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By F. J. Schuh

The drilling industry long has been plagued by failures in the bottom few joints of surface and intermediate casing strings. This paper presents an analysis of the various possible causes of failure and concludes that failures are caused by short-lived, high-energy torque impulses delivered from the drill string through the bit while drilling out the cementing plugs, cement and floating equipment. The magnitude of these torque impulses is shown to be a function of the rotational momentum of the drill string, and a method is derived to calculate the magnitude of these impulses. The available methods of strengthening the bottom joints are reviewed. It is concluded that, while present methods are ineffective, a combination of improved procedures for strengthening and minor restrictions on drillout practices will prevent failures. Introduction In most cases, failure in the bottom few joints of casing strings is not discovered until electric logs record that the bottom one, two or three joints have parted from the casing string and slipped down the hole. However, in some cases the parted section of casing uncovers a high-pressure or lost circulation zone, or shifts laterally restricting the passage of drilling equipment. In these instances extensive remedial work is required to realign the parted pieces and seal the exposed formations. Several methods used to strengthen the bottom joints of casing strings include locking set screws in the couplings, putting wedges in special collars, welding straps across the couplings, welding the couplings and, most recently, using epoxy resin-based, thread-locking compounds. Since none of these techniques has eliminated the problem, this study was initiated to find the cause of failures and to evaluate the available methods of prevention. Mechanics of Casing Failures An analysis of the various possible causes of failure indicates that the casing is unscrewed rather than broken and that therefore failure must occur before the shoe is drilled. Since there is no general agreement as to the causes of casing failure, some possible mechanisms were ATLANTIC RICHFIELD CO. DALLAS, TEX. considered in this analysis. Failure of the bottom joints of casing can occur by only one of three types of stress: tension, torsion or bending. The possible mechanisms of failure were evaluated by determining the forces required to cause casing failure by each of the stresses; and, where applicable, the possibility of failure by fatigue was considered. For casing to part under tension requires a downward load of more than the tensile strength of the casing. The lightest API weight H-40 grade casing requires a bit load on the bottom of the casing of 27,000 to 34,000 Ib per inch of bit diameter (Table 1). Since maximum drill collar weights seldom exceed 10,000 Ib per inch of bit diameter, it is apparent that casing strings cannot be parted by the downward load of the drill string. The second mechanism considered was failure by bending. This mechanism requires that the lowermost casing joints be free to be deflected laterally until the bending stress exceeds the strength of the pipe. To fail, the casing (at a height L above the shoe) requires a force and deflection' at the shoe of To deflect the casing shoe with the drill string obviously requires a dog-leg at the casing shoe. This dog-leg must have a rate of change equal to or greater than the change in curvature of the deflected casing, which is given by

Jan 1, 1969

By L. L. Newman

As soon as the Congress recognized the alarming rate at which our domestic oil resources were being depleted during the war, it took action to step up the rate of research and development which the Bureau of Mines had been conducting for several years on the production of synthetic liquid fuels from coals. Under Public Law 290, approved April 5, 1944, funds were authorized for the Bureau to proceed with research, development, design and construction of demonstration plants for the hydrogenation of coal, the synthesis of oil from carbon monoxide and hydrogen, and the distillation of oil from shale. During the latter part of 1944, when it became evident that the collapse of Germany was near, a Technical Oil Mission was organized to study the German techniques of synthetic oil production. Since the cost of hydrogen or synthesis gas is one of the major factors of expense in the operation of hydrogenation or synthesis gas processes, the Bureau of Mines considered it of prime importance to include on the mission gas engineers whose instructions were to examine closely the methods employed by the Germans in solving the problem of providing low-cost hydrogen or synthesis gas for their very extensive operations on synthetic liquid fuels. The Solid Fuels Mission and the Utilities Mission, as well as the Army and Navy Missions, also included teams for the study of German gas production. Although their objectives naturally differed from those of the Technical Oil Mission and from each other, it was recognized that there was considerable overlapping of their fields of investigation. Duplication of effort, however, was largely avoided through the close cooperation between the group leaders of these missions. For example, although I went to Europe as a member of the Technical Oil Mission, my first Gcrman assignment was actually made by Dr. Harry F. Yancey, leader of the Solid Fuels Mission— to investigate the brown-coal gasification methods in central Germany. The art of gasification in the United States and England, and to a large extent in the proximity of the coking-coal regions of Germany and the rest of continental Europe, depends essentially on two stages of operation; namely, carbonization and intermittent water-gas generation. As far as the United States is concerned, complete gasification in a single stage of operation is rarely practiced, except in gas-producer operations where the product is a relatively lean gas consumed close to the point of manufacture, and for water-gas production with anthracite as a generator fuel. Complete gasification of bituminous coal has been the subject of numerous investigations. Many relatively simple modifications of the water-gas generator have been tried to permit the direct gasification of low-cost bituminous coal instead of high-cost coke and anthracite for the production of water gas. Although varying degrees of Success have been achieved and the water gas produced generally has been higher in

Jan 1, 1947

By L. L. Newman

As soon as the Congress recognized the alarming rate at which our domestic oil resources were being depleted during the war, it took action to step up the rate of research and development which the Bureau of Mines had been conducting for several years on the production of synthetic liquid fuels from coals. Under Public Law 290, approved April 5, 1944, funds were authorized for the Bureau to proceed with research, development, design and construction of demonstration plants for the hydrogenation of coal, the synthesis of oil from carbon monoxide and hydrogen, and the distillation of oil from shale. During the latter part of 1944, when it became evident that the collapse of Germany was near, a Technical Oil Mission was organized to study the German techniques of synthetic oil production. Since the cost of hydrogen or synthesis gas is one of the major factors of expense in the operation of hydrogenation or synthesis gas processes, the Bureau of Mines considered it of prime importance to include on the mission gas engineers whose instructions were to examine closely the methods employed by the Germans in solving the problem of providing low-cost hydrogen or synthesis gas for their very extensive operations on synthetic liquid fuels. The Solid Fuels Mission and the Utilities Mission, as well as the Army and Navy Missions, also included teams for the study of German gas production. Although their objectives naturally differed from those of the Technical Oil Mission and from each other, it was recognized that there was considerable overlapping of their fields of investigation. Duplication of effort, however, was largely avoided through the close cooperation between the group leaders of these missions. For example, although I went to Europe as a member of the Technical Oil Mission, my first Gcrman assignment was actually made by Dr. Harry F. Yancey, leader of the Solid Fuels Mission— to investigate the brown-coal gasification methods in central Germany. The art of gasification in the United States and England, and to a large extent in the proximity of the coking-coal regions of Germany and the rest of continental Europe, depends essentially on two stages of operation; namely, carbonization and intermittent water-gas generation. As far as the United States is concerned, complete gasification in a single stage of operation is rarely practiced, except in gas-producer operations where the product is a relatively lean gas consumed close to the point of manufacture, and for water-gas production with anthracite as a generator fuel. Complete gasification of bituminous coal has been the subject of numerous investigations. Many relatively simple modifications of the water-gas generator have been tried to permit the direct gasification of low-cost bituminous coal instead of high-cost coke and anthracite for the production of water gas. Although varying degrees of Success have been achieved and the water gas produced generally has been higher in

Jan 1, 1947

By Hans Neuberger

In our everyday life, visual perception plays perhaps a more important role than any of the other senses with which we are equipped by nature. It is, therefore, quite understandable that the average person associates with the term ''atmospheric pollution," clouds of dust, palls of smoke or deposits of soot, phenomena which are so familiar to the residents of industrial cities. On the other hand, "air" is usually considered the prototype of the invisible, of the intangible, and any suspensions in the air which do not conform to this concept, are regarded as foreign to the atmosphere and thus as "pollution." According to Webster, the term "pollution" implies uncleanness, impurity, in short, something undesirable. Although the scientist often accepts popular concepts, he is generally inclined to suspect that apparently "obvious" phenomena imply, literally, "more than meets the eye." To show that this suspicion is also justified with regard to atmospheric pollution, is the objective of this discussion. It will be shown that what seems foreign to the air at first sight, is by nature an integral part of it, and that the more important aspects of pollution generally escape attention. The Atmospheric Constituents We can distinguish two classes of atmos-pheric constituents: the Permanent gases, chiefly nitrogen, oxygen, traces of argon, neon, and others, and the variable constituents which include water in its different states, carbon dioxide, ozone, and various suspensions, either in gaseous, liquid or solid form. These suspensions, known by the collective term "Aerosol,"20 will be considered in detail. Dust There are two general types of aerosols: the first type is represented by the socalled "neutral" particles,3 commonly known as dust and experienced by everyone, as it is the more conspicuous type of suspensions. It often represents a special problem to the mining engineer, the mechanical engineer, the industrial engineer, and many other professional men. Dust consists of finely divided solids derived from weathering, drilling, handling and preparation of rocks and coal. Dust may also consist of organic or inorganic particles resulting from manufacture of a variety of products such as flour, rubber, lime and steel, from traffic on land be it on the highways, on rails or in city streets, from decomposed vegetation or from volcanic eruptions. Perhaps the most reviled member of this class of suspensions is the soot and fly ashes from coal fires and other combustion processes. The cosmic source of dust, namely the injection of meteoric matter into the atmos-,,here, is of minor significance because the concentration of particles is exceedingly small despite the relatively large mass of material which invades the earth's atmos-phere from space.

Jan 1, 1949

By D. F. DeSante, A. S. Tetelman

MICROCRACKS are often introduced into commercial metals during fabrication processes such as swaging, cold rolling, deep drawing, and welding. These microcracks act as strain concentrators and may be capable of causing premature catastrophic failure of a component or weld. The present investigation was undertaken to determine whether high-temperature annealing treatments may be capable of reducing or negating the detrimental effects of such existing microcracks. Internal microcracks, ranging from 0.1 to 0.85 mm in length and averaging 0.23 mm, were introduced into polycrystalline Fe-3 pct Si tensile specimens (0.155 mm grain size) by the cathodic charging of hydrogen.1'2 The typical appearance of such microcracks and their associated strain patterns (made visible by the technique of dislocation etch pitting3) is shown in Fig. 1. The stress fields of the dislocation loops formed during plastic relaxation stabilize the microcracks so that, when the internal hydrogen pressure is removed: the microcracks stay open, rather than disappear as perfectly elastic cracks would be expected to do.' As shown in Fig. 2, such stopped microcracks cause a 36 pct decrease in the macroscopic cleavage fracture strength at -196°C.

Jan 1, 1969

By B. R. Palmer, G. Gutierrez B., M. C. Fuerstenau

Flotation responses of chrysocolla and rhodonite are correlated with electrophoretic mobility and infrared spectroscopy measurements. Flotation is effected in the pH ranges in which hydrolysis of the metal ions comprising the mineral occurs. The roles of mineral solubility and precipitate formation are suggested.

Jan 1, 1976

By Nicholas J. Grant, John S. Benjamin, Bill C. Giessen

In the course of a study of hard particle-duc tile binder composite alloys, interest arose in the nature of the products of the reaction between the inter metallic compound NiAl and the binder niobium. No published information was then available. A program to

Jan 1, 1967

By G. P. Conard, E. H. Rennhack

The generation of fibers composed of individual TiZn15 compound particles and their influence on crystallographic orientation in chill-cast, hot-rolled hypoentectic Zn-Ti alloys were explored. Metallo-graphic examination and X-ray diffraction data show that such fibers form a planar network after 50 pet reduction which eventually tends to suppress twinning at some critical reduction level (-90 pct) where the grain size approaches the interfiber, spacing. This leads to the development of a duplex-type projerred orientation through slip rotation consisting of an al-most ideal (0001)(2iiOj texture and a (0001) (1010) rotated component. Correlations between basal-plane rotation and secondary- creep rc11e sugg-est, however that prejerred orientation does not contribute in a major way to the creep resistance of these alloys. EFFORTS to improve the creep resistance of zinc through alloying without incurring a loss in fabricating properties have achieved only minor success with the exception of the very effective addition of titanium. Anderson, Boyle, and Ramsey,l for example, demonstrated that increasing the amount of thiselement from 0.05 to 0.23 wt pct produced a progressive, 45-fold increase in the inverse creep rate of hot-rolled

Jan 1, 1967

By W. E. Anderson, T. M. Brady

As part of a larger study to identify factors influencing the practical operating life of wire rope used on large draglines in surface coal mining, field trips to operating surface coal mines were made during late 1975. Wire rope performance information was obtained from personnel at 13 mine sites west of the Appalachians. Seventeen pieces of equipment, utilizing bucket sizes ranging from 30 to 220 cu yd (23 to 168 m), were documented. Draglines at large US surface coal mines can be represented as 120 machines having 60-cu yd (46-m3) buckets, moving 1.8 X 109 cu yd (1.4 x 109 m3) of overburden during 6650 hours of productive availability per year. Based on the limited field study, the calculated downtime resulting from rope-related causes averages 105.6 hours per year for each typical 60-cu yd (43-m3) dragline. The total loss in production from this source alone is thereby estimated at about 25 x 106 cu yd (19 x 106 m3) annually. Although study findings did not reveal anything about dragline rope life that wasn't known or practiced by one operator or another, most operators can expect improved rope life by periodic review of their practices and by adopting one or more life-improvement measures employed at other sites. Since rope productivity was found to vary by a factor of five among the sites studied, considerable improved average performance is possible. As little as 10% overall improvement would increase national productivity by 2 million cu yd (1.5 X 106 m3) of solid overburden removal. Associated savings in rope costs would be some $2 million annually, plus a large reduction of labor-related expenses. This report outlines preliminary findings which may prove useful to many operators in extending wire rope life. Some of these modifications or adjustments in maintenance/operating practices would not require capital investment. During the field survey, no company was found which had tried cost reductions by using presocketed dump ropes, or dump rope sheaves that opened like a snatch block, so these are suggested as possible improvements requiring modest capital input. Data Acquisition During the field visits, mine operators provided rope life information about their machines. Some of the rope life data consisted of gross averages; other data was in the form of detailed records, including rope construction and manufacturer, cutoff and resocketing periods, end-for-end switching, and downtime for rope change-out. Trends of average hoist rope life and average drag rope life determined from the field study are shown in [Fig. 1] as a function of bucket size. The three lines on the graph have slopes of 1, M, and 1/4. A comparison of the data shows that hoist ropes moved about twice as much material as drag ropes prior to retirement, although more than a two-to-one scatter within each category is evident. As expected, the larger machines with the larger buckets moved more total volume of material. The four pairs of solid symbols represent those data for which detailed rope life histories are presented in subsequent figures.

Jan 1, 1980

By D. T. Peters, J. C. Bisseliches, J. W. Spretnak

The pain boundary relaxation phenomenon in high-purity copper, 0FHC copper, and a precipitation-hardenable alloy o-fCu-2 uit pct Co has been studied by internal ,friction and elastic aftereffect techniques. The data were analyzed by assuming the broad distribution of relaxation times observed obeys a lognormal distribution law which enables calculation of the relaxation strength. Grain size had no effect on relaxation strength, although the peak width increased with increasing grain size and decreasing temperature. A double grain boundary peak was produced in high-purity copper by annealing to produce secondary recrystallization. The activation energy measured for 99.999 pct Cu is 37.5 * 3 kcal per mol and 46.5 kcal per mole for OFHC copper. A small peak in the Cu-Co alloy at about 220°C at 1 cps was deduced to be the grain boundary peak. Its height increased and its activation energy decreased with increasing aging time. Except for erratic peak positions the observations were consistent with the theory of pain boundary sliding. BEFORE the mechanism of the grain boundary internal friction peak in metals can be satisfactorily explained, the detailed characteristics of the relaxation process must be documented. Of interest are the effect of grain size on relaxation strength, the high-temperature background, and peak width and position. The effect on the grain boundary peak of a precipitate at grain boundaries and of the change in distribution of the particles with aging time must also be explained by any existing or forthcoming theory. The model which has received the most attention was proposed by KG' and zener2 and proposes that the anelastic strain results from sliding of adjacent crystals at grain boundaries. The sliding is limited by the interlocking of grain corners. It follows, according to this model, that the relaxation strength is independent of and the relaxation time is proportional to the grain size. The proportionality between grain size, D, and relaxation time, t, has been confirmed by K&' and Bisseliches . In this case, the internal-friction peaks of various specimens can be superimposed by plotting Q-' as a function of the parameter vD exp H/RT where v is the frequency and H the activation energy. However, the data of Starr et 01.' and Leak6 fit better to a parameter containing D to an exponent near two. A meaningful relationship is not always deducible from the shift of peak temperature with grain size. KG7 demonstrated that a twofold variation in grain size obtained by varying the amount of cold work followed by identical recrystallization anneals will cause a peak shift that is too large to be accounted for even by an exponent of two. Since the decreased grain boundary area existing with a larger grain size is exactly compensated for by an increased sliding distance, the relaxation strength should not decrease with increasing grain size. The height of the internal-friction peak has generally been observed to be rather insensitive to grain size as long as the average grain diameter does not approach the specimen diameter. Exceptions have been reported by Koster, Bangert, and Lang8 for copper, and by Leak6 for iron. The observations for copper could well have been confused by the presence df 0.3 pct0. The possibility that the peaks may simply be increasing in width with increasing grain size and that the relaxation strength, which is proportional to the area under the peak, may remain constant was not examined. his point has been checked in this investigation using high-purity copper. Atomic mechanisms to account for damping by sliding at grain boundaries have been proposed by KG7 and Mott. KG predicts the activation energy to be identical to that for self-diffusion. Mott's "island" model suggests the activation energy is nL where n is the number of atoms in an island and L is the latent heat of fusion per atom. Other authors have felt that a value equal to the activa-

Jan 1, 1964

By R. S. Shoemaker, D. L. Harris

Past investigations into the possibility of concentrating the low-grade iron ores of the Gogebic Range in Wisconsin have been hampered by the complex association of the constituent minerals. In part the problem arises from the fact that the iron occurs essentially as two minerals, hematite and goethite, having nearly the same chemical composition but exhibiting different physical properties. Individual grains of these minerals are usually so small that the ore must be ground to a size finer than 325 mesh if substantial liberation of the minerals is to be secured. Appraisal of beneficiation tests on this iron ore requires, therefore, some method of determining quantitatively the contents of constituent minerals in the various products of the beneficiation. Because of the chemical similarity of the two iron minerals, chemical analyses do not provide a means of differentiation. Although the minerals are different physically, they are both opaque and friable, and as the ore must be ground to a very fine size for liberation to be secured, quantitative microscopic methods of analysis are extremely difficult at best. In an effort to overcome these analytical problems, a quantitative X-ray diffraction analysis method has been developed at the University of Wisconsin for the research program on iron ore beneficiation.

Jan 5, 1955

By P. A. E. Armstrong

For hardening, the steel should be heated just above the critical temperature, as a properly forged steel quenched from this heat has some toughness, with maximum hardness and density. The quenching bath should be kept at approximately a constant temperature. In drawing or tempering, longer time periods at lower temperatures are better than the shorter periods at higher temperatures. A recent questionnaire brought out the following facts: The double-arc, double-taper bit and cross bit give the best service; resharpening of the drill steels most frequently was caused by wear of gage; chipping of bit was, with one exception, the second cause; breakage of shank was with one exception, the third cause; upsetting of bit, upsetting of shank, and breakage of body were the fourth cause. The direct cause of the necessity of resharpening given was poor heat treatment first, and faulty steel and severe rock conditions second. Rock-drill Steel By N. B. Hoffman Much of the drill steel produced in America is manufactured into hollow rods. After all forging has been finished the entire bar should be thoroughly annealed and heat trcated before the point is hardened and tempered, at least where the drill has heavy duty, such as working in deep holes and hard rock. A large number of tools of like character and doing work requiring similar properties are now being made of alloy steels; for instance a steel with a carbon content of 0.75 to 0.85 per cent., manganese 0.25 to 0.35, phosphorus under 0.020, sulfur under 0.030 and vanadium 0.18 to 0.23 has proved very satisfactory for chisels. A steel of this type properly manufactured will be far superior to the ordinary carbon steels, while at the same time is one whose price range should not prove prohibitive. Much of the cutting efficiency of a drill depends on proper heat treatment. This vanadium steel has a far greater safe hardening and forging range than ordinary carbon steels, making it more nearly foolproof. It will harden nicely at 1400" I?. but will also harden well and satisfactorily at 1550" F. retaining its quality of hardness and toughness in either case. Drill Steel from Hollow Ingots BY P. A. E. ARmstrong Hollow drill steel is made from a drilled billet with a sand-filled core or the drilled, pierced, or the drilled and pierced billet, not sand-filled, is rolled down over a projectile or ball much the same as in ordinary pipe manufacture. The first is the method generally used in this country; the second is used largely in Sweden. Swedish hollow drill steel has a

Jan 1, 1922

By Frank W. Clinard, Oleg D. Sherby

The effect of multiple an transformations on diffusion in a dilute iron alloy was studied. Inter-penetration between iron and an Fe-Co alloy was evaluated, under thermal-cycling conditions chosen so as to transform only the iron-rich side of the diffusion couple. It is shown that a small but consistent diffusion enhancement by a factor of two results when data from the transforming side of thermally cycled specimens are compared with predicted inter diffusion coefficients based on isothermal data. No enhancement is found when data from the mntransforming side of such couples are compared with predicted diffusivities. It is suggested that short-circuiting by moving pain boundaries is the most likely mechanism contributing to the observed diffusion enhancement from multiple phase transJormations in iron. Transformation-induced Point defects, dislocation-pifie short-circuiting, and point defects generated by dislocation motion are less effective in contributing to enhanced diffusion under the experimental conditions utilized. SO far as is known, no studies have been made of the effect of allotropic transformation on diffusion. previous to this investigation. Studies have been made, however, of the influence of transformation on the diffusion-controlled processes of spheroidization and sintering. Cullen1 has described a method of accelerating spheroidization in an AISI 1030 steel. Partial transformation between a and ? phases was uti-

Jan 1, 1965

By N. Arbiter, C. C. Harris

In 1961, a research program started at Columbia into the mechanical aspects of flotation,* and certain ends are now in view. The purpose of this note is to explain these tentative conclusions in the hope of stimulating discussion and eliciting new data, especially industrial data, with which to test the views expressed. The variables presently under consideration are impeller rotational speed, N, volumetric air rate, Q, and impeller diameter, D, the latter being the parameter chosen to designate cell size. The most favorable *The latest work 1 references all previous publications. chemical environment is not under discussion since the procedures for establishing it are better understood than those for optimizing N and Q by virtue of a longer history of more intensive investigation. THE GRADE AND RECOVERY SURFACES With a given ore, chemical treatment, and flotation machine, both grade, G, and recovery, R, are functions of N and Q. The GNQ and RNQ relationships are best viewed in terms of three-dimensional surfaces (Fig. 1) which are experimentally determinate.2 TO maintain grade at an acceptably high level, it is necessary for N and Q to lie within certain limits, and similarly with recovery. However, the ranges of N and Q for grade on the one hand and recovery on the other are rarely the same. Selecting the single N

Jan 1, 1970

By M. B. Bever, J. E. Reynolds

IN several alloys of iron, copper, and lithium as well as in some pure metals, martensite formed on cooling reverts to the parent phase upon heating to a temperature below the equilibrium temperature at which the parent phase becomes stable.' These martensitic transformations, therefore, are thermally reversible, although appreciable hysteresis may be involved. The martensitic reaction has long been

Jan 1, 1953

By L. F. Mondolfo, F. A. Crossley

SURFACE effects in the brittle fracture of materials such as glass and in the plastic slip of zinc and cadmium crystals are well known.' Recently, another surface effect has been found for zinc monocrystals. It has been observed that certain normally ductile zinc monocrystals become ex- tremely brittle when their surface is coated with a layer of oxide or copper plate.

Jan 1, 1952

By Tuncel M. Yegulalp, Peter G. Zambas

In planning an underground room-and-pillar mine, the selection of the shaft or portal location and the orientation of the main haulage arteries is of paramount importance, particularly in view of the high dependence of the cost of truck haulage on the proper definition of these parameters. In an effort to facilitate this selection a computer program was written which, by relating the truck characteristics to the areal configuration of the property or ore body, derives the volume-weighted total fuel and time requirements for hauling ore from every panel within the property to a specified portal or shaft location through a predetermined gridwork of haulage drifts. By varying the size and orientation of the gridwork and the location of the portal or shaft access, an infinite number of configurations can be investigated. The results of this analysis can be plotted to indicate the optimum conditions.

Jan 1, 1974

By N. E. Rogen, N. J. Grant

WHILE direct measurements of the growth of precipitate particles during aging is of fundamental value, few such measurements have been made. Direct measurements by means of optical or electron-microscopy and X-ray techniques are preferred, however, many of the aging studies have been based on indirect methods such as electrical resistivity and hardness. Because of the minute size of most precipitate particles (less than 1000A) the light microscope is of limited use while electron microscopy is subject to slowness, etching problems and consequent resolution problems. It is fortunate that alloys of the Nimonic type, based on Ni-Cr-Ti-Al, lend themselves to accurate and relatively easy particle size measurements. With proper balance of titanium and aluminum, the only aging precipitate is the gamma prime (r') Ni3,(Al, Ti)2 phase and this phase is the basis of the high-temperature strength of these allos.3-6 The Ni3(Al, Ti) phase is a face-centered-cubic, ordered structure with nickel atoms occupying the cube faces. Titanium atoms can replace three out of every five aluminum atoms and when substituting do so preferentially.2 Electron microscopy has shown that during aging of most of the commercial alloys of this type, precipitate particles are unusually uniform in size and distribution, and that the volume of (r') phase is large (20 pct).4,7 The aim of this investigation was to measure the growth of (y') phase during aging. In so doing, it was hoped that a clearer understanding of the aging process would be attained. X-ray line broadening was used as the measure of precipitate particle size. This technique was selected because it can measure and average the diameter of thousands of particles in one operation. The variations in hardness and matrix lattice parameter with aging were also studied and related to the particle size. EXPERIMENTAL PROCEDURE An alloy of the following composition was studied: Cr Ti A1 C Ni Wt pct 20.71 2.98 1.43 0.04 bal. At. pct 22.06 3.47 2.95 0.18 bal. The alloy, a 15- lb vacuum melt, was forged to 1/2-in. diam at a temperature of 1900" to 2200°F; was solution heat treated for 4 hr at 2000°F and water quenched; and was then aged in various ways. The ASTM grain size was 4 to 5. No (7') phase could be detected by X-ray analysis after solution treatment and electrolytic extraction. Aging was performed on 2-in. long specimens at 1400°, 1500°, and 1600°F for increasing times. One-half inch sections were removed after each time increment and were then electropolished in a solution of H3P04 saturated with chromium trioxide at a potential of 30 v and rectified with a tantalum electrode. Rockwell hardness measurements were taken using one side of the polished specimen. Matrix lattice parameter determinations were made on the other side using filtered chromium radiation references with the position of the (220) line of a silicon standard. To enable the precipitate particles of the (y') phase to be measured using X-ray line broadening techniques, it is first necessary to separate and concentrate this phase by electrolytic extraction. Extraction is necessary because the difference between matrix and precipitate lattice parameters is only approximately 0.5 pct and intensities of.the (y') phase lines are very weak relative to those of the matrix. The extraction techniques employed have been described before and found to produce a reasonably quantitative separation.398 A water solution of 15 pct H3Po4 is used at a current density of 0.5 amp per sq in. at 6 v. The precipitate particles are separated from the liquor by centrifuging and decanting and are then washed, dried and repowdered. A plot of the X-ray intensity vs diffraction angle for the (111) line of the precipitate particles was used as a measure of particle size. The intensity curve approximated the shape of Gaussian distribution function and its breadth was measured at the half height. The (220) line of a silicon standard was used to correct the measured line breadth for instrumental and other broadening errors. The Scherrer formula was used to calculate particle

Jan 1, 1961

By B. C. H. Steele, C. B. Alcock

In choosing solid oxide electrolytes for use in the measurement of thermodynamic quantities at high temperatures, the two most important criteria are the values of the partial ionic and electronic conduc tizities. Measurements of these conducticities have been made for some Group IVA oxides and solid solutions of these oxides with CaO, Y2O3, and La2O3. The total conductivities as a function of temperature. oxygen partial pressure, and composition were determined, as well as the electromotive forces of cells in which the oxygen partial Pressures of the electrodes were between 10-7 and 10-29 atm at 1000°C. Additional factors that influence the experimental arrangements, such as the operating temperature, the appropviate cell atmosphere, and electrode kinetics, are also discussed. IT has long been recognized that galvanic cells incorporating solid electrolytes can possess many advantages for the measurement of high-temperature thermodynamic data. Unfortunately, the electrical-transport properties have only been established for a few solid electrolytes, although attempts have been made, and are still being made, to use such materials as porcelain' and magnesia.' Kuikkola and Wagner have discussed3 and demonstrated4 various applications of solid electrolytes, and, in particular, their work stimulated the electrochemical measurement of oxygen activities using cells incorporating the solid oxide electrolyte, Zr0.85Ca0.15O1.85 The excellent characteristics of this oxide electrolyte have been confirmed by the investigations of Kingery et al.5 (oxygen ion diffusion), Carter and Rhodes6 (zirconium and calcium ion diffusion), and Weissbart and Ruka7 (electronic transference number). However the observations of Peters and Mobius,8 later confirmed by Schmalzried,9 indicated that the electronic component of zirconia-based electrolytes could become significant at low oxygen chemical potentials. Under these conditions, thoria-based electrolytes have obvious advantages arising from their superior thermodynamic stability. It was known that certain thoria solid solutions possessed defect fluorite structures containing anionic vacancies (cf. Zro.85Cao.l50O1. 85), although data on their electrical properties were conflicting. Kiukkola and wagner4 concluded that thoria-based electrolytes exhibited appreciable electronic conductivity, whereas Peters and Mobius8 mentioned that the electronic conductivity only became important at high oxygen partial pressures, but gave no further details. In addition, both Kiukkola and wagner4 and Peters and Mann'" had determined the oxygen chemical potentials associated with the Fe-FeO, Co-COO, Ni-NiO, and Cu-Cu2O equilibria, and it was not known whether discrepancies in their results could be attributed to the different cell design, or the thoria-based electrolyte used by Peters and Mann. These uncertainties have been resolved during the present investigation into the measurement of low oxygen chemical potentials, and transport properties of the relevant oxide electrolytes are presented and discussed. Other experimental difficulties associated with low oxygen chemical potential measurements are also described, with particular reference to the Nb-O system. 1. THEORETICAL CONSIDERATIONS Oxide systems of potential use as solid electrolytes possess a large energy gap between the valence and conduction bands. Little is known about the defects present in these wide-gap metal oxides as a function of impurity content and deviations from stoichiom-etry, or the mechanisms by which electronic charges move in these solids. For these materials it is convenient to represent the measured conductivity as the the sum of three terms: where a, is the conductivity due to positive hole conduction (p type), and oe is the electronic conductivity due to electron conduction (n type). U there is a large concentration of ionic vacancies fixed by composition then the ionic contribution will not be a function of oxygen pressure. Although the possibility of a pressure-independent electronic component also cannot be ignored, it is likely that such a term would only become significant at very high temperatures, and in general the positive hole conduction will increase with increasing oxygen pressure, and the electron conduction will increase with decreasing oxygen pressure. It follows that the total conductivity is related to oxygen partial pressure as follows:

Jan 1, 1965

By Burnham E. Field

The chemical industry is constantly looking for new materials which either are more resistant to corrosion than those now available or have improved physical properties to meet the requirements of higher temperatures and greater pressures. Attack by acids is one of the more important forms of corrosion and in the last few years the development of acid-resistant alloys has been quite rapid. Perhaps the most notable example is that of nitric acid, the problem of which has largely been solved by the chromium-iron and chromium-iron-nickel alloys. Sulfuric acid may be handled in lead, iron, or the iron-silicon alloys, depending on conditions. As to hydrochloric acid, no metal or alloy can be called entirely satisfactory for handling this acid under plant conditions.' The results of our investigations on the resistance of the nickel-molybdenum alloys to hydrochloric acid have been confirmed by those of Guertler, Rohn, Schulz, Jenge, and others12 but thus far only one such alloy has approached commercial production in Germany; this contains approximately 15 per cent. chromium and 7 per cent. molybdenum with the remainder chiefly nickel. Dr. S. W. Parr, as far back as 1914, developed a complex alloy known as "illium," with a nickel base and containing some molybdenum. 3 Dr. Parr was primarily interested in an alloy for lining bomb calorimeters, and while illium does show good resistance to acid it is too expensive for general use. Two United States

Jan 1, 1929