quartz dioritic, copper mineralization is commonly found in rocks of quartz monzonite to granite composition. These acid rocks appear to be the product of late stage magmatic K alteration of the original quartz diorites. Sulfide concentrations are considered to be in part dependent on the degree of K-silicate activity and the intensity of transverse structural deformation.

Jan 1, 1973

By H. I. Aaronson

THE TTT-curve for the beginning of transformation in hypoeutectoid steels containing appreciable amounts of relatively strong carbide-forming alloying elements often exhibits a "bay" at intermediate temperatures. In many of these steels, proeutectoid ferrite is the initial product of the decomposition of austenite not only at temperatures above the bay but also in an appreciable temperature range below the region of the bay. Hultgren has postulated that ferrite formed above the bay, termed "orthoferrite", contains the equilibrium concentration of alloying element at temperatures above the eutectoid range, and the extrapolated metastable equilibrium concentration at lower temperatures. The ferrite formed below the bay, on the other hand, termed "paraferrite", was assumed to inherit completely the bulk alloy content of the austenite without regard for the compositional requirements of equilibrium. As shown schematically in Fig. 1, the two types of ferrite were taken to have different Ae3 temperatures and different C-curves on a TTT-diagram. Their different kinetic behaviors were thus considered responsible for the bay in the TTT-curve for the proeutectoid ferrite reaction in this type of alloy steel.

Jan 1, 1962

By Auguste J. Rossi

As is well known, practically all the phosphorus of the ironores smelted in the blast-furnace passes into the pig-metal, increasing its fluidity, but diminishing its strength to such an extent that, if phosphorus exceeds a certain amount, the metal is only fit for fine castings, not required to resist strains, and it cannot be used for the ordinary purposes of good foundry-iron. No phosphorus being eliminated in the acid Bessemer process, the quantity admissible in pig-metal destined for that process must be very small, and hence the ores smelted must be strictly Bessemer ores, of which, in many districts, the supply is taxed to the utmost. On the other hand, very highly phosphoric pig, a metal of little or no value by itself, when refined by the Thomas-Gilchrist process in the basic converter, furnishes an excellent steel; but such pig-iron must be made from ores particularly high in phosphorus; and these ores are not everywhere abundant, and are much sought after for this special purpose. But there are many iron-ores containing a moderate, though still important, amount of phosphorus, which yield a pig-metal

Jan 1, 1897

By B. D. Cullity

AS methods for measuring fiber textures become more exact, it becomes justifiable to scrutinize an observed pole-density curve for evidence of minor texture components. These are disclosed by minor maxima or abnormally broad major maxima. One possible source of these minor components is twinning of the main component. In cubic metals and alloys, there are two kinds of twins: 1) Annealing twins in face-centered cubic metals. These are reflection twins on {Ill), and they can be expected to be present in recrystallization textures. 2) Deformation twins in body-centered cubic metals. These are shear twins on (112). Although usually formed only by impact, they might conceivably be present in the deformation texture of severely cold-drawn wire. Fortunately, both kinds of twinning lead to the same orientation relationships. It thus becomes possible to prepare a single list of angles between various planes in parent crystal and twin, which is helpful in examining pole-density curves for evidence of twinning in any cubic metal or alloy. Such a list of interplanar angles is given in Table I. This table consists of three parts, corresponding to the three major texture components—<100>, <110>, and <111>-most commonly found in the fiber textures of cubic metals. The table lists the angle between the pole of {hkl}, in either the parent crystal P or the twin T, and the fiber axis <uvu>. The crystals with <uvw> parallel to the wire axis are here

Jan 1, 1959

By Valentine R. Garflas

The Mexican oil fields, during 1921, produced in round numbers 203,000,000 bbl. of which 176,000,000 bbl., or 86 per cent., were exported, the bulk of these exports, or about 73.3 per cent., going to the United States. The Mexican exports were divided by grades as follows: Light crude, 47.0 per cent.; heavy crude, 22.0 per cent.; tops, 3.5 per cent.; fuel oil from light crude, 24.0 per cent. The balance, or 31/2 per cent., includes the bunker fuel shipments and the coastwise trade in Mexico, which is not classified as to grades. The figures show that, in importance, the light-oil fields form about 75 per cent. of the Mcxican petroleum industry. The production of the Panuco field has followed the general history of the American fields, and its gradual decline, which is at present foreshadowed, may be estimated as well as its ultimate economic life. On the other hand, the behavior of the light-oil fields to the south is unlike any in the world so far discovered, and as a result we have concentrated overproductions followed by sudden droughts, both sometimes equally unexpected. The coming in of two or three gushers within adequate pipe-line facilities will flood the market with 100,000 bbl. or more a day, while the flooding by water of a particular pool will, in a few weeks, remove from the market one-half the total production of the Mexican fields.

Jan 1, 1923

By Valentine R. Garflas

The Mexican oil fields, during 1921, produced in round numbers 203,000,000 bbl. of which 176,000,000 bbl., or 86 per cent., were exported, the bulk of these exports, or about 73.3 per cent., going to the United States. The Mexican exports were divided by grades as follows: Light crude, 47.0 per cent.; heavy crude, 22.0 per cent.; tops, 3.5 per cent.; fuel oil from light crude, 24.0 per cent. The balance, or 31/2 per cent., includes the bunker fuel shipments and the coastwise trade in Mexico, which is not classified as to grades. The figures show that, in importance, the light-oil fields form about 75 per cent. of the Mcxican petroleum industry. The production of the Panuco field has followed the general history of the American fields, and its gradual decline, which is at present foreshadowed, may be estimated as well as its ultimate economic life. On the other hand, the behavior of the light-oil fields to the south is unlike any in the world so far discovered, and as a result we have concentrated overproductions followed by sudden droughts, both sometimes equally unexpected. The coming in of two or three gushers within adequate pipe-line facilities will flood the market with 100,000 bbl. or more a day, while the flooding by water of a particular pool will, in a few weeks, remove from the market one-half the total production of the Mexican fields.

Jan 1, 1923

By Richard H. Rein, John Chipman

The activity of SiO2, in the entire liquid system SiO2-CaO-Mg0-A12O3 at 1600°C is calculated from the distribution of silicon between these slags and Fe-Si-C alloys saturated with either graphite or silicon carbide, the activity coefficient of silicon in these alloys, and the requisite thermodynamic data. The activities of the other components in the ternary systems SiO2-CaO-A12O3, SiO2-MgO-CaO, SiO2-MgO -A12O3 are computed from these data by the IrON blast-furnace slags can be regarded as consisting of the four major oxide components, SO2, CaO, MgO, and A12O3 along with minor proportions of other oxides and of sulfur. The purpose of this study is to measure the activity of silica in the liquid solutions of these four oxides at iron-making Gibbs-Duhem equation with the aid of the known free energies of several of the interoxide compounds and the accepted phase diagrams. Based on these activities, new data are Presented for the free energy of formation of a number of the interoxide compounds. The free energy of mixing the liquid metasilicates of CaO and MgO shows slight positive deviations from the ideal. temperatures and to obtain activities of the other components by application of the Gibbs-Duhem equation and the properties of several interoxide compounds. Recent investigations on the activity of silica in the SiO2-CaO-A12O3 system1-3 and recogntion of a serious error in older data for the free energy of formation of SiO2 (Ref. 4) have succeeded in bringing a fair degree of concordance into the results of different investigators. In the present study, the activity of silica is obtained from the silicon-distribution experiments described in a previous paper,&apos; the revised activity coefficient of silicon

Jan 1, 1965

By A. W. Ashbrook

From both economic and environmental aspects, the loss of organic materials from a solvent extraction process is of major concern. A decade ago perhaps the only consideration given to solvent loss was economic in nature. Today, the environmental -.and hygiene - impacts have to be seriously considered. In this section we shall deal essentially with the processing and economic aspects of solvent loss; the environmental aspects are discussed in a later section.

Jan 1, 1978

By R. W. Metsger

The metamorphic zinc-iron-manganese ore in the Grenvillian rocks of the Reading Prong m Sussex County, N.J. is unique. The singularity of its mineral composition and associations has fueled controversy among economic geologists and mineralogists for more than a hundred years. The silicate-oxide ore, in two synformal concentrations has been mined since about 1838. The Franklin mine was depleted in 1954, while the one at Sterling Hill is still producing. Although the two mines are perhaps best known for their almost three hundred mineral species and have been a mecca for collectors, they -- as importantly -- have provided a window through which to observe more than a billion years of geologic history. When pieced together, studies reveal a sequence of probable sedimentary deposition, intense folding, pseudo- viscous flow with attendant negative diapirism, uplifting, erosion, karstification, hydrothermal alteration, burial, faulting, igneous intrusion, uplift , saprolitization, and glaciation.

Jan 1, 1985

By Thomas Fraser, H. F. Yancey

Prior to the war just ended, Germany was the greatest coal producer in continental Europe. In 1943 the production of coal, bituminous and higher in rank, together with brown coal calculated to the equivalent amount of bituminous coal, is estimated to have been about 240 million metric tons, according to the War Department. Before the war production in Germany exceeded consumption. No other country in continental Europe except Poland had a large surplus. However, England&apos;s surplus was the largest in Europe as a whole. Before World War II the Ruhr Basin normally supplied about 70 pet of the total production of high-rank coal, the Saar and Aachen about 6 pet each, Upper Silesia about 14 pet, and Silesia and Saxony the remainder. Nearly one third of the brown coal was produced in the Rhineland, a little less than one half in central Germany nest of the Elbe River, and about one fourth east of the Elbe. Bituminous coal and brown coal together constituted by far the most important energy resources of the old German Reich. Bituminous coal furnished nearly 70 pet of the total energy requirement, brown coal supplied about 25 pet, and water power, wood, petroleum and alcohol together aggregated only 7 pet. Because it was the most important single mineral resource of Germany, an excess of coal enabled the Reich to import nearly all the other mineral products that she lacked, such as iron ore from Lorraine. The area adjacent to the coal fields was supplied with gas from an interconnected grid. Similar electric grids are based on brown coal with the power stations at the mines. Coal tar provided the foundation for the development of the extensive German chemical industries as exemplified by the I. G. Farbenindustrie. For almost a century, German scientists have been adequately supported both by the State and by industry in studying improved methods of utilizing coal. In Germany the mineral rights were reserved by the State and ordered eatraction of coal was enforced. Each lease comprised a relatively extensive area. which accounts for the generally large size of the mines and mining companies In 1938 there were 160 mines in the Ruhr, with a total output of 125 million tons but 90 pet of the production was controlled by 20 companies. By far the largest single coal-mining company in Germany was the Gelsen-kirchener Bergwerke A. G., which produced nearly 27 million tons in the Ruhr in 1937. Second was Saargruben A. G. a State-owned company operating in the Saar, which produced &apos;lore than &apos;3 million tons. Third was Bergwerksgesellschaft Hibernia A. G., with 10 million tons, also in the Ruhr. Briquettes are made from both bitumillous coal and brown coal, but in 1938 some 44 million toils of brown-coal bri-

Jan 1, 1947

By Thomas Fraser, H. F. Yancey

Prior to the war just ended, Germany was the greatest coal producer in continental Europe. In 1943 the production of coal, bituminous and higher in rank, together with brown coal calculated to the equivalent amount of bituminous coal, is estimated to have been about 240 million metric tons, according to the War Department. Before the war production in Germany exceeded consumption. No other country in continental Europe except Poland had a large surplus. However, England&apos;s surplus was the largest in Europe as a whole. Before World War II the Ruhr Basin normally supplied about 70 pet of the total production of high-rank coal, the Saar and Aachen about 6 pet each, Upper Silesia about 14 pet, and Silesia and Saxony the remainder. Nearly one third of the brown coal was produced in the Rhineland, a little less than one half in central Germany nest of the Elbe River, and about one fourth east of the Elbe. Bituminous coal and brown coal together constituted by far the most important energy resources of the old German Reich. Bituminous coal furnished nearly 70 pet of the total energy requirement, brown coal supplied about 25 pet, and water power, wood, petroleum and alcohol together aggregated only 7 pet. Because it was the most important single mineral resource of Germany, an excess of coal enabled the Reich to import nearly all the other mineral products that she lacked, such as iron ore from Lorraine. The area adjacent to the coal fields was supplied with gas from an interconnected grid. Similar electric grids are based on brown coal with the power stations at the mines. Coal tar provided the foundation for the development of the extensive German chemical industries as exemplified by the I. G. Farbenindustrie. For almost a century, German scientists have been adequately supported both by the State and by industry in studying improved methods of utilizing coal. In Germany the mineral rights were reserved by the State and ordered eatraction of coal was enforced. Each lease comprised a relatively extensive area. which accounts for the generally large size of the mines and mining companies In 1938 there were 160 mines in the Ruhr, with a total output of 125 million tons but 90 pet of the production was controlled by 20 companies. By far the largest single coal-mining company in Germany was the Gelsen-kirchener Bergwerke A. G., which produced nearly 27 million tons in the Ruhr in 1937. Second was Saargruben A. G. a State-owned company operating in the Saar, which produced &apos;lore than &apos;3 million tons. Third was Bergwerksgesellschaft Hibernia A. G., with 10 million tons, also in the Ruhr. Briquettes are made from both bitumillous coal and brown coal, but in 1938 some 44 million toils of brown-coal bri-

Jan 1, 1947

By R. I. Jaffee, C. M. Craighead, G. A. Lenning

THERE has been considerable discussion among A metallurgists and others interested in the development of titanium alloys as to the nature of the fine line markings which appear in the microstruc-tures of unalloyed titanium and a titanium alloys. These markings have been variously called x phase, etching pits, and twins. Figs. 1 to 3 show typical examples of the line markings as they appear, respectively, in high purity iodide titanium, commercial purity titanium rod, and a high purity a alloy containing 0.2 pct N. The commercial purity titanium sample, shown in Fig. 2, contains both line markings and some spheroidal retained-ß phase. The ß phase seen in this micrograph should not be confused with the line marking, since it originates from the iron present as an impurity in the sponge metal. It will be noted that the line markings seem to have a definite orientation pattern with respect to the grains and in titanium noticeably resemble the precipitation occurring in artificially aged high purity Al-Cu alloys. This similarity led to the hypothesis that the line markings observed in titanium and a titanium alloys resulted from precipitation of some unknown phase. With the work of Hägg1 and McQuillan2 as background, there was little reason to suspect hydrogen of being responsible for the line markings. Hagg reported that up to 33 atomic pct H was soluble in a titanium, and McQuillan reported an a solubility of up to 8 atomic pct. Furthermore, McQuillan examined metallographically a 5.1 atomic pct H alloy quenched from 300°C and stated that the structure appeared to be a single-phase a solid solution. Line markings have been observed frequently and were first noted by Jaffee and Campbell3 in 1949. They did not observe them in vacuum-annealed titanium and a Ti-O and Ti-N alloys, but did observe them in Ti-H alloys containing 0.25, 0.5, and 1 atomic pct H. They stated that it was doubtful that the markings were a second phase based on hydrogen, because 1 atomic pct was far from the accepted solid solubility of hydrogen in titanium. Finlay, Resketo, and Vordahl,4 in 1950, concluded that the markings were a true second phase as a result of observations on their etching characteristics. Anderson5 Commenting on these markings in titanium was inclined to associate them with hydrogen, but was loath to call them titanium hydride, because of the reported high solubility of hydrogen. Work at Battelle Memorial Institute for the Navy Bureau of Aeronautics," done concurrently with the work described in this paper, provided information on the experiment converse to that described by Jaffee and Campbell in 1949. This work showed that the amount of line markings in unalloyed titanium could be decreased by vacuum annealing at elevated temperature. It was suggested that this was the result of removal of hydrogen; previously, the data of Jaffee and Campbell9 howed that the markings appeared when hydrogen was added. Recent work at Battelle for the Ordnance Corps, Department of the Army, which is described here, now establishes the identity of the markings as a titanium hydride phase. A sample of high-purity titanium rod 1/4 in. diam, 0.009±0.001 wt pct H (0.43 atomic pct), Fig. 1, was resistance heated in a 0.05 micron vacuum for 41/2 hr at 1500°C. During the early states of heating, the pressure increased to 150 microns, indicating that gases were being evolved. After cooling in vacuum, the iodide titanium rod was analyzed for hydrogen. Vacuum-fusion analysis showed 0.0006 ±0.0003 wt pct H (0.03 atomic pct) to be present.* Metallographic examination of the vacuum-annealed rod showed only a transformed ß structure. There was no evidence of fine line markings, Fig. 4. A section of this vacuum-annealed rod was cold rolled to 0.040 in. thick sheet and annealed for 1 hr

Jan 1, 1953

By Terry G. Richard, Sunder H. Advani

A sequence of 250 unconfined compression tests were completed on a common marine shale indicative of the overburden strata of east- central Ohio. The samples were of a light gray clay shale of Pennsylvanian age. The shales considered are obvious layered materials with distinct bedding planes. For this reason there is sufficient evidence to consider this material as anisotropic in nature. With a properly chosen reference coordinate system this anisotropy can be reduced to a layered orthotropic characterization. This implies that the mechanical properties can be specified with regard to principal material directions. With this nature in mind a systematic study of the combined influences of strain rate and moisture conditioning was initiated. Of particular interest is the variations in unconfined ultimate compressive strength with variations in the controlled parameters of strain rate, moisture conditioning level and direction of testing. Results of this particular phase of the program are presented.

Jan 1, 1982

By J. A. Goebel, S. Rosen

IN the NiAl phase diagram the NiAl (CsC1-type) phase field extends over a large composition range. At elevated temperatures the nickel-rich phase boundary extends to a composition of about 70 at. pct Ni, a value which is within 5 at. pct of the Ni3A1 (Cu 3 Au-type) phase boundary.&apos; At room temperature, however, the maximum nickel content is only about 60 at. pct. Experiments have shown that alloys containing greater than 63 at. pct Ni when quenched from temperatures below 1000°C contain the equilibrium phases NiAl and Ni3A1. On the other hand, when these same alloys are quenched from temperatures above 1000°C and examined microscopically, a typically martensitic decomposition product appears in the microstructure as shown in the micrograph of Fig. 1. The structure of the martensitic phase has been determined by employing powder X-ray diffraction techniques to be an "ordered" AuCu type (Strukturbericht Llo, space group P/4 mmm - DL). The diffraction pattern of this phase differs from that of AuCu in the appearance of superlattice lines. The structure is shown in Fig. 2. The open circles represent nickel atoms and the half-shaded circles represent nickel and aluminum atoms which are randomly distributed. The sites represented by half-shaded circles would be occupied solely by nickel atoms at a stoichiometry of Ni3A1. The alloys used in this investigation were prepared from 99.99 wt pct Al and 99.99 wt pct Ni by arc melting charges of varying compositions in a water-cooled copper hearth using a tungsten electrode in a gettered argon atmosphere. In all cases chemical analysis agreed within $ at. pct with the nominal compositions of the alloys. Annealing treatments were carried out in a vertical resistance furnace through which a stream of argon gas was flowing. Specimens, which were wrapped in tantalum foil, were quenched by allowing the specimens to drop into a bucket containing iced brine. X-ray diffraction patterns were obtained from -325 mesh powder specimens by using a 114.8-mm

Jan 1, 1969

By N. H. Harrison, J. K. Rodgers, S. Regier

This paper presents comparisons of data obtained from a laboratory reservoir study and from a calculated behavior prediction with the actual production history of a condensate reservoir. A small non-commercial discovery was depleted under closely controlled conditions and the well fluids were sampled at frequent intervals. Data on the reservoir and production variables were accumulated on a fixed schedule. A laboratory reservoir study war made using the initial well fluid samples as charging stock. The production procedures and operating conditions were held constant throughout the study wherever possible and in general paralleled the field work. The well fluid compositions and the cumulative recoveries ar a function of the reservoir pressure were also calculated using conventional flash vaporization procedures and equilibrium constants. Comparisons based on the composition of the well fluid show good agreement, the laboratory study agreeing within experimental accuracy with the field work and the calculated data comparing equally well. The gas-oil ratios are also in good agreement, but with somewhat greater deviations at the higher pressures. In the overall picture, it is believed that a model st,~tiy can predict within experimental accuracy the production history of a condensate reservoir. Better equilibrium constants for the heavier hydrocarbons are needed in order to attain improved composition accuracy by calculation. INTRODUCTION In Aug., 1955, a gas condensate well was completed in San Juan County, Utah, that was initially thought capable of good commercial production. These conclusions were derived principally from core data and electric logs, which indicated good permeability, porosity and gas content. However, after the usual series of potential tests it was found that the reservoir pressure had declined some 22 per cent, and it was obvious that the zone tapped was but a small pocket or trap. It became apparent that, with a controlled depletion of a small reservoir, a unique opportunity was available to compare laboratory and calculated studies with an actual field depletion and to further the present knowledge of condensate reservoirs. FIELD WORK The Coalbed Canyon Well No. 1 was conventionally completed in the Paradox limestone formation to a total depth of 5,912 ft. The producing zone from 5,762 to 5,806 ft was perforated with four jet shots per ft. The wellhead and field equipment were also conventional, the major items consisting of a two-pass indirect fired line heater, a high- and a low-pressure separator with the necessary controls and accessories, gas meters, back-pressure regulators, flare stacks and condensate stock tanks. The initial testing of this well con-sisted of a series of flow potential and pressure build-up tests during which some 30 MMcf of gas was produced. The reservoir pressure declined from an estimated 2,300 to 1,782 psig during this period, from which it was concluded that the reservoir was very small. In order to approach steady-state conditions in the reservoir and so provide optimum conditions for making comparisons, the field depletion was programmed to approach, if possible, constant production conditions. Bi-hourly readings were taken of the tubing pressure, the pressure and temperature of the separators, oil and gas rates, and other pertinent operating data. The gas rate, as indicated by the orifice meter, was held constant by the adjustment of the choke in the line heater. The temperature of the first stage separator was held constant by adjustment of the line heater jacket temperature. Practical considerations of production made the maintenance oi a constant gas rate impossible. The test started with a gas rate of 4 MMcf/D and a separator pressure of 250 psig. This rate was maintained until the choke was fully opened. The gas rate then declined with the falling tubing pressure and production was continued until the rate was about 2

By P. G. Nahin, A. Grenall, R. S. Crog, W. C. Merrill

A progress report of an experimental investigation into the role of clay in reservoir performance is presented. The Paper gives some of the reasons for considering clay as a significant component and outlines the objectives of a broad field of stud) which it is intended to pursue. Descriptions of the analytical methods used are given; these include X-ray diffraction. elec tron miscroscopy, thin section petrography, infrared spec-troscopy, and cation exchange analysis. A suite of the more important clay minerals has been assembled and characterized l~y these methods for use as standards in core analysis. From the data obtained it appears that although no one method of analysis is diagnostic for all of the clay minerals the infrared technique shows considerable promise in this direction. For the present, one or more supplementary methods should be used to confirm the clay mineral identifications. The methods of analysis are applied to field cores taken from repesentative and widely differing strata especially as regards their susceptibility to damage by fresh water. well.; completed in the stevens and Gatchell zones in San Joaquin valley are I,articularly clear-cut examples of this behavior with stevens zone wells being more adversely affected by fresh water. cores from these zones have been studied and are discussed. It appears that differences in this behavior can be ascribed to differences in the nature of the contained clays. The value of the infrarecl spectra of the clay fractions in establishing the identity of the predominant clay minerals is given particular emphasis. INTRODUCTION It is a challenge to the technical resources of the petroleum industry that when the economic limit of production is reached, from 40 to 70 per cent of the oil in California reservoirs remains unproduced even by use of the best presently known methods of recovery. The magnitude of this abandoned volume of oil can be appreciated when it is considered that to 1950 in excess of 8 billion bbll has been produced from California reservoirs with estimated economically recoverable reserves in known fields and pools totaling nearly 4 billion bbl.24 If for every barrel of oil produced there is at least another barrel still in place, it is evident that the revenue obtained from the recovery of only a .few per cent of this volume would repay the cost of the required research manyfold. From well completion experience. production behavior, and a growing body of laboratory data it now appears certain that the mineral composition of a producing stratum has an important bearing on the productivity and ultimate yield. In addition to the organic component and water, the cores con,ist of gravel, sand. silt, and clay" in diverse variety of (a, composition and (b) texture. It is the composite effect of these two factors which is probably responsible in large measure for the way in which the oil flows to the well. The role of the clay and fine-size accessory minerals is not clear but there is a growing opinion, based on their physical and chemical properties, that it is a significant one. of particular importance are the prime facts: 1. The silt and clay fractions of the reservoir matrix possess the highest surface area per gram, and 2. The silt and especially the clay fractions are the most chemically reactive of the inorganic constituents present. Only within the last few years has the knowledge of clay mineralogy and the techniques of identifying the clay minerals reached such a stage as to enable reliable inquiry into the composition of argillaceous sediments.2,8,10,11,12,16,26 It is the purpox of this and succeeding papers to add to the fund of information on the role which these materials play in the production of petroleum from California formations by correlating their presence and associated properties with observed reservoir behavior. In the present paper attention is directed to their possible influence on damage by fresh water. OBJECTIVES The attack on this problem divides naturally into two broad phases: 1. Determination of the nature of the clays and their relationships to the other mineral components, and 2. Determination of the physico-chemical relationships between the clays and the interstitial fluids. In the work described in this paper the emphasis has been on phase 1, which stems logically from the necessity of identifying and understanding the materials to be dealt with in Phase 2. Based on the authors&apos; present opinion that not all of the minerals which occur in oil-bearing formation are of equal importance in their effects on the flow and recovery of oil, it was decided to focus attention first upon the clay minerals content and then. later perhaps. work into the field of the normally larger size non-clay minerals and fractions. The

Jan 1, 1951

By W. C. Merrill, P. G. Nahin, A. Grenall, R. S. Crog

A progress report of an experimental investigation into the role of clay in reservoir performance is presented. The Paper gives some of the reasons for considering clay as a significant component and outlines the objectives of a broad field of stud) which it is intended to pursue. Descriptions of the analytical methods used are given; these include X-ray diffraction. elec tron miscroscopy, thin section petrography, infrared spec-troscopy, and cation exchange analysis. A suite of the more important clay minerals has been assembled and characterized l~y these methods for use as standards in core analysis. From the data obtained it appears that although no one method of analysis is diagnostic for all of the clay minerals the infrared technique shows considerable promise in this direction. For the present, one or more supplementary methods should be used to confirm the clay mineral identifications. The methods of analysis are applied to field cores taken from repesentative and widely differing strata especially as regards their susceptibility to damage by fresh water. well.; completed in the stevens and Gatchell zones in San Joaquin valley are I,articularly clear-cut examples of this behavior with stevens zone wells being more adversely affected by fresh water. cores from these zones have been studied and are discussed. It appears that differences in this behavior can be ascribed to differences in the nature of the contained clays. The value of the infrarecl spectra of the clay fractions in establishing the identity of the predominant clay minerals is given particular emphasis. INTRODUCTION It is a challenge to the technical resources of the petroleum industry that when the economic limit of production is reached, from 40 to 70 per cent of the oil in California reservoirs remains unproduced even by use of the best presently known methods of recovery. The magnitude of this abandoned volume of oil can be appreciated when it is considered that to 1950 in excess of 8 billion bbll has been produced from California reservoirs with estimated economically recoverable reserves in known fields and pools totaling nearly 4 billion bbl.24 If for every barrel of oil produced there is at least another barrel still in place, it is evident that the revenue obtained from the recovery of only a .few per cent of this volume would repay the cost of the required research manyfold. From well completion experience. production behavior, and a growing body of laboratory data it now appears certain that the mineral composition of a producing stratum has an important bearing on the productivity and ultimate yield. In addition to the organic component and water, the cores con,ist of gravel, sand. silt, and clay" in diverse variety of (a, composition and (b) texture. It is the composite effect of these two factors which is probably responsible in large measure for the way in which the oil flows to the well. The role of the clay and fine-size accessory minerals is not clear but there is a growing opinion, based on their physical and chemical properties, that it is a significant one. of particular importance are the prime facts: 1. The silt and clay fractions of the reservoir matrix possess the highest surface area per gram, and 2. The silt and especially the clay fractions are the most chemically reactive of the inorganic constituents present. Only within the last few years has the knowledge of clay mineralogy and the techniques of identifying the clay minerals reached such a stage as to enable reliable inquiry into the composition of argillaceous sediments.2,8,10,11,12,16,26 It is the purpox of this and succeeding papers to add to the fund of information on the role which these materials play in the production of petroleum from California formations by correlating their presence and associated properties with observed reservoir behavior. In the present paper attention is directed to their possible influence on damage by fresh water. OBJECTIVES The attack on this problem divides naturally into two broad phases: 1. Determination of the nature of the clays and their relationships to the other mineral components, and 2. Determination of the physico-chemical relationships between the clays and the interstitial fluids. In the work described in this paper the emphasis has been on phase 1, which stems logically from the necessity of identifying and understanding the materials to be dealt with in Phase 2. Based on the authors&apos; present opinion that not all of the minerals which occur in oil-bearing formation are of equal importance in their effects on the flow and recovery of oil, it was decided to focus attention first upon the clay minerals content and then. later perhaps. work into the field of the normally larger size non-clay minerals and fractions. The

Jan 1, 1951