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By F. F. Craig

A series of both welter and gas puttern Hoods was made in the laboratory to study the oil recovery performances of .such operations. These tests were contlrrctt~tl on consolidated sandstone models, using oil. water, and gas. The model floods were scaled to reprotlrrce field performance under gas arid water five-spot injection. X-ray shadowgraphs permitted observation of the gross fluid movement within the models. A method was developed for applying the mobility ratio concept to water flooding and dispersed gas drives in a five-spot well pattern. The area1 sweep efficiency. tit breakthrough for dispersed gas drives is much higher than previorsly expected, Iying in the range of 50 to 100 per cent. A method is presented for predictitig the water-oil ratio performance of five-spot pattern water flood., in uniform sands. This method is verified experimentally for the cotidition of 120 free gas initially present and for va1ues of gas saturation normally encountered in fields following depletion operations. Prodrrction perfort?zut~cc for pattern gas injection is also predictable by this method. INTRODUCTION In field pattern hater flooding or dispersed gas injection operations, the displacing fluid (water or gas) is injected and oil is produced through wells which are, area-wise. small openings in a large container or rescrwir of oil. As a result, not all of the area between the injection and producing wells is necessarily contacted by the injected fluid by the time it first reaches the producing wells. The question arises in predicting oil recovery. as to what traction of the pattern area involved is contacted by either the injected water or gas due to the relative position of the injection and producing wells. This is the areal sweep efficiency. It is also desirable to know how well arrangement affects the oil production performance. A solution to this problem has been attempted by many means. Mathematical analysis¹,²,³, and electrolytic models', have been used to establish a breakthrough areal sweep efficiency of 73 per cent for a five-spot pattern in which the ability of the oil to flow ahead of the invading fluid is equal to the ability of the invading fluid to flow in the invaded zone. All of these studies simulate only one of many field conditions. Improved studies of areal sweep efficiency at breakthrough were made using the fluid mapper5, poten-tiometric models" and X-ray shadowgraph techniques. In these it was possible to study the effect of variations in mobility of the injected and displaced fluids, and so to cover a wide range of field conditions. The limitation of these studies is that, with these models, it was not possible to simulate the saturation gradient behind the flood front when oil is displaced by gas or water. In the most recent published technical paperS on the subject, a method was presented for predicting the oil recovery performance after breakthrough in a five-spot pattern water flood. The method involved correlations which were obtained experimentally using miscible fluids. One limitation of this work was that a saturation gradient, usually found in immiscible fluid displacement, was absent in these studies. Also the laboratory studies did not cover the situation of a water flood following oil recovery by depletion drive. as is the situation in most field water floods. The tests reported in this paper were made using oil. water, and gas, thus eliminating the simplifications of former studies. Also reported are laboratory studies on

Jan 1, 1956

By W. B. Gogarty, H. R. Bailey

Methods are presented for determining molecular diffusion coefficients by using data from, capillary flow experiments. These methods are based on a numerical solution (presented in a previous paper) of the partial differential equation describing the combined mechanisms of flow and diffusion. Results from this numerical solution are given and compared with the approximate analytical solution of G. I. Taylor. The numerical solution is valid over a much larger time range. These methods are applied to experimental results for the fluid pairs water-potassium permanganate solution and amyl acetate-orthoxylene. Both of these fluid pairs have approximately equal densities and viscosities. Graphical and numerical techniques are presented for deter mining diffusion coefficients from the flow data. Values obtained by these techniques are compared with values obtained by other methods. INTRODUCTION The molecular diffusion coefficient is known to be a variable in determining the amount of mixing in a miscible displacement process. The effect of molecular diffusion on dispersion in longitudinal flow through porous media -has been examined by different investigators. These investigators concluded that at low velocities of flow, the amount of dispersion is approximate1y proportional to the molecular diffusion coefficient. The influence of diffusion on fingering, channeling, and overriding has been mentioned by other investigators.4 Recent studies5,6 have been made on the effects of molecular diffusion in connection with the problem of gravity segregation. Many different methods have been developed for the experimental determination of molecular diffusion coefficients? These methods differ mainly according to boundary conditions selected and analytical procedures used. Nevertheless, all of these methods have the condition in common that the bulk fluids in which diffusion is occurring are stationary with respect to each other. In connection with a series of papers on mixing in capillary flow,8-10 Taylor suggested the use of a flow method for determining molecular diffusion coefficients. Additional studies 11-13 have been conducted on miscible displacements in capillary tubes, but the data from these studies were not used for the specific purpose of determining diffusion coefficients. The flow method proposed by Taylor results in a single value of the diffusion coefficient for the fluid pair used in the displacement experiments. This single value represents the true value for the fluid pair when the diffusion coefficient is independent of concentration. If the diffusion coefficient is a function of concentration, the single value obtained by the flow method gives an average value for the coefficient of the fluid pair. These average values are based on diffusion taking place over the entire range of concentration, i.e., from 0 per cent of one fluid to 100 per cent of that same fluid. In field applications of the miscible displacement process, gradients occur over the same range of concentration as are found in the displacements in capillary tubes. Molecular diffusion coefficients obtained from the capillary flow method should, therefore, be especially relevant to field operations. This investigation was undertaken to evaluate the feasibility of obtaining molecular diffusion coefficients from capillary -flow experiments. In making this evaluation, diffusion coefficients were first determined for two systems from data obtained in capillary flow experiments. These values of the diffusion coefficient were then compared to values obtained by other methods. MIXING IN CAPILLARY FLOW—THEORETICAL The theoretical basis for determining molecular diffusion coefficients from capillary flow experiments is the partial differential equation relating the mechanisms of flow and diffusion. For the case of laminar flow and with a fluid pair having equal densities and viscosities, the equation is given by

By W. A. Ver Wiebe

Under the impetus of new demands caused by the war, the oil and gas industries of Kansas established new records during the year 1942. In all, 1513 test wells were drilled, which is somewhat of a drop from the figure of 2113 for 1941. The 1513 tests yielded 800 new oil wells, 85 new gas wells, and 628 dry holes. Thus there was an increase in two categories, the gas wells and the dry holes. Considering that last year only 592 dry holes were completed out of a much larger total, the figure of 628 dry holes causes some concern among local operators. The increase in unsuccessful tests illustrates once more the fact that each year it is becoming harder to find the remaining oil pools. When the figures are broken down, it appears that western Kansas accounted for 1177 tests, of which 689 were oil wells, 33 gas wells, and 455 dry holes. The total potential daily initial production uncovered by the successful wells amounted to 753,178 bbl. of oil and 619,734,000 cu. it. of gas. The figures for new initial production indicate a substantial drop from last year's figure of 1,691,000 bbl., and the figures on gas are slightly higher. In 1941 the new gas as based on a daily potential was 508,000,-000 cu. ft. In eastern Kansas, 336 wells were drilled. Among these in were oil wells, accounting for a daily initial potential production of 16,199 bbl. The new gas wells numbered 52 and added 253,725,000 cu. ft. per day to the gas potential production of the state. The remaining tests, 173 in number, were dry. It is interesting and perhaps significant that about half (630) of the wells drilled in western Kansas were drilled by the independent operators. Among the large companies, the Cities Service Oil Co. drilled 163 wells; the Stanolind Oil and Gas Co., 52; the Skelly Oil Co., 39; the Continental Oil Co., 48; and the Shell Petroleum Co., 21 wells. In eastern Kansas the independent operators drilled 297 out of the total of 336 wells. Among the major oil companies the Cities Service Oil Co. drilled 19; the Phillips Petroleum Co. 7; and the Sinclair-Prairie Oil Co., 6 wells. The figures based on relative percentages of dry holes to successful oil or gas wells are revealing. In western Kansas almost one half of all wells drilled by the independent operators were dry holes. The major oil companies drilled approximately 547 wells in western Kansas, of which 379 were successful in finding either oil or gas. It thus appears that the major companies fared better than the independents. In eastern Kansas the major companies drilled 39 wells, of which 29 were successful in finding commercial quantities of oil or of gas. No less than 329 wildcat test holes were put down in western Kansas and 105 in eastern Kansas, or 434 in all, during 1942. Considerably more than half of these were drilled by independent operators; 223 in western and 99 in eastern Kansas. An exploratory hole 56 mile or more from production is regarded as a wildcat well in Kansas. On a percentage basis, about 80 per cent of wildcat wells were failures. In western Kansas only 20 per cent found either oil or gas. The failures were about equally distributed among the major

Jan 1, 1943

By B. A. Shaw

Historically, microwave tubes have been fabricated from massive metal and ceramic components. The current trend is to lighten tibes for airborne applications. The reqciiremenls of light weight and also reduced cost have created a novel approach to tube structure in which thin-film technology plays a major role. Although the electrical requirements of thin-film circuits in microwave tubes differ from those required or se,niconductor integrated circuits. the technology is basically similar. The stringent requirements of the micvowave tube have created sophisticaled thin-film techniques thut are of interest to the integrated-circuit industry in general. This paper describes a nunzber of thin-jilm techniques recently developed and discusses in detail the application of the technology in microwave tubes. The particular areas of interest are: 1) ceramic mounted thin-film slow-wave structures; 2) thin-film secondary emitters; 3) suppression of tube environnental multipactor by semiconducting' thin films; and 4) age-hardenable and dispersion-hardened thin metal films. SEVERAL thin-film techniques specifically applied to microwave power tubes are discussed in this report. There are two reasons for this work. One is the necessity of reducing weight and cost of microwave tubes and the other is related to overcoming problems in the tube operation by the use of applied thin-film technology. The major emphasis of this work has been on tube slow-wave structures. Other work in the area of secondary emission, either its suppression or its enhancement, is continuing; the most satisfactory results to date have been by utilization of thin-film technology. The requirements of high thermal and electrical conduction together with greater strength than normally obtained with elemental materials have led to the development of dispersion-hardened films. The paper will discuss: 1) ceramic-mounted delay-line microwave tubes; 2) multipactor and secondary emission; 3) hardened films. I) CERAMIC-MOUNTED THIN-FILM SLOW-WAVE STRUCTURES In a conventional crossed-field microwave tube, the slow-wave or delay-line structure is produced from two carefully machined components. One half of the structure is shown in Fig. 1. The other half is the mirror image of the first but is rotationally offset by a half a period. The combined structure now forms an interdigital type of slow-wave structure and is the anode of the tube as shown in Fig. 2. The period and finger length of an interdigital slow-wave structure are prescribed by the desired dispersion characteristics. The typical design is as shown in the first figure; it can be noticed that the finger width is several times greater than the finger thickness. Even assuming that it were mechanically possible to produce free-standing fingers of extremely small cross-sectional dimension, for example, 0.002 in. thick by 0.005 in. wide by 0.500 in. long, decreasing this finger width would increase the tube efficiency but would also decrease the thermal-conduction path, causing an increased temperature rise from intercepted rf current which in its extreme could easily cause finger melting. Hence, for free-standing lines of this type, the design is a compromise between mechanical capabilities, tube efficiency, and thermal dissipation. These structures are also expensive and tend to be heavier than purely electrical considerations would demand. In the present approach, we have transposed the three-dimensional structure previously shown into an essentially two-dimensional structure as shown in Fig. 3. The linear structure is used here for clarity of detail. The support member is a ceramic material and the line is deposited copper. The final tube design is shown in Fig. 4. Because of the backwall sup-

Jan 1, 1967

By W. A. Ver Wiebe

Under the impetus of new demands caused by the war, the oil and gas industries of Kansas established new records during the year 1942. In all, 1513 test wells were drilled, which is somewhat of a drop from the figure of 2113 for 1941. The 1513 tests yielded 800 new oil wells, 85 new gas wells, and 628 dry holes. Thus there was an increase in two categories, the gas wells and the dry holes. Considering that last year only 592 dry holes were completed out of a much larger total, the figure of 628 dry holes causes some concern among local operators. The increase in unsuccessful tests illustrates once more the fact that each year it is becoming harder to find the remaining oil pools. When the figures are broken down, it appears that western Kansas accounted for 1177 tests, of which 689 were oil wells, 33 gas wells, and 455 dry holes. The total potential daily initial production uncovered by the successful wells amounted to 753,178 bbl. of oil and 619,734,000 cu. it. of gas. The figures for new initial production indicate a substantial drop from last year's figure of 1,691,000 bbl., and the figures on gas are slightly higher. In 1941 the new gas as based on a daily potential was 508,000,-000 cu. ft. In eastern Kansas, 336 wells were drilled. Among these in were oil wells, accounting for a daily initial potential production of 16,199 bbl. The new gas wells numbered 52 and added 253,725,000 cu. ft. per day to the gas potential production of the state. The remaining tests, 173 in number, were dry. It is interesting and perhaps significant that about half (630) of the wells drilled in western Kansas were drilled by the independent operators. Among the large companies, the Cities Service Oil Co. drilled 163 wells; the Stanolind Oil and Gas Co., 52; the Skelly Oil Co., 39; the Continental Oil Co., 48; and the Shell Petroleum Co., 21 wells. In eastern Kansas the independent operators drilled 297 out of the total of 336 wells. Among the major oil companies the Cities Service Oil Co. drilled 19; the Phillips Petroleum Co. 7; and the Sinclair-Prairie Oil Co., 6 wells. The figures based on relative percentages of dry holes to successful oil or gas wells are revealing. In western Kansas almost one half of all wells drilled by the independent operators were dry holes. The major oil companies drilled approximately 547 wells in western Kansas, of which 379 were successful in finding either oil or gas. It thus appears that the major companies fared better than the independents. In eastern Kansas the major companies drilled 39 wells, of which 29 were successful in finding commercial quantities of oil or of gas. No less than 329 wildcat test holes were put down in western Kansas and 105 in eastern Kansas, or 434 in all, during 1942. Considerably more than half of these were drilled by independent operators; 223 in western and 99 in eastern Kansas. An exploratory hole 56 mile or more from production is regarded as a wildcat well in Kansas. On a percentage basis, about 80 per cent of wildcat wells were failures. In western Kansas only 20 per cent found either oil or gas. The failures were about equally distributed among the major

Jan 1, 1943

By A. J. McEvily, R. C. Boettner, C. Laird

The processes leading to fatigue failure in the low-cycle range were studied to obtain an understanding of the basis of Coffin's law. Particular attention was paid to the manner of mack nucleation and to the determination of the portion of the total lifetime spent in crack propagation. It was observed that cracks are nucleated at surface notches meated during reversed plastic deformation, Principally at grain boundaries, and that crack growth occupies greater than 75 pct of the fatigue life. When inclusions are present, they are often the primary sites of crack initiation. From consideration of the incremental distances advanced by a crack in each cycle and of the lifetimes of different materials, it appears that the universality of Coffin's law arises from the similarity of crack-tip strain for a given applied strain amplitude, irrespecti7:e of material. STUDIES of low-cycle fatigue have been particularly rewarding in that a simple correlation between fatigue lifetime and plastic-strain range has been shown to exist. This empirical relationship takes the forml,2 Nner=C [1] where N is the number of cycles to failure, Er is the plastic-strain range defined as the total plastic strain per cycle (the sum of the tensile plastic strain plus the compressive plastic strain), n, the exponent, is a constant independent of the material to a first-order approximation and often has a value of about 0.5, and C is a constant which for a number of ductile and metallurgically stable materials is approximately 0.65 for fully reversed strain.3 This relationship has been shown to be valid for a wide variety of metals and alloys and is often referred to as Coffin's law. However, it is yet not clear why so many different metals and alloys exhibit the same over-all behavior in the low-cycle range. Less is known about the mechanisms of fatigue failure in the low-cycle range than in the high-cycle range, but it is expected that the processes would have much in common. For example, an important characteristic common to both high-and low-cycle ranges is that fatigue crack propagation can occupy a considerable portion of the total lifetime. This has been shown by Laird and smith4 by a count of the number of ripples present on the fracture surface of copper specimens, each ripple corresponding to one cycle of load. On the other hand, some marked differences have been noted. For example, in copper,5 nickel, and aluminum4 there is a greater tendency for grain boundary cracking to occur as the strain amplitude is increased. The purpose of the present work was to study further the processes leading to fatigue failure in the low-cycle range and to obtain an understanding of the basis for the validity of Coffin's law. Particular attention has been paid to the manner of crack initiation and to the determination of the portion of total lifetime spent in crack propagation. MATERIALS A number of metals and alloys were tested, although more attention was focused on a particular few, once general trends had become apparent. Alloys were selected so as to investigate the effects of crystal structure, number of phases, stacking-fault energy, and impurity content. The materials in this grouping were: high-purity copper OFHC copper 1100 aluminum (commercially pure) 70-30 brass (Cu-30 wt pct Zn)

Jan 1, 1965

By R. Schuhmann Jr., P. J. Ensio

As a first step in a study of the physical chemistry of copper-smelting slags, experimental measurements were made of the oxygen pressure of simple iron-silicate slags in equilibrium with solid iron. The experiments consisted in bubbling CO2-CO mixtures through the slags in iron crucibles and in finding the equilibrium ratios of CO2 to CO. From the data, activities and partial molal heats of solution FeO and SiO2 in the slags were calculated. THE ternary system FeO-Fe,O,-SiO, is the simplest system which can represent adequately the important chemical properties of the slags formed in matte smelting and converting. Accordingly, the experimental study of slags in this system was started as the first step in a general research program on the thermodynamics of copper smelting. A recent paper by one of the authors' outlines this general research program and shows in some detail how information on thermodynamic properties of iron-silicate slags, especially information on oxygen activities, is essential to a full understanding of the chemistry of copper smelting. The FeO-Fe,O,-SiO, system also is the basis of slags produced in other processes, such as acid steelmak-ing processes, and is important in relation to the behavior of silicious refractories. In addition, data on the physicochemical properties of iron-silicate slags should contribute to a general understanding of the nature of slags, since at present such data for all kinds of slags are relatively meager. The principal quantitative information already available on iron-silicate slags consists in Bowen and Schairer's constitution diagram for slags in equilibrium with metallic iron,' Darken and Gurry's complete and precise thermodynamic study of the Fe-0 system,",' and Darken's study of the phase equilibria in the Fe-Si-o system. From the results of this previous work, it was clear that a complete thermodynamic study of ternary iron-silicate melts was a major undertaking which would have to be broken down into parts, including the working out of the ternary equilibrium diagram as well as extensive activity measurements on slags. The experimental measurement of oxygen activity, using CO-CO, and other gas mixtures as yardsticks of oxygen activity, was the basis of Darken and Gurry's study of the Fe-0 system. From the experimental measurements of oxygen activities over a large range of temperatures and compositions, they were able to calculate the activities of other species such as Fe, FeO, Fe,O,, etc., and also the other important thermodynamic properties in the Fe-0 system. At the start of the present investigation, it appeared that the same approach would be fruitful for the study of iron-silicate melts. Also, the experimental measurement of oxygen activities seemed particularly attractive because oxygen activity itself is a quantitative measure of oxidizing or reducing power, which is an important variable in copper-smelting slags. The slag compositions in equilibrium with yFe appeared most suitable for the first investigation of this kind, for the following reasons: 1—Good constitution data2 were available. 2—An iron crucible could be used, thus affording a simple solution to the refractory problem without introducing contarnination. 3—With Fe activity fixed, at unity with respect to a standard state of solid Fe, measurements of 0 activity could be followed by simple calculations of activities of FeO and other Fe-0 complexes and of SiO,. 4—This starting point afforded several possibilities for cross-checking with previous work,

Jan 1, 1952

By J. E. Spruiell, F. H. Patterson, B. F. Shuler

The microstructures and textures developed by the working of high-purzly thermochemically deposited tungstem sheet have been inuesligated. Greater than 60 pct reduction was required to deslroy the columnar grain structure which existed in the as-deposited sheet. With increasing reductions the texture gradu-ally charged from the initial as-deposited orientation with (100) parallel to the sheet normal to a (100}(011) ideal ovienlation with some spread about the rolling direction. This texture was retained after recrystalli-zation a1 2000°C. THE processes for depositing tungsten by hydrogen reduction of tungsten hexafluoride have been under development for the past several years.1,2 The nature of the deposition process is such that the as-deposited material contains a highly oriented columnar grain structure perpendicular to the deposition substrate. This well-defined columnar structure may be useful in certain applications293 but a wrought or equiaxed structure may be desired for some components such as tubing. Knowledge of the effects of working ther-mochemically deposited (TCD) tungsten is therefore necessary in order to establish the feasibility of obtaining worked and recrystallized microstructures and textures. The details of a recently developed technique for thermochemically depositing flat, uniformly thick tungsten sheet are presented with emphasis on the effects of deformation by rolling on the microstructure and texture. Although no work has been previously reported on the rolling and the annealing textures of TCD tungsten, there have been some determinations of textures for cold-rolled tungsten foil prepared from powder-metal -lurgy billets.4-8 The general description is that of a predominantly lurgy{100}(011) texture, with some spread about the rolling direction as an axis. pugh5 reports data both for cold-rolled and for annealed foil having about 96 pct initial cold work. He observed no change in texture, except for a decrease in the spread, for annealing treatments of 30 min at temperatures up to 1800°C. On annealing at 1900°C, both the low-temperature components plus new components which were described alternately as {001}(320) plus {001)(230) or as {100}(011) ± 12 deg about the sheet normal were observed. Above 1900°C, the new orientation existed alone, and it was stable up to 2500°C, the highest temperature that Pugh investigated. THERMOCHEMICAL DEPOSITION OF TUNGSTEN SHEET High-purity tungsten sheet was reproducibly deposited on the inner walls of a molybdenum mandrel by the thermochemical reaction WFs(g) + 3H2(g) - W(s) + 6HF(g). The mandrel was heated by a five-zone tube furnace which afforded a controllable fixed-temperature profile. Sheets measuring 1+ by 12 in. have been deposited with uniform thicknesses of up to 0.145 m. As shown schematically in Fig. 1, the purified reaction gases were metered into a mixing chamber at a Hz-to-WF6 ratio of 15 and preheated to 350°C. The flow rate of the WF6 was 300 cu cm per min at stp. These gases were directed through a conical injector into the deposition chamber. Inside this chamber hydrogen reduction of the WF6 to pure tungsten metal occurred on the hot walls of the molybdenum mandrel at a total pressure of 5 Torr. Typical temperatures for the five zones in the chamber were, respectively, 565", 540", 550°, 570°, and 590°C. The hydrogen fluorlde generated from the reaction, the excess hydrogen, and some un-reacted WF6 were pumped on through the scavenger

Jan 1, 1968

By J. N. Anderson

Developments in reverberatory furnace practice at Noranda over the period 1928 to 1953 are described. Features of interest are increasing furnace tonnage from 700 to 2000 tons per furnace day, the use of the suspended basic roof, and improvements in furnace fuel ratio. Points of comparison and contrast between Canadian and American furnace practice are given. OPERATIONS at the Noranda smelter have been described in a series of papers published between 1930 and 1945.1-4 In the present paper the development of reverberatory furnace practice over the 25 year period from the beginning of operations up to the present time will be reviewed and current furnace practice will be described in some detail. Particular attention will be given to those features which are characteristic of Canadian practice: first, the use of the suspended basic roof; second, the deliberate driving of furnaces to give tonnages in the range of 1400 to 2000 tons of solid charge per furnace day; and third, the continuous operation of furnaces at high tonnage for many years without any extended shutdown for repairs or rebuilding. Finally, points of comparison and contrast between reverberatory furnace practice in Canada and the United States will be discussed. The Noranda smelter, which started in December 1927, was built for the reduction of ore from the Horne mine where early development had shown a comparatively small tonnage of rich cop-per-gold ore of a grade and character which would require direct smelting. The smelter was designed for a capacity of 1000 tons of ore a day and originally consisted of eight roasters, two reverberatory furnaces, and two converters, together with necessary auxiliaries. The discovery of a large new body of ore in 1928 made it necessary to increase both the size and the scope of the reduction plant. A mill which was ultimately brought to a capacity of 3000 tons a day was built for concentrating low grade ore and in addition the capacity of the smelting plant had to be greatly expanded, so that for the next fifteen years every effort in the smelter was directed toward achieving maximum tonnage. Because the layout and design of the smelter made it impracticable to add a third furnace, it was necessary to increase the tonnage on the two original furnaces by improvements in furnace design and operation, roasting and converting equipment being added as required to meet the demands of increased furnace capacity. The smelter tonnage, which reached a peak in 1941, was curtailed in 1944 when it became necessary to operate on a one-furnace basis because of a reduction in the output of the Horne mine due to a shortage of labor. Two-furnace operation at a moderate tonnage was resumed in 1949. In the early years the smelter tonnage was made up almost entirely of Noranda ores and concentrates. However, since 1937 an increasing tonnage of ores and concentrates from other mines has been treated in the smelter. In recent years, with decreased production from the Horne mine, copper concentrates from several mines in the district, treated on a custom basis, have formed an important part of the smelter tonnage. A review of developments in reverberatory furnace practice at Noranda falls naturally into the following four periods: 1—1928 to 1935, the early years; 2—1935 to 1944, the period of greatest change and development; 3—1944 to 1949, one-furnace op-

Jan 1, 1955

By R. M. Jorda

The mechanism of parafin deposition and prevention has been studied in the laboratory using an apparatus which provides a quantitative means of studying parafin deposition on metal and plastic surfaces. The amount, hardness, adhesion, per cent wax and mean molecular weight of parafin deposits appear to be governed by surface roughness alone, all other conditions being constant. Tests of various plastic coatings indicate that most smooth, nonparafinic plastics are capable of reducing parafin deposits in oil wells, but flexible, highly polar, nonparafinic plastics are more suitable for providing long term resistance to parafin deposition in oil wells if the flow stream contains abrasive materials. INTRODUCTION The problem of paraffin deposition is one of long standing in the oil industry.' Crude oils often contain paraffins which precipitate and adhere to the liner, tubing, sucker rods and surface equipment as the temperature of the producing stream decreases in the normal course of flowing, gas lifting or pumping. Heavy paraffin deposits are undesirable because they reduce the effective size of the flow conduits and restrict the production rate from the well. Where severe paraffin deposition occurs, removal of the deposits by mechanical, thermal or other means is required, resulting in costly down time and increased operating costs. The troublesome paraffins are normal hydrocarbons ranging from approximately C15H38 to C38H78 mixed with small amounts of branched paraffins, monocyclic paraffins, polycyclic paraffins and aromatics.' The amount of paraffins found in crude oils varies from less than 1 to more than 30 per cent. Many publications are available which deal with this problem, and perhaps the most significant findings in recent literature are contained in a publication by Hunt3 ho developed the "cold spot tester", a really useful means of investigating paraffin deposition. Hunt's observations led to many generalized conclusions concerning the effect of surface roughness on paraffin deposits. He ascertained that there was an observable qualitative correlation between the severity of paraffin deposition and the roughness of the surfaces which he tested (cold rolled steel, stainless steel and several plastics). Because of the number of meaningful observations made by Hunt, his cold spot tester was modified somewhat and extensive tests were per- formed to study the quantitative relationship between surface roughness and the physical and chemical nature of paraffin deposits. LABORATORY TEST PROCEDURES The cold spot test apparatus consists of a flat circular plate mounted on a curved tube and positioned in a vessel containing a wax-oil solution (Fig. 1). The apparatus is arranged so that the temperature of the central portion of the circular plate can be varied by means of a circulating liquid stream; the test equipment includes provisions for maintaining a constant wax-oil solution temperature and stirring speed. In the paraffin deposition studies, the modified cold spot tester was used as follows. The cold spot probe consisted of a flat circular plat 2 in. in diameter and 1/8-in. thick positioned in the wax-oil solution kept at constant temperature. As in Hunt's earlier experiments," a cold liquid was circulated through a tube connected to the circular plate so that the liquid impinged on one side of the plate cooling the plate from the center outward, causing paraffin to deposit on the side of the plate exposed to the wax-oil solution.

Jan 1, 1967

By D. L. Albright, R. W. Kraft

Solidification experiments were conducted with the objective of testing the theory of eutectic colony formation. Appropriate control of variables in tests on a series of high-purity aluminum-copper specimens of eutectic composition resulted in the observation of three types of eutectic microstructures, these being a unique structure consisting of lamellae essentially parallel to one another, a banded structure, and the colony structure. Lamellar faults, which are morphologically similar in many respects to edge dislocation models in crystals, produced a complex substructure in these specimens. SOLUTE rejection at the advancing solid-liquid interface of a unidirectionally solidified single-phase metal can cause the liquid immediately in front of the interface to become constitutionally super-cooled below the equilibrium liquidus temperature. Constitutional super-cooling occurs if the solidification rate, R, is too rapid, or if the thermal gradient in the liquid at the interface, G, is too low. 1 This constitutionally supercooled layer in turn stabilizes a cellular rather than a planar interface.&apos; A similar cellular interface has been observed when lamellar and other types of eutectics were unidirectionally solidified, and it has been shown that the cellular interface led to the formation of eutectic colonies.&apos; The lamellar structure is fan-shaped at the edges of colonies (which correspond to valleys or grooves in the cellular interface) because the lamellae grow normal to the local interface. One of the possible mechanisms which might cause the formation of the cellular interface, in the case of solidifying eutectic alloys, is constitutional supercooling of the liquid with respect to a third component rejected by both phases of the eutectic.3,4 On the basis of the analogy between the solidification of single-phase metals and binary eutectics, a eutectic alloy should solidify with a planar interface if the ratio of G/R is sufficiently high to compensate for any impurity which might be present and causing constitutional supercooling. The fan-like microstruc-ture of eutectic colonies should not occur under these conditions and the lamellae should be parallel to one another and to the solidification direction for extended distances. The experiments conducted in this investigation were designed to test these ideas. Following a resume of the experimental procedure, the various microstructures observed during the study are described, and their relationship to the growth conditions which produced them is discussed. EXPERIMENTAL PROCEDURE The eutectic between an aluminum solid solution and 0 phase (approximate composition CuA12) was chosen for this work for the following reasons: it was known that a lamellar structure forms, the eutectic temperature is low enough to facilitate experimental work, and the components can be procured commercially in a very pure form. High-purity copper (est. 99.999 pct Cu, obtained from National Research Corp.) and spectrographic aluminum rods, having impurities other than copper estimated to be Zn-15 ppm, Mg-10 ppm, Fe-3 ppm, Na-2 ppm, Cd-1 ppm, and Mn < 1 ppm, were melted in a stabilized zirconia crucible in a vacuum induction furnace at a pressure of 10 pof Hg. The melt was superheated to about 1000°C to assure mixing, cooled to 780°C and cast into an investment mold which yielded sixteen cylindrical specimen blanks 1/2 in. in diam and 5 1/2 in. long. The casting was allowed to solidify under vacuum. This master heat had an analysis of 32.6 wt pct Cu and 67.4 wt pct A1 by difference. The cylindrical specimen blanks were remelted and solidified unidirectionally in an apparatus illustrated schematically in Fig. 1. An RF induction coil heated

Jan 1, 1962

By C. A. Stout, S. W. Nicksic

The materials that stubilize emulsions of some Southern California crude oils were isolated from the produced crude. These substances were separated into acidic and nonionic fractions by ion exchange chromatography. Each fraction was further broken into groups of homogeneous molecular weight composition by gel permeation chromatography. Both ionic character and molecular weight of the individual fractions are reflected in the properties of the original crude oil emulsion. Specifically, the more acidic and the higher molecular weight fractions appear to be the most effective stabilizers. INTRODUCTION The treatment of oilfield emulsions is a continuing problem for the oil industry. In almost all cases, these are water-in-oil emulsions. Much more is known about the formation and stabilization of oil-in-water (O/W) emulsions than of the water-in-oil (W/O) type. To understand W/O emulsions, more information is needed on the materials responsible for their formation and stabilization. This is especially true in the case of oilfield emulsions where the stabilizing materials are complex mixtures of large asphaltene-like molecules. To study the chemical and physical properties of these emulsion stabilizers, it is necessary first to separate them from crude oil. This separation was achieved in the case of two Southern California crude oils. The materials that were isolated appear at first to be little different from an asphaltene mixture. However, if a mixture of distilled water and mineral oil containing about 1 percent of the natural emulsion stabilizers is passed through a colloid mill, the W/O emulsion formed may be stored in the laboratory for many months without any sign of breaking. This could not be done using undifferentiated asphaltenes from the same wells, indicating that there is a real difference between these materials and ordinary asphaltenes. The colloid mill used to generate the emulsion was required because tile natural emulsion stabilizers had very little effect on oil-water interfacial tension. The one characteristic — complexity of composition — that emulsion stabilizers share with asphaltenes makes virtually impossible the exact structure determination of the components of the mixture. For this reason, it was decided to investigate first the influence of molecular weight on the ability of these materials to stabilize emulsions. The emulsion stabilizers were first separated into acidic and neutral fractions according to whether or not the material was retained on a weakly basic ion exchange column. The extraction procedure was not designed to remove basic components from tile oils, and no attempt to isolate such a fraction was made. Following this separation, selected fractions were analyzed by gel permeation chromatography. Gel permeation separates according to molecular size, largely independently of chemical or polar characteristics. A heterogeneous mixture is separated into a number of fractions having much more homogeneous molecular weight distribution. A number average molecular weight of each fraction is therefore close to the true molecular weight of the principal component of that fraction. The fraction weights, expressed as weight percent of the sample, and the number average molecular weight of a representative selection of the fractions, will be referred to in this paper as the molecular weight profile of the original sample. DESCRIPTION OF GEL PERMEATION ANALYSIS The first reported gel permeation analyses were for separating partially hydrolyzed protein molecules in an aqueous system using expanded starch granules. Most of the theoretical work on gel permeation has been done by biochemists.1 This theoretical treatment is still incomplete, but the

Jan 1, 1969

By David A. Thomas, John F. Peck

Fibrous microstructures and their development have been studied by metallography and by hardness and quantitative metallographic measurements. Thin, curved grains were observed in transverse sections of commercial tungsten wire and were developed in laboratory-drawn iron wire at reductions greater than about 70 pct. The unusual grain shapes are attributed to the nonuniform mode of deformation of the grains associated with the characteristic [I101 preferred orientation that develops in bcc metals during drawing. Transverse sections of heavily swaged iron wire showed a ospiral nebulao structure that appears to result from the elliptical shape of the cross section of the swaging dies and their rotary motion. Hardness and quantitative metallographic results show unusual trends that parallel the changes in microstructure. Other phenomena are considwed in light of the results, including the strength of fine wires of bcc metals, ocylindricalo textures, and the ductility of fibrous tungsten. 1 HE microstructure of tungsten wire in a longitudinal section shows grains highly elongated in the working direction, giving the appearance of a bundle of parallel fibers, Fig. l(a). Wires of tungsten and other bcc metals show a pronounced preferred orientation in which a [I101 direction is parallel to the wire axis.l The microstructure and texture of tungsten develop during warm working (working above room temperature but below the recrystallization temperature) into wire by swaging and drawing. Fibrous tungsten so produced has limited but useful room-temperature ductility, whereas annealed tungsten is brittle at room temperature. During an investigation of the effect of recovery annealing on the substructure of commerical 0.030 in. diam tungsten wire, it was found that transverse sections of the as-received material showed thin, curved grains, Fig. 1(b), instead of the expected equiaxed grains. The fact that Figs. l(a) and (b) show different sections of the same material at the same magnification is at first disconcerting, because the long dimension of the curved grains in the transverse section is several times the average fiber width in the longitudinal section. However, a longitudinal section cuts most of the curved grains across their narrow dimension, giving the appearance of a multitude of narrow fibers. On the other hand, the plane of a longitudinal section occasionally includes a long dimension of a curved grain, resulting in a broad ofibero, such as A in Fig. l(a). EXPERIMENTS AND RESULTS To investigate the origin of fibrous microstructures and particularly the unusual transverse-section structure of tungsten, rods of iron (also bcc) were drawn and swaged in the laboratory. One rod of annealed Ferrovac E was drawn in six steps to a total reduction in area of 87 pct (0.10 to 0.036 in. diam), and a second rod was swaged to the same reduction, using approximately the same reduction steps. Longitudinal and transverse sections of the swaged and drawn iron wires are shown in Fig. 2, for reductions in area of 39, 73, and 87 pct. A fibrous microstructure in longitudinal section is first evident at 73 pct reduction, and it is further developed at 87 pct reduction. The grains in transverse section remain equiaxed until about 73 pct reduction, when they become somewhat elongated and curved. At 87 pct reduction, the drawn wire shows thin, curved grains in the transverse section, similar to those observed in tungsten. The transverse sections of the iron wires swaged 83 and 87 pct reduction in area show the striking ospiral nebulao structure in Fig. 2(d). This struc-

Jan 1, 1962

By Johannes Moeljono, Werner Wenzel, Heinrich Wilhelm Gudenhau

As an important mechanism for increasing production of the suction-draft-sinter process, it has been shown that gas permeability through the sinter layer plays an important role. Methods to increase production rates have been indicated and suggestions for carrying out the process have been made to improve the rate of production, reduce the fuel consumption, and at the same time obtain a uniform sinter. Laboratory experiments were conducted at the Institute for Ferrous Metallurgy of the Technical University at Aachen to illustrate these methods. Methods of Increasing Gas Penetration Through Sinter Layers The following are of fundamental importance in determining the process cycle during the sintering of iron ores: 1) Generation of maximum temperature, since its form and range determine sinter quality. 2) Propagation velocity of the temperature maximum which controls the attainable output. 3) The convective heat transfer which influences the velocity of travel of the temperature maximum.

Jan 1, 1974

By W. C. Ellis, M. E. Fine

WHEN certain binary Fe-Ni alloys are worked cold and then stabilized by a stress-relief anneal, their Young&apos;s moduli are nearly invariant over a substantial temperature range determined by composition and work-anneal history.&apos; In the present investigation addition of molybdenum to such alloys (besides increasing the yield strength) was found to diminish the sensitivity of the thermal coefficient of Young&apos;s modulus to composition changes. Such alloys are of interest for applications requiring 1 a metal with controlled, low temperature coefficient of Young&apos;s modulus and substantial magnetic permeability.&apos; Young&apos;s modulus ordinarily decreases with rising temperature. In ferromagnetic alloys a change in modulus on heating due to loss of ferromagnetism modifies the .temperature dependence. Far below the Curie temperature ferromagnetism alters the modulus in two ways: a—Addition of the energy of magnetization, a function of interatomic distance, changes the relation between interatomic energy and distance.&apos; This lowers the modulus in the Fe-Ni and Fe-Ni-Mo alloys of this investigation. b—An applied stress changes the ferromagnetic domain arrangement so that linear magnetostriction contributes to the strain and further lowers the modulUs.~ Since in the alloys of this investigation both effects lower the modulus, loss of ferromagnetism on heating changes the slope of the modulus-temperature curve in a positive direction. With increasing temperature the slope of the modulus-temperature curve, due to progressive loss of ferromagnetism, becomes less negative, goes through zero (the modulus is minimum), becomes positive, and resumes its normal negative value above the Curie temperature.&apos; The increase in modulus and decrease in curvature in the modulus-temperature curve occurring on work hardening have been attributed to a reduction in effect (b).&apos;. Vn the absence of ferromagnetism work hardening through introduction of residual strains would be expected to decrease the modulus.&apos; Alloy Preparation—Test Methods Four series of alloys having nominal molybdenum contents of 5, 7, 9, and 10 pct and containing 47 to 58 pct Fe (the analyzed compositions are given in Table I) were melted in air and cast as bars weighing from 2 to 6 lb. The charge consisted of electrolytic nickel, Armco iron, molybdenum (99+ pct) or ferromolybdenum (62 pct Mo), manganese, and aluminum as a deoxidizer. The bars were swaged cold to the desired diameters with intermediate anneals. Alloys in this composition range are reported" to be face-centered cubic and ferromagnetic at room temperature. The Curie temperatures" decrease with molybdenum. For example, keeping the Ni/Fe ratio at unity and increasing the molybdenum from 0 to 17 pct decreases the Curie tempera- ture from approximately 500°C to room temperature. (The 17 pct Mo alloy requires quenching to retain a single phase.~) Young&apos;s modulus at a series of temperatures from —50" to 100°C was determined by a dynamic method previously described.&apos;, " In this method Young&apos;s modulus is calculated from the resonant frequency (in this case approximately 50,000 cycles per second) of a rod sample (approximately 2 in. long) vibrating longitudinally in the first mode. The densities of the samples at room temperature, Table I, were determined by the standard method of weighing in air and reweighing in redistilled bromobenzene. The linear coefficients of expansion, Table I, needed to calculate the sample length and density at the temperature of measurement, were obtained by observing the change in length (22" to 100°C) of an 8 in. gage distance with a two microscope cathetometer. The values of density and coefficient of expansion in the few samples checked are independent of treatment to the accuracy reported. This was assumed to be general for all the samples. The modulus values are accurate to &0.05x101&apos; dynes per sq cm. However, values of thermal change in modulus are accurate to 20.005~ 10" dynes per sq cm. Young&apos;s Modulus Values at 25°C: The modulus values of O&apos;, 5, and 10 pct Mo alloys at 25 °C are plotted in Fig. 1 as functions of nickel. After working cold, the samples were either recrystallized at 950" to 1000°C or given a low temperature stabilizing anneal at 400° C. The 400°C anneal does not reduce the hardness nor cause recrystallization. Annealing at 400 °C does

Jan 1, 1952

Edward Dyer Peters, the only child of Henry Hunter Peters and Susan Barker Thaxter, was born in Dorchester, Mass., June 1, 1849. From his father he was a descendant of the Peters family of Ipswich and Andover, Mass., whose earliest ancestor settled in Essex County in 1659; while upon his mother&apos;s side he descended from several old Hingham families, as well as from the Quineys and from Governor Bradford. Between the ages of fourteen and sixteen he was a student at the Episcopal School for boys in Cheshire, Conn. Near the school was an old tin mine, and he used to spend his Saturday afternoons exploring it. When Edward was sixteen, his father sold his property in South-borough, and for the next three years lived in Europe. Sept. 26, 1865, Edward entered the Royal School of Mines at Freiberg, Saxony. In the summer of 1867 he joined his family on Lake Geneva, and spent a part of the season in that vicinity, going to Chamounix and taking other trips. Extract from a letter to his father: Elbingerode, Harz, Aug. 30, 1868: I left Freiberg with my friend Lilienthal, on Wednesday the 19th of August, reached Leipzig in the evening and spent the night in that city: the next morning we took the cars and in the afternoon reached Eisleben, in Prussia, which was to be our first stopping-place; there are immense copper-mines and smelting-works at this place, and the method of working the mines is very peculiar ... The next morning we got up at five and spent the whole day in the smelting-works where I obtained a number of drawings of the furnaces they use here and a good many valuable data. Saturday morning we got up at four o&apos;clock, and descended a mine about three miles from the town; the Director of this mine was one of the most intelligent and agreeable men that I ever met; he accompanied us in the mine and explained everything that was new to us. The system of mining at Eisleben is peculiar to this town, and is not used at any other place in the world; the copper ore comes in narrow, flat veins eighteen inches high, at the utmost, consequently the men work lying flat on their left side and using the pick with both hands: the ore is carried out of the side passages into the main ones, in very low waggons about twelve inches high, and four by two feet; the boys who pull these waggons have a board buckled to their left thigh and their left arm; they pass their bare foot through a strap in the waggon and wriggle along on their side dragging the waggon after them, with their foot, almost as fast as a man can walk above ground. In the afternoon we walked over to Hittstadt, about twelve miles, and remained there Sunday and Monday. Monday night, at ten o&apos;clock we went out to one of the smelting-works, to see the refining of the copper; this is only done at night, so we worked there from ten in the evening till eleven the next morning, and came home all blackened up and with blistered hands, for our skin was not quite so tough as that of the workmen: at noon the same day we took the stage to Ascherls-leben, and then the train to Stassfurt, where there are immense salt-mines, as well as factories for the manufacture of bromium, which latter process is, however, kept a profound secret, so we had very little hope of seeing anything but the salt mines; we were talking with our landlord about our disappointment, that evening, when he told us that the director of the Bromium works was sitting in the next room with no company but his glass of beer, so we went over to him, introduced ourselves as Americans, and actually succeeded in persuading him that it could do his business no earthly hurt if he showed us his works; at last he consented, after making us give our word of honor

Jan 1, 1919

By J. Marin, H. A. B. Wiseman

This paper presents results of an experimental study dealing with the plastic stress-strain relations of aluminum alloy 14s-T6 subjected to combined biaxial tension and compression stresses. Plastic stress-strain relations for both constant and various types of variable stress ratios were determined and a comparison made with the simple flow theory of plasticity. THIS investigation was undertaken for two main purposes: 1—to obtain plastic stress-strain relations for Alcoa 14s-T6 when subjected to various combinations of biaxial stresses, and 2—to determine the validity of the flow theory in predicting plastic stress-strain relations for combined stresses. The biaxial stresses used were tension combined with compression. These stresses were produced by subjecting a thin-walled tube to axial tension and torsion. Various types of combined stress conditions were investigated. To provide control test data and information on the influence of biaxial stresses on the strength, the usual constant stress ratio type tests were made. These tests showed that the biaxial yield strength agrees approximately with the distortion energy theory. However, the Prager semi-empirical theory agrees best with the test results. For these constant stress ratio tests the plastic stress-strain relations were found to agree approximately with the flow theory. (For constant stress ratio the flow and deformation type theories are identical.) In view of the fact that the constant stress ratio tests cannot distinguish between the flow and deformation theories, a number of variable and special biaxial stress tests were made. These tests showed that the flow theory is inadequate, since large differences exist between the experimental and theoretical results. Special tests were also conducted to check the validity of the isotropic yielding assumption. This assumption is made in the linear-type flow theory. In these tests specimens were loaded in tension to predetermined values beyond the proportional limit stress. The tension load was removed from the specimen and the specimen was subsequently loaded in torsion to fracture. Other tests were applied with the order of torque and tension loading reversed. The nominal stress-strain curves for these two tests approximately coincide indicating that the assumption of isotropic yielding is valid. In addition, these tests verified the requirement by the slip theory of plasticity that prestraining below 140 pct of the proportioned limit stress in either torsion or tension did not influence the subsequent plastic stress-strain relations in tension or torsion. Another type of test was conducted to check the assumption that the axes of principal stress and strain coincide during plastic flow and variable stress conditions. These tests were conducted by applying combinations of axial tension, internal pressure, and torsional loads such that the axes of maximum principal stress could be rotated through 90" during the loading path. The results of those tests showed that the angle between the axes of principal stress and strain varied greatly and that the assumption of coincidence between axes of principal stress and strain is not valid. Introduction In various metal processes including forming of sheets, rolling of bars, and extrusion of rods, metals are subjected to stresses beyond the yield strength of the material. Often these stresses are not simple stresses acting in one direction, but are combined stresses acting in more than one direction. Structural and machine members are often subjected to combined stresses. To adequately determine the factors of safety for these members, it is necessary to know the plastic stress-strain relations of the material used for various combined stress conditions. Various theories have been proposed for predicting the plastic stress-strain relations for combined stress in terms of the simple tension plastic stress-strain relation for the material. To determine which theory might be adequate, test results must be obtained for various combined stress conditions, in order to compare the actual with the assumed theoretical behavior. Although there is considerable test data available for combined stress conditions in which the principal stress ratios are constant, relatively little test information is available for vari-

Jan 1, 1954

By J. D. Wood, J. T. Smith

ALLOYS with a dispersed second phase in a metallic matrix are generally much stronger than the matrix itself. Plastic deformation in dispersion-strengthened alloys is usually confined to the matrix phase when recovery processes are active, while in the absence of recovery both phases may yield.&apos; The alloy system studied in the present research was WC-12 wt pct Co and consisted of noncoherent WC particles dispersed in the cobalt matrix. Some particle-to-particle contact existed but not enough to produce a continuous WC skeleton. The microstruc-ture of the WC particles was characterized by very straight edges, forming a trapezoidal shape in any plane of polish. Previous investigations with WC-Co alloys at room temperature have shown that fracture of the WC particles occurs in transverse rupture testing.&apos; Room-temperature slip was reported for WC particles after indentation for hardness measurements.3 Elevated-temperature deformation of WC particles in a WC-12 pct Co alloy was suggested by recent electron microscope studies of specimens deformed at 900&apos; to 1000°C.4 In highly deformed alloys, the WC edges were serrated in contrast to the usual straight or smooth appearance. WC-12 pct Co and WC-15 pct Co alloys have been previously studied under elevated-temperature com-pressive-creep conditions by the present authors. Electron microscope studies of two-stage replicas from deformed specimens showed no evidence of slip or fracture of the WC particles. These specimens were brought to temperature and allowed to equilibrate prior to the application of the creep load. It was believed that the load-application rate, a crosshead speed of 0.005 in. per min on an Instron universal testing machine, was sufficiently low that recovery within the cobalt matrix was sufficient to limit the deformation to this matrix. A series of experiments was performed to evaluate the influence of loading rate on the deformation of WC-Co alloys. A WC-12 pct Co alloy was selected for these determinations. The average WC particle size was 4.45 p with an average linear separation between particles of 0.59 p. The selected temperature was 800°C and was monitored with a Chromel-Alumel thermocouple attached to the specimen. Testing was conducted in an argon-atmosphere chamber to prevent oxidation of the WC-Co specimens. This chamber was mounted on an Instron universal testing machine equipped to apply the load at a fixed rate. Each specimen was loaded to 110,000 psi compression stress at 0.05 and 0.5 in. per min. The loading rate was monitored prior to insertion of the test chamber and was found to be almost precisely the nominal rate selected. The specimens were raised to temperature and held to equilibrate with the surroundings, and then the load was applied and held for 4 hr to duplicate the exposure time utilized for the creep specimens. The time to reach full load at a crosshead speed of 0.005 in. per min was some 500 sec and was reduced to 50 and 5 sec as the loading rate was increased to 0.05 and 0.5 in, per min, respectively. The model developed by Ansell,&apos; when recovery processes do not occur, considers that fracture or deformation of the dispersed particles is necessary to relieve back stresses on dislocation sources and allow dislocations piled up against particles to sweep out in the matrix to cause plastic deformation; he further states that, even at elevated temperatures, the dispersed-particle deformation is necessary for yielding in the absence of recovery. For the case of straight dislocation segments piled up against a straight barrier, such as the straight-sided WC particles, the shear stress, 7 exerted on a particle is: where h is the spacing between particles (0.59 p), a is the applied stress (110,000 psi), p, is the shear modulus of the matrix (6.7 X lo6 psi at 80O°C), and b is the Burgers vector of the matrix dislocation. From Eq. [I], the shear stress, 7, exerted on the WC particles when no recovery occurs is of the order of 6 X lo6 psi at 800°C. The limiting stress, F, that will

Jan 1, 1969

By G. Britsianes, T. L. Joseph

THE reduction of a lump of iron ore is a complicated sequence of up to three reactions proceeding simultaneously in a gas-solid system. As the ore moves down the blast furnace into zones of higher temperature and higher reducing power, it is successively reduced through the three oxides of iron into metallic iron. The reduction process involves much more than chemical problems. Physical factors add to the complexity of the overall process. Under optimum conditions, reduction of the ore is completed at a level about one-half way down the blast furnace stock column. At this point, the ore undergoing reduction has attained a temperature of about 1000°C and has been in the furnace for about 6 hr. On the practical side, the behavior of the ore during smelting has been of great interest to operators. Unsatisfactory blast furnace operation on burdens containing magnetite ore or badly slagged sinter has often been attributed to poor re-ducibility. The question of reducibility has also been raised in formulating quality standards for agglomerates such as nodules, briquettes, and pellets. In the present investigation, the solid phases formed during reduction were studied as a step toward a better understanding of the overall process. Equilibrium Studies The iron-oxygen equilibrium diagram shown in Fig. 1 reveal; a number of facts pertinent to the gaseous reduction of iron ores. This diagram is from the work of Darken and Gurryl, 2 and represents a correlation of the best available data. Four solid phases may exist during the complete reduction of hematite to metallic iron. These are hematite (Fe2O3), magnetite (Fe3O4), wustite (FeO), and iron (Fe). The wustite phase is a solid solution which is not stable below 570°C. At this temperature the solid solution undergoes a eutectoid-type of decomposition into the phases, magnetite and iron. Thus above 570°C, the diagram dictates that a hematitic ore should pass through a four-phase sequence on reduction to metallic iron. Below 570°C, only hematite, magnetite, and iron should appear. Information on the iron-oxygen system has been derived largely from CO and H2 reduction equilibria. The Fe-C-0 relationships have been studied extensively by R. Schenck and his coworkers and well summarized by H. Schenck.3 More recent studies have been made by Darken and Gurry.1, 2 Data from these sources have been combined and plotted in Fig. 2. With respect to the Fe-H-O system, the works of Emmett and Schultz4 seem the most reliable, and these data have also been included in Fig. 2. Certain physical properties of the solid phases of the iron-oxygen system are summarized in Table I. The crystallographic information is of special interest as much of the present work has been concerned with the X-ray analysis of the products of reduction. Reduction with Hydrogen The reduction of ore with hydrogen is the net result of two or more gas-solid reactions. Above 570°C, the reaction sequence may be represented by stoichiometric stages as follows: 3Fe203+ H2e2Fe,O, + H20 [1] 2Fe3O, + 2H2 6FeOw + 2H2O [2] 6FeOw + 6H3 ^ 6Fe + 6H=O [3] Fe2O3 + 3H2 ^ 2Fe + 3H,O. [4] These reduction reactions follow the general form: A (solid) + B (gas) e C (solid) + D (gas). This type of gas-solid reaction has been investigated by Langmuirl&apos; who has shown that such reactions can occur only at the boundary between the two solid phases. Furthermore, a nucleus of the second phase must initiate the reaction. Once such an interface exists, the reaction proceeds through a layer of the solid reaction product (C). The specific mechanisms involved will depend a great deal on the properties and condition of this particular layer. A number of heterogeneous reactions such as the dehydration of single crystals of copper penta-hydrate and the calcination of limestone follow this type of process. It should be noted that the inter-facial type of reaction also occurs even in dense polycrystalline material which simulates a mono-crystalline behavior.

Jan 1, 1954

By C. W. Allen, B. D. Cullity

The proportional limit of iron crystals in torsion is governed by the resolved shear stress in the most highly stressed slip systems, averaged around the specimen circumference, and does not obey a critical resolved shear stress law. Crystals of most orientations exhibit a stage of easy plastic deformation, akin to easy glide in tensile or shear specimens. Transient deformation, similar to that which occurs in single crystals of other materials, is also observed. THE torsional deformation of single crystals of magnesium (hcp) and aluminum (fcc) has been described recently by Choi et al.,&apos; especially with respect to the criterion for the orientation dependence of the onset of plastic flow in these materials. The purpose of this paper is to present results of torsion tests of iron single crystals and thus to extend this yield criterion to a bcc metal. In addition to considering the variation of proportional limit with crystal orientation, this paper also briefly treats work hardening, transient deformation, and the mechanism of plastic flow in iron. The effects of the method of surface polishing and the chemical purity of the iron have been investigated. STRESS DISTRIBUTION It is convenient to express the stress at any point of a cylindrical crystal stressed in torsion in terms of t0, which is the shear stress acting at the surface on a plane normal to the axis of the cylinder and in a direction tangential to the cylinder. This stress is given by To = 2T/pr3 [1] where T is the applied torque and r the specimen radius. The shear stress t, resolved in any chosen slip system is given in terms of 7, by1 Ts/TO = sin 0, cos d sin (0, -) + cos , sin d sin d - ) [2] where 0 and d are the angles between the specimen axis and the slip plane normal and slip direction, respectively; h is the angular circumferential position on the specimen at which t, is being determined, measured from an arbitrary reference plane which includes the axis;o and d are the angular coordinates of the projections of the slip plane normal and slip direction on a transverse section with respect to this same reference plane. Slip in iron occurs in a <1ll> direction on the {ll0}, (1121, and (123) planes, which together comprise 48 slip systems. A complete evaluation of the stress distribution in an iron crystal stressed in torsion would therefore require a calculation of Ts/T0 as a function of for 48 different slip systems. Fortunately Gough,&apos;who studied the behavior of iron crystals in alternating torsion, was able to simplify this problem considerably. He showed that it was sufficient to consider a kind of average slip plane for each slip direction, namely the mathematical plane of maximum resolved shear stress containing the slip direction considered. This simplifying approximation is possible because, for each slip direction, the active slip plane or planes lie very near this mathematical plane of maximum shear stress. Vogel and rick&apos; have critically reviewed the early work of Taylor and Elam,13 Taylor,14 and Fahrenhorst and schmid8 from which the identification of the above crystallographic planes as slip planes in the bcc lattice largely stems. While their criticism is clearly justified, their own results do little to clarify the issue. The role of cross slip (screw dislocations changing glide planes) is evidently so important in this case, as Read3 has suggested, that methods for deducing slip systems from observations of gross slip traces are inadequate, such traces commonly arising from complex dislocation motion. Thus the treatment given here involving the plane of maximum resolved shear stress seems a logical simplification especially in view of Gough&apos;s2 study of a iron. There is, however, an assumption built into the subsequent treatment the comparative validity of which is difficult to assess, namely, that slip in all slip systems in iron may be characterized by a common critical resolved shear stress. The shear stress 7, resolved in a slip direction defined by d andd, and on the plane of maximum shear stress containing this direction, is found by first maximizing 7s/70 with respect to either Oo or 4,. The slip plane coordinates are then eliminated by using the relation between 0, ,o and d, d, namely,

Jan 1, 1963