Search Documents

By Charles S. Barrett

NUMEROUS determinations1-7 of the tex-ture of cold-rolled polycrystalline iron, steel, and ferritic alloys have been made with good agreement among the various observers as to the principal features of the texture common to all, but there has been no adequate explanation of the texture in terms of the behavior of individual grains. This study presents an explanation of the texture based on the observed rotation of single crystals when deformed in a manner similar to a grain in the aggregate, a method we have found useful in leading to a better understanding of compression and tension textures;8,9,10 in particular, the aim has been to determine experimentally the end orientations of rolled single crystals of iron. These are discussed in connection with the point of view of Wever1 and of Boas and Schmid2 that the rolling texture is a simple compression texture (compression normal to the rolling plane) superimposed on a simple tension texture (tension in the roll-ing direction), and the point of view of Kurdjumow and Sachs3 that three ideal end orientations exist.

Jan 1, 1940

By K. R. Evans

The yield and fracture characteristics of a Ti-8 pct A1 alloy have been examined at room temperature as a function of exposure temperatures to 1700°F. Em-brittlenzent of the alloy is observed to occur following exposures below 1280°F, the critical temperature for formation of ordered Ti3Al particles. Presence of Ti3Al particles results in an increase in the yield and flout stresses which, for a given exposure time, are a maximum at the critical temperature. Embrittlement is attributed to the occurrence of plastically induced fracture controlled by the increase inflow stress. This interpretation is compatible with the decreasing ductility and increasing crack popagation rates observed with increasing exposure time below the critical temperature. Slip line observations and measurements of the gain size dependence of the yield stress indicate that the slip character of the alloy is not influenced by exposure treatments below the critical temperature. ThE potential usefulness of Ti-A1 alloys in structural applications has prompted considerable interest in studies of their microstructure and mechanical characteristics. The relatively recent surge of interest in the system and at the same time its complexities are indicated by the fact that despite numerous recent efforts14 there has not even been general agreement upon a phase diagram for the system. However, most of the Ti-A1 alloys of commercial interest range in aluminum content from 5.0 to 8.5 wt pct where most investigators achowledge the existence of the ordered Ti41 phase. Goldak and parrs confirmed the existence of Ti41 from X-ray diffraction analysis of the stoichiometric composition while Blackburn6 has determined its presence in commercial Ti-8 pct A1 alloys by electron diffraction analysis and dark field transmission microscopy. The embrittlement of Ti-8 pct A1 alloys was initially reported by Crossley and carew7 who showed that aging in the temperature range of 750" to 1110°F resulted in extreme brittleness. This behavior was later confirmed and correlated by Soltiss to the presence of long-range order in the commercial Ti-8 pct Al-1 pct Mo-1 pct V alloy (Ti-8-1-1) which exhibited anomalous creep and yield strength behavior at 950°F. This investigation was designed to study the mechanical characteristics of a binary Ti-8 pct A1 alloy in order to further examine the nature of the embrittlement behavior reported for the alloy system. EXPERIMENTAL PROCEDURE A Ti-8 pct A1 binary alloy was obtained from the Wah Chang Co. in the form of 0.050 in. sheet. The chemical composition of the alloy is given in Table I. Heat-treatment of the alloy was conducted in evacuated vycor capsules for the tensile sDecimens (1.25 bv 0.25 in. gage section) and in evacuated stainless steel jackets for the crack growth-rate panels. All specimens were annealed at 1700°F for 24 hr and water quenched before an exposure at elevated temperatures. Tensile testing was conducted at room temperature in an Instron testing machine equipped with a pushbutton control for instantaneous control of the cross-head motion. In this manner the change in stress, Aa, accompanying an increase in strain-rate by a factor of 10 was measured immediately after yielding. The crack growth-rate panels used were 3 by 18 in. with a precrack 0.33 in. long cut into the center of the panel. The panels were cycled at a maximum gross stress of 40,000 psi at a maximum to minimum tension stress ratio of 20. Cycling of the specimens was continued until the crack propagated the width of the panels. The crack length was intermittently measured during slow crack growth. EXPERIMENTAL RESULTS Correlation of Embrittlement to the Critical Temperature for Ordering. Blackburn6 has found that the critical temperature, T,, for the formation of Ti41 in a Ti-8 pct A1 alloy with an interstitial content on the order of that given in Table I is approximately 1245°F. The relationship between the ductility of the binary alloy used in this investigation and T, was estimated from tensile tests on specimens which were exposed for 24 hr at various temperatures followed

Jan 1, 1970

CAPTAIN JOHN H. BALLAMY John H. Ballamy, Captain on the Regimental Staff of the 103d Engineers, was killed near Fismes, on August 9, 1918. Captain Ballamy was born at Plymouth, Pa., in 1886 and graduated from the High School of that town in 1903. In the following year he began work as a coal miner, and at the same time began the study of mining engineering in the evening and any other spare time. He continued this diligent and energetic practice for many years. For sixteen years he continued in the employment of the Delaware, Lackawanna & Western Railroad Company's coal mining department, first as a practical miner, next as rodman on the survey corps, of which he soon became chief, then draftsman and mining engineer in the company's office. In January, 1916, he was promoted to the position of district engineer in charge of mining engineering work. He became a member of this Institute in September, 1917. CAPTAIN JOHN H BALLAMY. Captain Ballamy's military experience began at the same time as his engineering practice. He was a charter member of Company A, Engineers, N. G. P., which was organized ten years ago. He saw service on the Mexican border as First Lieutenant of this Company, and remained in that position until November, 1916. In July, 1917, he was again called into service and was sent to Camp Hancock, Ga., with the 103d Regiment of Engineers. Before joining this regiment he attended a school for officers at Fort Sill, Okla., where he received special training in field fortifications. In December, 1917, he was commissioned Topographical Captain on the Regimental Staff, and in April, 1918, preceded his regiment by about six weeks to France, where he again attended an officers' training school. He rejoined his regiment on July 15, near Chateau Thierry and was killed near Fismes on August 9, 1918.

Jan 11, 1918

By Enid C. Plante

INTRODUCTION To extend our knowledge of the flotation behavior of sulphide minerals, the response of the following minerals to ethyl xanthate as collector was studied by captive bubble and cylinder flotation tests: antimonite (Sb2S3), arsenopyrite (FeAsS), covellite (CuS), marcasite (FeS2), orpiment (As2S3), pyrrhotite (FeS) and tetrahedrite (4CU2S, Sb2S3). Lollingite (FeAs2) was also examined to determine if its behavior could be correlated with that of pyrite or marcasite (FeS2). EXPERIMENTAL METHOD Mineral for Flotation and Contact Tests Mineral was prepared in the manner already described' and its behavior both freshly ground and "oxidized" was studied. Tests in which the mineral was allowed to oxidize for various periods showed that a uniform response to xanthate was reached in two days or less. Oxidation Products The soluble oxidation products from most of the above minerals were measured and their effect on the flotation of the mineral studied. The mineral samples were wet ground to minus-52 mesh and deslimed, and 20 g of this material placed in 200 ml of distilled water of a measured pH value, and C02 free air bubbled through each suspension at a constant rate (about 1 bubble/sec) for 5 days. It has been shown1 that the size of the mineral is unimportant in the rate of formation of oxidation products and that probably the supply of oxygen to the mineral is the rate-determining step. At the end of 5 days the pH value of the supernatant liquid was measured again, the mineral filtered off and the soluble products determined. Methods for estimation of sulphur acids, ferrous and ferric iron and copper have already been described.1 No satisfactory method was found for antimony. Arsenic was estimated as the arsenate.2 FLOTATION OF "UNOXIDIZED" MINERALS WITH ETHYL XANTHATE AS COLLECTOR Fig I to 3, 4, 6, show the effect of alkali and cyanide as depressants for the minerals with 25 mg potassium ethyl xanthate per liter as collector at 35°C. Wark and Cox3 have shown that with ethyl xanthate as collector, galena, pyrite and chalcopyrite show a greater tolerance to cyanide and hydroxyl ions at room temperature than at 35°C. Covellite (Fig I), marcasite (Fig 2) and pyrrhotite (Fig 3) behave similarly. The independence of the curves for pyrrhotite at 35°C with respect to cyanide

Jan 1, 1947

Total U.S. mineral production reached an estimated $17.8 billion for 1960, 4 pct above 1959 and second only to the record high of $18.1 billion established in 1957. As a group, metals achieved a rise from $1.6 billion in 1959 to $2.0 billion this year, an increase of 28 pct. Similarly the value of nonmetallic production including fuels (i.e., natural gas, petroleum, natural-gas liquids, asphalt and related bitumens, carbon dioxide. anthracite. bituminous and lignite coal, peat, and helium) rose from $15.5 billion in 1959 to approximately $15.8 billion in 1960. However, this 2 pct increase in the total value of non-metallic production was due to an increase in the value of the fuels ($11.8 billion in 1959 to $12.2 billion in 1960) which offset a drop in value of the other nonmetallic minerals ($3.7 billion in 1959 to $3.6 billion in 1960).

Jan 2, 1961

By M. K. Foster

Ten horizontal retort zinc blocks of a modified Hegeler design are in operation at Nueva Rosita, Coahuila, Mexico, and produce approximately 170 t of spelter daily, or 62 000 t/year. A block consists of two furnaces of 448 retorts each, making 8960 retorts as the plant complement. Each furnace block is fired with natural gas and air maintaining the combustion mixture in the furnace always slightly reducing. No attempt to recover energy through waste heat boilers is made. The spelter moves to market by rail and truck either in palletized bundles weighing approximately 1060 kg, as loose slabs weighing 26.5 kg each, or as 1088 kg ingots. At present 46% of the metal is exported and 54% is consumed domestically in Mexico. The present day trend toward equalized or alloyed spelter, as well as special shaped castings results in sales of 35% of the entire plant's production. Sulfuric acid is also produced by the Contact Process using vanadium pentoxide as the catalyst. The plant is basically a Monsanto contact system, producing approximately 68 t of 100% sulfuric acid daily. Both 98.5% sulfuric acid and 20% oleum are available. All of the acid made is consumed in Mexico. Shipments are made in 26,900 dm3 tank cars.

Jan 1, 1970

By R. J. Colony

DEPOSITS of iron are widely scattered in the folded Cretaceous rocks and the associated igneous intrusives of Puerto Rico. Most of them are too small for commercial development, but a few have aroused some scientific and economic interest, among them the large body of residua] limonite at the west end of the island near Mayaguez1-6 (Fig. 1) and the mixed hematite and magnetite deposit on the southern slopes of the Sierra de Cayey, about four miles north of Arroyo.7-9 Neither of these orebodies has been developed, nor have investigations of the widely distributed deposits of magnetite, which include all the remaining occurrences of iron deserving of economic consideration, proceeded beyond the exploratory stage. With the possible exception of the mixed deposit near Arroyo, the magnetite is directly associated with andesitic and dioritic intrusives, which invade the Cretaceous rock section, and the bulk of it, occurring in calcareous sediments, is clearly of contact-replacement origin. The small deposit on Rio Portugues, north of Ponce, is found in a limestone band near its contact with an andesite dike.10,11 Two deposits of unde-

Jan 1, 1935

By Richard McCaffery

CONTENTS PAGE 1. Research on Blast-furnace Slags (A Progress Report). By Richard S. McCaffery 5 2. Determination of Viscosity of Iron Blast-furnace Slags. By Richard S. McCaffery, Clarence H. Lorig, Ira N. Goff, Joseph F. Oesterle and Oscar O. Fritsche 27 3. Effect of Magnesia on Slag Viscosity. By Richard S. McCaffery, Joseph F. Oesterle and Oscar O. Fritsche 55

Jan 1, 1931

By G. T. Engel, W. G. Gruzensky

Jan 1, 1960

By A. A. Stripling

The Cretaceous limestone wells of the Mara/Maru-caibo Dist. of Venezuela are extremely prolific producers. To maintain production on cessation of natural flow, large scale gas-lift operations were commenced involving high production rates on caring Flow. For the design of these gas-lift installations it was essential to have some knowledge of the pressure gradients involved in casing flow, so that the required injection pressures, optimum gas injection raws, etc., could be forecast. This paper presents a method of calculating these annular pressure gradients. Basically the method makes use of an energy balance equation coupled with an empirical energy loss factor derived from field data. The calculations have been put in a form suitable for "punch card-type" calculating machines. A set of gradient curves for Mara/Maracaibo conditions covering flow rates up to 12,000 B/D, and GOR's of 500 to 2,000 cu fd/bbl is presented. From these curves the flowing BHP can be predicted from surface data and the vertical pow performance under varying conditions of gas injection can be estimated. The method has been applied to La Paz and Mam gas-lift operations for over three years and has given consistently accurate results. INTRODUCTION The Cretaceous limestone fields of the Mara/Maracaibo area in Venezuela are characterized by the presence of widely distributed fissure systems. Under these conditions individual wells frequently have extremely high potentials and such wells are generally flowed on the casing-tubing annulus in order to reduce the pressure loss in vertical flow. To maintain production on cessation of natural flow, an extensive gas-lift system was planned. As a first approach to this gas-lift design problem, an attempt was made to construct a set of empirical flowing gradient curves from the available subsurface pressure data. Such a method has been used successfully for tubing-flow conditions in California by Gilbert'. Unfortunately, the empirical construction of casing-flow gradient curves presents additional difficulties, as pres- sure bombs cannot bc run in the casing-tubing annulus against high rates of flow. Thus, the Full flowing gradients cannot be defined by actual measurement and the best that can be done is to obtain spot pressures at the tubing shoe. Under these conditions a vast accumulation of BHP data is required to construct a set of gradients. To the La Paz and Mara fields the majority of the available flowing pressure measurements fall into a relatively narrow GOR range, in the neighborhood of the solution ratio. While there appeared to be reasonable prospects of constructing gradient curves for this limited range, measurements at higher GOR's, which were of major interest for gas-lift operations, were relatively few and the prospects of constructing empirical curves cor~spondingly remote. As an alternative approach, the possibilities of a mathematical analysis of vertical flow conditions were investigated. May and Laird2fV n 1934 presented an excellent analysis of the vertical-flow conditions in the Anglo-Iranian Oil Co.'s fields. Their analysis was based on an energy-balance equation and calculated the losses due to kinetic energy, friction and slippage separately. By combining these losses with the total calculated available energy, the required depth-pressure traverse could be deduced. On applying the method to La Paz conditions, good results were obtained for tubing flow at high tubing-head pressures. However, for lower wellhead pressures (300 psi and under) the discrepancy between calculated and measured values increased appreciably. It was considered that this was probably due to energy losses caused by slippage or liquid hang-up in a continuous gas phase, for which it was difficult to visualize any analytical approach. In 1952 Poettmann and Carpenter4 presented a method of pressure gradient calculation which, while based on an energy-balance equation similar to that employed by May and Laird, made no attempt to evaluate the various components making up the total energy loss resulting from irreversibilities of flowing fluids. Instead, they proposed a method of analysis which assumed that all significant losses for multiphase flow could be correlated in a form similar to that of the Fanning equation for frictional losses in single-phase flow. They then derived an empirical relationship linking measurable field data with a factor which, when applied to the standard form of the Fanning equation, would enable the energy losses to be determined. The total available

By Ott F. Heizer

The mines and the mill of the Nevada-Massachusetts Co. are on the east slope of the Eugene Mountains, in Pershing County, Nevada, 8 miles northwest of Mill City, a station on the Southern Pacific R.R. and on the Victory Highway. Fig. 1. Supplies and, concentrate are transported by truck over an automobile road of easy grade. The property is at an average elevation of 5500 ft. and climatic conditions are generally favorable for continuous operation throughout the year. The ore treated is supplied by two adjoining mines, the Stank and the Humboldt. Physical and mineral characteristics of the ores produced by these two mines are substantially similar, although variations occur in hardness and mineral distribution.' The economic mineral is scheelite (CaWO4), composed, when pure, of 80.6 per cent tungstic trioxide (WO3) and 19.4 per cent lime (CaO).

Jan 1, 1935

By Sherwin F. Kelly

One of the most succinct and illuminating perspectives of the field of geophysical exploration to appear in recent years is an article by E. A. Eckhardt, in the magazine Geophysics for October 1949. Although his review covers the year 1948, many of the data presented are apropos to a review of 1949, and form a pertinent background for a consideration of current progress. He presents charts of the world-wide distribution of gravimeter and seismograph activity in oil exploration, which show that surveys in the United States accounted for practically 68%; of all gravity work and 80%; of all seismic activity. Canada ranked second, with a proportion of roughly 6%, in each case; South America accounted for about the same percentage of seismic work, and double that amount for gravity surveys. Within the United States, Texas and Louisiana were the scenes of the greatest activity, both claiming about 60% of all surveys by each method.

Jan 1, 1950

By H. T. Kennedy, J. E. Little

An empirical equation for the prediction of the viscosity of several pure paraffin hydrocarbons and nitrogen is presented. It involves temperature, pressure and six constants of the material, and it applies reliably to both liquids and gases. The equation is similar in form to van der Waal's equation of state. For the paraffin hydrocarbons methane through r-hexane and nitrogen, an average absolute deviation of 1.9 percent was obtained on 1,006 data points described in the literature by 14 authors. When this equation is extended to complex, liquid hydrocarbon mixtures, a correlation was obtained with an average absolute deviation of 9.9 percent. INTRODUCTION Equations describing the flow of gas and liquid through porous media contain the viscosity coefficient of the fluid. If other pertinent variables remain constant, the volume rate of flow is inversely proportional to this coefficient. In dealing with condensate fluids and volatile oils, however, the compositional effects resulting from changing pressure materially affect the viscosity. The effect of compositional changes also may be significant in certain secondary recovery or pressure maintenance processes, notably miscible displacement or gas injection. Early attempts to describe the performance of reservoirs utilized a volumetric material balance method wherein gas and liquid in the reservoir were identified as produced gas and liquid at the surface. This method of analysis proved adequate for reservoirs at moderate temperature and pressure that contained gas with moderately low amounts of condensable materials. The volumetric material balance procedures for "black oil" reservoirs leave much to be desired when applied to condensate and volatile oil reservoirs because phase behavior and compositional changes are relatively more important in these cases. The alternative is a compositional material balance, which in turn, requires a correlation of properties of the reservoir fluid with composition. This paper supplies this correlation in regard to viscosity, for reservoir crude oils. REVIEW OF LITERATURE The literature contains many empirical equations describing the effects of composition, temperature and pressure on the viscosities of pure liquids and binary liquid mixtures. However, the applicability of a majority of these equations is limited to very low pressures and to a small number of systems. Most of them, when applied to complex hydrocarbon systems, are of little value. The lack of utility of the majority of equations results from the fact that they were developed to show the separate effect of temperature, pressure or composition on viscosity, but not to predict the viscosity as a function of all three variables. And with the few exceptions noted below, they were developed to apply to much simpler systems than hydrocarbon mixtures. Eakin1 developed an equation for the viscosity of pure light hydrocarbons applicable in the gas, liquid and dense fluid regions, and in its most general form is written as µ - µo =A(ebP - e-cpk) The pure component viscosity at atmospheric pressure and temperature T, µo, was calculated using the Sutherland equation: µo = BT3/2/T + S The constants in Eakin's equation permitted the term e-CPk to become quite small at high densities (above 0.215 gm/cc), and the general equation would simplify to

Jan 1, 1969

By F. W. Maclennan

The following is a list of members who died in 1929. It is compiled from reports to the Secretary's office. Biographical sketches published in Mining and Metallurgy are indicated in the last two columns. Issue Containing Year of Date of Biography Election Name Death 1929 Page 1922 Adams, Waldo Peck................................ June 2 September 435 1903 Argall, Joseph.................................... Nov. 1 1894 Austin, Leonard S................................. Oct. 30 December 580 1905 Bailed, Melbourne.........................Dec. 12 May* 280 1890 Barringer, Daniel M.............................. Nov. 30 February* 119 1895 Batchelleb, HENRr R.............................. Jan. 15 March 167 BINGHAM Charles E............................. 1923 Bibkett, E. H..................................... Apr. 23 August 394 1913 Bibbell, Robert W................................. Jan. 18 April 214 1926 Blackmar, Don C.................................. June 4 March* 189 1920 Bosworth, T. O.................................... Jan. 18 April 214 1894 Boucher, Arthur S..........................Jan. 6 May 257 1927 Brandenthaler, R. R.............................. Dec. 14 January* 64 1889 Bretherton, S. E............................... Oct. 4 December 581 1911 Brunton, F. K................ .. Aug. 17 1924 Brush, Charles F................................. June 15 September 436 1925 Cameron, Frank N........................May 16 July 349 1891 Chambers, Robert E.............................. May July 348 1908 Clark, J. Murray................................. Dec. 3 August* 407 1883 Clymer, edward T............................. Oct. 13 December 579 1914 Cofpey, George T................................. May 8 July 349 1901 Cooke, L. H....................................... Aug. 23 November 537 1915 Cousins, George W........................ June 30 February* 118 1886 Cowles, A. H...................................... Aug. 13 September 436 1892 Crane, Theron I............................. Nov. 2 December 579 1921 Crowell, Samuel B................................ Dec. 9 January* 64 1907 Curtis, Bracey.................................... Jan. 31 April 215 1895 de Batz, Rene........ ............... January March* 189 1928 Dines, Tyson S.................................... March May 257 1909 Dufourco, R. G............................. January November 537 1920 Ericsson, Eric A.................................. Apr. 4 April* 231 1920 Erlenborn, Willi....................... Nov. 10 March* 189 1888 Farish, John B.................................... Nov. 14 December 580 1891 Ferguson, Vincent........................... Mar. 8 May 257 1917 Finucane, T. R.................................... Mar. 22 February* 118 1921 Foch, Ferdinand................................... Mar. 20 1885 Foucar, Edouard I....................... Jan. 3 March 167 1880 Francklyn, Charles G............................. Jan. 11 April 214 1925 Friedl, Arthur J.............................. July 9 September 435 1894 Fuller, James W. Jr............................... April 4 1876 . Goodale, Charles W.............................. April 11 May 258 1912 Graybill, John..........................Dec. 11 June* 320 1887 Gritzner, F. A.................................. Mar. 26 July 394 1906 Gunther, C. Godfrey.............................. Deo. 26 February* 118 1900 Haggen, Edward A.............................. Apr. 22 October 488 1895 Hall, Benjamin M........................Nov. 19 March* 189 1913 Harper, Walter S................................. Feb. 15 August 394 1921 Hawley, William S................................ Apr. 20 June 298 1920 Herd, Walter ... . . . ..... Aug. 23 September 435 1889 Holt, Marmadtjke B............................... Dec. 26 February* 118 1928 Husk, Albert D .... ................June 9 December 580 1920 Hutchinson, S. Pemberton......................... Feb. 16 April 214 1926 Ivanoff, Constantine L............................ Mar. 7 June 298 1914 Jaeger, Frederick..... .............July 28 October 488 1891 Jennings, Robert E.......................Oct. 30 December 580 1922 Johnson, Homar L................................. Sept. 17 October 483 1927 Johnson, Homer H................................. Mar. 21 May 257 1918 Jones, Jesse L ..... ...............Jan. 22 April 214 1892 Jones, Thomas J................................... June 18 October 488 1883 JoOet, Cavalier H................................. Mar. 29 May 258 1881 Kennedy, John S . . . . ... ..........Apr. 22 August 394 1881 Kennedy,- Hugh.................................... May 23 September 435 1895 Kebvin, James H................................... September October 488 1926 Kkom, L. J........................................ Dec. 24 January* 64 1905 La Follette, Harvey M........................... Sept. 19 November 538 1920 MacDonald, Alexander............................ May August 394 1904 Marengo, Paolo................................... May 257 1925 Maxwell, Allison R............................... May 7 November 538

Jan 1, 1930

By W. L. Connell, O&apos

The properties of some heavy liquids which can be used in sink-float separations are discussed with major emphasis being given to the halogenated hydrocarbons. Data are presented on density, viscosity, thermal characteristics and the effects of moisture and temperature on the corrosiveness of the liquids towards various materials of construction. The toxicity of these materials, the hazards involved in handling them, and the procedures for handling them safely are also discussed. True liquids have certain advantages over colloidal suspensions for sink-float separation of minerals which makes their use especially advantageous when close separations, fine particle sizes or water-soluble minerals are to be treated. For best separating results, the medium should have an easily controlled, uniform, stable density. Here, true liquids have the advantages of allowing closer control of density and of not requiring agitation to maintain a uniform den- sity in the equipment. Low viscosities are desired in a separating liquid so that rapid separations of fine material can be made. Many liquids have lower viscosities than the colloidal suspensions at operating gravities of 1.4 to 5.0. For economic reasons and to prevent contamination of the product, the separating medium must be easily and completely removed from the ore. Normally, true liquids must be more completely removed than the cheaper suspensions and thus cause more problems in this area. The fact that the medium should not react with the minerals, air, water or the common materials of construction limits the choice of liquids which can be used, but many are available which are sufficiently stable. A more serious objection to the use of true liquids is that many of them present a toxic hazard to operating personnel and users of the product. Most true liquids are toxic to some extent, but modem knowledge of toxicity allows us to recognize the hazards inherent in handling them and enables us to design around them. Three types of true liquids are available for this use: 1) Halogenated hydrocarbons cover the gravity range from 1.2 to 3.3. They are generally more volatile and less viscous than the other liquids.

Jan 1, 1963

By Y. Oka, H. Majima

When a rock particle is subjected to an external force, internal stresses and deformations are experienced by the particle. Assuming that the breakage of a rock is mainly due to tensile stresses generated by the action of a pair of concentrated loads, F, directed in compression towards the loading points at the shortest distance, as illustrated in Fig. 1, the stress and deformation experienced by a particle of irregular shape can be determined with the aid of the theory of elasticity. According to the photoelastic experiments made by one of the present authors,' the stress states in a rock particle of irregular shape are quite similar to that of an inscribed sphere of diameter x, as indicated in Fig. 1, but accompanied by the faint stresses, in the vicinity of the particle outside of the inscribed sphere. Therefore, the stress components in an irregularly shaped particle can be estimated by referring to stress components in a sphere. Applying polar spherical coordinates to an elastic spherical body, as shown in Fig. 1, the stress components are all expressed as multiples of F /x2 and more or less influenced by the loading angle and Poisson's number m. In general, the energy w, acting on a rock particle is defined as the product of loading compression F

Jan 1, 1970

By W. H. Yarroll Discussion by W. A. Griffith

W. A. Griffith (Head, Research Department, Phelps Dodge Corp., Morenci, Ariz.) - It is gratifying to see the increasingly common use of classical statistical procedures by metallurgical researchers. Mr. Yarroll has given excellent illustrations of the utility of multiple correlation analysis of complex metallurgical data. Our experience in applying these procedures to historical plant operating data has differed, however, from that which he suggests. The uninitiated frequently assume that the volumi-

Jan 1, 1969

By D. S. Pye, J. P. Gallus

Successful hydraulic pressure treatment of oil and gas wells that have long producing intervals, multiple pay zones, fluid thief zones, or natural or induced fractures has long been a serious problem plaguing the petroleum industry. High fluid-injection rates, straddle packers, ball sealers, and either liquid or solid additives to the treating fluids are being used to cope with this difficult and costly problem.l-6 The use of ball sealers and straddle packers is limited, in practice, to wells that have been completed with perforated cemented casings or liners. Well stimulation with ball sealers and straddle packers is usually successful as long as the cement remains competent. The other techniques of diverting are used with all types of completions. However, there are two significant disadvantages of the high rate method: excessive horsepower requirements, and the need of large treating-fluid volume. Consequently, most well stimulation techniques that involve diverting depend upon ball sealers or granular materials. Liquid diverting agents, and some of the solid ones in use today, frequently will cause formation damage. On the other hand, the most popular particulate diverting agents often are so soluble in the treating fluid that they become largely ineffective; their particle size is severely reduced as they dissolve while being transported through thousands of feet of pipe to the formation face down hole. In our attempts to deal with the shortcomings of these diverting agents, we experimented with a large variety of potentially suitable deformable materials the solubility of which could be controlled. Following are the criteria for the diverting agent sought: 1. The material must be effective in reducing fluid loss to thief zones, including existing fractures and very high permeability layers in the formation to be pressure treated. 2. The material must have enough strength to bridge under the treating pressure. 3. The material must be insoluble or slowly soluble in the treating fluids so that the particles retain sufficient size to be effective after they reach the formation face. 4. The material must be completely soluble in the produced oil or condensate liquid so that it can be removed readily; it must not cause formation damage. A number of products consisting of various polymers blended with waxes and other solid hydrocarbons were examined. All these materials satisfied the criteria for a diverting agent and also exhibited some degree of plastic deformability. On the basis of initial tests of strength and hardness, several blends of wax and polymer were selected for extensive testing in the laboratory and the field. These compounds have congealing temperatures ranging from 140 to 190F; they are insoluble in water and soluble in oil. They conformed, therefore, to the criteria specified for a theoretically superior diverting agent. Laboratory and field tests were conducted using these wax-polymer materials to demonstrate that the use of a deformable diverting agent can significantly improve fluid diverting performance. Data in this

Jan 1, 1970

By C. Norman Cochran

The pllnse diagvam for the NaF-AlF3 system was used to calcutate an ionic model for the NaF-AlF3 system. Assuming an ideal solution,a series of simultaneous equations expressing equilibria be-tween solid and liquid phases at the euleclic, perilec-tic, and melting points were solved for the activities of the ionic species, the dissociation constants, and the entropies and heats of fusion. The calculations suggest the existence of A13F1415 ions in addition to the F-1+AlF6-3 , and AlF4-4 ions previously proposed by others. The calculaled valnes give better agreement with vapor pressures than the previous model without Al3Fl14-5. Additional possible vefinements of the model are proposed. CRYOSCOPIC1 investigations and density data2 for the NaF-A1F3 system have previously been used to study the dissociation mechanism of Na3A1F6 and to derive equilibrium constants for its dissociation to NaF and NaAlF,. Depending primarily on the heat of fusion assumed for cryolite, the dissociation constants ranged between 0.02 and 0.18 from cryoscopic studies, and from 0.09 at 1273°K to 0.16 at 1363°K from density data. In most cases the values were unable to reproduce satisfactorily the experimental liquidus lines very far on the A1F3 side of the Na3A1Fe composition. This suggested the existence of at least one other ionized compound in the melt besides NaA1F4 in the Na3A1F6-A1F3 side of the system. This is assumed to be liquid Na&13F14 (chiolite), which is already established as a stable solid in phase studies of this system. MODEL FOR THE MELT The melt is assumed to be an ideal solution with ion activities equal to anion fractions. The only cation in the model is sodium so that Temkin and simple anionic activities are identical. Although the compounds are completely ionized to Na' and the respective anion in the melt, molecular rather than ionic notation is used throughout this work. The Na3A1Fe is assumed to dissociate to NaA1F4 and NaF as in the former model, and Na&13F14 to dissociate to Na3A1Fe and NaA1F4. Other valid dissociation equilibria can be written involving these four compounds, but all of these can be obtained by combinations of the two described dissociation reactions and, thus, are automatically considered in these calculations. The model allows for no free AlF3 so that compositions for NAIF3 > 0.5 (mole fraction A1F3 on the NaF-A1F3 basis) cannot be treated. The question of the existence of free AlF3 in the melt will be discussed again later. The constants in the model were evaluated from points along the entire known liquidus line of the NaF-A1F3 system. Previous work employed only the liquidus line or densi- ties near the Na3A1F, composition. The liquidus line compositions used in the solution of the model are from unpublished work by Mr. P. A. Foster, Jr., for compositions between the Na3A1F6 melting point and the Na&13F14-A1F3 eutectic, and from the published works of Grjotheim,1 Phillips,3 and Foster4 for the remainder of the system. The relationships used in solving for the desired dissociation constants and heats and entropies of fusion are listed in Table I, and the points along the liquidus line at which each apply are indicated to the right of the relationships. The mole fractions of each of the separate species in the melt are symbolized by N. Relationships [I] and [2] are the respective dissocia-ation constants, Kl and K2, of Na3AIF6 and Na5A13F14 for this model. For simplicity, these constants will be assumed to be independent of temperature. Relationship [3] follows from the assumption of the ideal solution. The expression relating the values of N to the experimental values of NAIf3, is given in Relationship (41. Relationships [5], [6], and [7] each state the equilibrium between a compound in the melt and its pure solid phase for the portion of the liquidus lines where it precipitates. The heats of melting, AH,, and entropies of melting, AS,, used in [5], [6], and [7] are assumed to be independent of temperature. The compositions and temperatures of all five invariant points (two melting points, two eutectics, and one peritectic) along the liquidus lines from NAIF3 = 0 to NAIF3 = 0.5 were employed in the solution. The eutectic and peritectic compositions were particularly useful because each of these is involved in one more equation than other points along the liquidus lines and thus reduces the number of points required to solve for the constants. Also, their use assures that the inflection points in the derived liquidus line will correspond exactly with those on the experimental liquidus line. The total number of equations is 5k1 — 1, where n is the number of experimental composition points used. The number of unknowns is 4n + 5 (4n- 3 values of N, 3 values each of AH, and AS,, and 2 values of K). Thus, six points must be used in the solution to obtain an equal number of equations and unknowns. The one additional required experimental composition was taken on the liquidus line between the Na3A1Fe melting point and the Na3A1F6-Na5A13F14 peritectic. Previous work indicated this was a difficult portion of the curve to fit. The temperature used for the point was 1161°K, the same as for the NaF-Na3A1Fe eutectic. This choice of temperature gave two points with identical NNa3AIF6 values which simplifies the algebraic solution. The second point at this temperature is denoted 1161°'K. PROCEDURE FOR SOLUTION OF EQUATIONS Values were assumed for NNa,AIF and NNaF at the NaF-Na3A1F6 eutectic at 1161°k. By an iterative procedure, the corresponding values for NNa5A13F14 and NNaAlF4 at 1161°K were determined from 131 and 141. A value was assumed for NNaAlF4 at 1161°'K and

Jan 1, 1968

By M. T. Simnad, C. E. Birchenall, M. H. Davies

THE marker movements observed by Davies, Simnad, and Birchenall during the growth of magnetite on wustite have been misinterpreted. It is the purpose of this note to correct the original interpretation. In that investigation wustite specimens were prepared by oxidizing pure iron disks in water vapor until the iron was consumed. Argon was used as a carrier gas for the water vapor and on the complete conversion of the metal to its oxides ('FeO' plus a small amount (10 pct) of surface Fe3O) the water supply was bypassed and the specimens were annealed in argon alone in order to equilibrate the wustite with the overlying magnetite. After cooling, the magnetite was ground off, a crude magnetic test being employed to determine its complete removal. Radioactive silver streaks were then applied to the surface and the specimen was oxidized completely in water vapor to prevent hematite formation. After complete oxidation the markers were found to enclose about 80 pct of the magnetite with the other 20 pct lying outside the markers. This observation was interpreted to mean that oxygen transport was four times as great as iron transport during the growth of the magnetite. The conclusion would have been correct if, as in the case of wustite growing on iron, all the iron had started from one side of the marker and all the oxygen from the other side initially. Actually a material balance is required. For simplicity, take wustite to be exactly FeO, and magnetite to be Fe3O,. Then at the start of the reaction 3 FeO + O -> Fe,O., All of the iron and three-fourths of the oxygen of the final product will be within the marker inter- faces. The other fourth of the oxygen is in the gas phase outside the marker. From the experimentally determined final position of the markers simple calculation shows that one-fifth of the total iron has crossed the marker interface, while one-twentieth of the total oxygen has crossed in the reverse direction. The simplified result favors iron transport in the ratio four to one. However wiistite is not stoichiometric FeO. At 900°C, the temperature of the measurement, the composition is about FeO When the material balance for the same experimental result is repeated, assuming the product will be 1 mol of Fe3O4, it is found that 0.6 gram atoms of iron and 0.19 gram atoms of oxygen must have passed the marker in the same direction. (This is readily apparent from the reaction to form 1 mol of Fe3O4 SFeO The total oxygen supplied from the atmosphere is 0.61 gram atoms, but the iron which passes the marker interface, i.e., 0.6 gram atoms, requires 0.8 gram atoms of oxygen to convert it to Fe,O,.) If all the transport during magnetite growth is due to iron ion diffusion, then the marker would enclose about 85 pct of the final magnetite and the original measurement is in error by about 5 pct. This error is probably less than the uncertainty in locating the markers by autoradiography. The possibility also exists that the starting wustite was not quite saturated with oxygen and underwent further enrichment with consequent envelopment of the marker before magnetite caught up with the marker interface. In any case it appears that these measurements actually favor iron ion diffusion in magnetite overwhelmingly as the factor controlling its growth, although further experimental measurements are needed to eliminate the error in material balance described. Such studies are planned.

Jan 1, 1954