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By P. R. Kalischer

In the production of alloys by powder metallurgical processes it is often necessary or desirable to include one or more cornponents that tend to form very stable oxides. Included in this group of metals are aluminum, manganese, magnesium, silicon, and a few others. In many cases it is not necessary for the sintered compact to have full density and the other physical characteristics of a cast alloy and in that event no undue precautions need be taken. If, however, it is required that the sintered part be entirely homogeneous, and have maximum density and physical properties, some method must be found to reduce the surface films of oxide, which are always present on the metals, and for the metals mentioned above this is always extremely difficult, if not impossible. since the production of high-density alloys is of particular interest to powder metallurgists, some experiments were undertaken to devise methods of reducing the refractory oxides. For this work, alloys of iron, nickel, and aluminum were chosen because aluminum oxide is one of the most stable oxides and because these alloys in the right compositions form excellent permanent magnets. All of the pertinent properties of the magnets could be accurately and delicately measured by density measuremerits and magnetic tests of sufficient scope to give a complete demagnetization curve. From such a curve the maximum coercive force, residual magnetism, and energy products could be obtained and compared with the same properties for a cast material. Any lack of homogeneity, density, or solid diffusion would be immediately apparent as a decrease in the magnetic properties. Nature and Removal of Surface Barriers The early work of the present investigation was based upon published processes.* In the published information it was claimed that by intimately mixing iron, nickel, and iron-aluminum alloy (50 Per cent Fe, So Per cent Al) powders, compressing such a mixture into the desired shape and size, and then sintering (heating to a temperature below the melting point of the component metals) in hydrogen at 1200°C. or higher, a sound, homogeneous article could be made having the desired physical size, shape, and strength, and good magnetic characteristics. However. this early work showed clearly that something in the powder compress was inhibiting diffusion and the process was almost entirely unworkable. In the initial phase of the investigation samples of iron powder, nickel powder, and iron-aluminum alloy powder were pressed into separate bars and sintered in hydrogen. Both the iron and nickel powders sintered

Jan 1, 1941

By Earl S. Greiner, Eric R. Jette

The constitution of the iron-silicon alloys containing from 14 to 33.4 weight per cent silicon has been studied by a number of investigators, whose results have been reviewed in a monograph published by the Engineering Foundation1. In these previous researches, the solubility of silicon in iron was determined by thermal, microscopic or magnetic methods and the compound Fe3Si2 was reported to be stable at temperatures from 0 to approximately 1030' C. This paper describes the results of an X-ray investigation of the solubility of silicon in iron and gives data which prove that the Fe3Si2 phase is unstable below 825" C. In order to obtain the present results on the solubility of silicon in iron, the authors have utilized the lattice constants of the alpha-phase iron-silicon alloys given in a previous publication2, and also some additional data which will subsequently be described. Materials and Methods The alloys used in this investigation are listed in Table 1. They were prepared in 30 or 50-gram ingots by melting specially purified silicon and electrolytic or carbonyl iron in alundum crucibles under a pressure of less than 1 mm. of mercury. The purity of the silicon, electrolytic and carbonyl irons has been given by the authors in previous publications2, 5. The ingots were homogenized in vacuo at approximately 1000" C. for at least 96 hr. and then slowly cooled. The homogenized specimens were ground to powder in a hardened steel mortar. This powder was passed through a 150 or 200-mesh screen and sealed in evacuated quartz, Jena or Pyrex glass tubes and heat-treated as noted in the various tables. Specimens 23A, 24B, 33 and 35 and the specimens heated for one month at 700" C. were quenched by quickly removing the tubes from a horizontal tubular furnace and dropping them into water. The other specimens were quenched by means of a drop-quenching device, which has been described previously3.

Jan 1, 1937

By J. W. Martin, L. K. Singhal

Grain boundary M23CB precipitates have been shown to form by a process involving the migration of an austenite grain boundary, and each plate of precipitate is in parallel orientation with one of the austenite grains constituting the boundary. The carbide distribution and morphology appear to be sensitive to grain boundary mis orientation. Some areas of austenite grain bowzdary permit the development of an array of M,C, particles, some of which are in parallel orientation with one grain and some with the other grain constituting the boundary. Massive carbide at grain boundary triple points is also shown to be in parallel orientation with one constituent grain. PREFERENTIAL precipitation during aging of carbides of the type (Fe,Cr)23C6, usually written MZ3C6, in grain boundaries of quenched austenitic stainless steels has been widely recognized. M23C6 has a complex cubic crystal structure' which contains ninety-two metal atoms and twenty-four carbon atoms per unit cell. Less energy is involved in forming grain boundary precipitates than in the formation of intragranular precipitates, and the process is further enhanced by the accelerated diffusion rates in the boundaries and by the probability of segregation of chromium atoms and carbon atoms to the region of the grain boundaries during prior solution heat treatment in order to reduce lattice strain. Early electron micrographic studies2, 3 involving either extraction replica or normal replica techniques established the geometric or dendritic form of the carbide particles, although this approach led to dis- pute as to whether the particles grew within the plane of the boundary or grew into the matrix.4-6 More recent thin-foil studies' have claimed to identify a discontinuous precipitation process involving M23C6 at grain boundaries, and the object of the present work was to attempt to clarify the situation using modern electron micrographic and diffraction techniques. 1) EXPERIMENTAL 1.1) Material. The steel selected for this work had a base composition of 24 pct Ni-25 pct Cr-3 pct Ti and contained about 0.04 pct C. The full analysis if given in Table I. This alloy was in the form of strip which had been hot- and cold-rolled to a thickness of 0.6 mm. 1.2) Heat Treatment. Specimens 4 cm long by 1 cm wide were solution-heat-treated for 3 hr in argon at 1150°C, followed by water-quenching. Specimens were subsequently aged in vacuo at 750°C for periods up to 500 hr. 1.3) Preparation of Electron Microscope Specimens. The heat-treated strips were cut bv spark machining into discs of 3 mm diam and 0.6 mm thickness. he-discs were dished on both sides using an electrolytic jet of 15 pct HCl electrolyte at 80 v. Final electro-polishing of the discs was carried out using 10 pct perchloric acid, 20 pct glycerol, and 70 pct ethanol at 10 v. The current density was kept below 300 ma. cm"2 by cooling the electrolyte to 0" to 5°C. As soon as a small hole appeared, the electropolishing was stopped and the specimen was quickly washed with ethanol.

Jan 1, 1969

By L. W. Davies

ONE of the most important applications of the zone-melting process of Pfann1 concerns the refining of materials with respect to impurities whose distribution coefficient k differs from unity. The repeated passage of molten zones along an ingot concentrates the impurities for which k < 1, for example, towards the end to which the zones move. It is desirable to know the ultimate distribution of impurity after the passage of an infinite number of zones of constant length; this is also the distribution which is unchanged by the passage of a further molten zone.

Jan 1, 1959

By G. Bhat, J. F. Libsch

A STUDY of the kinetics of embrittlement in engineering alloy steels during tempering has indicated that the presence of alloying elements may define two distinct regions of embrittlement: 1) at 800° to 1000 °F, termed low temperature embrittle-ment, and 2) in the temperature range 1150 ° to 1250°F, termed high temperature embrittlement.13 It has been suggested that embrittlement in each region may be due to a different mechanism. At intermediate temperatures and extended times the course of embrittlement may be influenced by the superposition of the embrittlement occurring in the two regions. Furthermore, low temperature embrittlement has been known to decrease as the temperature is raised slightly above the maximum embrittlement range.&apos; Jaffe and BuffumV ave presented data for a Ni-Cr steel illustrating the removal of the em-brittlement occurring at 932°F by reheating to 1250°F for an hour. Their data further shows that embrittlement proceeds continuously with increased time at 1250°F, becoming pronounced at long times. They interpreted this behavior as a retrogression phenomenon involving the solution of the small nuclei of precipitate formed at 932°F as the temperature was increased, and reprecipitation of larger nuclei stable at 1250°F, with the reoccurrence of embrittlement. It appears desirable to reconsider this explanation in the light of the two regions of embrittlement proposed by the authors1 for some alloy steels. In addition, it appears desirable to determine any influence of a preconditioning treatment in each temperature range upon subsequent development of low and high temperature embrittlement. It is thus the object of this investigation to study the characteristics of the two modes of embrittlement proposed in a commercial Ni-Cr alloy steel (AISI 3140). Experimental Details Material—The material used in this investigation was commercial AISI 3140 steel bar stock, received as % in. hot-rolled rounds. The steel analysis was as follows (in percentages): C, 0.39; Mn, 0.79; Si, 0.30; S, 0.028; P, 0.015; Ni, 1.26; and Cr, 0.77. Material Processing and Heat Treatment—The bar stock was first ground to 0.430 in. squares and cut into specimens 23/4 in. long. These specimens were austenitized at 1650°F for 1 hr and oil

Jan 1, 1958

By Harmon F. Fisher

In the course of a comprehensive investigation for the development of the electrical process for the dehydration of oil-field emulsions, the writer has had an unusual opportunity to direct and execute a number of related, parallel studies concerning crude oil emulsions and extending over a period of nearly six years. Among these was an investigation utilizing the microscope for studying both the general characteristics of crude oil emulsions, the nature of their electrical charge and the action of an alternating current field in causing coalescence of the finely dispersed, more or less permanently suspended, emulsion particles into larger droplets of such mass that subsequent dehydration would follow by the ordinary process of settling, further agglomeration of the water droplets and, finally, separation into commercially dry, pipe line oil and a clean water discharge. It is not the purpose of this paper to enter into a detailed discussion of the highly specialized subject of microscope technique, nor into a theoretical discussion concerning the origin of the electrical charge on the emulsion particle or concerning the mechanism of the electrical phenomena occurring during the electrical treatment of oil-field emulsions. In a short paper of this character one can hope to touch on only a very limited discussion of the theoretical aspects of crude oil emulsions. The subject of emulsions and colloids is comprised in a comparatively young science in which, however, very rapid progress is being made and consequently it is undergoing many changes; a tentative conclusion valid today may be overthrown tomorrow. Nor would it be a simple science even if it were no longer undergoing this rapid progress; a thorough study of emulsions is based upon a knowledge of such fundamental subjects as molecular structure, ionization and other electrical phenomena, surface chemistry, surface and interfacial tension phenomena, viscosity and other factors too numerous to discuss here and the fundamental theories of which are still undergoing more or less change. Therefore this paper will confine itself largely to a generally descriptive discussion, a sufficiently detailed outline of the microscope technique and a brief comment on

Jan 1, 1931

By D. Krammer, E. S. Machlin

The effect of a brior high-temperature creep strain on the low-temperature ductility of commercially pure nickel has been evaluated. The low-temperature (-196°C) ductility decreases linearly with an increase in prior high-temperature (920°C) creep strain. The effect is experimentally correlated to the formation of inter crystalline cracks and voids during the prior high-temperature creep strain. The magnitude of the effect is also believed to be a function of the notch sensitivity of the material. SEVERAL mechanisms have been presented to explain the process of inter crystalline cracking in metals undergoing high-temperature creep. zenerl has suggested that grain boundary relaxation of shear stresses could build up high stresses at ob- stacles to grain boundary shear and thereby nucleate a crack. Chang and rant&apos; have experimentally demonstrated that cracks do form at obstacles to grain boundary shear such as lines where three grains meet. The role of vacancies in the mechanism of high-temperature inter crystalline cracking has been explored by Machlt with the conclusion that the nu-cleation of voids by vacancy condensation is almost

Jan 1, 1960

By Craig R. Barreft, Oleg D. Sherby

The steady-state creep characteristics of pure polycrystalline copper were studied in the temperature range 400" to 950°C and in the stress range 400 to 7000 psi. Tests were conducted in dry deoxidized hydrogen and all specimens exhibited high ductility before fracture. Two activation energies for creep were established as a function of temperature. Above about T/T, = 0.65, the activation energy for creep was 48,000 cal per mole whereas between 0.5 and 0.65 T, it was 28,000 cal per mole. The observed temperature dependence of the activation energy for creep follows the same trend as exhibited by the self-diffusion coefficient of copper in copper single crystals and silver in silver single crystals. It is therefore believed that the rate-cmtrolling mechanism in creep of copper in the stress and temperature range studied is diffusion-dependent and is probably associated with a dislocation-climb process. The low activation-energy region is attributed to enhanced volume difFusion from the presence of dislocations which act as short-circuit paths for diffusion. THERE is extensive experimental evidence1,2 that the activation energy for creep, Q,, for pure poly-crystalline metals tested at temperatures above one half the absolute melting temperature (0.5 Tm) is a constant and equal to the activation energy for volume self-diffusion, Qsd This equality is generally interpreted as meaning that creep in this temperature range is controlled by a dislocation-climb process. The existence of high-temperature creep activation energies not equal to the respective self-diffusion values has been suggested both theoretically3"5 and experimentally.6-8 Two examples of apparent nonequality between Q, and Qsd have been reported for the cases of silver7 and copper,&apos; where activation energies for creep much lower than those for self-diffusion persist to rela- tively high temperatures (up to 0.6 T,). These observations suggest that dislocation climb may not be the only important process in the high-temperature deformation of these metals. That dislocation climb does indeed occur relatively slowly in these two metals due to their low stacking-fault energy has been suggested by many investigators.9-10 Although the creep behavior of copper has been studied extensively at low temperatures, the high-temperature activation energy for creep is not well-defined. The data of Feltham and Meakin8 indicated that Q, is temperature-dependent above one half the melting temperature, equaling a value of -30,000 cal per mole at temperatures up to 550°C and increasing to a value of -49,000 cal per mole at 700°C. No data has been reported above 700°C. The value of 49,000 cal per mole is very near the value of Qsd for copper reported by Kuper et al." as 47,100 cal per mole. In view of the lack of high-temperature creep data and the apparent temperature dependence of Q, for copper the present investigation was undertaken to determine the value of Q, over the temperature range of 400" to 950°C. It was hoped that such a study would clearly document the temperature dependence of Q, and yield significant information as to the nature of the rate-controlling creep mechanisms. MATERIALS AND PROCEDURES The material used in this investigation was high-purity OFHC copper. After rolling and recrystal-lization treatments spectrographic and chemical analyses showed only 0.0008 pct Ag, 0.0002 pctCa, 0.0002 pct H2, and 0.002 pct O2 as trace impurities indicating a purity of greater then 99.995 pct. Specimens were machined from cold-rolled sheet and the gage sections polished with 2/0 emery paper prior to annealing treatments. Annealing was done in both vacuum and dry deoxidized hydrogen atmospheres. No variation in creep strength was found as a result of the different annealing atmospheres. The final annealing temperature was either 700°, 800°, or 1000°C depending on the temperature range to be studied. These treatments resulted in average grain diameters of 0.03, 0.4, and 1.0 mm, respectively. The precise mechanical-thermal history of these

Jan 1, 1964

By P. Ramachandraraa, T. R. Anantharaman

THE technique developed by Duwez, Willens and Kle-ment&apos; for rapid solidification of molten alloys in small quantities by ejecting them on to a highly conducting substrate with the aid of a shock wave has come to be known as "liquid quenching" or "splat cooling" in literature and has already been applied to alloys of many binary systems.&apos; The very high cooling rates of the order of l060 to 1080 per sec obtained in this technique and the consequent drastic undercooling of the melt have led to such striking results as formation of new amorphous and crystalline metastable phases and extension of solid-solubility limits in many alloy systems. The cooling rates in these experiments can, however, be neither accurately measured nor effectively controlled and hence the occurrence of either more than one metastable phase or appreciable differences in constitution in splat-cooled alloys of the same composition cannot be ruled out.3 In fact, workers in two laboratories have reported formation of two different cubic metastable phases in liquid-quenched Au-Si alloys containing 17 to 20 at. pct si.4,5 The present note deals with some new and interesting results obtained in a Ag-21 at. pct Ge alloy and a Au-27 at. pct Ge alloy subjected to the liquid-quenching treatment at different cooling rates. Two alloys of nearly the same composition had earlier been rapidly solidified by the standard "gun technique" in the same laboratory and shown to solidify in nonequilibrium structures, viz., an hcp phase (a = 2.987Å;c =4.718Å) in the Ag-Ge system6,7 and both hcp (a = 2.885Å; c = 4.754Å) and tetragonal (a = 11.627A; c = 22.491Å) phases in the Au-Ge system.3 Apart from different substrates (copper and stainless steel), different melt temperatures (50º to 500°C above the liquidus), and different capillary sizes (0.4 to 1.5 mm diam) in the "gun technique", slower cooling rates of the order of l050C per sec were also obtained in the present work by replacing the substrate by water at room temperature in a modification of the technique due to Olsen and Hultgren.8 No attempt was made to measure the cooling rate in any experiment. The products varied from fine powder (>40 pct by wt—200 mesh) obtained by quenching in water to thin flakes and foils (11.0 sq mm to 4.0 sq cm) produced by splat cooling. They were subjected to the Debye-Scherrer method of X-ray examination in each case. In case of the Ag-Ge alloy, in addition to the expected metastable hcp phase,6 a coexistent tetragonal phase (a = 5.093,Å; c = 7.009Å) was detected in some experiments. Eight weak X-ray reflections from this phase could be identified, two of them being the same as reported earlier.7 With increase in the cooling rate, the dominant hcp phase seems to be first accompanied by traces of silver or germanium and then either homogeneous or mixed with traces of this new tetragonal phase. The splat-cooled Au-Ge alloy showed generally the expected hcp and tetragonal phases,3 but sometimes traces of germanium were also present. Further, two new tetragonal phases with the following lattice param ters could be clearly identified in samples quenched

Jan 1, 1970

By Eugene McAuliffe

The management of The Union Pacific Coal Co., which operates a group of coal mines in Southern Wyoming, believes in the value of applied psychology as a productive factor in the work of getting out coal. Operating almost wholly through the medium of mechanical loading machinery, the company has for some years paid a bonus, equivalent to one-half the labor saving made above a determined average output per shift worked, on a given machine. No penalty is attached where the established output is not obtained, but in 1933 the men on one class of machines earned an average premium of $0.633 per shift on 56.4 per cent of the tonnage loaded. On another class of machine, the men earned an average premium of $0.686 per shift on 28.4 per cent of the tonnage loaded An increase of 36 per cent in tons loaded per man-shift has resulted since the program was instituted. This coal company has also been very successful in reducing mine accidents through prizes awarded in an unusual way. At the close of the year, every man whose particular mine section passes through the year without a lost-time accident is given a ticket entitling him to participate in a safety drawing where an automobile is awarded as first prim.. There are also a number of cash safety prizes which are similarly awarded. Some 1500 persons attend the drawing, which excites much interest and attention. The particular plan employed, the payment of production bonus awards and safety prizes, is foundationed upon collective. rather than individual effort, and, once gotten under way, has proved to be substantlally self-cnforcing.

Jan 1, 1934

By I. M. Bernstein

The steady-state creep behaviov of zirconium and zivcaloy-2 was examined in the temperature vatlge 520° to 620°C A1 low stresses the creep rates were cimracterized by a linear stress dependence; at highev stresses the stress dependence was much more pronounced. Temnperature-cycling tests yielded values for the aclivation enevgy for creep. Various tlzeories were examined in the ligltt of- the experimental re-sults and it mas concluded that the low-stress creep behavior is the result of the stress-direcled diffusion of vacancies along gain boundaries. It has been observed,"&apos; usually under conditions of high temperature and low stress, that creep deformation can occur for which the steady-state creep rate is linearly dependent on the applied stress. For magnesium and certain magnesium alloys, Harris and ones&apos; and ones&apos; have argued that this type of creep occurs by mass transfer as a result of the stress-induced generation and migration of vacancies, along a gradient defined by the stress direction. Jones&apos; demonstrated that the rate-controlling diffusion path is sensitive to grain size and temperature, and that by suitable control of these variables creep could occur by vacancy diffusion either predominately along grain boundaries or through the lattice. Recently, Jones3 suggested from an examination of limited high-stress data for zircaloy-2, composition in Table I, that significant diffusion creep could occur at low stresses, at least between 375" and 500°C, controlled by grain boundary vacancy diffusion. This process could have an important implication in assessing the role of zirconium alloys as a structural or cladding material in certain classes of nuclear reactors, since it predicts creep deformation far in excess of any estimates based on extrapolating slip creep data from higher stress levels. If the diffusion creep process occurs it should be possible to describe the total steady-state creep rate of zirconium and its alloys as the sum of two terms, Eq. [I]; the first term relates to a slip creep process important at high stresses and which is manifested by a much more pronounced dependence of creep rate on stress4 than diffusion creep and the second to a process controlled by mass transfer,5&apos;6 dominant at low stresses: where A and BI are parameters which can depend on structure, Ql and Q2 are the activation energies for the particular creep process occurring, and n describes the sensitivity of the creep rate on stress. It is the purpose of this paper to present some direct experimental evidence in support of this view. It is recognized that other analytical approaches have been proposed to explain data of this kind and these will also be discussed. 1) EXPERIMENTAL PROCEDURE Flat creep specimens (gage length 1 by 0.25 by 0.02 in. approx) were prepared from cold-rolled, argon-remelted, crystal bar zirconium and cold-rolled commercial-grade zircaloy-2, the analyses of which are given in Table I. The specimens were annealed at a pressure of < 10-5 Torr at temperatures from 625" to 675°C for 2 hr and slow-cooled. This treatment produced stable grains of average size (defined here by the average linear intercept) of for zirconium and -4xin. (-10 p) for zircaloy-2. The specimens were tested in a dead load tensile creep rig. The stress was maintained constant by adjusting the applied load after approximately each 1 pct of strain. The specimen temperature was controlled to better than +1°C. This system had a small thermal lag, so that rapid temperature changes were possible. To minimize corrosion, the specimens were tested in high-purity (99.95 pct) argon, further dried,

Jan 1, 1968

By Laurance S. Reid, Joe A. Porter

Gas dehydration plays an important part in the production of natural gas. Effective dehydration prevents formation of gas hydrates and the accumulation of water in transmission Systems,2,6,7 insuring uninterrupted gas deliveries at maximum efficiency under the most adverse weather conditions. At the present time, most gas companies require a maximum water vapor content of seven lb per million standard cu ft of gas. so that virtually all gas tendered for sale must he dehydrated to meet this specification. For a number of years it has been common practice to produce gas and gather it at a common point for dehydration prior to discharge into the transmission system.1,3,11,16,17 However, higher transmission line pressures, long gathering lines and relatively low ground temperatures have made it necessary to dehydrate gas at. or near. individual. wells in order to gather gas from a number of newly developed fields without unusual difficulty. Where gas has been dehydrated at pressures ranging from 300 to 800 psi in the past. future trends indicate that these processes may be operated at pressures as high as 2,000 psi. Economics of gas dehydration are of great importance, partitularly where facilities must he provided to process relatively small quantities of gas, such as the production from an individual well. Although the adsorption of water vapor from gas on a granular sorbent material such as activated bauxite, activated alumina, or one of the alumina-silica gels is highly effective and produces virtually "bone dry" gas, the cost of a small unit of this type is substantially greater than that of an absorption process which, through proper selection of the absorbing liquid, will dehydrate the gas sufficiently to meet pipe line specifications. For this reason, a great deal of emphacis has been placed on the development of small, inexpensive dehydration units8,24 and the search for more effective absorb. ent liquids has been intensified. A wide variety of methods for dehydrating gas are known&apos; and many of these have been used in industry. Earlier applications of the absorption process employed concentrated solutions of calcium and lithium chlorides as the absorbent. The severe corrosion problems inherent in handling these solutions and the relatively small dew point depressions obtained caused early abandonment in favor of, or conversion to. diethylene glycol when it was found that aqueous solutions of this organic liquid were more hygroscopic than the brines and were non-corrosive. Processes employing diethylene glycol-water solutions are widely used for gas dehydration at pressures ranging as high as 1,200 psi.13,14,15 At nominal pressures a dew point depression of 45° to 50°F may be be and the data of Russell et al." indicate that a minimum dew point is obtained from the effluent gas at a pressure of approximately 1,200 psi when the gas is in equilibrium contact with a 95 per cent by weight diethylene glycol solution. In a number of instances the dew point depression obtained with diethylene glycol-water solutions is not sufficient to produce a specification product without cooling the inlet gas. In a recent search for a better absorhent, triethylene glycol was used in a small commercial dehydration unit and subjected to rather exhaustive field tests.&apos; The data obtained were encouraging and indicated that, at pressures ranging from 300 to 500 psi, triethylene glycol porduced a substantially greater dew point depression than diethylene glycol. These results led to an investigation of the system natural gas-water-triethylene glycol in an effort to obtain vapor-liquid equilibrium data, to determine pressure limitations, and to develop other data pertinent to the design of gas dehydration processes. A review of the literature has failed to reveal any data which permit reasonably accurate calculation of the vapor-liquid equilibrium conditions for a solution of water and triethylene glycol in contact with natural gas at high pressure. Since these constituents form a non-ideal system, the Poynting equation18,21 or the usual combination of Raoult&apos;s and Dalton&apos;s laws19,20,22 would not be valid. Correction of Raoult&apos;s and Dalton&apos;s laws by the use of activity coefficients2&apos; is not feasible for available data are insufficient for the prediction of the actual increase in the ratio of the activity of one component in the vapor phase to its activity in the liquid. Therefore. experi-

Jan 1, 1950

By W. M. Hirthe, E. H. Greener, D. R. McCann

It has been proposed1&apos;2 that, at low temperatures, point defects are a strengthening factor in inter-metallic compounds whereas, at high temperatures, the deformation is diffusion-controlled and, therefore, an increase in the concentration of point defects tends to soften or increase the plasticity of a compound. More recent investigations, including those of Bloem and Kroger&apos; on PbS, Kramers and smith4 on TiO, and Nadeau5 on LiF, have extended this concept to ionic crystals. Rutile (TiO2) is a tetragonal transition metal oxide which has a defect structure over at least the compositional range. The defect in near-stoichiometric rutile is either an oxygen ion vacancys or a titanium ion interstitial.&apos; This investigation does not contribute to resolving the defect question but either defect would satisfy the results obtained. Six specimens having the same orientation, see Fig., 1, utilized in an independent investigation1&apos; were cut with a diamond saw from a single-crystal boule purchased from the Linde Co. Three specimens were annealed in air at 1200°C for 4 hr and slowly cooled to room temperature in a period of 12 hr. The remaining specimens were reduced in a vacuum of l0 mm Hg at 1200°C for 4 hr and cooled at the same rate in vacuum. The reduced specimens were weighed before and after reduction and, assuming the weight loss to be oxygen, the corresponding oxygen-to-metal ratio is 1.998. All specimens were chemically polished and etched utilizing the techniques described by Hirthe, Adsit, and Brittain." The specimens were embedded in acrylic resin and mounted on a leveling vise in a Kentron micro-hardness tester. A 200-g load was applied to a Knoop indenter with a descent time of 18 sec and a dwell time of 20 sec. Eight indentations were made on a near (171) surface, approximately 3 deg from the (lii) plane, for each orientation of the major axis of the indenter relative to the crystal structure. The dependence of microhardness on orienta-

Jan 1, 1963

By A. P. Young, L. I. Marsh

HE relationship between microstructure and *- fracture is of interest in many metals and alloys. This relationship is sometimes established by examining the fracture surfaces and the flat surfaces near the fracture path in tensile samples. However, it is often difficult to tell from examining the fractured sample whether the fracture is intergranular, intra-granular, or a mixture of both. Also, it is often of interest to follow the progress of slip, twinning, or crack formation along the fracture path before fracture occurs. The ambiguity concerning the type of fracture generally can be resolved if the area along the path of ultimate fracture can be photographed at inter-

Jan 1, 1959

By R. G. Turner, M. G. Hubbard, A. E. Dukler

Gas phase hydrocarbons produced from underground reservoirs will, in many instances, have liquid phase material associated with them, the presence of which can affect the flowing characteristics of the well. Liquids can come from condensation of hydrocarbon gas (condensate) or from interstitial water in the reservoir matrix. In either case, the higher density liquid phase, being essentially discontinuous, must be transported to the surface by the gas. In the event the gas phase does not provide sufficient transport energy to lift the liquids out of the well, the liquids will accumulate in the wellbore. The accumulation of the liquid will impose an additional back pressure on the formation that can significantly affect the production capacity of the well. In low pressure wells the liquid may completely kill the well; and in the higher pressure wells there can occur a variable degree of slugging or churning of the liquids, which can affect calculations used in routine well tests. Specifically, the calculated bottom-hole pressures used in multirate backpressure tests will be erroneous if the well is not removing liquids on a continuous basis, and gas:liquid ratios observed during such a test may not be correct. Several authors1,3,8,14 have suggested methods to determine if the flow rate of a well is sufficient to remove liquid phase material. Vitter14 and Duggan&apos; proposed that wellhead velocities observed in the field would be adequate for keeping wells unloaded. Jones8 and Dukler3 presented analytical treatments resulting in equations for calculating, from physical properties, the minimum necessary flow rate. An analysis of these studies indicates the existence of two proposed physical models for the removal of gas well liquids: (1) liquid film movement along the walls of the pipe and (2) liquid droplets entrained in the high velocity gas core. Although there probably is a continuous exchange of liquid between the gas core and the film, they will be treated separately for the purposes of this study. The development and comparison of these separate models with experimental data will permit the determination of which, if either, is the controlling mechanism for the removal of liquids from gas wells. The Continuous Film Model Liquid phase accumulation on the walls of a conduit during two-phase gas/liquid flow is inevitable due to the impingement of entrained liquid drops and the condensation of vapors. The movement of the liquid on the wall is therefore of interest in the analysis of liquid removal from gas wells. If the annular liquid film must be moved upward along the walls in order to keep a gas well from loading up, then the minimum gas flow rate necessary to accomplish this is of primary interest. The analysis technique used follows Dukler2 and Hewitt5 and involves describing the profile of the velocity of a liquid film moving upward on the inside of a tube. The minimum rate of gas flow required to move the film upward is then calculated.

Jan 1, 1970

By J. W. Lacey, F. H. Brinkman, J. E. Faris

This paper presents an analysis of the high-pressure, gas-driven LPG-slug process, based on fluid flow tests in areal models. Two types of tests were made. One series was made in low-pressure models which permitted observation of fluid movement. Three completely misci-ble analog fluids were used. A second series of tests was made in high-pressure models using methane, propane and a light refined oil saturated with methane at room temperature and 1,550 psig. Under the test conditions of room temperature and a pressure level of 1,550 psig, the phase diagram for the fluids used is similar to those for many of the field systems where the process is considered for use. A method for using these laboratory data to calculate field performance of the process is outlined. As a result of this work, it is concluded that small banks of LPG (5 per cent HV or less) are not effective in increasing oil recovery in horizontal reservoirs. Znstead, where small banks are used, the driving gas quickly penetrates the LPG bank because of fingering and channeling; and from this point on, the process behaves essentially as an immiscible gas-injection project. The validity of this conclusion was substantiated by: (1) laboratory studies of the effect of rate, model size and mobility ratio on miscible displacement in areal models; and (2) calculation of field recovery, which compared closely with actual field recovery. INTRODUCTION Field applications and pilot tests of the gas-driven, LPG-bank, oil-recovery process are on the increase. Most of these tests are employing small banks (2% to 5 per cent hydrocarbon volume) of LPG, which is miscible with both the driving gas and the oil in place, in an effort to attain an effective yet economical miscible displacement of oil by gas. The expectation of miscible displacement with small banks is based on the concepts that: (1) lengths of solvent-oil mixed zones, measured during miscible displacements in long slim cores, are representative of those that will occur in the field; and (2) areal sweep efficiencies5 measured in electrolytic model studies are applicable to miscible displacement in reservoirs. Our experimental evidence indicates that the mixed-zone lengths and sweep efficiencies mentioned are not applicable to miscible displacement in reservoirs. In this paper we present an evaluation of the gas-driven, LPG-bank oil-recovery process based on fluid flow experiments in areal models. These results are used to predict the performance of a field pilot test of this process, and the results are compared with the actual test results. THE EFFECTIVENESS OF LPG BANKS The effectiveness of LPG banks of various sizes in accomplishing miscible displacement of oil by gas was determined by displacement tests in a model representing one-quarter of a confined five-spot pattern. The model, 12 X 12 X 1/4 in. in size, was packed uniformly with glass beads. It was operated at a pressure of 1,550 psig and at room temperature; the fluids used were methane, propane and refined oil saturated with methane at 1,550 psig. The saturated oil had a viscosity of 1.2 cp at room temperature. The results of these tests are shown in Fig. 1, where recovery is plotted as a function of the volume of fluid injected for: (1) an immiscible-gas drive with an oil-to-gas viscosity ratio of 85; (2) three sizes of LPG banks; and (3) two completely miscible displacements with mobility ratios of 85:1 and 10:1. (The miscible displacement data plotted are the averages of several tests.) The results show that a 2½ per cent bank of LPG does not increase oil recovery over that obtained by immiscible-gas drive. The 7 and 17 per cent banks are, respectively, about 30 and 50 per cent effective (with reference to the M = 85 miscible-displacement curve) in increasing oil recovery at the point where 2½ hydrocarbon volumes (HV) of fluid have been injected. The percentage effectiveness of the banks at a given volume of fluid injected is defined as Recovery by Bank — Recovery by Gas Drive Recovery by Miscible Recovery by Flooding Gas Drive We conclude from these results that banks of LPG smaller than about 5 per cent HV in an individual stratum will cause from little to no increase in oil recovery. This finding was substantiated by work in low-pressure models, which permitted visual observation of fluid movements. In these tests, three completely miscible fluids having the same viscosity ratios as those used in

By Margaret G. Scroger, Luke L. Y. Chang, Bert Phillips

Using the sealed-system technique, isothermal sections at 1000°, 1400°, and 1700°C for the system Co-W-O hare been determined. The equilibrium data were obtained by microscopic and X-ray diffraction examination of samples winch had been equilibrated in pellet form fit sealed capsules and subsequcelly quenched. The only ternary phase in the system is CoWO, which mells congruentlly at approximately 1280°C. At 1000°C, this ternary phase exists in equilihrinm with all the allows and oxide compounds in the hounding binary systems. At 1400°C, liquid forms in thin oxygen-rick region near the CoWO4 composition and only one phase assemblage in the system (W + WO2 + H&apos;5CV7) contains no In order for tungsten to be used to its full potential as a refractory metal. it is necessary that coatings be developed which will preclude oxidation of the metal. It is true that coatings now in use do protect tungsten for short periods at temperatures near 1700 °C. but no coating has been developed which protects adequately at or above this temperature where the use of tungsten is most required. This situation exists despite the great effort in recent years to develop such coatings. and it has become evident that success in this area can be achieved only after a more fundamental knowledge of the thermochemical and therrnophysical propertics of tungsten oxidation and tungsten -metal oxidation is obtained. In our 1aboratories. a project liclrriel. At 1700°C, tungsten is the ouly solid phase which is stctble, and a large range of compositions melt to two liquids, one metallic and one oxidie. The sealed-system method of etjuilibra lion prevents the determination of the partial pressure of oxygen and the total gas pressure orer the condensed phases at equilibrium. This data is not available and can be obtained only by some other method. We can generalize on these unknowns and indicate that both partial pressure of oxygen and total pressure of the gas phase must increase as compositions change from the W-Co binary toward the oxygen apex and as temperatures increase. has been initiated which is directed at providing some of this fundamental information through a study of metal-tungsten-oxygen reactions and equilibria and the properties of any intermediate phases which result. This paper is based on a part of this program in which the system Co-W-O was studied between 1000° and 1700°C. I) RELEVANT INFORMATION FROM THE LITERATURE A) The Notable Lack of High-Temperature Work on Metal-Tungsten-Oxygen Systems. It should be pointed out that there has been no published report (of which we are aware) which deals with the study of a metal-metal-oxygen system at 1700°C. Also, there has been no report on a complete metal-luugsten-oxgen system at any temperature. As a matter of fact. before this program started. The

Jan 1, 1965

By G. Koves

The behavior of case-hardened AISI C-1213 free -machining steel under complex impact-fatigue -wear load conditions was investigated. The inherently poor dynamic properties of the steel are mainly affected by the stress distribution in the case, component shape, and tempering. Cold-riveted components showed unexpectedly high dynamic strength compared to basic parts. A compromise beatment—which provides good dynamic properties, reasonable wear resistance, and fair riveting characteristics—zuas developed. A number of mechanical components in data-processing machines are made of free-machining carbon steel. Although, selected primarily due to manufacturing requirements, components made of these grades frequently undergo complex heat treatment and must sustain impact-fatigue loads. A typical free-machining steel is the AISI C-1213 grade, which is a resulfurized and rephosphorized open-hearth steel. While the undesirable effects of sulfur and phosphorus on the mechanical properties are well-known, data on dynamic properties are scarce.1"3 Rapid rotating or oscillating motion while carry- ing a high cyclic load requires a combination of wear resistance with high endurance limit and impact toughness. The inherently poor dynamic properties of the free-machining steel are further degraded by the machining, which introduces local stress-concentration areas. While the heat treatment (usually case hardening) improves some mechanical properties, it necessarily impairs others. Another problem arises when components, such as studs, must be fastened by riveting. The high crack-sensitivity of the free-machining steel, especially in the presence of a hardened case, makes this operation difficult. In view of the preceding considerations, it is of interest to investigate the behavior of a typical component under complex impact-fatigue-wear loading conditions in order to explore the effects of material, machining, and heat treatment, to obtain specific data on the dynamic characteristics of free-machining steel, and to arrive at a process which would adequately utilize the inherent qualities of this material. EXPERIMENTAL PROCEDURE To simulate actual service conditions, a typical component was selected, based on frequency of application, complexity of load, and processing difficulties. The dimensions and shape of the component—a stud used in many electromechanical document-handling machines—are shown in Fig. 1.

Jan 1, 1964

By H. M. Chance

Stretching from New York southwestwardly to Georgia is a great range of hills and mountains consisting of pre-Palæozoic schists, slates, .and gneissic and granitoid rocks, known locally by many different names; in Pennsylvania as the South mountains, the Berkshire or Durham and Reading hills, and in Virginia and farther south as the Blue ridge. To the northwest of this range lies the " Great Valley," underlain by Lower Silurian limestones, and known as the Lehigh valley, Cumberland valley, Shenandoah valley, valley of Eastern Tennessee and Georgia and by other local names, but all these are parts of one valley, geologically and geographically continuous from New Jersey to Georgia. Lying upon and along the northern flank of this range of mountains, and dipping northwestwardly under the limestone of the valley, is the Potsdam formation (Primal or No. 1 of the Pennsylvania Geological Survey), which consists of sandstone or conglomerate overlain by slates. The latter are sometimes arenaceous and occasionally are replaced in part by sandstone. This formation varies from a few feet to several hundred feet in thickness. At the outcrop the slates are completely decomposed, oxidized or disintegrated, forming a belt of clay several hundred feet wide occupying the interval between the outcroppings of the sandstone and limestone. This clay-belt includes a more or less continuous series of iron-ore (brown hematite) deposite, which have been, and still are, extensively worked. The belt is more or less continuously milleralized with iron throughout its length, and hundreds of large deposits of ore have been developed and worked, producing many millions of tons of ore.

Jan 1, 1909

By A. E. Powers

YEARS of experience and research have shown that molybdenum, tungsten, and vanadium are among the most useful and effective elements in augmenting the high-temperature strength of heat-treatable, ferritic steels. Grün, for example, in conducting an early survey of the strengthening effects of various elements in annealed, low-carbon steel at 750° and 930°F (400° and 500°C), found molybdenum and vanadium to be the most effective.&apos; Holtmann comprehensively studied the strengthening effects of molybdenum and vanadium in quenched and tempered steels at 930°F as a function of microstructure and carbon content.&apos; He found creep strength to be related to the saturation of the austenite at the austenitizing temperature, such that strength is increased by alloying until the y loop is reached—the terminus of complete austenitization. Beyond this degree of alloying, the inability to heat treat will result in lower strength, at least for low and moderate creep temperatures. Tungsten, owing to higher cost than molybdenum, has been little used in ferritic high-temperature steels. As a result, very few investigations have been made of its high-temperature strengthening ability, and reliable data on its effectiveness are not available. Grün rated tungsten far less effective than molybdenum at 930°F (500°C) on a weight-percentage basis.&apos; However, Tammann has found that tungsten is as effective as molybdenum in raising the recrystallization temperature of iron. For this reason Smith, in a review of the subject, has advocated a re-examination of the influence of tungsten on the high-temperature strength of steel.&apos; In any study of the effects of alloying additions on high-temperature properties, recognition must be made of the many variables involved, some of which can be controlled but have been ignored in innumerable investigations of the past, and some of which are difficult or even impossible to control. One cannot, for example, assign a definite strengthening index to any one alloying element, for this will be dependent upon the microstructure (heat treatment and mechanical treatment), testing con- ditions (temperature, time, and stress), and the complete composition of the steel (accompanying alloying elements, impurities, etc.). One ever-appear ing variable, hardness or tensile strength at room temperature, may be eliminated by heat treating all of the alloys to a single hardness level. An attempt may be made to control the variable of primary quenched structure by oil or water quenching the test specimen. The control of such variables may not be possible in cases of widely varying compositions, but at least such deviations should be recognized. Material and Procedure The alloys, made as 30-lb ingots in an induction furnace, all had the same base composition of about 0.18 pct C, 0.85 pct Mn, and 0.48 pct Si. They were grouped as follows: Mo Group—Containing up to 5.2 pct Mo. W Group-Containing up to 6.0 pct W. V Group—Containing up to 3.3 pct V. Mo-V Group—Containing up to 2.7 pct Mo and up to 1.4 pct V. Mo-W Group—Containing up to 2.5 pct Mo and up to 2.5 pct W. The steels, listed in Table I, were forged to ¾ in. sq bars and the material for the high-temperature, rupture-test specimens was further swaged to %-in. round bars.

Jan 1, 1957