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By Ernst A. Hauser

IN a paper published three years ago,' the term "silicic chemistry" was used for the first time to emphasize the increasing importance of the chemistry of silicon in science and technology. The development through which the colloid chemistry of siliceous matter has gone since then is in itself ample proof that the coining of this new term for this branch of colloid science was not presumptuous. Until quite recently, however, silicic chemistry concerned itself only with the composition and colloidal properties of natural and synthetic siliceous matter, but had not paid much attention to the genesis of this matter, particularly to that of the clay minerals. What is even more disturbing, particularly from an educational point of view, is the fact that neither mineralogy, geology, nor metallurgy has fully realized the important role colloidal phenomena must have played in the genesis of our planet and the formation of minerals generally speaking. Considering the importance of colloid chemistry today in the fields just mentioned, it is not surprising that the theories most agreed upon by geologists and mineralogists for the origin of clay minerals are not acceptable from a strictly colloid chemical point of view for the genesis of these most important and most abundant components of the earth. Of all the theories pertaining to the origin of clay minerals, those still most accepted by geologists and mineralogists are the "residual clay" and the "transported clay" theories.15 The former is based primarily on the assumption that the formation of clay minerals is the result of surface weathering of fresh rocks, or is due to the action of solutions. Taking the action of water on orthoclase as an example, the most recent ideas have been summarized by H. Jenny13 as follows:

Jan 1, 1952

By H. K. Birnbaum

The termination of a twin lamella in the interior of a crystal requires accommodation of the strains at the tip of the twin which result from coherency of the twin and matrix. In zinc and magnesium crystals,

Jan 1, 1960

By HOWARND N. EAVENSON

THE year 1930 resembled the preceding one in the coal industry in continuing the era of falling prices and 'of the abandonment of unprofitable mines. Practically all coal prices fell, and in the steam sizes during the last half of the year this was particularly true, due to the small industrial demand. No new mines of any size were opened in the bituminous coal industry, but there was a steady increase in the number of cleaning plants of all kinds built in all fields. It is estimated that at least nine million tons per year were added to the previous total of washed coal. The largest washing plant started during the year was that of the Buckeye Coal Co., at Nemacolin, Pa., with a capacity of 650 tons per hour. Fig. 1 shows - the mixing-bin, conveyor galleries, washing-plant and skip hoist, and Fig. 2 the 120-ft. Dorr thickener for collecting the 48-mesh material from the wash water. Dryers are used for drying the steam coal product. The following statement by J. R. Campbell shows the effect of cleaning on Pittsburgh coal in Greene County: "With the advent of the 650-t.p.h. efficient washing plant in Greene County at the Nemacolin mine of the Buckeye Coal Co., it has undoubtedly been demonstrated that the potential coking-metallurgical coals of the county can be brought within the pale of the highest grade high-volatile coals for steel manufacture. A few months' operation indicates that 9% per cent ash in the raw coal can be easily reduced to under 7 per cent ash in the washed coal and the sulfur from 1.60 per cent in the run of mine to 1.20 per cent sulfur in the washed coal.

Jan 1, 1931

By J. F. KENP

THE White Knob copper-deposits are situated about three miles south of Mackay, on the Salmon River .branch of the Oregon Short Line Railroad, in Custer county, Idaho. An outline-map of this district is given in Fig. 1. The deposits have been known and spasmodically worked for many years, and a total of over 3.5 miles of tunnels, shafts and other workings has been driven with a view to their development. These extensive excavations have exposed the deposits sufficiently to permit a careful geological examination. The peculiar features which give special interest to this paper are the branching, free-like form of the ore-bodies; the absence of zones of secondary enrichment in the partly oxidized pyritic deposits, and the fact that while the deposits are associated in a general way with the contact of an eruptive rock with limestone, which it penetrates, the garnetization has taken place not in the limestone, as is the usual case, but in the igneous

Mar 1, 1907

By Frederic P. Dewey

This old and well-known method of determining silver is, in bullion work, so far superior to the furnace-assay that it is looked upon with reverential awe by many, if not by most, users, and its ease of execution, with proper equipment, commends it highly where much commercial bullion work on silver is required. The method is so thoroughly well known that a description of it here may seem to be unnecessary, but many thousands of determinations are annually made by it in the U. S. Mint Service and its practice is there reduced to an art. This is necessary both for the sake of economy of time, and because high-grade work with it requires constant practice. It is useless for a person who uses it only occasionally to expect to attain high accuracy with it, without spending more time upon a detemination than is warranted in a busy commercial laboratory. It is always employed in the Mint service whenever possible, but its chief field is in the determination of silver in standard silver (ingots and coin), which is 900 fine in silver and 100 fine in copper, and I shall first briefly outline its use on this metal and then take up various points in detail, especially as related to the accuracy of the results obtained. For this determination 1,115 mg. of standard metal are weighed and transferred to a glass-stoppered bottle, the metal is dissolved in nitric acid, and 100 cc. of a standard solution of NaCl run in. The bottle is then vigorously shaken and a measured portion of a decimal salt solution added, and again shaken, if necessary. These operations are repeated until the silver is precipitated. Standard metal being 900 fine, 1,115 mg. should carry 1,003.5 mg. of silver, which is a convenient figure to work with.

Jan 1, 1914

By Mark R. Lamb

THE treatment of slime is of special interest to those engaged in cyaniding gold- and silver-ores. The usual practice is to make as small a percentage of slime as possible. In many instances the slime is given no treatment, but is impounded in dams in the hope that the future will develop some method of economically treating this product. The filter-press was the first step upward from ordinary decantation, but, on account of heavy labor-charge and high cost, its use has been limited to high-grade material. The slime at the Combination mill at Goldfield averages perhaps $20 per ton, and although the values are quickly dissolved the filter-press installation was not entirely satisfactory, resulting in the erection of the canvas-cell filter, developed by Chas. Butters and his staff. This filter is a great improvement over the filter-press, and the following description of it will be of interest to those engaged in treating slime produced in crushing ores, especially in view of the fact that, by the use of this filter, slime can be treated at a lesser cost and with a higher percentage of gold- or silver-extraction than in the ordinary treatment of sand; and, moreover, the initial outlay for an all-sliming plant is less than that for the ordinary sand- and slime-plant. The economy of construction of the Butters filter-plant is clearly shown in Figs. 1 and 2, which illustrate the 20-frame filter of 40 tons capacity, now being installed by the Nevada Goldfield Reduction Co. In this construction the slime-pump is so connected that it can pump to or from either tank or the filter by changing the valve-settings-a combination which is necessary in this particular installation, since sufficient fall is not available for filling and discharging the filter by gravity. Ordinarily, a slime-plant comprises: a filter-box with frames

Jan 1, 1907

By William P. Blake

The ancient city of Guanajuato, the capital of the State of that name, has been built up and sustained chiefly by the milling industry based upon the veins of the Veta Madre and La Luz. It is distant about twelve hours, by rail, from the City of Mexico. Its elevation above the sea is about 6300 ft., and it has a salubrious climate. The population, at the date of my visit in 1891, was estimated at from 80,000 to 100,000 persons. The place is justly celebrated for the antiquity, depth and extent of the mines, the magnitude of the deep shafts, and the enormous total yield of the district in silver and gold, which is comparable with that of the Comstock Lode in the United States. Several important public institutions are located at this center. The State office for the records of claims and of the statistics of mining and production is known as the Deputacion de Mineria. The Mining College, with its fine collection of ores and minerals from the mines of the region, is highly interesting to mineralogists. A mint for the coinage of silver, but not of gold, coins from four to twelve millions of' silver dollars annually. The silver received at the mint is melted in an open-hearth furnace, and is ladled out and cast into long and thin bars, which are rolled down to the proper thickness for the blanks. The bars contain some gold which is not parted. There is an export of dore bars to Germany, amounting in value to from $1,000,000 to $1,500,000 annually. There were, in 1891, upwards of forty reduction-works in and about the city where the silver ores were treated, chiefly by the ancient patio method. In these works were 65 Chilean mills, 301 arrastres of large size, and 936 of smaller dimensions. There were 36 steam engines, but mule-power was generally used at the ar-

Jan 1, 1902

By William F. Boericke

KIRKLAND LAKE and Porcupine in 1931 accounted for more than $41,625,000 of Ontario's total gold production of $43,117,688. For the first time, the younger camp surpassed the older in gold output, producing $21,734,000 against $19,891,000 for Porcupine. Present output of both camps is increasing, and should pass the record figures of 1931 before the year is out. In May of this year, Porcupine mines milled 285,759 tons, with a bullion value of $1,810,009; the corresponding figures for Kirkland mines are 149,188 tons and $2,104,757. A much higher average value per ton for Kirkland ore, $14.10 against $6.33 average for Porcupine accounts for the difference. The two fields are about 100 miles apart by rail, and there are important differences in the character of the ores, which accounts largely for the difference in milling costs and in final tailing values, despite excellent metallurgical work in both the fields.

Jan 1, 1932

This brief resume of the events transpiring in Mexico, culled from the daily New York newspapers since the last Bulletin went to press, does not show any degree of improvement in the situation. U. S. WITHDRAWS ARMY FROM MEXICO The American invasion of Mexico lasted less than 24 hours. The troops which crossed the Rio Grande June 15 to put a stop to the firing that was causing death and injury in El Paso were back in their billets on the American side of the border the next night. They had broken up the battle between Villa rebels and the Carranza garrison and driven the rebel forces headlong out of Juarez and into the hills. The Carranza Consul, Garcia, and Gen. Francisco Gonzales are reported by American officials to be pessimistic, if not indignant, at the swift reprisals made by the Americans against the stray shots which were falling in El Paso during the Villa attack on Juarez. In announcing his action in ordering Americans into Mexico Brigadier General Erwin in a formal statement said he had done-so to prevent the indiscriminate firing into El Paso by rebel soldiers, endangering the lives of Americans. "But on no account were they to undertake an invasion into Mexico," continued the statement. Americans with interests in the vicinity of Chihuahua are alarmed lest Villa, smarting under the defeat administered his troops by the American forces, should make a campaign of destruction. General Candido Aguilar, President Carranza's confidential ambassador to the United States, issued to the press, on June 17, a formal statement that "the government and people of Mexico consider as a violation of Mexican sovereignty the crossing of United States soldiers into Mexican territory" and expressing the hope ?that the situation created by the latest occurrences in Juarez will be satisfactorily adjusted between the two countries." Discussion of Mexican affairs was evoked in both houses of Congress by the crossing of the Rio Grande by American troops.

Jan 8, 1919

By H. G. Schneider

THE Smackover oil and gas field lies in Ouachita and Union Counties, Ark., in the south-central part of the state, in T.15 and 16S., R.15, 16, and 17W. It is 10 miles north of El Dorado, the principal business and railroad center in the south-central part of the state, and extends from the town of Smackover in all directions. Productive territory having an aggregate area of nearly 55 sq. mi. has been developed. It extends 6 miles from north to south and 12 miles from east to west. The field may be divided into two parts: the east district, which includes the area east of the town of Smackover, and the west district, which includes the area west of the town of Smackover. In relation to the neighboring productive fields of Arkansas, the Smackover field is 9 miles north of .the El Dorado oil and gas field, 8 miles slightly west of north of the East El Dorado oil and gas field, and 16 miles east of the Stephens oil field. Smackover was discovered in May, 1922, when the Oil Operators Trust drilled well No. 1 on the J. T. Murphy farm, in the southeast quarter of sec. 8, T. 16S., R.15W. This well is located almost, on the top of the Norphlet dome and was drilled to the Nacatoch sand. It had an initial open flow volume of 30,000,000 cu. ft. of dry gas per day, and a rock pressure of 950 lb. per sq. in. In July, 1922, the V. K. F. Co. completed the first oil well in sec. 29, T.15S., R.15W., on the north side of the Norphlet dome, and 3 miles north of the first gas well. This well started the active development of the north and northwest sides of the dome.1

Jan 3, 1924

By C. K. Leith, W. J. NEAD

(Glen Summit Meeting, June, 1911.) . ONE Of the most significant developments in the iron industry in recent years has been the discovery and opening of enormous reserves of low-grade ore in eastern and northeastern Cuba. The two principal fields are the Mayari and the Moa, situated on Nipe bay, in the Province of Oriente. A less well-known district of the same type is that of Baracoa, at the east of the island, and another is in Camaguey province in central Cuba. In the comprehensive estimates of the iron-ore reserves of the world, published during the summer of 1910 by the International Geological Congress in Sweden,' these Cuban deposits are estimated at about 2,000,000,000 tons. Certain it is that the reserve is a large one. The Spanish-American Iron Co., the Juragua Iron Co. (Bethlehem Steel Co.), the U. S. Steel Corporation, and others have been active in this exploration.. The Spanish-American Iron Co. has established a port for the handling of these ores at Felton, has built a railway 16 miles to the ore-fields, and has opened up deposits for steam-shovel mining. Its expenditures have reached an aggregate of about $6,000,000 in preparation for the handling of these ores. Shipment of the ore to Sparrow's Point, Md., has begun and may be expected to rise to a considerable amount in the near future. The ore reaches this point at a cost per unit of iron considerably lower than Lake Superior ores, and the presence of a low percentage of nickel gives a desirable steel. It is not the purpose of this article to consider these ores from a commercial stand-point, but rather to discuss their-origin. If our conclusions are correct, they throw light on the character of the deposits which should have some commercial significance. 1 The Iron Ore Resources of the World, an inquiry made upon the initiative of the Executive Committee of the Eleventh International Geological Congress, Stockholm, vol. ii., p. 795 (1910).

Mar 1, 1911

By Will Mitchell

The classical definition of a beneficiation engineer as one who treats an ore in order to separate and discard worthless fractions by essentially physical means is obsolete. Technology in the profession has advanced so rapidly during the last two or three years that educators have not been able to coin definitions to keep up with the pace. In the past some people have hesitated to include leaching or even agglomeration as minerals beneficiation, because of the major chemical changes involved. This view has fallen by the wayside, especially because a majority in the profession have become actively involved in extraction and pyro processes that go far beyond the original definition of mineral dressing. To say that there is a great revival of interest in leaching is putting it mildly, for the uranium business, like the gold business, now depends almost entirely on leaching. This revival of leaching, long overdue in mineral engineering, has been stimulated this year, especially as a result of the relaxation of security restrictions surrounding the recovery of uranium from its ores. It has brought new unit operations to minerals beneficiation, namely ion exchange and solvent extraction. These operations have appeared as resin-in-pulp, solvent-in-pulp, and liquid-liquid systems. In many cases these leaching and separation procedures, now reaching the production stage, have been engineered by minerals beneficiators. The trend toward leaching has also had impact on the technology of beneficiating other nonferrous minerals, especially copper, manganese, columbium, tantalum, nickel, cobalt, titanium, and the rare earths.

Feb 1, 1956

By C. R. Austin

THE investigation described in this paper deals with the development of high-temperature alloys of the Konel series over a considerable period of time at the Research Laboratories of the Westinghouse Electric and Manufacturing Co. The word "Konel" has been coined to designate a class of alloys which are essentially nickel-cobalt-iron with other elements added, usually in small quantities. Most of these alloys contain titanium, usually about 2.5 percent. The main consideration related to strength at high temperatures but the thermionic characteristics of the alloys was also of considerable importance. It is, however, with the mechanical properties at elevated temperatures that we are herein concerned. Much attention has also been devoted to their age-hardening characteristics. There is little need to stress the utilitarian aspect of this subject, as it has been discussed frequently. Alloys exhibiting superior properties at normal or elevated temperatures rapidly find many suitable applications. There may be some question, however, as to what constitutes a "superior alloy, " or an alloy that may have good service possibilities at high temperatures. The problem is complex and various means have been employed to predict the useful life that may be expected of a material. In recent years the "creep limit" has been used as the best means of evaluation. Such tests necessarily are prolonged and hence collection of data is very slow. In a general survey of many alloys therefore the creep test is not desirable and recourse must be had to much shorter time tests in order more rapidly to select alloys which appear to show promise. For this reason the present survey has been made using the high-temperature tensile test and a bend' test developed by Howard Scott.1 In the tensile test the conditions have been standardized for all tests, so that values obtained are at least comparable, one alloy with another, although the absolute values recorded merely indicate the mechanical properties at the given temperature under a definite rate of loading.

Jan 1, 1931

By C. R. Austin

Tan investigation described in this paper deals with the development of high-temperature alloys of the Konel series over a considerable period of time at the Research Laboratories of the Westinghouse Electric and Manufacturing Co. The word "Konel" has been coined to designate a class of alloys which are essentially nickel-cobalt-iron with other elements added, usually in small quantities. Most of these alloys contain titanium, usually about 2.5 per cent. The main consideration related to strength at high temperatures but the thermionic characteristics of the alloys was also of considerable importance. It is, however, with the mechanical properties at elevated temperatures that we are herein concerned. Much attention has also been devoted to their age-hardening characteristics. There is little need to stress the utilitarian aspect of this subject, as it has been discussed frequently. Alloys exhibiting superior properties at normal or elevated temperatures rapidly find many suitable applications. There may be some question, however, as to what constitutes a "superior alloy, " or an alloy that may have good service possibilities at high temperatures. The problem is complex and various means have been employed to predict the useful life that may be expected of a material. In recent years the "creep limit" has been used as the best means of evaluation. Such tests necessarily are prolonged and hence collection of data is very slow. In a general survey of many alloys therefore the creep test is not desirable and recourse must be had to much shorter time tests in order more rapidly to select alloys which appear to show promise. For this reason the present survey has been made using the high-temperature tensile test and a bend test developed by Howard Scott.1 In the tensile test the conditions have been standardized for all tests, so that values obtained are at least comparable, one alloy with another, although the absolute values recorded merely indicate the mechanical properties at the given temperature under a definite rate of loading.

Jan 1, 1931

By Dell P. Williams, Howard G. Nelson

The tensile behavior of magnesium single crystals at a temperature of 26º ± 2ºC was investigated at varying pressure levels from 760 to 8 X 10-8 tow. For crystals deformed at a constant linear strain rate of 0.061 min-1. there was no apparent effect of the vacuum environment down to 10-8 torr. However, from a vacuum of 10-5 torr down to the lowest pressure attained (8 x 10-8 tor,), the effect of the vacuum environment was to increase the strain at the end of the first linear (or easy-glide) stage and to decrease the slope of this stage; the magnitude of this effect was found to be dependent on pressure. The slope of the second linear stage was also decreased at the lower pressure levels; however, this effect appears to be caused primarity by the vacuum effect on the first linear stage. The magnitude of the vacuum-environmrnt effect was also found to be dependent upon strain rate. The reduction in flow stress at 5 x 10-8 torr, as compared to the stress in air, was obserced to be about 10 pct for a strain rate of 0.0250 min-' and 70 pct for a strain rate of 0.67 min-1. No systematic effect of pressure on the critical resolvled shear stress was observed. The data interpreted in terms of a modified form of Mott's work-hardening mechanism for hexagonal metals. It has long been known that surface conditions influence the mechanical behavior of materials. Roscoe 1 demonstrated the importance of surface conditions on mechanical behavior by testing cadmium crystals with oxide layers. He found that the "apparent" critical resolved shear stress for cadmium was increased approximately 2.5 times by the presence of an oxide layer 1000 atoms thick. The magnitude of this effect was dependent on film thickness with crystals having films less than 20 atoms thick still showing a definite increase. This observed strengthening could not be attributed to any strength of the oxide film because of 1) the thinness of the films and 2) an observed increase in the flow stress as deformation proceeded. Harper and cottrel12 obtained similar results on zinc crystals which had been etched and steamed to give artificially thick oxide films. However, in the course of this study, they also carefully examined the very early stages of plastic flow for zinc crystals which in one case had been electrolytically polished and in the other had been lightly etched to produce a thin film. They then found that the critical resolved shear stress for both surface treatments of the crystals was actually identical but that the etched crystal exhibited a much more rapid initial hardening rate. This had not been noted previously. This result indicated that, in fact, the film caused an increase in the stress for continuation of slip, rather than for the initiation of slip. Lipsett and King3 investigated the effect of evaporated gold films on the plastic behavior of cadmium single crystals. For large angles (=75 deg) between the specimen axis and the normal to the slip plane, they found that the stress-strain curve of the coated specimen always lies above that for a clean specimen. The shear strain at the end of the first linear stage was greater in clean specimens than in coated specimens and the slope of the second linear stage was

Jan 1, 1965

By F. N. Rhines, A. S. Nemy

The mode of high-temperature tertiary creep of 523-0 aluminum alloy was found to be strongly stress dependent. The occurrence of necking and/or fissures during tertiary creep exhibited a sequence with varying stress, wherein fissures with no necking occur at a minimum stress and necking with no fissures occur at a maximum stress. At an intermediate stress, tertiary creep begins without necking but with fissures in a region just beneath the external surface, followed by necking and the development of fissures along the axis of the specimen. The results are interpreted in terms of grain boundary gliding and the hydrostatic stresses produced by restraints to grain boundary gliding. THERE appear to be two possible reasons for the existence of a period of accelerating elongation prior to rupture during high-temperature creep in metals; namely, 1) a change in the structure of the metal itself, leading to a change in its response to loading, and 2) a reduction in the cross section of the metal resulting in a higher unit loading. Howe,' by annealing and retesting broken low-temperature creep specimens, found that irreparable damage is done once a metal is subjected to creep. Andrade2 first pointed out the association between the reduction in cross section and the increase in creep rate. The present research was designed to investigate both of these factors by retesting specimens machined from material which had been subjected to high-temperature creep testing short of rupture. EXPERIMENTAL METHOD An aluminum alloy, 52s-0, was selected for these studies because it is constitutionally simple, is strong enough to be relatively insensitive to mechanical damage during machining,3 and undergoes accelerating creep in a convenient temperature range. This alloy is hardened by 2.6 wt pct Mg in solid solution and is not subject to overaging effects; it has a very small quantity of an insoluble impurity phase, Mg2Si, finely dispersed throughout its micro-structure. Creep specimens, similar in design to ASTM 0.252-in. tensile specimens, were machined from 3/4-in. round stock and the surfaces were electro-polished. A 24-hr anneal at 500°C was then applied to stabilize the grain size to an average diameier of 0.27 mm. Subsequent heating for as long as 700 hr at the intended test temperatures produced no change in the tensile properties, indicating a well-stabilized state of the material. Corresponding to each of the typical testing conditions listed in Table I, one creep specimen was tested to destruction and this test was employed as a guide in the selection of times for subsequent tests. Duplicate creep tests were then run to various points along the creep curve to produce specimens which were used to determine changes in mechanical properties and microstructures. The latter were examined at the midsections of the specimens. Other specimens were tested to various stages of tertiary creep, after which they were remachined to new cylindrical test specimens, electropolished and re-tested in creep. RESULTS The major findings of this investigation may be illustrated by a comparison of the results of three sets of creep tests. These were run at 400°C at three stress levels, namely 750, 1000, and 1500 psi. In presenting these results in Figs. 1, 5, and 8, the creep curves are given in pairs: That curve of each pair which is drawn through filled circles corresponds to the initial test, and the curve drawn through open circles (and designated by - R) represents the result of retesting the same specimen after machining to a new cylindrical surface. The load was readjusted to the original unit stress at the beginning of each retest.

Jan 1, 1960

By C. Land, R. Hultgren

Heat contents of four Cr-Ni alloys were determined in a diphenyl ethev calorimeter. Aside from ferromagnetic effects, Kopp's law of additivity of heat capacities is approximately fol-lowed, in disagreement with earlier results of A. W. Foster. In 1934 Foster1 reported heat-capacity measurements of dilute solutions of chromium in nickel, primarily as a study of the effect of alloying on the ferromagnetic Curie temperature. He found that, apart from the Curie temperature effect, the general level of heat capacities was reduced 10 pct by the addition of 1 pct Cr; 20 pct by the addition of 2 pct Cr. His measurements of pure nickel essentially agreed with accepted values. These results indicate that small amounts of dissolved chromium cause an increase in the Debye temperature of nickel, presupposing a change of frequency of interatomic bonding vibrations which is much larger than should be expected. If Foster's results were verified, therefore, they would have important implications for bonding theory. The only other heat-capacity measurements in this system seem to be those of Taylor and Hinton,' who studied anomalies which they attributed to super-lattice formation at 25 at. pct Cr. At temperatures above the anomaly, Taylor and Hinton found heat capacities at this composition were quite normal, approximately obeying Kopp's law of additivity. EXPERIMENTAL WORK In order to verify or disprove the remarkable results of Foster, the heat contents of four dilute solid solutions of chromiunn in nickel were measured in a diphenyl ether calorimeter. This instrument, described elsewhere,, operates on the principle of the Bunsen ice calorimeter, but uses diphenyl ether as the working substance. Diphenyl ether melts at the convenient temperature of 26.S°C and supplies a more sensitive measure of heat than ice. The hot sample, in an atmosphere of argon, is dropped from a furnace at a measured temperature into a chamber which is surrounded by a mixture of solid and liquid diphenyl ether. The heat from the hot specimen melts some of the solid without chang- ing the temperature of the calorimeter. The amount of solid melted, and therefore the number of calories released by the specimen, is measured from the increase of volume of the mixture, which pushes mercury down a graduated capillary tube. The apparatus has been standardized against the known heat content of pure platinum. Heat loss during the dropping of the specimen was estimated by comparing the heat content of an empty platinum capsule with a solid platinum ball of the same radius and degree of polish of the surface. Repeated tests demonstrate the precision of measurement to be closer than *0.3 pct. Smoothed experimental results are listed in Table I. The tabulated values for pure nickel are taken from kelley, several measurements were made which agreed closely with this tabulation. For chromium, however, no similar agreement was found. The values tabulated were taken from a thorough study of chromium with the diphenyl ether calorimeter which will be published elsewhere.= Suitable plots of the data showed the expected ferromagnetic anomalies in the low-chromium alloys, while the 11 pct alloy shows no ferromagnetic anomaly, but a different, small anomaly below 900°K. This is perhaps the same anomaly found in CrNi, which was once attributed to superlattice formation,' but is probably due to some other cause, such as antifer-

Jan 1, 1960

By W. J. Joslin

The frontal-advance equation can determine how the fluid withdrawal rate and subsurface operating pressure influence oil recovery from pressure-maintained reservoirs having characteristics favorable for efficient vertical segregation. For effective vertical segregation in formations having low dip angles, the requirements are: thick, massive sands, low viscosity oil and high vertical permeability with few discontinuous shale members. This approach has been successfully applied to the LL-370, which is a massive Eocene sandstone reservoir containing crude with an average gravity of 26" APT, a dip of only 3" and vertical permeability of ½ darcy. The average gas cap saturation was calculated for various rates of vertical gas-oil contact movement corresponding to a wide range of reservoir producing rates. This method also evaluated the effect of different pressure maintenance levels on oil recovery. Applicability of this procedure for calculating the present oil saturation in the LL-370 gas cap has been substantiated from field performance, where the oil saturation was computed by comparing oil recovery with the gas cap volume vacated. INTRODUCTION During the natural depletion history of the LL-370 reservoir, located in Lake Maracaibo, Venezuela, excellent vertical segregation resulted in the formation of a thin gas zone over a substantial portion of the oil-productive area. Subsequently, gas injection forced this thin gas-saturated zone slowly downward, reducing the oil saturation in the gas cap to a low value. The oil recovery has been raised considerably above earlier predictions where vertical segregation effects were under-estimated. In order to determine the maximum efficient producing rate and optimum operating pressure for this reservoir, a vertical gas frontal-advance analysis has been made through application of the fractional flow equation. LL-370 RESERVOIR CHARACTERISTICS The reservoir consists of a truncated monocline of massive. highly-permeable Eocene sandstone, called the B-b formation, covering an area of more than 13,500 acres. The original oil in place was 2.17 billion STB. Internal non-sealing faults subdivide the structure into four blocks called the B-6-x.6, 10, 11 and 13, which are effectively bounded by major faulting on the flanks, an unconformity updip to the west, and an immobile aquifer to the southeast. The producing formation occurs at an average depth of 5,250 ft subsea and has a closure of more than 1,500 ft. A typical producing section has a net oil sand thickness of 170 ft. Scattered throughout the section are a few randomly-positioned shale lenses which increase in thickness and areal extent downdip. The reservoir rock and fluid properties vary with depth. The permeability and produced oil gravity are 1600 md and 28" API at the top, compared to 300 md and 18° API at the water-oil contact. The productivity of updip wells is, therefore, much higher than the reservoir average. The reservoir oil was originally saturated at the crest, grading to a slight degree of undersaturation at the water-oil contact. There was no original gas cap; and material balance and the field performance indicate no water influx. Except for the northern B-6-x.6 block, the fluid and rock properties have already been published.' Average LL-370 reservoir properties are shown in Table 1. RESERVOIR PERFORMANCE UNDER NATURAL DEPLETION Fig. 1 shows production performance from 1939 to date. Early development was gradual, with 30 wells pro-

Jan 1, 1965

By I. R. Kramer

The delay time for single crystals of iron, zinc, and pre-strained aluminum was measured under conditions of high-speed deformation. The delay time of aluminum was found to be affected by the orientation of the crystal. Under the dynamic conditions employed, tile calculated "activated volume" term appears to be very small for the three metals studied. IN a previous paper,1 it was shown that under dynamic testing conditions at 78° K, there was a delayed yield in single crystals of aluminum and copper which had been cold-worked prior to testing. The experimental results also indicated that the delay-time effect was not due to the interaction of dislocations with impurity atoms or vacancies, but rather to a dislocation-dislocation interaction since aluminum which has not been prestrained shows no delay-time phenomenon. In this paper, some data are reported on the effects of orientation on the delay time of aluminum single crystals; the delay time of zinc single crystals saturated with nitrogen and the delay time of iron single crystals also were measured. EXPERIMENTAL PROCEDURE Aluminum (99.997 pct) and zinc (99.999 pct) crystals, 1/2 in. in diam and 8 in. long were grown by the Bridgman technique. The iron single crystal was supplied by Dr. R. Maddin. The zinc crystals containing nitrogen were prepared by melting high-purity zinc in a graphite crucible and the nitrogen was introduced by additions of ammonium chloride. The liquid zinc was then drawn up into glass tubes of 1/2 in. diam and allowed to solidify. The rods were cooled to room temperature before the transfer to the mold for conversion into single crystals. The orientation of all specimens was determined by the Laue' back-reflection technique, Fig. 2 and Table I. To prepare for the delay-time measurements, the crystals were cut with a fine jewelers saw and the ends carefully machined. The specimens then were electrolytic ally polished to remove the cold-worked metal, mounted in a special fixture and hand-lapped. As a final step, the crystals were annealed in evacuated tubes. Specimens of aluminum crystals, Nos. 24 and 26, were compressed 0.5 and 2 pct, respectively, in the direction of the later impact. The zinc specimens were aged at 50°C for 15 min, In the case of iron, only two specimens could be obtained. To obtain sufficient data, it was necessary to resort to a reaging treatment. After each delay-time test, the specimens were aged at 65° C for 100 min. This treatment, according to Clark,2 is sufficient to restore the original delay time. It is believed that although the specimens were plastically deformed approximately 10-4 pct, after each test the delay-time values are reliable. The delay-time measurements were made in an apparatus similar to that described previously.' Single crystals approximately 1 in. long and having a diameter of 1/2 in. were placed in a pendulum which consisted of a bar 1/2 in. in diam and 8 ft long, designed with a crystal holder to accommodate the specimen at low temperatures. The crystal was held at a position 2 ft from the front part of the pendulum. This portion of the apparatus was supported on a fine molybdenum wire. A projectile bar of the same diameter and length comprised the other portion of the apparatus. This bar was supported on

Jan 1, 1962

By R. M. Asimow, J. J. Svitak

Tile crilical resoll,r,d shear stress, CRSS, for slip of slow1y cooled Ag-All single crystals was measured at 201K. Tlze importance of short-range order and Suzuki sogregalion was inrestigated by deter~rlining llze ciic.cl of quenching on the CRSS. Thr obserz.ed rfrtenching effects were generally small and indicate that short-range ordcr and Slczuki srgregation do no1 account for n significant portion of the solid-solution strengthening in this system. However, all alloys slzozcwi yield drops ulhich rilere heat- lreat nrenl-sensiline THERE have been a number of mechanisms proposed to explain alloy strengthening in the Ag-Au system. The effectiveness of some of the proposed mechanisms, especially those that depend on Suzuki segregation1" or on short-range order,2-6 SRO? should be strongly dependent on heat treatment. Since internal friction investigations in this system indicate that there is stress-induced order,' we must also consider the possibility of local atomic rearrangement or short-range ordering in the stress field of a dislocation. There is not complete agreement whether these mechanisms should be most effective in raising the flow stress, in causing yield drops. or some combination of these two effects. This work was undertaken to determine the effects in the Ag-Au system of mechanisms that depend on segregation or order by using known but drastically different cooling rates following a high-temperature treatment. By comparing the critical resolved shear stress, CRSS, for slip measured after a very slow cool and again after a fast cool (quench) of the same crystal, it is possible to determine the effect of cooling rate on CRSS* and on yield drops. The single-crystal CRSS was determined at several compositions because there has been no data published across the phase field since the publication of room-temperature flow stress by Sachs and Weerts.' EXPERIMENTAL PROCEDURE Starting with materials of 99.999 pct purity, single-crystal specimens of random orientation 1.25 mm square by 4 cm long were prepared with 0, 10, 14, 25, 30. 50, 70. 75. 80, 90. and 100 at. pct Au. Crystals were grown in an inert atmosphere using a modified Bridgman technique with a growth rate of 1.5 cm per hr in a gradient of 3°C per cm. To obtain a maximum practical degree of SRO, the crystals were cooled at a rate of 275'C per hr to about 310°C and then cooled at 6°C per hr to approximately 200°C. Specimens were tested in tension immersed in an alcohol bath at -72°C (201°K) at a strain rate > = 0.003 mm"1 to determine the CRSS (7). The activation volume of several crystals was determined from the flow stress increment (72 - T1) for a tenfold increase in strain rate. The total shear strain varied from 0.05 to 2.3 pct but was generally less than 0.4 pct. After testing, each crystal was then held at 500°C for 10 min, quenched into brine at -35°C and. after storage at -71°C for 1 day, retested in tension using a procedure identical to that of the first test. The quenching apparatus, see Fig. 1, was designed to enable accurate temperature control and rapid quenching while preventing specimen contamination and accidental deformation. Test data from a specimen with a fine thermocouple spot-welded to it indicated a cooling rate of 104C per sec. The relatively low heat-treatment temperature was chosen to minimize quenching defects caused by a large vacancy

Jan 1, 1970