Search Documents

By Albert J. Phillips

As early as 1824, Haidinger' described crystals of native copper that were, according to Dana,2 " probably twinned parallel to the octahedral plane and normal to this axis." In 1837, Rose3 very clearly demonstrated that native copper crystals were commonly twinned on the octahedral plane. Lasaulx,4 in 1882, described polysynthetic octahedral twins and stated that enclosed twinning lamellae were observed. Even on crystals formed artificially by electrolysis, twinning was observed as early as 1886, by Brown.5 Many other descriptions of twinning in native copper and in gold and silver are to be found in the literature, and in every case with which we are acquainted the twinning is conformable to the spinel law; i. e., the octahedral plane is both twinning and composition plane. Metallurgists have long been familiar with the straight-sided bars or bands that commonly occur within the irregularly outlined grains of metallic crystalline aggregates. They are certainly found in nearly all metals of the face-centered cubic type after cold working and annealing. If a specimen showing these bands is rotated, keeping the angle of incidence of the illuminating beam constant, they usually exchange color contrast periodically with their respective matrix crystals. Also slip lines, when produced in these specimens, nearly always show a change in direction upon passing through the bands, giving rise to the "stairway" effect often illustrated in metallurgical textbooks. Apparently the only quantitative observations on bands of this sort were made by Osmond and Cartaud6 on austenitic steel. They selected,

By P. K. Koh, H. A. Lewis, H. F. Graff

New data on the distribution of silicon between slag and carbon-saturated iron at 1600Oand 1700OC are presented which, in combination with previously published data, permit the determination of silica activities over a broad range of compositions in the CaO-Al2O3-SiO2 system. The distribution of silicon between graphite-saturated Fe-Si-C alloys and blast furnace-type slags in equilibrium with CO has been described in previous publications.1"3 In this past work the silica-silicon relation was established at temperatures of 1425" to 1'700°C for slags containing up to 20 pct A12O3. This paper presents the results of additional studies at 1600" and 1700° C which extend the silicon distribution data at these temperatures for CaO-A12O3-SiO, slags over a range from zero pct Al2O3 to saturation with Al2O3, or CaO.2Al2O3. The upper limit of SiO2 is set by the occurrence of Sic as a stable phase when the metal contains 23.0 or 23.7 pct Si at 1600" or 1700°C, respectively. The activity of silica over the expanded range is determined directly from the distribution data.3 Recently4-7 other investigators have studied the activities of SiO, and CaO, principally in the binary system, using different methods and obtaining somewhat different results. EXPERIMENTAL STUDY The experimental apparatus and procedure have been fully described in previous publications.1, 3 Six new series of experimental heats have been made, four at 1600° and two at 1700°C. Master slags of several fixed CaO/Al203 ratios were pre-melted in graphite crucibles, and these were used with additions of silica to prepare the initial slag for each experiment. Slag and metal were stirred at 100 rpm and CO was passed through the furnace at 150 cc per min. The initial sample was taken 1 hr after addition of slag at 1600°C or 1/2 hr after addition at 1700°C. The run was normally continued for 8 hr at 1600°C or 7 hr at 1700°C, and the final sample was taken at the end of this period. Changes in Si and SiO2 content indicate the direction of approach to equilibrium, and in a series of runs where the approach is from both sides this permits approximate location of the equilibrium line. Fig. 1 shows the results of such a series of 15 runs at 1600°C for slags of CaO/Al,O3 = 1.50 by weight. Figs. 2 and 3 record other series at 1600°C and Fig. 5 a series at 1700°C with fixed CaO/Al0 ratios. The results of the experiments at 162003°C have been reported in part in a preliminary note.3 In the experiments recorded in Figs. 4 and 6, the slags were saturated with A12O3 (or with CaO.2A12O3 within its field of stability) by suspending a pure alumina tube in the melt during the course of the run. The final slag analyses were used to establish the liquidus boundaries8 in the stability fields of CaO.2Al2O3 and of Al20,. ACTIVITY OF SILICA The free-energy change in the reaction has been calculated by Fulton and chipman2 from recent and trustworthy data including heats of formation, entropies, and heat capacities. The more recent determination by Olette of the high-temperature enthalpy of liquid silicon is in satisfactory agreement with the values used and therefore requires no revision of the result which is expressed in the equation: SiO2 (crist) + 2C (graph) = Si + 2CO(g.) [1] &F° = + 161,500 - 87.4T The standard state for silica is taken as pure cristobalite and that of Si as the pure liquid metal. Since the melts were made under 1 atm of CO and were graphite-saturated, the equilibrium constant for Eq. [I] reduces to K1 = asi /asio2. The value of this constant is 1.77 at 1600°C and 16.2 at 1700°C. Through K1, the activity of silica in the slag is directly related to the activity of silicon in the equilibrium metal.

Jan 1, 1960

By C. A. Bruch, J. F. Duffey

On the basis of metallographic and cooling-rate studies of 15 U-Zr alloys, a new version of the 6 phase region of the U-Zr phase diagram is proposed. IN several published diagrams of U-Zr alloy system:' there is good agreement that at elevated temperatures complete solid solubility exists between y uranium and ß zirconium. Similarly, there is reasonably good agreement concerning the uranium-rich and zirconium-rich ends of the diagram. However, there is no agreement concerning the nature of the diagram at intermediate compositions and at temperatures below about 650°C. The early work of Saller et al.8 hows an intermediate phase, 6. In a later diagram by Saller and Rough' shown in Fig. 1, the d phase field is drawn with dotted lines, indicating doubt that this phase exists. The diagram of Summers-Smith2 does not show the d phase. More recently Holden and Seymour' have shown that in the composition range 40 to 60 wt pet Zr, the high-temperature ? phase, which is body-cen-tered-cubic, transforms to an ordered structure, 8. They found that the order-disorder transformation occurs between 595° and 610°C, and presented a diagram based on the study of four different alloy compositions. Most recently Saller et a1.5 presented a new diagram which differs with respect to the composition limits of the 8 field from the others proposed by these authors. The purpose of the present investigation was to determine the boundaries of the d phase field. Experimental Procedures and Results Alloys—Buttons, weighing 80 g of 15 different alloy compositions were prepared by arc melting Mal-linckrodt uranium and iodide-process zirconium in a water-cooled crucible. A controlled atmosphere of argon and helium was maintained in the furnace. Prior to making each button, a sacrificial button of zirconium was melted to increase the purity of the furnace atmosphere. Each alloy was then melted six times to improve its homogeneity. Subsequently the alloy buttons were jacketed in copper and hot rolled to slabs at 775°C. From these slabs, specimens were machined for chemical, thermal, and metallographic analyses, Table I gives both the estimated chemical composition of the alloys, and the values which were obtained by analysis. The oxygen contents varied from 0.013 to 0.032 pet, nitrogen from 0.0014 to 0.014 pet, and carbon from 0.0013 to 0.011 pet. The purity of the alloys ranged from 99.947 to 99.975 pet. Thermal Analysis—The specimens for thermal analysis were blocks 11/4 x 1/4 x % in. The bead of a calibrated thermocouple was placed between two of these blocks and molybdenum wire was wrapped around the assembly. Each assembly was sealed in a quartz capsule having an argon atmosphere. The capsule was placed inside a refractory crucible which was heated in a furnace. Using a method described by Smith,' the emf of a differential thermocouple, with junctions inside and outside of the refractory crucible, was used to activate the

Jan 1, 1959

By Frank Firmstone

IN 1871, two furnaces at the Glendon Iron Works, which had been blown out on account of the "coal strike," were altered from the open-top plan with side flues for collecting the gas, to closed tops with cup and cone. In one furnace the suppression of the side flues permitted a considerable alteration in the profile, but in the other (No. 5) no change in this respect was made; the side flues were simply bricked up and new ones cut through the sides close to the top. This furnace was in blast over four years, and we can, therefore, form a pretty good idea of the effect of the alterations on the furnace process. The principal dimensions are; Height 72'; greatest diameter, 18'; diameter at tuyeres, 8'; diameter of top, 10'; diameter at stock line (point at which the top of the materials is kept), 11'; cubic contents, 11,900 cubic feet. The table below shows the average results for periods of twenty-six weeks each. 1st, of the open-topped furnace; 2d, of the furnace with the first charger used, which was an ordinary cup and cone (diameter of cone 5' 2") 3d, with the charger used ever since, a "double" cone 7' 5" diameter outside, having a central opening 3' in diameter. The diagram (Plate II) shows the daily variations, in the grade of the irons for the same periods.* * In calculating the average grade of each day's iron, each twelve hours was taken by itself whenever more than two kinds of iron were made in the 24 hours, and the diagram drawn accordingly. By counting, it will be found that there were more such days with the single cone than with the "double" cone, and more with this than with the open top. † Anthracite.

Jan 1, 1876

By C. T. Holland

This discussion is concerned with those com-J- paratively infrequent bumps that eject material from the failed mass with enough energy to wreck heavy machinery and seriously injure or kill people. In such cases there is a loud report, and the pressure waves set up in the mine atmosphere wreck ventilation controls several hundred feet from the site of the failure. Vibrations are induced in the earth's crust which may be detected several miles from the point of origin, and explosive gases may be released in large quantities." Usually a dense suspension of dust is produced from the failed mass, together with dust placed in suspension by the resulting air blast. These rock bursts or bumps have also been called mountain shots, bounces, pillar bursts, and crumps. Such occurrences, when extensive, are serious catastrophes, and may force abandonment of the mine.' CAUSES OF ROCK BURSTS Rock bursts in coal mines have occurred in sev-eral places under diverse geological conditions, mining methods, and/or practices. A study of many such occurrences indicates that they depend on the following conditions: 1) cover thickness of 500 ft or more, 2) cover composed of strong members and having a strong member lying close to or on the coal bed, and 3) a floor that does not readily heave. The minimum thickness of cover under which coal mine rock bursts occur is based on observation. Under unusual circumstances involving very strong roof members and/or mining systems, and/or practices especially likely to induce bursts, a burst conceivably could occur under less roof. Under special circumstances rock bursts have occurred in marble quarries almost at the surface.' Furthermore, under very heavy cover it is likely that controlling roof members need not be as strong and as close to the coal bed to cause bumps. Just what constitutes a strong roof or roof member is open to question. Obviously the strength of a roof member is determined by its thickness, the distance between bedding planes across which little or no bond exists, the spacing and development of joints, and the inherent strength of the rock material. Strata sections showing roofs under which rock bursts in coal mines have developed are illustrated in Fig. 2. In several instances the strength of rocks composing the roof of mines developing bumps has been tested. The tests (Table I) show that these rocks develop considerable strength in compression, bending, and shear and that in some cases the strengths are very high. No quantitative data are available concerning joints in roof members over coal beds where rock bursts have occurred, but the author has examined many mines subject to bursts and has received the impression that joints in the shales immediately over the coal beds are always present and well developed. In the main sandstone or conglomerate members themselves, however, where observed, he has yet to see a fracture system indicating well developed joints. Undoubtedly joints are present, but the evidence indicates that they are few, poorly developed, and widely spaced. In a mine subject to bumps, moreover, actual measurements of roof spans up to 225 ft between supports under a cover of about 800 ft have been made before roof failure occurred. Such spans signify strong roof. In coal beds subject to rock bursts, the bottom rock is usually a sandy shale. A few tests (Table I) have been made on the floor rock of coal beds. Observations in mines indicate that they are usually weaker than roof rocks and that under load they show more plastic effects. Observation in ground subject to bursts invariably indicates a relatively strong floor highly resistant to heaving, although some heaving may occur. Other factors listed as favorable to rock bursts are: 1) mountainous surface; 2) steeply dipping beds; 3) proximity of faults, folds, and other similar geologic structures. Many bursts have occurred in mines under mountainous country, although many bursts in mines under a surface with little relief indicate that thickness of cover, not relief, is the essential factor. In steeply dipping beds, many bursts occur in mines that are essentially flat, and rock bursts have been recorded in beds dipping as much as 35o Most rock bursts in the U. S. occur in beds that dip less than 10 pct. It is also true that most U. S. coal is produced from beds dipping less than 10 pct. Geologically, faults are regarded as providing stress relief, but in the vicinity of faults, as well as sharp folds, it would seem that residual stresses could be present. The fact that rock bursts occur in areas remote from faults and sharp folds suggests that their presence is not necessary for this phenomenon to take place. There have been many bursts close to faults and folds, and it may be assumed that occasionally such structures accentuate their occurrence3 The conditions and circumstances under which they occur, coupled with the effects produced, leave In the Crowsnest Pass coalfield, British Columbia, a rock burst is estimated to have released 1.8 million cu ft of methane.

Jan 1, 1959

By Haydn H. Murray, Sam H. Patterson

The term "clay" is somewhat ambiguous un¬less specifically defined, because it is used in three ways: (1) as a diverse group of fine-¬grained minerals, (2) as a rock term, and (3) as a particle-size term. Actually, most persons using the term "clay" realize that it has several meanings, and in most instances they define it. As a rock term, clay is difficult to define be¬cause of the wide variety of materials that com¬pose it; therefore, the definition must be gen¬eral. Clay is a natural earthy, fine-grained ma¬terial composed largely of a group of crystalline minerals known as the clay minerals. These minerals are hydrous silicates composed mainly of silica, alumina, and water. Several of these minerals also contain appreciable quantities of iron, alkalies, and alkaline earths. Many defini¬tions state that a clay is plastic when wet. Most clay materials do have this property, but some clays are not plastic; for example, halloysite and flint clay. As a particle-size term, clay is used for the category that includes the smallest particles. The maximum-size particles in the clay-size grade are defined differently on various grade scales, Soil investigators and mineralogists gen¬erally use 2 micrometers as the maximum size, whereas the widely used scale by Wentworth (1922) defines clay as material finer than ap¬proximately 4 micrometers. Some authorities find it convenient to use the term "clay" for any fine-grained, natural, earthy, argillaceous material (Grim, 1968). When used this way, the term includes clay, shale, or ar¬gillite, and some argillaceous soils. Even though no standard definition of the term clay is accepted by geologists, agronomists, engineers, and others, the term is generally un¬derstood by those who use it. Clay is an abun¬dant natural raw material, and it has an amaz¬ing variety of uses and properties which will be discussed in this chapter. Clays rank among the leading industrial min¬erals in both tonnages produced and total value. Their importance is indicated in Table 1, which lists the 1970, 1971, and 1972 production and values according to the U.S. Bureau of Mines (Ampian, 1972). Adequate reliable statistical data on which to summarize world production of clay are un¬available; this paragraph outlines the world re¬quirements for clay only in a very general way. According to one estimate, the world bentonite production in 1972 was 3.5 million tons (Anon., 1973a), but in the authors' opinion it was prob¬ably at least 5 million tons. The total fuller's earth produced was at least 1.5 million tons and may have been as much as 2 million tons. The total world kaolin production in 1972 was more than 10 million tons. Approximately 7 million tons of this total was produced in only two regions-the Georgia-South Carolina kaolin belt in the United States and the Cornwall re¬gion, United Kingdom. The world's 1972 out¬put of ball clay, which is also produced pri¬marily in the United States and the United Kingdom, was approximately 1.5 million tons or perhaps a little more. The total world fire clay production in 1972 was probably about one and one-half to two times and the miscellaneous clay production three times the United States production. As industrial minerals, clays are a complex group that consists of several mineral commodi¬ties, each having somewhat different mineral¬ogy, geologic occurrence, technology, and uses. In this chapter these commodities are organized

Jan 1, 1975

By M. von Heimendahl, G. Thomas

The microstructure of TD-Ni has been examined by transmission electron microscopy in the extruded, annealed. and deformed states. The tensile properties hove been correlated with the observed microstructures and the results ore com-pared with those obtained from pure nickel. The important conclusions are that the thorin particles in TD-Ni act as strong burriers to dislocntion motion during both deformation (slip) and annealing (climb). During deformation. the dislocations tangle around the particles and a cell structure is devleloped after 10 pct or more strain. The cell size appears to be determined by the spacing of the largest particles and is about five times smaller than that in pure nickel for the same strain. The higher work-hardening rate in TD-Ni compared to nickel is probably due to the more rapid rate of dislocation multiplication in the alloy as a result of dislocation-particle interactions. The Th0,particles inhibit recrystallization and twin growh so that some strengthening may arise from the high density of small annealing twins. THE strengthening of materials due to the presence of a dispersed second phase has been the subject of considerable experimental and theoretical investigation in recent years. One of the newest dispersion-strengthened alloys to be developed is TD-Ni,1 a system of approximately 2 vol pct thoria (ThO2) dispersed in a matrix of commercially pure nickel. This material is fabricated by powder-metallurgical techniques and offers high-temperature stability and useful mechanical properties virtually to the melting point of the base metal. While the mechanical properties of this system have been investigated,2,3 there have been no reports in the literature concerning the microstruc-ture of TD-Ni and its correlation to mechanical properties. This paper describes a transmission electron microscopy investigation of the micro-structure of TD-Ni together with its mechanical properties. The results are compared with the structure and properties of pure nickel.

Jan 1, 1964

By W. L. Zeigler

THE tailing from the gravity concentration plant of the Hecla Mining Co., Gem, Idaho, was former-ly loaded into railroad cars to be used for ballast, highway surfacing material, or concrete work, or dis-posed of by an aerial tramway, which dumped it into another gulch. The tailing averages about 1.2 per cent lead and 0.8 oz. silver to the ton. Further treatment for the recovery of the valuable metals had been investigat-ed several times with results that did not warrant the construction of a retreatment plant; but early in 1925 experimental work was again started with small tests, and later with a 10 tons per day flotation test plant. This showed that the tailing could be ground and treat-ed by flotation at a profit. It was decided to make the new flotation plant an addition to, rather than incor-porate it in the old concentrator, the original capacity of which had been increased many times, the present arrangement being by no means ideal. The old mill buildings were of timber and board contruction, creat-ing more or less fire hazard, so all new construction was made fireproof. Construction work on the new plant was started in the middle of July, 1925, and the plant was placed in operation early in December. The building is of concrete and steel with hollow tile walls, steel sash and corrugated asbestos roofing. The ball-mill floor has for its foundation a cellular reinforced concrete block about 14 ft. deep, extending to cemented river gravel, and the cells filled with tailing to give weight to the block. Overhead, built into the steel frame, is a 5-ton hand-operated traveling crane. With both ball-mills running fully loaded, there is not the slightest trace of vibra-tion in the foundation or building. The flotation floor is of reinforced concrete beam construction and spans Canyon Creek. Adjustable plunger feeders are arranged under the the tailing-bin, which feed by gravity to a 14-in. eleva-tor, discharging to a short 18-in. conveyor. From the conveyor the tailing is discharged into a dividing hop-per, from which point the plant is arranged in three separate units. Each unit consists of a ball-mill in closed circuit with a classifier, and an 8-cell flotation machine and has an approximate capacity of 300 tons per 24 hours.

Jan 8, 1927

By John L. Walter

A sintered compact of iron containing 0.007 vol fraction of glass , prepared 6). powder rnetullurgtcal lechniques, was rolled lo foil, 0.001 in. /hick. The foil sullrples were anneuled a1 650° to 850°C in hydrogen. Pri,narj recryslullization prodtnced large grains which Lc3ere highly elongnled in the rolling direclion und which had an unusual prgferred orientation. The glass parlicles assumed a stringerlike dispersiorz on working; llie slrinyers were parallel lo the rolling direction and to the long axis of the grains. The same unusual grain structure, preferred orientation, and stringerlike dispersion of purticles are found in heal-ily rolled and annealed foil of tungsten which has heen doped wilh small amounts of aluminum, silicon, and polassiutvt. Both the proper dispersion of the particles and severe working (reductions in excess of 98 pct) are necessary to produce the elongzcted grain structure. RECENTLY, the author reported on the origin of the elongated or "nonsag" grain structure in tungsten foil which was doped with aluminum, silicon, and potassium.' It was observed that particles, identified as mullite (Al6Si2Ol3), were present in the doped ingot (as sintered) and at all stages of processing from ingot to sheet or wire. It was shown that the particles, being plastic at tungsten working temperatures (up to 1550"C), underwent a "stringing out" parallel to the working di-direction. It was concluded that these strings of particles were responsible for the formation of the highly elongated interlocking grains observed in doped tungsten wire or sheet. To give further credence to this explanation of a long-observed but not understood phenomenon, it was decided to design a new system, one which was analogous to the doped-tungsten system. Thus, a bcc metal, iron, was chosen to be doped with glass which would be plastic at reasonable working temperatures for iron. The glass chosen was a #0080 Corning lime glass which melts at about 810°C. This is approximately the same fraction of the melting point of iron (0.6) as the melting temperature of mullite is of tungsten. It will be shown that all the observed unusual features of the doped tungsten are duplicated in the glass. doped iron, even to the preferred orientation of the grains in the recrystallized sheet. In the tungsten sheet the preferred orientation consists of two components, (1i3)(691) and (013)(362), neither of which has been observed as a component in textures of primary recrystallized bcc metals. EXPERIMENTAL PROCEDURE The glass, in the form of fine powder, was added to high-purity electrolytic iron powder and mixed dry. The particular composition chosen was 0.007 vol fraction of glass. After mixing, the powder was mechanically pressed to a disk 0.5 in. diam and 0.15 in. thick at a pressure of 5000 psi. The pellet was sintered, in pure dry hydrogen, for 2 hr at 8 50°C. The sintered pellet was then heated to 750°C and rolled to 50 pct reduction of thickness in two passes, with reheating between passes. The rolling temperature was then reduced to 600°C and the slab was rolled to a thickness of 0.050 in. Rolling to 0.010 in. was accomplished in several passes at 300°C. Final reductions to 0.003 and 0.001 in. were taken at room temperature. This rolling temperature schedule was similar, in terms of the fraction of the melting point, to that used in the rolling of the doped tungsten. The total reduction of thickness was in excess of 99 pct. Samples of the rolled foil were lightly electro-polished and annealed for 1 to 6 hr at temperatures of 650" to 85O°C in hydrogen. Samples for transmission electron microscopy were thinned on a Disa Electropol using AC-1 electrolyte.

Jan 1, 1968

By J. Stuart Warner

The reaction COSO4(c)?CoO(c) + So3(g)was investigated from 950° to 1170OK by two different methods. The sulfate was decomposed in a previously evacuated space and Pso3 calculated from the measured total pressure on the assumption that Pso2 = 2P02. The sulfate was also decomposed under conditions of controlled oxygen pressure. The difference in the results obtained by these experimental techniques is attributed to the effects of thermal diffusion. The standard free energy change for the reaction is given by ?F° = 66,292 + 17.273T log T — 102.57 T (±300 cal/mole). It was found by DTA and X-ray diffraction studies that CoS04 undergoes a transformation at 617°± 4°C. THE metal sulfates may decompose directly to the oxide or pass through one or more intermediate basic sulfates. Provided the oxidation state of the cation does not change in the course of the reaction, the decompositions may be described in general as follows: One of the major objectives of this work was to determine the validity of Eq. [3] as much of the existing sulfate data has been calculated from decomposition pressures by Eq. [5]. The type of apparatus generally used for these measurements consists of a reaction vessel at high temperature which communicates with a manometer at room temperature. A temperature gradient is thus imposed on the gas phase causing thermal diffusion which brings about a partial separation of the different gaseous species present in an initially uniform mixture. The basic theory and experimental facts associated with this phenomenon are summarized elsewhere1 and it will suffice to state here that the heavier gaseous species diffuses down the temperature gradient. Since thermal diffusion destroys the homogeneity of the gas phase, it is not necessarily true that Pso2 = 2Po2 in any particular volume element of the gas phase even though there are twice as many molecules of SO, as of 0, in the gas phase considered as a whole. Under these conditions, the decomposing sulfate gives off SO, which dissociates to SO, and 0, and all three species are distributed throughout the system by thermal diffusion. However, the sulfate will continue to dissociate until the equilibrium value of PSo3 is established on the hot zone. Thermal diffusion may distribute SO2 and O2 throughout the gas phase in any way so long as Eq. [2b] is satisfied in the hot zone; i.e. Pso2(Po2)1/2=K3pso3. When a steady state is reached, we can characterize Pso2 in that

Jan 1, 1962

By R. G. McQueen, E. G. Zukas

THE production of isotropic fine-grained ingot iron would be most useful since physical measurements associated with the elastic properties of iron are influenced by the size and orientation of the individual grains. This can be accomplished at present for small samples by established metallurgical procedures, but for large samples (in excess of 2 in. diam by 1 in. thick) it is virtually impossible to produce reasonably small uniform grains with random orientation. Such pieces can, however, be produced by impulsive loading followed by a suitable recrystallization treatment. The shock loading system employed is diagrammed in Fig. l. Here the 3/8-in. iron plate is accelerated by the plane-wave initiated high explosive charge through a 1 5/8-in. air space. Collision of this plate and the specimen of interest generates a shock wave in excess of 300 kbars which passes through the specimen. For this type of work it is not necessary to use machined parts: for example, the ingot iron pieces are saw cut from the billet so that they can be inserted in short sections of iron pipe. The recovered specimens are less distorted, however, if the air gap between the iron sample and pipe is filled with Woods metal. The dimensional changes resulting from this type of loading technique are minor, usually less than a 10 pct reduction in thickness. Compressive yield

Jan 1, 1962

By W. T. Weller

In Part I, a study of pressure build-up curves calculated for conditions under which both oil and gas flow led to the conclusion that the presence of a dispersed free gas phase in an oil reservoir must be taken into consideration to estimate accurately average reservoir pressure and permeability from build-up curves. Familiar methods based on the assumption of no free gas can be extended to the two-phase case by using total compressibility and mobility in place of single-fluid compressibility and mobility. These methods give correct values for average pressure and permeability when gas saturation is small. Errors become larger as the gas saturation increases. However, for the use to which the results will be put, the methods are satisfactory for reservoir engineering purposes. An improved method of calculating the performance of depletion-type reservoirs is presented in Part 2. Because the mathematical relationships describing simultaneous flow of oil and gas are quite involved. simplifying assumptions are made to provide means of obtaining approximate solutions of reasonable accuracy. One such approximate method now in use is the constant-GOR solution. It involves the assumption that at any instant, the ratio of total gas flow rate (both free and disolved) to oil flow rate is the same at all points in the reservoir. The approach is not applicable unless the free gar saturation in the reservoir is everywhere greater than the critical gas saturation. This paper presents a modification which, by avoiding the constant-GOR assumption, makes the method applicable to all reservoir conditions, and so far appears to be more accurate than the constant-GOR solution and to he comparable in required compuctation time. PART I— BUILD-UP CURVE ANALYSIS INTRODUCTION Pressure build-up characteristics of shut-in wells have been used for many years by engineers to evaluate average reservoir pressure, effective permeability thickness of the pay section, effectiveness of well completion (skin effect) and reservoir size. A number of methods of analysis have appeared from time to time."" Without exception, these methods are based on the assumption that the reservoir contains but one fluid of constant small compressibility and constant mobility. It has been suggesteda" hat these single-fluid methods may be applied to data from reservoirs containing both oil and gas by substitution of some effective total properties of the multiphase system in place of the corresponding single-phase properties. The present investigation was undertaken primarily to evaluate this approach. METHOD A number of theoretical build-up curves were calculated for conditions of two-phase flow, under the assumption of certain reservoir and fluid properties, and were analyzed by single-fluid methods with appropriate total compressibility and total mobility values for the corresponding single-fluid properties. Results of the analyses were compared with the assumed conditions. The theoretical build-up curves were completed by procedures similar to those of West, Garvin and Sheldon." Since these calculations require a considerable amount of computer time, an attempt was made to derive an approximate calculation method. The attempt was unsuccessful for calculating build-up curves, but the effort did result in a new approximate method of calculating the performance of solution gas drive reservoirs, which appears to be an improvement over the constant-GOR method" used previously (see Part 2). The West, Garvin and Sheldon calculations involved the following assumptions: (1) the reservoir is circular and completely bounded, with a completely penetrating well at its center; (2) the porous medium is uniform and iso-tropic, with a constant water saturation at all points; (3) gravity effects can be neglected; (4) compressibility of rock and water can be neglected; (5) the composition and equilibrium are constant for oil and gas; (6) the same pressure exists in both the oil phase and the gas phase; and (7) no afterproduction occurs, i.e., the well is shut in at the sand face for build-up. These assumptions make it possible to describe two-phase flow of oil and gas by the partial differential equations:

Jan 1, 1967

By H. H. Reamer, B. H. Sage

The formation volume and the relative volume of the liquid Phase of mixtures of Condensate and gas from five different parts of a field in the Louisiana area have been established experimentally. These studies included gas-condensate ratios as high as 25.000 cu ft/bbl at pressures up to 5,000 psi. The gravities of the tank condensates were between 53.9° and 63.9° API. The compositions of the condensate and gas samples inves-ligated are presented in tabular form. The formation volume. the relative volume of the liquid phase. and the specific volume of the mixtures are available. A rough correlation of the formation volume as a function of pressure. temperature, and gas-condensate ratio has been presented. This correlation i-considered applicable only to the range of conditions covered in this investigation for systems of similar nature and com-position. INTRODUCTION Often a knowledge of the influence of temperature. Pres sure, and relative quantities of condensate and gas upon the volumetric behavior of fluid*. from a given field has been employed in estimating the Conditions existing in the reservoir. The early work of Beecher and Parkhurst' and the more rrcent Studies of the Dominguez' and San Joaqnin Valley Field;: are examples of experimental studies of this character. Correlation of the volumetric behavior of naturally occurring hydrocarbon mixtures has Proved To be feasible' . at low gas-conden-sate ratios-; for fluids*. from a single geographic area. Progres 5 is being made in the Prediction of the volumetric behavior of distillate systems at high gas-condensate ratios and pressure.. However. the estimation of the retrograde". ' dew-point pressure still remains uncertain and probably can best be established by experiment. For this reason it appears of interest to make available experimental information about the volumetric behavior of mixtures of condensate and gas from five different part.; of a single field. This material shows a rough similarity to data for mixtures of condensate and gas from San Joaqnin ' Valley Fields. In the present paper. 110 attempt has been made to coordinate the available information on tbe volumetric behavior of fluids from condensate fields. It appears hopeful that progress can be realized by the utilization of recently developed equa-tions of state.!' However. the primary problem in any such correlation is the proper identification of the components and constituents of naturally occuring systems. Additional experimental information may be required to permit the determination of the values of the constants of the equation of state for References given at end of paper. Manuscriptt received in the office of the Petroleum Branch June 11. 1951. *For present purposes low gas- condensate ratios will he considered as those below 3,000 cu ft/bbl, and the region of high gas-condensate ratio will be limited to compositions containing more than 5,000 cu ft of pas per bbl of condensate. Mixtures Containing between 3,000 and 5.000 CII ft OF gas per bbl will be considered of intermediate gas-condensate ratio.

Jan 1, 1952

By B. M. Larsen, W. E. Shenk, T. E. Brower

Shortly after our previous paper on this subject was printed1 we located a source of uncertainty in the results arising from the unexpected fact that hydrogen slowly reduces silica at 1100" C. in presence of iron, even when the iron nowhere touches the silica, although in absence of iron it does not do so. This difficulty has been completely obviated by the use of a small high-frequency furnace, which enables us to heat the specimen for analysis without raising the temperature of the silica vessel to a point at which any appreciable reduction of the silica glass occurs. We now describe this modification of procedure, and present some typical results obtained with it. For any given specimen of steel, the results are entirely definite and reproducible, but their precise significance is still open to some question, as indeed is true of all methods of oxygen determination SO far developed. Further elucidation of this question is to be expected from the cooperative comparison of the several methods now under way under the auspices of the Bureau of Standards at the instance of the Iron and Steel Division of the A.I.M.E. Apparatus The final form of apparatus we have used is identical with that described and illustrated in our previous paper, except for the substitution for the Globar furnace of a small high-frequency furnace actuated by a vacuum tube oscillator2 0f about 1.5 kw. capacity, and for a slight modification of the containing vessel. This transparent silica vessel is illustrated in Fig. 1 of this paper. Its enlarged portion is about 5 cm. in diameter and 13 cm. long. The silica tube for inlet of hydrogen is fused into this bulb and ends beneath the metal "bucket" holding the steel sample. This sample is in the form of fine millings. The "bucket" is suspended by a platinum wire from the cap of Pyrex glass. The high-frequency

Jan 1, 1934

By E. A. Smith, E. R. Parker

METALLURGISTS and engineers have always been interested in the mechanism of high-speed deformation because metals are rapidly deformed in various applications and manufacturing processes. The deformation of metals by impact loads has recently engaged the attention of a number of investigators. Many of their results have not been disclosed but some of the published investigations1-8 have shown that the tensile strength, yield strength and elongation generally increase with increasing strain rate. The investigation reported herein is an attempt to determine the reason for this increase in strength and elongation. Single-crystal copper specimens were broken in tension at impact velocities up to 100 ft. per sec. The distribution of slip bands in the fractured crystals was found to depend upon the strain rate. In the bars broken at high speeds, the slip bands appear to be more numerous. This might account for the higher strength as well as the greater elongation. EXPERIMENTAL PROCEDURE Single crystals of copper (approximately 99.98 per cent) were made in graphite molds by the conventional method of lowering the mold out of the hot zone of a hydrogen furnace at a rate of one inch per hour. Solidification progressed from the bottom upward, forming a single crystal. The crystals were about 0.30 in. in diameter and 4 in. long. They were made into test bars by sliding threaded steel bushings over each end of a crystal and then flowing silver solder between the crystal and the bushing. The inside diameter of the bushings was slightly greater than the diameter of the crystals, to allow space for the silver solder. The bushings were placed so that the gauge length of the crystals was one inch. The assembly is shown in Fig. I, with two views of a fractured crystal. Annealed polycrystalline copper bars of similar shape were machined from solid stock. X-ray measurements were made on all single crystals to determine their orienta¬tions. The results are shown in Fig. 2, where the location of the axis of each specimen is indicated on a standard projection. The bars were broken in a commercial variable-velocity tension im¬pact machine, which has been described in detail elsewhere.7,8 The stress and strain were recorded by means of wire strain gauges and a special commercial oscillo-raph, also described in detail elsewhere.9,10 The equipment and method can be briefly described as follows. The impact machine consists of a motor-driven flywheel containing a two-pronged hammer. This hammer is held retracted in the flywheel

Jan 1, 1944

By Akinobu Kasami, Keiji Maeda, Makoto Naito, Masaharu Toyama

Gap electroluminescent diodes have been prepared by the vapor phase diffusion of zinc into n-Gap crystals which were grown from a gallium solution (10 wt pct Gap) doped with tellurium and Ga203. A marked improvement in the efficiency of the red electrolumines -cence has been achieved by heat treatment after diffusion. External quantum efficiencies of diodes annealed under optimum conditions are 0.2 to 0.6 pct at room temperature, or about 200 times higher than the efficiencies of diodes quenched after diffusion. The optimum dopant concentrations in the gallium melt from which the crystals were grown are 3to6 x at. pct Te and 4 to 8 x 10-2 mol pct Ga203. The efficient diodes are characterized by linearly graded junctions with an i-layer 0.1 to 0.2u thick. Annealing increases the emission intensity by a factor of 20 to 50 and decreases the current density to 1/3 to 1/8 that of quenched diodes at a given bias. The decrease in current is attributed to an annihilation of deep recombination centers in the depletion layer. The increase in emission intensity is interpreted in terms of an increase in lifetime of minority carriers and an increase in the relative intensity of red-to-infrared emission. The dependence of these quantities on the tellurium and oxygen doping levels is also discussed. A number of studies have been made of the red light emission from for ward-biased Gap diodes.' At room temperature this emission band is centered at 7OOO? with a spectral width of nearly 1000?. Low-tempera-ture photoluminescence indicates that this emission is due to either the radiative annihilation of an exciton bound to a pair of zinc and oxygen atoms substituting on nearest neighbor lattice sites2,3 or the radiative recombination of an electron bound to this Zn-O pair with a hole bound to an isolated zinc shallow acceptor.3 An emission band is also observed with a spectral peak at 9800?. This infrared emission has been shown to be due to the recombination of an electron trapped at an isolated oxygen deep donor with a hole trapped at an isolated zinc acceptor.4 The red emission from Gap diodes is fairly efficient at room temperature because the nearest neighbor Zn-0 pair forms a deep electron trap at 0.3 to 0.4 ev below the edge of the conduction band.2'4 In diodes grown by liquid epitaxy an external quantum efficiency of 2.1 x 10-2 (photon/electron) has been attained by heat treatment at relatively low temperatures.5 This heat treatment was found to increase the efficiency by a factor of 3 to 6. However, no detailed studies have-been reported on the effects of heat treatment. We can only cite Onton and Lorenz's work6 on the change ; in the relative intensity of red-to-infrared emission. Heat treatment has also been tried on junctions built in during growth, but contrary to expectations the efficiency decreased. In-diffusion is a simple and controllable method of fabricating p-n junctions. For Gap, zinc is generally used to form a p-type layer on n-type crystals. The emission efficiencies of in-diffused diodes are, however, extremely low in comparison with liquid epitaxial diodes.' Although efficiencies as high as 2 x 1O-3 have been reported, values from 10-6 to 10-4 are generally obtained by typical diffusion techniques. Out-diffused diodes are known to be a little more efficient than in-diffused diodes. Nevertheless, the quantum efficiency is at most 7 x 10- 3 and ordinarily of the order of 10-4.8 NO results have been reported on heat treatment of either in-diffused or out-diffused diodes. This paper reports a marked improvement in the efficiency of the red emission observed for in-dif-fused diodes as a result of heat treatment after diffusion. The method described reproducibly yields diodes with external quantum efficiencies of 2 to 6 x 10-3. The observed dependence of efficiency on annealing time and on doping level will be discussed in terms of the lifetime of minority carriers and the formation of Zn-O complex pairs. EXPERIMENTAL A) Diode Fabrication. The n-Gap crystals used in this study were grown from a saturated gallium solution by a slow cooling method.8 The Gap content in the gallium melt was fixed to 10 wt pct corresponding to a growth temperature of about 1100 Tellurium was chosen as the n-type dopant and added to the melt in concentrations ranging from 0.001 to 0.06 at. pct. Oxygen was added in the form of Ga2O3, whose concentration was varied from 0.004 to 0.2 mol pct. The resulting crystals were platelets with well-developed (111) surfaces. Typical electrical properties were Hall mobilities of 130 to 30 sq cm per v-sec and carrier concentrations of 1016 to 10" cm-3 at room temperature. Diodes prepared from crystals with relatively low doping levels, in which u = 130 to 100 sq cm per v-sec and n = 0.6 to 6 x 1017 Cm-3, were examined in detail. The p-n junctions were produced in these n-Gap crystals by the diffusion of zinc from the vapor phase by the following procedure. The platelets were carefully lapped on both sides to a thickness of 150 to 200 u while maintaining the (111) orientation. After being etched in hot aqua regia, the crystals together with the zinc were sealed in an evacuated 12 mm ID quartz ampoule 20 cm long. The crystals and the zinc were then separated from each other at opposite ends

Jan 1, 1970

By J. G. Mravec

The SO-called gas-tube method as developed by Hare, Peterson and Soler for determining the type and content of gases in molten steel is particularly adapted for determining the hydrogen content in molten steel. The development of this method has been quite completely discussed in a paper published by these co-workers in 1937.' The purpose of this paper, therefore, is to familiarize with this method those who arc not well acquainted with it. The principle of the gas-tube method is as fol1ows: One end of an evacuated gas tube is sealed with a very thin copper disk. when this end of the tube is immersed in a test spoonful of molten steel, the copper disk melts almost immediately, allowing a portion of the steel to be drawn up into the evacuated space. Any dissolved gases, and those produced by reactions between the components of the steel during freezing, are liberated into the unfilled portion of the sampling tube. A blob of steel that forms on the immersed end of the tube after the sample is drawn up seals up the end, making it airtight again. The evolved gases are subsequently drawn out of the gas tube through a suitable valve and analyzed by means of an Orsat apparatus. The volume of the sampling tube is sufficiently large so that a pressure considerably below atmospheric is produced after the gas evolution. The low pressure is necessary to effect a nearly complete removal of gases from the steel. Construction oF Sampling Tube The sampling gas-tube apparatus is illustrated in Fig. I. Seamless S.A.E. tubing used for section A is first cut into 7-ft. lengths. Through cxperiencc it was found necessary to use two sizes of tubing for this part, "is-in. and 3/4-in., respectively. The smaller tubing is generally used on the hotter or lower carbon steels. If the inside wall of the tube A is coated with grease or oil, it should be burned out before being machined as follows: One end is machined on the inside diameter to a depth of 34 in., so as to form a seat for a 7/8-in copper disk, which is stamped out from 0.005 to 0.007-in. thick copper sheet. The other end is machined on the outside diameter to a diameter of 1 5/16 in., to take a small reservoir or trap member I?. About 4 in. below the same end, a 1/2-in. hole is drilled to receive the 1/2-in. copper tubing leading to the large reservoir C. The inside of tube A is then thoroughly cleaned with a round wire brush, such as is generally used to clean out shotgun barrels. It is very important that the surface be absolutely free of rust or any nonmetallic coating. Next, the thin copper disk is soldered in place with low-melting silver solder.

Jan 1, 1945

By Clyde Williams

IN this war as in no former one, the use of metals has been the major factor governing success. For building new plants, new transport facilities whether by land, sea, or air, for our mechanized army, and for nearly all weapons, iron and steel has provided the basic material. Being the world leader in iron and steel production in peacetime, we soon adapted plants to production for war. Starting with a production of 66,000,000 tons of steel ingots in 1940 from a rated capacity of 80,000,000 tons which only could be reached by straining every productive device available, our industry expanded to 86,000,000 tons in 1942, and ultimately to 96,000,000 tons. To do so required expansion of every unit operation including mining, rail and water transportation, blast-furnace and steelmaking facilities, and rolling mills. New plants not only had to be built in record time but more output for each operation was essential. This performance required skillful operation and engineering techniques and also a better understanding of the physics and chemistry underlying such complex operations as the working of a big blast furnace. A vastly increased pig iron production made possible the great output of steel by an industry that had depended on scrap for its basic raw material even though sufficient scrap was unavailable. This was done by conversion of pig iron in the Bessemer either into steel or into a low-carbon product that was subsequently used in place of scrap in the open¬hearth steel furnace. Furthermore, by duplexing from the open-hearth to the electric furnace, and the construction of many new electric furnaces, our output of electric-furnace alloy steel was greatly increased. Moreover, techniques were developed by which alloy steel could be made in the open hearth with the result that our production of alloy steel reached the fantastic figure of 15,000,000 tons a year.

Jan 1, 1945

By Albert J. Phillips

As EARLY AS 1824, Haidinger1 described crystals of native copper that were, according to Dana,2 "probably twinned parallel to the octahedral plane and normal to this axis." In 1837, Rose3 very clearly demonstrated that native copper crystals were commonly twinned on the octahedral plane. Lasaulx,4 in 1882, described polysynthetic octahedral twins and stated that enclosed twinning lamellae were observed. Even on crystals formed artificially by electrolysis, twinning was observed as early as 1886, by Brown.5 Many other descriptions of twinning in native copper and in gold and silver are to be found in the literature, and in every case with which we are acquainted the twinning is conformable to the spinel law; i. e., the octahedral plane is both twinning and composition plane. Metallurgists have long been familiar with the straight-sided bars or bands that commonly occur within the irregularly outlined grains of metallic crystalline aggregates. They are certainly found in nearly all metals of the face-centered cubic type after cold working and annealing. If a specimen showing these bands is rotated, keeping the angle of incidence of the illuminating beam constant, they usually exchange color contrast periodically with their respective matrix crystals. Also slip lines, when produced in these specimens, nearly always show a change in direction upon passing through the bands, giving rise to the "stairway" effect often illustrated in metallurgical textbooks. Apparently the only quantitative observations on bands of this sort were made by Osmond and Cartaud6 on austenitic steel. They selected,

Jan 1, 1928

By J. Laskowski

J. Laskowski (Associate Professor, Dept, of Mineral Processing and Coal Preparation, Silesian University of Technology, Gliwice, Poland) -Referring to the papers by J. A. L. Campbell and S. C. Sun, I must say that I am very pleased to see that type of work, because it is the only way to progress towards an understanding of flotation mechanisms. All those interested in the science of the surface chemistry of coals would find these papers a valuable contribution to the literature. In their extensive research, the authors attempt to synthesize their findings into a theory of coal flotation. To do this, the zeta potential of bituminous coals and their lithotypes, as well as that of an anthracite coal, was measured and H+ and OH- ions were found to be potential determining ions. The measured ZPC of bituminous coals was at a pH range from 3.5 to 4.6 and for the anthracites between 2.0 and 4.5. The authors have pointed out that since the hydrophobicity is pH-controlled, the flotation mechanism should also be. The Campbell and Sun papers confirm a good many of the conclusions on surface properties of coals reported in recent years. It is noteworthy to point out that the ZPC found in the paper on bituminous coals was approximately pH 4, similar to the ZPC for the anthracite coal. In fact, we have been investigating different coals from low to high ranks. Thus, the plot of the pH for ZPC against rank could be derived and this curve-an electrocapillary one-indicates a pH near which the hydrophobicity of the coal surface should be at maximum. This can be proved by so-called salt flotation, which, in a sense, can be treated as method of surface charge measurement. It is obvious that the salt flotation experiment is possible when the native hydrophobicity of the mineral surface is high, e.g., when the solid surface does not have an orienting influence on an adjacent water layer and the hydration layers are controlled by the electrical double-layer potential. The addition of electrolyte or a change of pH which decreases the thickness of the stabilizing double-layer "opens up" the hydrophobic surface micro-area mosaic. Thereby the surface becomes hydrophobic and particles become floatable. The orienting influence of surface on hydration layer increases even after very slight oxidation and flotation is affected by it. It seems that such an explanation agrees reasonably well with those of Campbell and Sun.

Jan 1, 1972