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By L. C. Brown, S. K. Behera

The diffusion rate in Ag-Sb couples is sensitive to con~pressive load with the width of Ag3Sb, the only phase present in the diffusion zone, increasing with stress up to 800 psi and remaining constant above this. Kirkendall marker experiments show silver to diffuse much faster than antimony in Ag3Sb and incipient porosity may therefore develop at the Ag/Ag3Sb interfnce restricting the transfer of atoms from the silver into the diflusion zone. Application of compressive stress reduces the tendency for porosity to develop and so increases the growth rate. In a recent paper Brown et al.1 observed a significant increase in the thickness of Cu2Te in Cu-Te diffusion couples on application of a compressive stress as low as 20 psi. Similar stress effects have also been observed in the Fe-A1,2 Al-u,3 arid cu-sb4,5 systems. It has been suggested that the increase in growth rates of intermetallic phases in these systems is due to a decrease in the amount of Kirkendall porosity with applied stress. In the present paper, results are presented of the effect of compressive stress on diffusion in Ag-Sb, together with a detailed examination of the Kirkendall effect. The Ag-Sb phase diagram6 shows that antimony has a moderate degree of solid solubility in silver, 5.7 at. pct at 350°C, but that there is essentially no solubility of silver in antimony. There are two intermediate phases— (hcp7) from 8.8 to 15.7 at. pct Sb and Ag3Sb (orthorhombic8) from 21.8 to 25.9 at. pct Sb. EXPERIMENTAL Diffusion couples were prepared from fine silver of 99.95 pct purity and from antimony of 99.7 pct purity. Both the silver and antimony were produced in the form of discs 1/2 in. in diam by approximately $ in. thick, with surfaces ground flat to 3/0 emery paper. Diffusion anneals were carried out in the apparatus previously described.1 A compressive load was applied to the diffusion couple through a lever arm system, with a reproducibility estimated to be ±10 psi. All runs were carried out in a protective hydrogen atmosphere. Following the diffusion anneal specimens were sectioned and polished and the width of the diffusion zone was measured metallographically. Composition profiles were measured using an electrostatically focused electron probe with a spot size of 10 , counting on Sb L radiation. Corrections for matrix absorptiori and fluorescent enhancement9 were not required. S. K. BEHERA, formerly Graducate Student, Department of Metallurgy, University of British Columbia, is now Postdoctoral Fellow, Whiteshell Nuclear Laboratories, Atomic Energy of Canada Ltd., Pinawa, Manitoba. L. C. BROWN, Junior Member AIME, is Associate Professor, Department of Metallurgy, University of British Columbia, Vancouver, B.C., Canada. Manuscript submitted June 14, 1968. IMD RESULTS Fig. 1 shows an electron probe traverse of a typical diffusion zone. In all couples examined only one intermediate phase was observed and the composition of this phase, 23 wt pct Sb, was in good agreement with the composition of Ag3Sb, 23 to 28 wt pct Sb. The presence of this phase was confirmed by X-ray diffraction of filings taken from the diffusion zone. The probe traverses showed no detectable solid solubility in either the silver or the antimony although the phase diagram indicates that some antimony, up to 6.5 wt pct pct Sb, should be in solid solution in the silver. However the width of this portion of the diffusion zone would be expected to be very small in view of the low diffusion coefficient in the silver, 4 x 10-l6 sq cm per sec at 350°C, 10 compared with that in the Ag,Sb, estimated as 3 x 10-8 sq cm per sec in the present work, and this region would therefore not be expected to be seen in the probe traverse. Application of stress resulted in a significant increase in the width of the diffusion zone, Fig. 2. At 350°C, the thickness of Ag3Sb increased from 250 at 0 psi to 400 p at the limiting stress of 800 psi, indicating an apparent 150 pct increase in the diffusion coefficient. Similar behavior was also observed at 400°C, indicating that the stress effect is not characteristic of just one temperature. The growth of Ag3Sb at 350°C and at various stresses is shown in Fig. 3. In every case the growth rate was parabolic indicating diffusion control. The kinetic curves all passed through the origin showing that delayed nucleation of Ag3Sb was not responsible for the stress effect and that it was a real growth effect. A series of tests were carried out in which diffusion was allowed to take place at a lower stress following an initial high stress diffusion anneal. Speci-

Jan 1, 1969

By H. M. Chance M

The following tables have been compiled from the annual reports of the Inspectors of Mines, to determine the percentages of fatal and non-fatal casualties from roof-falls and explosions of fire-damp. As we cannot assume that every accident has teen recorded by the inspectors ; as many casualties terminating fatally after the lapse of a considerable period, are inevitably recorded as " non-fatal;" and as clerical errors may have crept into the compilation,* the figures of these tables cannot be considered absolutely correct, but the summary is sufficiently reliable to show the features I wish to differentiate. Under the heading " Miscellaneous" are included all accidents not directly attributable to explosions of fire-damp, roof-falls or fails of coal. Prominent among the numerous causes included under this head are premature or delayed explosion of blasts, accidental explosion of powder or cartridges, accidents from mine cam, falls in shafts, machine accidents, sliding of loose coal in pitching breasts, suffoca tion by choke-damp, etc., comprising in all 48 per cent. of the total number of casualties.

Jan 1, 1882

By Gerald G. Griswold, James O. Greenslade, Cherie Tilley, Richard Reseigh

INTRODUCTION The Harrison Western Corporation, a leading Denver based mine contracting and engineering concern, is presently engaged in sinking two 1,006 m (3,300 ft) shafts for the Phillips Uranium Corporation at their Nose Rock Project, approximately 13 miles northeast of the small community of Crownpoint in McKinley County, New Mexico. The Nose Rock Project is the first attempt by the Phillips Uranium Corporation to tap the deep uranium reserves in what has become known as the Grants Mineral Belt. (See Figure 1) Project Description Phillips Uranium Corporation's plan for the large 2700 metric ton per day (2950 tons/day) mining facility calls for a series of deep access and ventilation shafts ranging from 4.27 m (14 ft) to 5.49 m (18 ft) in diameter to approximate depths of 1,006 m (3,300 ft). The initial pair of shafts consists of one production shaft and one ventilation shaft separated by a distance of 91 m (300 ft). The interbedded layers of sedimentary sandstones and shales to be penetrated by the shafts contain several major water producing aquifers, the deepest being the mineralized zone called the Westwater Canyon Member of the Morrison Formation. A series of temporary and permanent water pumping stations is planned. Generally, the temporary stations are located above major aquifers to facilitate water removal while sinking through the aquifer and the permanent stations constitute what, in the final mode, will be the mine dewatering system. In addition, Phillips Uranium Corporation has In- stalled and is maintaining a system of depressurization wells that temporarily pump the major aquifers and considerably reduce the water inflows during shaft construction. The major aquifers are also chemically grouted prior to sinking. Site work for the project was initiated in the fall of 1976. Full scale shaft sinking commenced in November of 1977 on the 4.88 m (16 ft) diameter ventilation shaft and on the 5.49 m (18 ft) production shaft by another contractor. Harrison Western Corporation began work on the project on November 4, 1979 wlth the production shaft at a depth of 633 m (2,076 ft) and the ventilation shaft at a depth of 474 m (1,554 ft). This paper will address only the portion of shaft sinking completed by Harrison Western. Geology and Hydrology The Nose Rock Project is located on the Chaco Slope in the southern extreme of the San Juan Basin in northwest New Mexico. The southern San Juan Basin is generally bound by the Defiance Uplift to the west, the Zuni Uplift to the south and the Nacimiento Uplift to the east. The Grants Mineral Belt occupies most of the southern portion of the San Juan Basin and this project is located on the northern extreme of the Grants Mineral Belt. The San Juan Basin is comprised of sedimentary rock of continental, marginal-marine and marine origin, that dip northward from the Zuni Uplift and Chaco Slope into the interior of the San Juan Basin. (See Figure 2) Major Formations The major geologic formations to be penetrated range from mudstone and shales to siltstones and sandstones. The sandstones are highly productive aquifers which, under static conditions, would flow artesian. Water temperatures in the aquifers are high and therefore are a force to be dealt with. Temperatures range from 18ºC (65OF) in the upper aquifers to 48ºC (118º'F) in the lower. The mudstones are generally bentonitlc. (See Figure 2) GALLUP SANDSTONE: The Gallup Sandstone is the first major regressive wedge in the San Juan Basin of the Cretaceous era and at this project is about 35 m (115 ft) thick. It is medium grained and prior to depressurization carried a hydrostatic water pressure of over 72.5 kg per cm2 (1,031 psi) which 1s artesian. Compressive strength ranges from 334.7 kg per cm2 (4,760 psi) to 421.8 kg per cm2 (6,000 psi). Water temperature is approximately 30°C (86°F).

Jan 1, 1982

By H. M. Chance

Asst. Geologist, Pennsylvania Geological Survey THE following tables have been compiled from the annual reports of the Inspectors of Mines, to determine the percentages of fatal and non-fatal casualties from roof-falls and explosions of fire-damp. As we cannot assume that every accident has been recorded by the inspectors; as many casualties terminating fatally after the lapse of a considerable period, are inevitably recorded as "non-fatal;" and as clerical errors may have crept into the compilation,* the figures of these tables cannot be considered absolutely correct, but the summary is sufficiently reliable to show the features I wish to differentiate. Under the heading a Miscellaneous" are included all accidents not directly attributable to explosions of fire-damp, roof-falls or falls of coal. Prominent among the numerous causes included under this head are premature or delayed explosion of blasts, accidental explosion of powder or cartridges, accidents from mine cars, falls in shafts, machine accidents, sliding of loose coal in pitching breasts, sltffouration by choke-damp, etc., comprising in all 48 per cent of the total number of casualties. * Compiled by Mr. Maxwell Chapman

Jan 1, 1882

By E. V. Watts

The D-7 zone of the Ventura Avenue field is of special interest because the initial reservoir pressure at 92.00 ft nearly equaled the pressure exerted by the overburden. While the phenomenon has been observed elsewhere in the world, there is no record of a previous case in California. Such high pressures have been attributed to sealing of the reservoir, followed either by emergence of the beds or by compaction of the sediments in various ways. Oil in the D-7 zone is undersaturated. At pressures above the bubble point, oil is recovered by the slight expansibility of the reservoir framework and its liquid contents. More than 40 pct as much oil probably will be recovered by this mechanism as will be recovered by internal gas drive after pressures pass below the bubble point. Operations are handicapped by sand and pipe troubles. Introduction The Ventura Avenue field has been under development since 1915. It has long been considered a "high-pressure" field, but interest was heightened by the extreme conditions encountered in the recent development of the so-called D-7 zone. The original reservoir pressure in this pool is estimated to have been 8300 psi at a depth of 9000 ft below sea level, or 9200± ft below the surface. A fluid pressure approaching that exerted by the overlying sediments has been encountered in other parts of the world, but never before in California to the degree observed in the D-7 pool. With few exceptions, the original pressure in California fields is about equivalent to the static head of water below the water table in the outcrop. Structure The Ventura anticline is a prominent feature of the Ventura basin, being traceable on the surface about 17 miles.' The Ventura Avenue field is at the apex of the anticline. It is about one mile wide and five miles long, the major axis lying in an east-west direction. The productive limits cover an area of about 2300 acres. The entire anticline has been severely folded and faulted. The productive portions in particular are broken up by three major thrust faults having a general east-west strike. The resultant four fault blocks are termed the A, B, C, and D blocks, respectively. Certain electric-log intervals are assigned numbers. Fig I is a diagrammatic north-south section of the field near the crest, looking west, and shows three of the four fault blocks. To the west, the upper fault divides into two branches, which define the B block. Wells penetrating a fault may duplicate over 1000 ft of formation. However, the greater fault movement is the strike shift, which is believed to exceed 2500 ft both between the A and C blocks and between the C and D blocks. The location of water is irregular and unpredictable. A few intermediate waters exist, while some strata have more than 2000 ft of productive closure.

Jan 1, 1948

By E. V. Watts

The D-7 zone of the Ventura Avenue field is of special interest because the initial reservoir pressure at 92.00 ft nearly equaled the pressure exerted by the overburden. While the phenomenon has been observed elsewhere in the world, there is no record of a previous case in California. Such high pressures have been attributed to sealing of the reservoir, followed either by emergence of the beds or by compaction of the sediments in various ways. Oil in the D-7 zone is undersaturated. At pressures above the bubble point, oil is recovered by the slight expansibility of the reservoir framework and its liquid contents. More than 40 pct as much oil probably will be recovered by this mechanism as will be recovered by internal gas drive after pressures pass below the bubble point. Operations are handicapped by sand and pipe troubles. Introduction The Ventura Avenue field has been under development since 1915. It has long been considered a "high-pressure" field, but interest was heightened by the extreme conditions encountered in the recent development of the so-called D-7 zone. The original reservoir pressure in this pool is estimated to have been 8300 psi at a depth of 9000 ft below sea level, or 9200± ft below the surface. A fluid pressure approaching that exerted by the overlying sediments has been encountered in other parts of the world, but never before in California to the degree observed in the D-7 pool. With few exceptions, the original pressure in California fields is about equivalent to the static head of water below the water table in the outcrop. Structure The Ventura anticline is a prominent feature of the Ventura basin, being traceable on the surface about 17 miles.' The Ventura Avenue field is at the apex of the anticline. It is about one mile wide and five miles long, the major axis lying in an east-west direction. The productive limits cover an area of about 2300 acres. The entire anticline has been severely folded and faulted. The productive portions in particular are broken up by three major thrust faults having a general east-west strike. The resultant four fault blocks are termed the A, B, C, and D blocks, respectively. Certain electric-log intervals are assigned numbers. Fig I is a diagrammatic north-south section of the field near the crest, looking west, and shows three of the four fault blocks. To the west, the upper fault divides into two branches, which define the B block. Wells penetrating a fault may duplicate over 1000 ft of formation. However, the greater fault movement is the strike shift, which is believed to exceed 2500 ft both between the A and C blocks and between the C and D blocks. The location of water is irregular and unpredictable. A few intermediate waters exist, while some strata have more than 2000 ft of productive closure.

Jan 1, 1948

By William Glenn

In their account of chromium, Roscoe and Schorlemmer (Treatise on Chemistry, London, 1879) state that "In 1762 Lehmann, in a letter to Buffon, de nova minerœ plumbi specie crystalline rubra, described a new mineral from Siberia, now termed crocoisite." In 1786 Lehmann analyzed it (Nicholson's Jour., Dee., 1798) and found that it contained chiefly lead, and that the " mineralizers " were arsenic and sulphur. It was next examined in 1189 by Macquart and Vauquelin, who stated that it contained an intimate mixture of iron, alumina, and lead peroxide. The account of their work was published over the name of Macquart. Vauquelin (Louis-Nicolas) was a Norman peasant, who had studied in the village school, and at the age of fourteen was a laboratory-boy in a pharmacy at Rouen. Later, he found his way to Paris, and in 1789 was assistant to Fourcroy, a pharmacist and a teacher of note. It was here that he met Macquart, with whom he did the work on Siberian red lead, and at this time his friend Cheradame taught him his Latin.

Jan 1, 1896

By A. B. Young

In the original design of the flue system, the flues from the roasters delivered their gases to a large brick dust chamber which discharged into another flue with stack connection, as shown in Fig. 1. The treater is so situated that the gases are taken by it directly from the chamber and discharged again into the flue. The complete installation comprises two treater units, only one of which has been installed at present. The treater is essentially a flue 1.0 ft. high, 12 ft. wide, and 61 ft. long. (3 by 3.6 by 18.5 m.). Suspended inside, vertically and running lengthwise, are four banks of No. 20 corrugated iron plates; each bank is 10 ft. long, making an effective treater length of 40 ft. The spacing from center to center of the rows of plat,es is 9 1/8 in. (23 cm.) giving six-

Jan 1, 1921

By G. T. Murray

The aging behavior of a Cu-Ti (3.2 at. pct Ti) alloy has been followed by electrical resistivity, hardness, and metallographic changes. The resistivity data indicate two principal processes, the first causing a sharp decrease in resistivity, and the second, which occurs over a long period of time, a much smaller rate of decrease. Lamellar nodules, Widmanstätten platelets, and homogeneous continuous precipitation was observed. The Widmanstätten platelets grow at the expense of the latter. When this study was initiated, little information was available on the aging behavior of copper-base titanium alloys. Several articles'-3 that appeared in the early 1930's showed that these alloys could be strengthened by precipitation, but a detailed study was not made. Within the past year, however, two other more comprehensive studies4'5 have been reported in the literature, one consisting primarily of an investigation of mechanical properties, the other

Jan 1, 1961

By C. D. Hall, F. E. Dollarhide

Conventional static tests of fluid-loss agents do not realistically simulate conditions in a fracturing treatment. The dynamic tests reported here show that fluid-loss volume is better represented as proportional to time, rather than as the square root of time. This leads to a different equation for fracture area. The leak-off rate increases with increasing shear rate at the fracture wall, but appears to approach a limiting value. Pressure effects are minor. Spurt loss ordinarily is not affected by the flow velocity in the fracture and is inversely proportional to concentration of agent. The filter cake, once it is well established, is resistant to damage by the flow of plain fracturing liquid (without fluid-loss agent). The latter two findings indicate that a treatment employing a high-concentration spearhead followed by plain fluid can offer a more economical treatment under suitable conditions. INTRODUCTION The successful design of hydraulic fracturing treatments depends on accurate knowledge of the fluid-loss properties of the fracturing fluid. Howard and Fast,' in giving the basic equation relating fracture area to fluid and treating parameters, described three mechanisms which might control the rate of fluid leak-off from the fracture. One mechanism usually is dominant in a given well treatment. For each mechanism, the leak-off velocity is inversely proportional to the square root of time, and the proportionality constant is designated as the fracturing-fluid coefficient. For the wall-building type of fluid-loss agent, the coefficient is determined by a filtration test in a pressure cell, usually with a rock wafer or core as the filter medium. In these static tests, the cumulative volume generally is proportional to the square root of time, after an initial spurt volume. The static-fluid-loss test is not representative of the con,-&tions under which a fluid-loss agent performs in a fratturing treatment. The marked difference between the dynamic- and static-fluid-loss behavior of drilling fluids reported in the literature2,3 implies that dynamic testing is also needed with fracturing fluids. We have therefore undertaken a study of the dynamic-fluid-loss behavior of fracturing fluids. The testing apparatus has also afforded opportunity to evaluate the resistance of the filter cake to removal or damage by flowing fluid containing no fluid-loss agent, with and without sand. The results of these studies offer a means for more accurate evaluation of fluid-loss agent performance, and point the way to a "spearhead" fracturing technique which may offer more economical treatment for some wells. EXPERIMENTAL METHODS The dynamic-fluid-loss testing method is applicable to any type of wall-building fracturing fluid. The present study aimed first at finding what phenomena are involved, and therefore has been limited in the number of materials tested. All of the results specifically reported herein are for kerosene containing a commercial solid fluid-loss agent, which is commonly used at 50 lb/1,000 gal of oil. Another agent in liquid form, used usually at 20 ga1/1,000 gal oil, has shown all the same phenomena in dynamic tests, and generally the same level of fluid-loss control as the solid agent. The dynamic-fluid-loss core cell used in all tests is shown in Fig. 1. The fracture was simulated by the an-nulus between a 2.03 in. OD sandstone core and the surrounding pipe. Annulus widths of 0.234 and 0.117 in. were used, and the core was 3.5 in. long. The annular geometry provides a uniform fluid velocity and a well-defined shear rate over the entire filtering surface, and permits a large filter area (144 sq cm) in a reasonably compact cell. The leak-off fluid passed into a 0.5 in. diameter axial hole in the core. A hollow steel rod through this hole was threaded into a rounded "streamliner" upstream of the core, and into a mounting stud downstream. The streamliner and the stud had the same outside diameter as the core. In all tests except those where sand was circulated, the mounting stud had protruding rings which constricted the annulus, to minimize any tendency for channeling of the fluid to the side exit port. The ends of the core were sealed by Neoprene, steel and Teflon washers. The leak-off fluid was conducted from the hollow rod to an exit tube, through a metering valve (a fine-pitched needle valve) and a quick-opening toggle valve in series, and into graduated cylinders for volume measurement; Two separate circulating systems were used in the experimental program. The extensive initial testing was done at 50 to 150 Psi. The fluid was circulated by a variable speed Moyno pump, and the flow rate was read by a rota-meter flow meter. The filtration Pressure was supplied by holding a back-pressure with a throttling valve. The discharge streamcould be diverted into any of four sections

Jan 1, 1965

By W. D. Smith

It has been 5 years since the writer left the Philippine Islands and while in that country his chief work did not lie in this field, though he has visited all but one of the localities mentioned in this article. The principal field studies relating to oil were M de by his colleague, Mr. Wallace E. Pratt. The writer's investigations ealt with the general stratigraphy and paleontology of the Philippines. with the exception of the investigations made by Mr. Pratt and the writer very little information on this subject is available. A number of geologists in the employ of large oil companies have visited the Islands from time to time but, following the general rule, the public has scarcely ever been permitted to learn anything of the results. The writer is indebted to the Bureau of Insular Affairs, Washington, for late information regarding recent legislation in the Islands relating to petroleum. All the known oil seeps, petroleum residues, such as ozocerite, and natural-gas emanations are associated with Tertiary sediments. The chief seeps and most promising prospects are located as follows: 1. Bondoc Peninsula (lower end), Tayabas Province, Southeast Luzon. 2. The west coast of the island of Cebü from Alegria north to, and perhaps beyond, Toledo. 3. Central Mindanao not far from Lake Lanao. 4. The ozocerite veins on the Island of Leyte in the northwestern part in the vicinity of the town of Villaba. 5. Natural gas from some deep wells in Tertiary shale formations on the eastern flank of the Cordillera and extending out under the plain on the island of Panay. The first mention in geological literature, to the writer's knowledge, of gas or petroleum in the Philippines is found in the description of the Island of Panay by the Spanish geologist, Abella, in the year 1890. In 1898, an oil well was being dug on the estate of Smith Bell & Co., an English concern, near the town of Toledo on the west coast of Cebu. In

Jan 1, 1921

By J. W. Hickman, E. A. Gulbransen

In a previous paper' the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300' to 7o0°C. except for copper, wherc the range selected was 100' to 500°C. The results of these studies were presented in graphical form as existence diagrams of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviatiois in lattice Darameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: 1. The existence diagrams of various alloys. 2. The effect of the structure of the alloying metal on the existence diagram of iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body-centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K4²B, Nichrome V, Hipernik, Inconel, Stellite "²I," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1947

By E. A. Gulbransen, J. W. Hickman

In a previous paper' the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300' to 7o0°C. except for copper, wherc the range selected was 100' to 500°C. The results of these studies were presented in graphical form as existence diagrams of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviatiois in lattice Darameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: 1. The existence diagrams of various alloys. 2. The effect of the structure of the alloying metal on the existence diagram of iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body-centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K4²B, Nichrome V, Hipernik, Inconel, Stellite "²I," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1947

By J. B. Cheatham, C. E. Murphey

Presently, computer control of Borobolic direction cannot be obtained during drilling, and most straight-holc drilling methods attempt to resist hole deviation rather than control direction. Many of the theories advanced as possible explanations of the cause of hole deviation are Summarized berein. A new correlation of physical partables is introduced to indicate bow factors such iis drill collar stiffness clearance and hit weight influence borehole deviation, .A methord is proposed for predicting the rate of change of hole angle when drilling conditions are changed. INTRODUCTION Control of borehole direction during drilling can be difficult and costly. Unintentional crooked holes are often lrilleti in dipping formations and many times directional drilling is required when the surface location is not directly above the target area —- for example, at offshore and mountainous locations. Prilllng progress can be greatly hindered in either air or liquid drilling when it be comes necessary to use low bit weight to prevent excessive hole angle build-up. If hole inclination becomes too great, drill pipe drag becomes excessive and fishing risks are increased, logging is more difficult and problems of differential sticking, key seating and fatigue failures may be encountered. Dog-legs and key seats are more serious problems than steep inclination angles: therefore, reducing rate of direction change is preferred to attempting to maintain absolutely vertical holes. Consequently, a straight inclineti hole is preferable to a nearly vertical crooked hole containing numerous dog-legs. In this paper, theories of the cause of hole deviation and analyses of drill string behavior under down-hole conclitions are summarized. Methods for computing hole deviation are presented und systems for resisting deviation as well as neans for provic!ing control of holt- direction are iliscusseI. A new correlation of physical variables is introduced tu indicate how factors such as drill collar stiffness, clearance and bit weight influence borehole deviation. A method is oroposeti for predicting the rate of change of hole anFrle when drilling conditions are clianged. IIEVIEU' OF PREVIOUS WORK ON HOIaE DEVIATION Significant progress in the theoretical analysis of hole deviation problems has been made in the past 1 5 years. The pioneering work has been primarily a result of the efforts of Lubinski and Woods.l-5 In 1950, Lubinski 1 considered the buckling of a drill string in a straig:rt vertical hole, a problem also considered by Willers6 in 1941. It wns concluded that very low bit weights must be used to prevent hole deviation resulting from drill collar buckling. The use of conventional stabilizers was proposed2 in 1951 by Mac Donald and Lubinski as a method for permitting greater Sit weights to he carried without drill collar buckling. These authors pointed out that a 2° nearly vertical spiral hole can cause severe key seatinp, and drill pine near, wilereas n 3 straight inclined hole with deviation all in one direction, while not vertical, will not result in serious drillirig or producing problems. Studies were continued with an investigation of straight inclined holes by Lubinski and Woods3 in 1953. In this paper they concluded that perfectlv vertical holes cannot be drilled even in isotropic forriations unless extremely low bit P-eights are used. .l'l~ey postulated that constant drilling conditions produce holes of constant inclination angle and varying conditions cause the hole to drill at a neiv equilibrium angle. This analysis was not concerned with drill string buckling since it was based on an equilibrium solution in which the ~irill string Was presumed to lie along the lower side of the hole abcrve the point of tangency. Weight of the drill collars below the point of tangency tends to force the hole toyard the vertical, whereas the weight on hit tends to force the hole aurav from the vertica l. The concept of an anisotropic formation Lvas introduced as an empirical method for explaining actual drilling data and as a means for extrapolating known deviation data to otiier conditions of hit

Jan 1, 1967

The following is an incomplete list of members and guests who called at Institute headquarters during the period Feb. 10, 1918 to Mar. 10, 1918: W. G. Anderson, St. John, N. B., Canada. Charles E. Locke, Boston, Mass. L. M. Banks, Camp Meade, Md. E. T. Lednum, Joplin, Mo. P. E. Barbour, Albany, N. Y. C.' K. McDonald, Washington, D. C. Alan M. Bateman, New Haven, Conn. C. T. Malcolmson, Chicago, Ill. Graham Bright, Pittsburgh, Pa. Stuart B. Marshall, Badin, N. C. J. F. Callbreath, Washington, D. C. T. C. Merriman, New Haven, Conn. J. E. S. Clark, Riverside. Cal. Arvid E. Nissen, Gary, Ind. G. H. Clevenger, Palo Alto, Cal. Herbert G. Officer, Conway, S. C. George C. Crossley, Trenton, N. J. J. E. Parker, Bulawayo, Rhodesia, S. Afr. R. H. Eagles, Palmerton, Pa. Francis R. Pyne, Elizabeth, N, J. Charles Enzian, Pottsville, Pa. Alfred Hull Ramage, Joplin, Mo. Albert H. Fay, Washington, D. C. H. H. Stoek, Urbana, Ill. David B. Gemmill, Crown King, Ariz. G. M. Taylor, Colorado Springs; Colo. Ronald Harris, London, Ont., Canada. Charles Tubby, St. Paul, Minn. Wm. J. Hayes, Colombia. So. America. J. B. Tyrrell, Toronto, Canada. B. B. Hood, Chrome, N. J. Edmund W. Westervelt, Ymir, B. C. 0. P. Hood, Pittsburgh, Pa. Carl Zapffe, Brainerd, Minn. H. M. LaFollette, LaFollette, Tenn. W. S. Boyd, formerly superintendent of mines of the Ray Consolidated Copper Co., has been appointed assistant general manager. William Campbell, Professor of Metallurgy, at Columbia University, is acting as metallurgist at the New York Navy Yard.

Jan 4, 1918

By D. L. Albright, G. A. Colligan

An investigation has been conducted to determine the nature of the crystallographic substructure of nickel and a 1.0 wt pct Ag-Ni alloy which had been undercooled 105°C prior to solidification. A rotating back-reflection X-ray technique and modified Weissmann diffractometer were used to orient single-crystal sections from these poly-crystalline ingots and to determine the substruc-tural features of these single crystals, The sub-grain size in the pure nickel ingot is 0.5 mm diam while the silver-doped nickel subgrain size is only 0.1 mm diam. The misorientation between adjacent subgrains is approximately 1 deg of arc in both ingots, and the spread of orientation of sub-grains about the mean orientation of the crystal is 5 deg of arc in both ingots. The addition of silver results in a stable impurity substructure which is preserved during isothermal solidification and subsequent cooling to room temperature. In the absence of silver the initial impurity substructure is destroyed by dislocation interactions which produce a secondary substructure which grows to a size five times larger than the initial substructure. THE process of undercooling a metal entails cooling of the molten sample below the equilibrium freezing point without the occurrence of solidification, i.e., by exercising proper constraint over the experimental variables contributing to nucleation in the melt. The current work of walker1 and Colligan Metal reports undercooling large continuous samples of nickel by imposing appropriate restrictions upon the parameters of solidification. The silver-nickel equilibrium diagram3 reveals the presence of a monotectic reaction at 1435°C. At this temperature the maximum solid solubility of silver in nickel is approximately 3 wt pct, but this solubility decreases with decreasing temperature and the solute is rejected as a silver-rich liquid phase at temperatures below 1435°C. Thus, the 1.0 wt pct solute should be held in solution during undercooling and solidification and subsequently precipitate as a silver-rich liquid phase at grain and subgrain boundaries following solidification during cooling below 1435. This assumes no solute segregation sufficient to cause the monotectic reaction. One would expect this second phase to inhibit grain and subgrain growth by retarding dislocation motion after solidification is complete. The effectiveness of silver addition in growth retardation of high-angle grain boundaries has been demonstrated by Colligan and suprenantS4 The principal [l00] dendrite growth directions in a 2 wt pct Ag-Ni alloy undercooled 53 all radiated from the nucleation site. A similar pure nickel ingot undercooled 59°C exhibited a random orientation of [l00] dendrite directions with respect to the nucleation site. Since undoped nickel ingots do not retain any evidence of the casting or solidification texture and silver-doped ingots do retain this texture, it is reasonable to assume that considerable grain growth has taken place in the pure nickel. These particular experiments were performed in order to reveal the differences, if any, in the features of the crystallographic substructure of undoped undercooled nickel and silver-doped undercooled nickel. 1) EXPERIMENTAL PROCEDURE Data are reported on selected specimens from two massive (approximately 260 g) undercooled ingots of nickel. One ingot consisted of electrolytic nickel and the other of this same material with 1.0 wt pct addition of high-purity silver. Powder patterns were taken of both the as-received and as-solidified materials; in all cases the reflections recorded were attributable to the individual elements nickel and/or silver. Fig. 1 is a. schematic diagram of the apparatus employed for the undercooling experiments. The equipment consists in part of a fused silica crucible for containing the charge. A fused silica tube encloses the system, which is covered by a brass cap to permit partial sealing of the inert atmosphere. This cap contains a hole through which a Pt-Pt 13 pct Rh thermocouple is inserted for temperature measurement. The charge is inductively heated under a purified argon atmosphere.

Jan 1, 1963

By W. S. Landis

IN brief, this is the story of an attempt to Americanize a process originally developed in Europe. The story will be recited in two sections, the first dealing with the process as developed by the European engineers; the second containing the improvements and modifications of American origin, together with some details of the operating results of the unit as finally assembled. Developments in other directions in this same field have not, up to the present, pointed out an economic future for the process, therefore our record here is largely a report of development progress. Whether some particularly favorable location will be found at some future time for a commercial installation cannot as yet be fore-told. The project is now at a standstill. The peculiar tools of the electrometallurgist should be of great interest to the zinc smelter. The low thermal efficiency of the zinc retort, its comparatively small-scale unit and its intermittent cycle as it stood in 1925, should make this art a particularly fertile field for the electric fur-nace. Yet in spite of years of work recorded in volumes of literature, and an expenditure of large sums of money, there is not a single electrothermic zinc smelter operating anywhere in the world. In this industry the electric furnace plays only a secondary part today.

Jan 1, 1936

By R. H. Oliver

The purposes, types, preparation, and testing of flocculants are discussed. A flocculation compendium is included, indicating choice of flocculant for a given set of conditions. An economic evaluation of the process is presented. Solid-liquid separation is a major expense in most mineral processing flowsheets today. Proper use of flocculation can often lower the overall cost of a solid-liquid separation by reducing the size of sedimentation or filtration equipment. PURPOSE OF FLOCCULATION When is use of a flocculant justified in terms of overall process economy? 1) when it results in process improvement, such as producing a clear liquor for electrolysis, precipitation, ion exchange, or solvent extraction; 2) when it results in satisfying requirements of pollution abatement ordinances; 3) when it results in increased recovery of values that would otherwise be lost; or 4) when it results in considerable savings in capital expenditure due to use of smaller equipment. When can the use of a flocculant adversely effect overall process economy? 1) when it results in increased filter cake moisture, 2) when it results in decreased filtration rates, 3) when it results in considerable bulking of sedimentation underflow, 4) when it contaminates either the supernatant or sludge, or 5) when the cost of using the flocculant is greater than the savings due to its use. First step in consideration of flocculants for a given application is establishment of desired goals in terms of increased clarity of effluent, increased recovery of solids, or decreased size of equipment. The most economical solution to a solid-liquid separation problem is that combination of equipment and flocculant costs which meets the established goals at the lowest total annual expenditure. This economic decision can be made only after technical data has been obtained as outlined in next four sections. TYPES OF FLOCCULATION Flocculation is a process wherein individual particles are united into more or less tightly bound agglomerates or flocs, thereby increasing effective particle size of solids suspended in a liquid. Degree of flocculation of a suspension of finely divided solids in a liquid is controlled by a combination of probability of collision between particles and probability of adhesion after the collision has occurred.' Probability of collision can be increased commercially through use of a paddle-type flocculator, combination flocculator, and clarifier or flocculating-type feedwell. Probability of adhesion usually can be increased by addition of a reagent known as a flocculant. Reagents act as flocculants through one or a combination of three possible mechanisms. The first is electrolytic neutralization of inter molecular repulsive force due to Zeta potential. This neutralization enables Van der Waal's cohesive force to hold the particles together after they collide.' The second is the precipitation, within a definite pH range, of voluminous metallic hydroxide flocs which entrap fine particles. This process is known as coagulation.14 Third is the bridging of two or more particles by either natural or synthetic long-chain, high-molecular-weight organic polymers. This bridging is accomplished by adsorption of two particles at different sites on the same molecule or by bonding of two molecules, each adsorbed to a different particle. Considerable effort has been expended in explaining the action of these polyelec-trolytes and detailed accounts are available in the literature. CHOICE OF FLOCCULANTS It is impossible, at the present time, to specify the optimum type or amount of flocculant for a given application from a knowledge of the material to be treated. The standard procedure is to choose reagents or combination of reagents most likely to be effective on the slurry; then test them.' The accompanying Flocculation Compendium (Table I) contains details of all currently available reagents sold as flocculants and it should be used when selecting the group of reagents for tests. This selection can be based on information listed in columns 4 and 5. Column 4 presents industries in which each floc-

Jan 1, 1961

By T. B. Counselman

An iron blast furnace of 1000 tons daily capacity will produce a 100,000 cu. ft. per minute of blast-furnace gas. This contains a 25 per cent of carbon monoxide, and has a B.t.u. value of about 95. gas is used primarily for heating the stoves of the blast furnace, secondarily, under boilers, for steam production. Occasionally it is used in gas engines. The raw gas coming out of the furnace carries about 10 grains of dust per cubic foot of gas, under best operating conditions. With furnace "rolling" or slipping, this quantity may temporarily be gre increased. This dust would, of course, deposit on the checkers o: stoves, or plug the burners under the boilers; therefore the gas : be cleaned. Flow Sheet The first step in the cleaning operation, as shown by the flow s Fig. 1, is a dry dust catcher, of which there are several forms, partially cleaned gas next goes to a primary wet washer, where v sprays knock down most of the solid particles. If further cleani desired, the gas may then go to electrical precipitation. Again, the removed is collected in water. Dry dust catchers reduce the dust col from 10 grains to between 4 and 6 grains per cubic foot, and rec roughly half of the total flue dust in the gas. The wet washers rea most of the remaining dust, reducing the dust content to about 1/4 per cubic foot. Electrical precipitators, if used, further reduce the content to about 0.01 grain per cubic foot of gas. The flow sheet s the dust content of the gas at various steps in the treatment and als content of solids in the water. It should be noted that some plant less water on the primary wet washer than indicated, and that ofte solids content of the scrubber water will be 300 grains per gallon, or much higher. Reasons for Recovering Flue Dust.—There are two main incentive recovering flue dust from the scrubber water: (1) the value of the (2) stream or lake pollution, where such a reason applies.

Jan 1, 1937

By R. R. Harvey

Recent evidence has indicated that the films forming at crude oil-water interfaces are the result of naturally occurring su,rface-active components in the crude oil rather than oxidation products resulting from exposure of the oil to air. Since the presence of such films may strongly affect the displacement of oil from porous media, a knowledge of their composition and formatiorz is of fundamental importance. In this study, without the assumption of a specific mechanism, film formation is considered to involve the transfer of a weakly surface-active species in solution in the oil to the oil-water interface. The film gas law and the Gibbs adsorption equation may thus he applied to the system. The rigid films which form upon decrease of the oil-water interfacial area are considered a result of the very slow rate of re-solution of the film material into the oil. When the shrinkage of the interface is very rapid, the amount of film material leaving the interface is negligible, and the system may then be treated in the same manner as an insoluble film. The combination of these treatments leads to a new concept of the film factor in which it may he quantitatively related to the concentration of film-forming material at the interface. Suitable experiments can then yield the following information. 1. Original concentration of surface-active species in the oil. 2. The change of concentration with time. 3. Concentration of surface active species at the interface. 4. The change of this concentration with time. 5. Interfacial tension of the system at any time and its variation with time. 6. Equilibriunz concentrations for a given set of conditions. 7. Concentration requirements for solid film formation. 8. Molecular diameter of the adrorbed species. These calculations may be made solely from data taken from measurements on the original oil. While using the pendant drop method of interfacial tension measurement of crude oil-water systems, Bartell and Niederhauser' remarked on the thin, transparent, pliable, solid films or membranes which were often formed at the interface between crude oil and water. As a result of their observations of these films, Bar-tell and Niederhauser concluded: 1. The films are formed by material from the oil adsorbed at the interface rather than by a reaction at the interface. 2. The adsorption of the film-forming material is a rather slow process. 3. There are good indications that the process is reversible; i.e., the film constituents may re-dissolve into the oil. 4. The film will spontaneously spread over any new surface formed. 5. The process of adsorption at the interface is accompanied by a decrease in the interfacial tension of the system. Although they had proved that film formation was not due to a reaction at the interface, Bartell and Niederhauser were unable to demonstrate conclusively whether these film-forming constituents were present in the original reservoir oil or whether they were formed as oxidation products after exposure of the oil to air. Recent evidence seems to point to their presence in the original oil. Although the true nature of the film-forming constituents is still uncertain, these conditions would be fulfilled by the assumption of the presence of a slightly soluble surface-active component in the original oil. This component would migrate to a freshly formed interface because it would thereby lower the free energy of the system. The component at the surface constitutes an expanded monolayer which would become compressed, upon retraction of drop, due to the slow rate of re-solution of the film components into the bulk of the oil. It is possible, by involved extraction processes, to separate or at least concentrate this film-forming fraction. However, using the assumptions made above, the technique of monolayer film study may be applied to reveal much of the nature of the adsorbing material without resorting to an actual separation of the film-forming constituents.