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By G. A. Collins

Being much interested in efficiency-work in general, and an ardent reader of writings on this subject by Frederick W. Taylor and others, as applied to manufacturing-plants, and having served my apprenticeship from mucking to the engineering design of ore-dressing and underground plants, I hope that this paper will lead others to investigate the field more fully, to the improvement of general mine- and mill-operations, as well as the advancement, intellectually, physically, and financially, of the employee and his relations with the employer. If a man who is prepared to look closely and observe broadly starts in Canada and zig-zags from camp to camp to southern Mexico, taking time casually to inspect mines, mills, and smelters, he will be pitifully impressed by the great difference in customs, and the general waste of labor, time, and money throughout the country. He will so seldom observe a dollar's worth of results given in exchange for a dollar spent that he will form a poor opinion of operating-efficiency and management. This highly-scientific department, requiring an amount of skill and executive ability equaled in few, if any, of the professions, certainly falls short of the standard established in our greater manufacturing industries. It is easily said that this is due to the diversity of conditions in mining, milling, and smelting. But on second view it must be admitted that there is room for tremendous improvements in nearly every mining-organization. The proposal of such improvements is often met by the argument that any mine is but a temporary affair, yielding such profits as to make efficiency-work of no consequence; but any business which is profitable and worth doing at all is worth doing on a basis which gives the greatest return on the investment.

Jan 1, 1913

By Arthur F. Taggart

MR. CHAIRMAN: Congratulations! Your four-ring milling show this year was a dandy. It cleared our minds, for a few hours at least, of what Hitler, Hirohito, the New Deal, and the tribe in the Treasury are trying to do to strangle American enterprise. We mustn't forget this, but it's a relief to get our thoughts away from it occasionally. GRINDING-There was a further contribution to the excellent work that the Allis-Chalmers laboratory staff has been doing for the grinding fraternity in compiling-and publishing-a carefully quantitative list of comparative resistances of ores and other materials to comminution (T.P. 1579, Bond-Maxson). A diagnostic accuracy of ± 10 per cent was claimed for estimates based on these figures. Are they really that good? How about some of you men in the field writing M&M about it?

Jan 1, 1943

By K. D. Jacob, H. L. Marshall, D. S. Reynolds

All types of commercial phosphate rock produced throughout the world contain fluorine in quantities ranging from approximately 0.4 to 1.3 per cent in the Curacao and Christmas Island phosphates to 3.1 to 4.2 per cent in the phosphates of the United States and North Africa1. For a given type of rock, the fluorine content is usually roughly proportional to the phosphorus content. Significance of Fluorine in Phosphate Rock On the basis of chemical and X-ray diffraction studies, Hendricks and co-workers2 concluded that fluorapatite, Cal10F2(PO4)6, is the essential phosphatic constituent of the commercial types of domestic phosphate rock. On the other hand, Bredig and co-workers3 have recently advanced the opinion, also based on X-ray diffraction studies, that the mineral phosphates usually contain carbon dioxide in the apatite lattice, and that the phosphate rocks of the United States are really fluorcarbonate apatites. However, the domestic types of phosphate rock do not seem to differ greatly from coarsely crystalline fluorapatite in their behavior toward chemical reagents in general, and for the purpose of this paper it will suffice to consider fluorapatite as being the essential phosphatic constituent of these types of rock. The available data1 indicate that the different commercial types of domestic phosphate rock usually contain about 12 to 52 per cent more fluorine than theoretically is required to form fluorapatite with all the phosphorus. Calcium fluoride (fluorite) has been definitely identified in only a very few of the samples that have been examined1,2. Bredig and co-workers4 state that fluorapatite can take into its crystal lattice excess calcium fluoride to the extent of approximately 70 per cent of that theoretically required by the formula Ca10F²(PO4)6 without causing more

Jan 1, 1938

By D. S. Reynolds, K. D. Jacob, H. L. Marshall

All types of commercial phosphate rock produced throughout the world contain fluorine in quantities ranging from approximately 0.4 to 1.3 per cent in the Curacao and Christmas Island phosphates to 3.1 to 4.2 per cent in the phosphates of the United States and North Africa1. For a given type of rock, the fluorine content is usually roughly proportional to the phosphorus content. Significance of Fluorine in Phosphate Rock On the basis of chemical and X-ray diffraction studies, Hendricks and co-workers2 concluded that fluorapatite, Cal10F2(PO4)6, is the essential phosphatic constituent of the commercial types of domestic phosphate rock. On the other hand, Bredig and co-workers3 have recently advanced the opinion, also based on X-ray diffraction studies, that the mineral phosphates usually contain carbon dioxide in the apatite lattice, and that the phosphate rocks of the United States are really fluorcarbonate apatites. However, the domestic types of phosphate rock do not seem to differ greatly from coarsely crystalline fluorapatite in their behavior toward chemical reagents in general, and for the purpose of this paper it will suffice to consider fluorapatite as being the essential phosphatic constituent of these types of rock. The available data1 indicate that the different commercial types of domestic phosphate rock usually contain about 12 to 52 per cent more fluorine than theoretically is required to form fluorapatite with all the phosphorus. Calcium fluoride (fluorite) has been definitely identified in only a very few of the samples that have been examined1,2. Bredig and co-workers4 state that fluorapatite can take into its crystal lattice excess calcium fluoride to the extent of approximately 70 per cent of that theoretically required by the formula Ca10F²(PO4)6 without causing more

Jan 1, 1938

By P. Douglas, G. M. Leak, B. Mills

The sinusoidal surface relaxation technique has been used to measure the surface self-diffusion coefficient of spectroscopically pure nickel over a wide temperature range under a hydrogen atmosphere. A kink in the Arrhenius plot has been observed. In the temperature range T/T 0.98 to 0.80 (T in O K and T, is the melting temperature) the average self diffusion coefficient is given by Below the temperature T/T,- 0.80a decrease in the slope of the log Ds us 1/T plot is observed. This is associated with a diffusion process characterized by a lower activation energy (-20,000 cal mole'') and smaller preexponential term (-10- sq cm sec"). A series of experiments were carried out at T/Tm = 0.61 under a hydrogen atmosphere of higher oxygen partial pressure than for the rest of the experiments. It was found that Ds was significantly depressed due to oxygen adsorption. This evidence supports the opinion that the low temperature process (activation energy -20,000 cal mole-') is unlikely to be due to oxygen adsorption. An interesting feature of the present data is that the transition temperature (T/Tm - 0.80) is a function of orientation. For a small number of crystals of measured orientation the transition temperature was observed to be higher towards the low index (100) pole. Theories of surface diffusion are briefly reviewed and it is concluded that the present reszuts are best explained by invoking a surface roughening process. GJOSTEIN has recently analyzed available surface diffusion data for a wide range of metals. He suggested that two mechanisms were operative for fcc metals, an adatom process at high temperatures and a vacancy process at low temperatures. Results for nickel can be summarized as follows. At low temperatures (T/T, - 0.3 to 0.44) under ultra high vacuum conditions, Melmed2 measured an activation energy Q of 21 kcal mole-' using field electron emission microscopy. At higher temperatures (T/T - 0.7 to 0.9) under a vacuum of 10- ' torr, Maiya and lakel measured y as 39 kcal mole-' using the multiple scratch smoothing technique. The present work was undertaken to try to find out if two distinct processes could be observed. High temperature results give Q about 47 kcal mole-': there is evidence also for a low temperature value of about 20 kcal mole-'. These measurements were all made under a hydrogen atmosphere, in the temperature range 860" to 1412°C. Concurrent with the present study Bonze1 and jostein> have also observed a break in the Arrhenius plot for the (110) surface of nickel. These measure- ments under ultrahigh vacuum conditions using the laser diffraction technique are in excellent agreement with the work reported here under hydrogen annealing conditions. THEORY The available surface relaxation techniques include single and multiple scratch smoothing and grain boundary grooving. The processes have been compared in detail by Gjostein for conditions where surface diffusion dominates6 and Mills et al? where volume diffusion dominates. In summary the relevant points are as follows. Grain boundary grooving gives an average Ds for the two surfaces adjacent to the boundary and this can, to some extent, be simplified by using symmetrical bicrystals. This technique has been used to study the effect of environment on Ds for silver and copper.'-'' Scratch techniques yield Ds values for the small orientation range exposed by the scratches (-2 deg). The multiple scratch process is preferable because the profile rapidly becomes sinusoidal and can then be interpreted theoretically in a relatively simple way. Also corrections for mass transport processes other than surface diffusion can be introduced easily. Mullins" considered a sinusoidal profile described the wavelength of the profile. After time t the profile can be described by the equation The terms A, A', C, and B which account, respectively, for contributions due to evaporation-condensation, diffusion through the gas phase, volume diffusion through the lattice, and surface diffusion are defined as: where Ds = the surface self diffusion coefficient ys = the surface energy per unit area p = the equilibrium vapor pressure over a flat surface pa = the equilibrium vapor density over a flat surface DG= the diffusion coefficient of vapor molecules in the inert gas DM = the mass transfer diffusion coefficient which for a pure cubic metal is Dv/f where Dv is the radiotracer diffusion coefficient and f is the correlation factor H = the molecular volume V = the surface density of atoms, il2'3 M = mass of an evaporating molecule

Jan 1, 1970

By L. V. Gregor, C. F. Aliotta, P. Balk

The structure of silicon surfaces, thermally oxi&zed in dry oxygen and in steam, was studied using the electron microscope. It was found that the structure on the original (etched) surface is retained at the outer surface of the oxide, whereas the oxide-silicon interface is smoothed out considerably. This supports the idea that, both in oxygen and in steam, the oxidation reaction occurs at the oxide-silicon interface. Mechanical damage of the original silicon surface affects the rate of oxidation. It also changes the chemical properties of the oxide, as shown by the enhanced rate of etching in buffered HF at the locations of damage. However, the oxide at the originally damaged surfaces still exhibits a high electrical breakdown strength. Exposure of thermal oxides to P205 or BzOs vapor, which will yieldphospho- or borosilicate layers, results in complete annihilation of all fine structure on the surface. Reaction of silicon with C02 gives a surface film which probably does not consist of pure SiO,. THERMAL oxidation of silicon yields uniform and strongly adhering oxide films which are normally amorphous and continuous. Contamination and surface imperfections have been reported to cause local crystallization and the formation of pinholes."' The parabolic-rate law of film growth observed by several workers for the oxidation both in steam and in dry oxygen at higher temperatures suggests that diffusion of one or more reactants through the oxide is the rate-deter mining step. One of the dif-fusants is an oxygen species and oxide is continuously formed at the oxide-silicon interface. This was concluded for high-pressure steam oxidation by Ligenza and spitzer5 from an infrared-absorption study of the isotopic exchange of oxygen. Jorgensen arrived at the same conclusion for the oxidation in dry oxygen by measuring during oxidation the resistance change between silicon and a porous platinum marker electrode in the oxide. Recently, Pliskin and Gnall' reported similar conclusions concerning the growth mechanism from controlled etch studies using a phosphosilicate marker. The work communicated in the present paper was aimed at studying oxide growth on locally damaged silicon substrates and relating it to the chemical behavior and electrical breakdown properties of the films. Since etched and oxidized silicon surfaces normally appear to be very smooth when examined by optical microscopy except for some occasional pits, it was decided to use the electron microscope as a tool. In this way, the detection of surface roughness and damage on a scale comparable to or smaller than the thickness of the film is possible. Also, the microstructure of the original substrate surface constitutes a built-in marker which represents a minimum of perturbation to the growing oxide layer, and no foreign material is introduced. Thus information on surface reactions and additional evidence on the location of oxide formation in steam and in oxygen could be obtained. EXPERIMENTAL Electron micrographs7 were obtained using a Philips EM100 electron microscope. Collodion surface replication was used since this is a nondestructive technique and thus permits replicating the same surface at different stages of processing. In order to establish the effect of different treatments it was found essential to make successive observations of the same area by using a reference point. Reference points were conveniently provided by scribing a small v mark on the original surface with a silicon carbide tip. This procedure yields damaged and damage-free areas near the reference point. Upon replication, the samples were thoroughly cleaned before subjecting them to the next process step. Mechanically lapped silicon wafers (Dow-Corning, 100 ohm-cm p-type, cut perpendicular to the (111) direction) were chemically polished in a rotating beaker with a mixture of 1 part HF (48 pct), 2 parts glacial acetic acid, and 3 parts HNO3 (70 pct) by volume. This procedure yields a smooth surface with a faint "orange peel'' structure due to a "ripple" less than 20002i deep. Oxidation in steam or oxygen was carried out in an Electroglas tube furnace. Steam oxidations were always preceded and followed by a brief exposure to oxygen at the same temperattre. The thicknesses of the oxide films under 3000A were determined with a Rudolph Model 436-2003 ellipsometer,' whereas those over 3000A were measured using the VAMFO technique. In the present study, a solution of 300 g of N&F in 25 ml HF (48 pct) and 450 ml water was used to detect areas of increased chemical reactivity in the

Jan 1, 1965

By D. Turnbull, J. H. Hollomon, J. C. Fisher

Application of the concepts of nu-cleation and growth to the analysis of experimental transformation data has led to valuable descriptions of phase transformations, an outstanding example being the transformation austenite —* pearlite which has been examined with particular care by Mehl and co-workers.&apos;-5 In addition to the pearlite transformation, the proeutectoid fer-rite and proeutectoid carbide transformations are known to proceed by nucleation and growth. Martensite, on the contrary, until recently was thought to form by a mechanism involving neither nucleation nor growth; however, extension of standard nucleation theory6 suggests that martensite, bain-ite, and the other products of austenite decomposition all grow from nuclei in the parent phase. The theory that martensite forms by nucleation and growth is strongly supported by recent experimental work of Kurdjumov and Maksimova.7 The concepts of nucleatioli and growth have been fruitful also in providing a sound basis for quantitative theoretical treatments of the kinetics of phase transformations. For example, Volmer and Weber8 and Becker and Döring9 developed the theory of nucleation from fundamental considerations to a point where excellent agreement was obtained with the results of experiments on the condensation of supercooled vapors. As a result of their analysis, the kinetics of vapor-liquid transformations now can be predicted. It seems probable that application of the theories of nucleation and growth to a quantitative study of austenite decomposition similarly will clarify the nature of the individual transfor: mations involved, and will enable the calculation of austenite transformation kinetics. In the present paper, the theories of nucleation and growth are applied to the austenite ? martensite transformation in steels. The analysis begins with a discussion of nucleation in single component systems. Martensite appears to be coherent with the parent austenite, hence the nucleation theory is modified to include the effects of elastic distortion. Nucleation in the two component iron-carbon system then is discussed, for most steels are primarily alloys of these two elements. Finally, M. temperatures and martensite transformation curves are calculated for each of several alloy steels of varying carbon and chromium content, and are compared with those determined experimentally by Lyman and Troiano10 and Harris and Cohen.11 Nucleation Theory NUCLEATION IN SINGLE COMPONENT SYSTEMS6,12-14 The work required for reversible formation of a region of phase within the parent a phase is expressed conveniently as the sum of two terms: W1 = Aa, the product of the area of the interface and the interfacial free energy, and W2 = VAf, the product of the volume of the region and the free energy increase per unit volume associated with the transformation. The total work is therefore W = Aa + VAf. When a is more stable than ß, Af is positive and W increases without limit as the volume increases. The transformation a ?ß does not occur. It is nevertheless true that small regions of phase ß enjoy temporary existence here and there in the a. The equilibrium number of ß regions of given size is proportional to exp(— W/kT) per unit volume of a, assuring that larger (ß regions occur with diminishing probability. When a is less stable than ß, Af is negative and W passes through a maximum as V increases. Assuming for simplicity that regions of ß are spherical, as is true when the interfacial tension is isotropic and there are no elastic strains, W = 4r2a + (4/3)*r3Af The maximum value of W is W* = 16iro3/3Af2 [1] for regions with radius r* = -2o/Af. [2] For single component condensed systems it has been shown14 that the steady rate of nucleation of 0 per unit volume of untransformed a is nearly proportional to exp[- (W* + Q)/kT] where Q is the activation energy for the unit processes of adding or removing one atom from an embryo or nucleus. If To is the temperature at which a and ß are in equilibrium, the rate of nucleation is a maximum at a temperature 0 < T < To where (W* + Q)/kT is a minimum. P regions smaller than critical size are called embryos; they tend to grow smaller and disappear, only exceptionally growing larger. Regions equal to or larger than critical size are called nuclei. A critical size nucleus may grow indefinitely large or may shrink back to a, either process decreasing the free energy of the region.

Jan 1, 1950

By B. B. Rath, Hsun Hu

In wedge-shaped bicrystals of zone-refined aluminum it is observed that (111) pure tilt boundaries migrate under the driving force of their own inter-facial free energy. The boundary velocity is a power function of the driving force. The driving force exponent decreases with decreasing angle of misorien-tation. For example, at 64O°C, the exponent decreased from 4.0 for a 40 deg to 3.2 for a 16 deg tilt boundary. An evaluation of the driving force acting on the boundaries during their motion indicates that for low driv-forces, up to about 2 x l03 ergs per cu cm, the velocity is relatively independent of misorientation, whereas at higher driving forces a 40 deg tilt boundary exhibits the highest velocity. The measured activation energy for boundary migration approaches that for bulk self-diffusion at low driving forces, decreasing from 33 to 27 kcal per mole as the driving force is increased from 1 x l0 to 5 x l03 ergs per cu cm. These results are compared with current theories of grain-boundary migration. In previous experimental studies of grain boundary migration the driving force has been limited to a difference in stored energy across the boundary. This stored energy has been introduced into the crystal either by prior deformation1-3 or by grown-in lineage structure. A part of the energy stored in the deformed crystal is released by recovery either prior to or concurrently with grain boundary migration, thus introducing an uncertainty as to the magnitude of the driving force responsible for grain boundary migration. The grown-in lineage structure, though thermally stable during annealing, neither provides conditions under which different levels of energy may be stored in the imperfect crystal nor provides a control of orientation difference across the migrating boundary of a growing grain. Furthermore, because of variation in the lineage structure, it is difficult to determine accurately the energy stored in the imperfect crystal. Several investigations of grain boundary migration during normal grain growth have also suffered from difficulties in estimating the driving force because of uncertainties in the principal radii of curvature.~ In the present investigation the velocity of pure tilt boundaries in zone-refined aluminum bicrystals of selected orientation (40, 30, and 16 deg around the [Ill] tilt axis) has been measured in the absence of a dislocation density difference across the moving boundary, thus eliminating the previous experimental difficulties. The driving force for boundary migration is derived from a gradient of the total interfacial free energy of the migrating boundary in wedge-shaped bicrystals. A similar method was attempted by Bron and Machlin in a study of grain boundary migration in silver. However, they found that one of the crystals was deformed and consequently the motion of the boundary was partly due to a difference of stored energy across the boundary. The observed behavior of boundary velocities as affected by the driving force is examined in the light of the predictions of the current theories of grain boundary migration.7"10 The effect of boundary misorientation on velocity is compared with the theory of " which is based on a dislocation core model for high-angle boundaries. EXPERIMENTAL METHOD Seed-oriented bicrystals of zone-refined aluminum, 2.5 cm wide, 0.5 cm thick, and 12 cm long, containing tilt boundaries with a common (111) axis, were grown from the melt in the direction of this axis. Spectro-graphic analysis, reported earlier,&apos;&apos; indicated the purity of the crystals to be 99.999+pct. Three such bicrystals containing 16, 30, and 40 deg tilt boundaries were used. Wedge-shaped specimens were prepared from these bicrystals by spark cutting followed by electrolytic polishing. The angle of the wedge was usually 40 deg and the specimens were usually 0.25 cm thick. The intercrystalline boundary was located within 0.2 to 0.5 cm from the tip of the wedge. Fig. 1 shows a section of an oriented bicrystal containing an outline of a wedge-shaped specimen. The crystallographic directions shown in Fig. 1 represent the orientation of one of the crystals (the larger section of the bicrys-tal); the orientation of the other crystal differs only by rotation around the common [lil] axis. The parallel faces of the wedge always corresponded to the common (171) planes in both crystals, whereas the orientation of the side faces varied, depending on the misorientation angle. The bicrystal orientations were determined

Jan 1, 1970

By J. F. Enrietto

Internal friction measurements were used to determine the effect of manganese on the solubility and precipitation kinetics of nitrogen. Manganese, in concentrations up to 0.75 pct, has little effect on the solubility at temperatures above 250°C. On the other hand, at Concentrations as low as 0.15 pct, manganese inhibits the formation of iron nitrides, especially Fe4N, even though it may not form a precipitnte itself. The precipitation and solubility of carbides and nitrides have been extensively investigated in the pure Fe-C and Fe-N systems.1-3 In recent years, some effort has been ispent in studying the influence of substitutional alloying elements on the behavior of carbon and nitrogen in ferrite.4 -7 In particular Fast, Dijkstra, and Sladek have investigated the effect of 0.5 pct Mn on the internal friction and hardness during the quench aging of Fe-Mn-N alloys.&apos;, &apos; They found that at low temperatures (below 200°C) the presence of 0.5 pct Mn greatly retarded quench aging. For example, after 66 hr at 200°C very little precipitation had taken place in the iron alloyed with manganese, whereas precipitation was complete after a few minutes in a pure Fe-N alloy. The effect of varying the manganese content and the details of the precipitation process were not mentioned in these papers. Fast&apos; postulated that manganese causes a local lowering of the free energy of the lattice with a resulting segregation of nitrogen atoms to these low energy sites. The segregated nitrogen atoms are bound so tightly to the manganese atoms that they cannot form a precipitate. The internal friction measurements of Dijkstra and Sladek tended to confirm the concept of segregation of nitrogen around manganese atoms, and the increase in free energy on transferring a mole of nitrogen atoms from a segregated to a "normal" lattice site was computed to be - 2800 cal. Dijkstra and Sladek9 distinguished between two types of precipitates: ortho, a nitride of appreciably different manganese content than that of the matrix, and para, a nitride with a manganese content essentially that of the matrix. With each type of precipitate a solubility, again designated ortho or para, can be associated. Since the internal friction maximum in alloys which were aged several hours at 600" C dropped almost to zero, Dijkstra and Sladek9 concluded that the ortho solubility must be very low. The effect of temperature on the ortho and para solubilities has no1: been investigated. There are obviously several gaps in our knowledge concerning the influence of manganese on the behavior of nitrogen in a-iron. It was the purpose of the experiments described in this paper to determine the following: 1) The ortho and para solubilities of nitrogen as a function of temperature. 2) The details of the precipitation process at elevated temperatures. 3) The effect of varying the manganese concentration on the above phenomena. EXPERIMENTAL PROCEDURE Internal friction is conveniently employed in studying the precipitation of nitrides and/or carbides from a -iron because it is one of the few parameters, perhaps the only one, which is not affected by the presence of the precipitate itself. For this reason, internal friction techniques were heavily relied upon in the present experiment. A) Preparat of -. All specimens were prepared from electrolytic iron and electrolytic manganese. Alloys containing 0.15, 0.33, 0.65, and 0.75 wt pct Mn were vacuum melted and cast into 25 lb ingots. After being hot rolled to 3/4 in. bars, the ingots were swaged and drawn to 0.030 in. wires. The wires wen? decarburized and denitrided by annealing at 750° C for 17 hr in flowing hydrogen saturated with warer vapor. To obtain a medium grain size, - 0.1 mm, the wires were then heated to 945oC, allowed to soak for 1 hr, furnace cooled to 750°C, and water quenched. Subsequent internal friction measurements showed that this procedure reduced the nitrogen and carbon concentrations of the alloys to less than 0.001 wt pct. The wires were nitrided by sealing them in pyrex capsules containing anhydrous ammonia and annealing them for 24 hr at 580°C, the nitrogen being retained in solid solution by quenching the capsule into water. Immediately after quenching, the wires were stored in liquid nitrogen to prevent any precipitation of nitrides. By varying the pressure of ammonia in the capsule, it was possible to produce any desired nitrogen concentration. B) Internal Friction. The internal Friction measurements were made on a torsional pendulum of the Ke type,&apos;&apos; a frequency OF 1. or 2 cps being used. For

Jan 1, 1962

By G. L. F. Powell

g samples of Cu-20 wt pct Ag alloy have been mdercooled to a maximum of 197°C by melting under a slag of commercial soda-lime glass in a vitreous silica crucible. No grain refinement of the primary copper was observed in samples undercooled to the maximum of 197°C. When the samples contained a small amount of oxygen, the copper dendrites were partially recrystallized at undercoolings greater than 97°C. In previous papers&apos;-3 reporting the grain structure of undercooled silver and copper, it was observed that grain refinement was dependent on both undercooling and oxygen content. Grain refinement occurred in undercooled silver when the degree of undercooling exceeded the range 153" to 175"C, while in Ag-0 alloys (0.12 wt pct) fine equiaxed grains were exhibited when undercooling was greater than 50°C. Similarly, copper samples undercooled as much as 208°C displayed fan-shaped growth from a single nucleation site, while the grain structure of Cu-O alloys (0.08 wt pct) was fine and equiaxed at undercoolings larger than 150°C. Thus the presence of oxygen greatly reduced the undercooling at which grain refinement occurred. It was also observed that the change in grain size resulted from recrystallization and was not due to an enhanced nucleation rate in the liquid-solid transformation. It is possible that the influence of oxygen on recrystallization is due primarily to its presence as a solute element. walker4,&apos; reported that, although a grain size change did not occur in pure nickel until the undercooling exceeded 150°C, small grains were observed in samples of Ni-Cu alloy solidified at small and large degrees of undercooling. Jackson et al.6 suggested that the fine grained structure of the Ni-Cu alloy resulted from the melting off of dendrite arms during recalescence. This remelting process may occur in alloys as a result of segregation during freezing which causes a variation in liquidus temperature from point to point within a dendrite. It was therefore decided to undercool copper with a metallic alloying element to ascertain whether the presence of a metallic solute would have a similar effect to oxygen in inducing grain refinement. A Cu-Ag alloy was chosen, since both metals had been shown to behave similarly on undercooling. The alloy Cu-20 wt pct Ag was selected since the eutectic constituent outlines the initial growth form of the primary copper, so that the as-frozen grain structure is not obscured if subsequent recrystallization occurs. This paper describes the results of undercooling experiments carried out with Cu-20 pct Ag samples undercooled to a maximum of 197°C and the effect of oxygen content on the grain structure of the undercooled samples. EXPERIMENTAL Melting was carried out in a small cylindrical resistance furnace using "fine" silver granulate and oxygen-free high conductivity copper. The procedure adopted was to melt the required quantity of silver in air in a clean vitreous silica crucible for approximately 15 min, freeze, and add granulated commercial soda-lime glass to form a complete surface slag cover, after which the sample was melted and frozen several times to reduce the oxygen content. The glass slag cover was approximately 3 in. thick. Pieces of copper (=50 g) were added to the crucible until the required quantity to make 350-g samples of alloy had been charged. Each piece was added quickly to the crucible which was held at a temperature slightly above the melting point of silver. The piece was quickly pushed beneath the glass to minimize oxidation and any oxide coating usually decomposed before the piece had settled down into the silver. After the full quantity of copper had been added, the melt was stirred with a silica rod to hasten homogenization and a Pt/Pt 13 pct Rh thermocouple enclosed in a vitreous silica sheath inserted for temperature measurement. Heating and cooling curves were recorded on a potentiometric chart recorder fitted with a zero suppression unit. The milli-voltage range of the recorder was adjusted so that temperatures could be read to 1°C. Heating and cooling curves were taken every hour until three consecutive readings gave the same solidus-liquidus range, consistent with the solidus-liquidus range for this alloy composition by reference to Hansen and Anderko.7 Metallographic examination of samples frozen at this stage, failed to show any variation in composition from bottom to top of the ingot. Consequently, it was considered that the melt was homogeneous at this stage and undercooling experiments were then car-

Jan 1, 1970

By T. H. Janes

NATURAL abrasives of some type are found in all countries of the world. In order of their hardness the principal natural abrasives are diamond, corundum, emery, and garnet, which are termed high grade, and the various forms of silica, including pumice, pumicite, ground feldspar, china clay and, most important, sandstone. The properties qualifying materials for use as abrasives are hardness, toughness, grain shape and size, character of fracture, and purity or uniformity. For manufacture of bonded grain abrasives such as grinding wheels, the stability of the abrasive and its bonding characteristics are also important. No single property is paramount for all uses. Extreme hardness and toughness are needed for some applications, as in diamonds for drill bits, while for other purposes the capacity of the abrasive to break down slowly under use and to develop fresh cutting edges is of greatest importance, as with garnet for sandpaper. In dentifrices, soaps, and metal polishes, of course, hardness and toughness are objectionable. First among the natural abrasives, industrial diamonds are essentially of three types: l—bort, which includes off-color, flawed, or broken fragments unsuitable for gems; 2—carbonado, or black diamond, a very hard and extremely tough aggregate of very small diamond crystals; and 3—ballas, a very hard, tough globular mass of diamond crystals radiating from a common center. Bort comes from all diamond-producing centers, carbonados only from Brazil, and ballas chiefly from Brazil, although a few of this last group come from South Africa. By far the largest producer of industrial diamonds is the Belgian Congo; the Gold Coast, Angola, the Union of South Africa, and Sierra Leone supply most of the remainder. There is no production in Canada, which imports $6 to $9 million worth of industrial diamonds annually. Industrial diamonds find innumerable uses in modern industry. They are used for diamond drill bits for the mining industry; in diamond dies for wire drawing; in diamond-tipped tools for truing abrasive wheels and for turning and boring hard rubber, fibers, and plastics; and in diamond-toothed saws for sawing stone, glass, and metals. High-speed tool steels, cemented carbides, and other hard, dense alloys can be cut, sharpened, or shaped efficiently only with diamond-tipped tools and diamond grinding wheels. .. Second only to the diamond in hardness is corundum, an impure form of the ruby and sapphire gems consisting of alumina and oxygen (Al²O³) with impurities such as silica and ferric oxide. Corundum generally crystallizes from magmas rich in alumina and deficient in silica, as in the nepheline syenites of eastern Ontario. Grain corundum is used in the manufacture of grinding wheels; very coarse grain is used in snagging wheels. Both types of wheels are employed in the metal trades, where the hardness of corundum, coupled with its characteristic fracturing into sharp cutting edges, makes it an ideal cutting tool. The finest corundum (flour grades) is used for fine grinding of glass and high-precision lenses. From 1900 to 1921 Canada was the world&apos;s leading producer of corundum. Following this period the deposits located in northern Transvaal of the Union of South Africa supplied more and more of the world&apos;s requirements, and since 1940 South Africa has provided almost the entire output, which has ranged between 2500 to 7000 tons a year during the last decade. Minor amounts have also been produced in Mozambique, India, and Nyassaland. Opportunities for Mining Corundum Corundum deposits in southeastern Ontario are of three types, which may be described as follows: 1—Scattered, irregularly-shaped deposits of coarse-grained corundum which could be mined by means of small pits. About 10 groups of such deposits are known. Although the tonnage of individual deposits of this type is not great, it has been estimated that several years&apos; ore supply is available for a small tonnage operation. Deposits average about 9 pct corundum. 2—Large irregular deposits of coarse-grained corundum which would require mining by adit with possibly a scavenger operation on the remains of former surface deposits. The Craigmont deposit of this type produced about 20,000 tons of corundum concentrate during operations between 1900 and 1913. Most of the readily available surface ore was removed by operators during that time. Reserves of ore above road level have been estimated to average 7 pct corundum, but none of the so-called reserves have been blocked out, or even indicated, by diamond drilling. From 1944 to 1946, 2025 tons of

Jan 1, 1955

By Rich Akerman

as 1866, I wish to assure both these gentlemen that I had not seen the section when I designed mine, :md even if I had, I should not have then dared to put it forth as a standard for English rail makers; tind the soundness of my opinion has a simple but conclusive proof in the statement made concerning the extra price which was at that time required for their production. I need not say that I highly approve of the original Welch section, for it is in principle similar to the design which I made ufteen yeam subsequently; and from a professional point of view I would fully concecle to Mr. Welch the credit of first designing the modern steel-rail section. From com- mercial, matter of tict, and practical point of view, he was, however, before his time by many years; or to put it in another way, rail making was ten years behind its time when the new metal steel was first introduced for rails. If his design has been incorrectly identified with my name (as the sections are similar in principle, though they differ in thickness of flange and web), I beg to say (1st) that I much regret the misun- Understanding which has arisen through no fault of niine, aud (2d) that no confusion has been intentionally created by me. It is a pity that the section designed so long ago has not been made public at an earlier date, as it would make a really goal stand- and pattern, anil even now be quite equal to present requirements. In conclusion, I wish to say that I have never desired to claim any invention or novelty by the publication of my sections; they Were put forth as being such as English railmakers could and would produce at the ordinary market. price, and as being the best and most suitable to be so obtained. Had Mr. Welch or Mr. Holley put forward theirs ten or fifteen years ago, I should have been the first to recommend theru. In fact I should have been glad to see their narnes associated with rail patterns in their own country, in the same way as mine has been. PROFESSOR RICH. AKERMAN, STOCKHOLM, SWEDEN: i AGREE with your (Mr. Sandberg&apos;s) views that it is too early yet to stipulate only one definite chemical composition in the rails. Such a stipulation, I think, might he justified, if it were not for the manganese; but this metal changes the properties of the iron aud steel in tho same direc- tion ae carbon, silicon. and phosphorus, by increasing its tensile strength, stiffness, hardness, and brittleaess. If the iron and steel does not only contain carbon and manganese but also phosphorus,

Jan 1, 1881

By R. Schuhmann

PROBLEMS in expressing, interpreting, and using size-distribution data recur in many phases of mineral dressing; therefore it is desirable that size analyses be expressed in such a form, either numerically or graphically, that comparisons can be made readily. The size distribution of comminuted material is a result of a specific physical operation on the material and therefore should be governed by some definite physical principle, or cause-effect relation. Although this principle has not been discovered, it has been found that the size distribution of comminuted, homogeneous solids may be expressed by relatively simple mathematical equations. Two equations in particular, proposed by Gaudin1 and by Rosin and Rammler,2 respectively, have stood out, both having wide demonstrated ranges of application. The form and the method of application of the two appear almost irreconcilably different on the surface, but, as will be shown, they are asymptotic in the fine sizes when expressed in the same units. This paper gives the results of a further study of the Gaudin and Rosin-Rammler relations, made with the object of developing a form of size-distribution equation that will be more usable and more significant-particularly in comminution studies, both for interpreting the nature of size distribution and for evaluating surface. The work is summarized in the following: I. An equation relating cumulative per cent finer to particle size in the fine sizes is derived from Gaudin&apos;s original equation. That equation relates weight per cent retained on one size and through the next larger size in a geometric series of sizes to size (of the retaining screen, for example). 2. Comparisons with Gaudin&apos;s equation and with the Rosin-Rammler equation show that the cumulative equation applies to the fine sizes of all size distributions that fit either of these earlier relations, and, furthermore, has some advantages over each. 3. A simple graphical method of surface calculation based on the cumulative-equation plot is evolved and illustrated. 4. Additional confirmation of the cumulative equation was obtained in the more severe test of sizing down to the limit of a sedimentation balance a sample of jaw-crushed quartz. The equation was closely followed over a 20o-fold range in size, from approximately 0.4 mm. (35 mesh) down to 0.0023 mm. (2.3 microns), the lower limit of the size analysis made. There is no indication that the equation will not hold further to well below 2.3 microns. 5. Calculations of the surface produced in the jaw-crushing test mentioned above showed that at least 8o per cent of the total new surface was on particles finer than 35 mesh (about ½ 5 of the crusher setting). The minus 35-mesh portion was only

Jan 1, 1940

By W. M. Baldwin, J. T. Brown

The effect of hydrogen on the ductility, c, of SAE 1020 steel at strain rates, i, from 0.05 in. per in. per rnin to 19,000 in. per in. per rnin and at temperature, T, from +150° to —320°F was determined. The ductility surface of the embrittled steel reveals two domains: one in which and the other in which The usual "explanations" of hydrogen embrittlement are in accord with the first of these domains only. THE purpose of this investigation was a fuller A characterization of this of the investigation effects of varying temperature and strain rate on the fracture strain of hydrogen-charged steel. To be sure, it is known that low and high temperatures remove the embrittlement that hydrogen confers upon steels at room temperature,1 * see Fig. la and b, and that high strain rates have a similar effect,&apos;-&apos; see Fig. 2a, b, and c. However, the general effect of these two testing conditions on the fracture ductility of hydrogen-charged steels is not known, i.e., the three-dimensional graphical representation of fracture ductility as a function of temperature and strain rate is not known—only two traverses of the graph are available. The need for such a graph is not pedantic. To demonstrate this point, Fig. 3a, b, and c shows three of many three-dimensional graphs, all possible on the basis of the two traverses at hand. The important point (as will be developed in the Discussion) is that each of them would indicate a different basic mechanism for hydrogen embrittlement. It will be noted that the four types of ductility surfaces in Fig. 3a, b, and c may be characterized as follows: Material and Procedure Tensile tests were made at various temperatures and strain rates on a commercial grade of % in. round SAE 1020 steel in both a virgin state and as charged with hydrogen. The steel was spheroidized at 1250°F for 168 hr to give the unembrittled steel the lowest possible transition temperature. The steel was charged cathodically with hydrogen as follows: The specimen was attached to a 6 in. steel wire, degreased for 5 min in trichlorethylene, rinsed with water, and fixed in a plastic top in the center of a cylindrical platinum mesh anode. The assembly was placed in a 1000 milliliter beaker containing an electrolyte of 900 milliliters of 4 pct sulphuric acid and 10 milliliters of poison (2 grams of yellow phosphorous dissolved in 40 milliliters of carbon disulphide). A current density of 1 amp per sq in. was used which developed a 4 v drop across the two electrodes. All electrolysis was carried on at room temperature. Temperatures for tensile tests were obtained by immersing the specimens in baths of water (+70° to + 150°F), mixtures of liquid nitrogen and isopen-tane (+70° to —24O°F), and boiling nitrogen (-240" to-320°F). Specimens were tested in tension at strain rates of 0.05, 10, 100, 5000, and 19,000 in. per in. per min. The 0.05 and 10 in. per in. per rnin strain rates were obtained on a 10,000 lb Riehle tensile testing machine, the 100 in. per in. per rnin rate on a hydraulic-type draw bench with a special fixture, and the 500 and 19,000 in. per in. per rnin rates on a drop hammer. The fracture ductility of hydrogen-charged steel at room temperature and normal testing strain rates (-0.05 in. per in. per min) is a function of electro-lyzing time, dropping to a value that remains constant after a critical time.&apos;* Under the conditions of • The hydrogen content of the steel continues to increase with charging time even after the ductility has leveled off to its saturated value.&apos; this research the saturated loss in ductility occurred at approximately 30 min, see Fig. 4, and a 60 min charging time was taken as standard for all subsequent tests. After charging the steel with hydrogen, the surface was covered with blisters. These have been described by Seabrook, Grant, and Carney.&apos; The original diameter of the specimen was not reduced by acid attack, even after 91 hr. Results The ductility of both uncharged and charged specimens is given as a function of strain rate in Fig. 5, and as a function of temperature at four different strain rates in Fig. 6. These results are assembled into a three-dimensional graph in Fig. 7. It is seen that the locus of the minima in the ductility curves of the charged steels divides the ductility surface into two domains. At temperatures below the minima,

Jan 1, 1955

By A. S. Grove, C. T. Sah, E. H. Snow, B. E. Deal

A summary of- several recent investigations in to the properties of the metal-oxide-silicon system is presented. A major portion of these studies makes use of the MOS capacitance-z)oltage method of&apos; analysis. The particular areas of investigation which are reported include: 1) a general survey of the electvical properties of thermally oxidized silicon surjbccs; 2) a study of ion migration through silicon dioxide films ; 3) measurements of electron and hole mobilities in surface inversion layers; 4) a study of impurity redistribution due to thermal o.ridatiotz; and 5) measurements of the rates of oxidation oj-heavily doper7. silicon. THE importance of the metal-oxide-semiconductor (MOS) system in the semiconductor industry is well-known. In addition to its importance in the "planar" device technology,&apos; the MOS structure is now also used in the fabrication of active solid-state devices. Consequently, extensive efforts have been made recently to obtain a better understanding of the characteristics of this system. A summary of some studies of the MOS system conducted in our laboratories during the past year is presented. For the most part these studies used silicon as the semiconductor, along with silicon dioxide and aluminum as the other two components of the system. Since the MOS capacitance-voltage method of analysis was used extensively in these studies, we will first briefly describe its nature and consider some of the possible causes of deviation of experimental observations from the simple theory. We will then outline the various related areas of investigation carried out in our laboratories and will briefly indicate some of the results. It should be noted that the purpose of this paper is merely to provide a brief summary of MOS studies. More detailed discussions of the various areas of investigation are given in the references cited. PRINCIPLES OF THE MOS C-V METHOD OF ANALYSIS&apos; A sketch of the MOS structure is shown in the upper portion of Fig. 1. In this case the insulating film is Si02 and the semiconductor p-type silicon. If a large negative bias is applied to the metal field plate, holes are attracted to the silicon surface. The silicon then behaves much like a metal and the capacitance measured is that of the oxide layer alone, Co. If a small positive bias is applied to the aluminum, holes are repelled and a region depleted of majority carriers is formed at the silicon surface. This depletion I-egion adds to the width of the dielectric and the measured capacitance begins to drop. With increasing positive bias, the width of the electrical depletion region increases. At some large positive bias an inzevsion regiotr is formed at the surface and additional charges induced in the silicon appear in the form of electrons in this narrow inversion region. Thus the depletion-region width approaches a maximum value and, consequently, the capacitance reaches a minimum value and then either levels off or rises again depending on the measurement frequency and the rate of equilibration of the minority carriers in the inversion layer.3 Band diagrams, along with the corresponding charge distributions, are shown in Fig. 1 for the above bias conditions. If minority carriers cannot accumulate at the surface to form an inversion region, the depletion-region width continues to increase with increased positive bias and the capacitance drops toward zero as in a reverse biased p-n junction. The effect of a work-function difference $hs between the metal and the silicon, and of surface charges per unit area Qss located at the oxide-silicon interface, is simply to attract charges in the silicon much like the applied bias. It can be shown that this results in a parallel shift of the capacitance-voltage characteristic along the voltage axis by an amount corresponding to AV = -$bIs + Qss/Co. Theoretical curves have been calculated4 giving the capacitance of the MOS structure C normalized to the oxide capacitance Co vs the quantity VG here VG is the voltage applied to the metal field plate. In Fig. 2 such calculations are shown as points for a particular oxide thickness and bulk impurity concentration for a p-type semiconductor. (For an n-type semiconductor the curves would be mirror images of these.) All three cases, i.e., low frequency. high frequency, and depletion, are indicated. Also shown in the figure are recorder tracings of the characteristics of actual devices. These characteristics have been shifted along the voltage axis to compensate the effect of surface charges and work-function difference. It is evident that agreement between experiment and theory is good. The nature of this shift along the voltage axis is

Jan 1, 1965

By E. Buehler, H. J. Levinstein

The temperature ranges in which the three inter-metallic phases in the Nb-Sn system form have been determined and the composition and structure of two of the three phases has been established. The kinetics of the formation of Nb3Sn in cored wire samples has been studied in the temperature range of 800° to 1050°C. From 800°to 950°C the rate of formation increases by four orders of magnitude. The rate-controlling step for the formation process in this temperature range appears to be the diffilsion of tin through NbSn. At higher temperatu~es a change occurs in the mechanism of the formation process such that up to a temperature of 1050°C the rate of formation of Nb3Sn does not increase above the rate observed at 950°C. For temperatures helow 950°C the current-carrying capacity of the wire increases with increased percent reaction reaching a maximum value when the formation process is 90 to 95 pct complete. The maximum current-carrying capacity obtainable in this temperature range is independent of the temperature. Above 950°C tlze current-carrying capacity obtainable in the wire decreases with increasing temperature of formation. A model is proposed which accounts for the ohserved behavior. RECENTLY, Buehler et a1.l reported the results of an investigation of the process variables which influence the superconducting properties of Nb3Sn-cored wire. These results indicated that at least four variables affect the properties of the manufactured wire. These include composition, particle size of the starting powder mix, temperature of heat treatment, and time of heat treatment. In order to understand completely the role of these variables, it is necessary to have an accurate knowledge of the phase equilibria in the Nb-Sn system. At the present time, phase-equilibrium diagrams for the Nb-Sn system have been published by a number of investigators.2-5 The diagrams differ as to the number of phases present, the composition of the phases, and the temperature range of stability of the phases. The present investigation was undertaken in order to resolve these differences. Since the investigation of Buehler et al. demon- strated that the length of time at the temperature of heat treatment affected the superconducting properties of Nb3Sn, it is apparent that it is necessary to understand the kinetics of the formation process as well as the equilibrium conditions before a complete understanding of the system is possible. As a result, the kinetics of formation of the various phases in the system were also studied in this investigation. EXPEFUMENTAL PROCEDURE Diffusion couples and sintered powdered compacts were employed in the phase-diagram investigation. The diffusion couples were made by filling 1/8-in.-ID monel-sheathed niobium tubes with tin. The monel sheath was employed to facilitate drawing.&apos; The tubes were then drawn to a tin-core diameter of 32 mils. Samples approximately 3 in. long were then cut from the drawn composite. The tin was drilled out of the ends to a depth of 1/4 in. and niobium-wire plugs were inserted into the ends and peened over. The monel was removed by etching in concentrated nitric acid, after which the samples were sealed in evacuated quartz bulbs and heat-treated in a resistance-wound tube furnace. The samples were quenched into ice water upon removal from the furnace. The diffusion couple samples were examined metallographically employing a chemical etching solution consisting of 10 ml of saturated chromic acid per g of NaF. In addition, two anodizing solutions were used for phase-identification purposes. The first was the picklesimer7 solution; the second consisted of equal parts by volume of 30 pct H2O2 and concentrated NH4OH to which 1 g of NaF was added per 25 ml of solution. The anodizing conditions for the second solution were 2 v and 100 ma with a tin cathode. The powdered compacts were made by pressing previously mixed powders of 99.9 pct pure Sn and 99.6 pct pure Nb supplied by the United Mineral Co. into cylinders 3/8 in. in diameter by 1/2 in. long. The cylinders were then sealed in quartz tubes and heat-treated in the same manner as the diffusion couples. The samples were examined metallographically and by X-ray diffraction techniques. Since it was desirable to be able to correlate the kinetic data with current-carrying capacity, the type of specimen chosen for this part of the investigation had to be a compromise between the optimum system for studying kinetics and one which was suitable for making current-carrying capacity

Jan 1, 1964

By N. Van Wingen

EFFective sand permeabilities can be ascertained from core analysis if the laboratory data are compensated to allow for the presence of connate or residual water. Such adjustments can be made by applying empirically derived correction factors. Effective sand permeabilities can be estimated also from analytical studies of field depth-pressure measurements. In one method the time rate of pressure build-up after a well is shut in from steady-state flow is required, and in the other the direct measurement of a steady-state rate of flow and the corresponding equilibrium pressure. The results of the investigation discussed in this paper demonstrate that these methods for determining mean effective sand permeabilities can be correlated. Introduction In recent years many investigators have demonstrated the practical value of an accurate knowledge of the physical and dynamical characteristics of reservoir sands containing oil and gas. Of these factors, which serve to completely define a porous medium as a container or carrier of fluids, the dynamical characteristics are of particular interest to the production engineer because they afford a direct measure of the rate at which the oil or gas content of a reservoir will become available. The constant that defines dynamically the porous medium as the carrier of a homogeneous fluid in viscous motion is the "permeability." Coke-analysis Method The generally accepted practice in com-piling permeability data has been to analyze in the laboratory core samples taken in the course of drilling through the productive horizon, and to obtain the mean measure of the productive ability or permeability for the interval open to production by graphical integration of the permeability profile. An average permeability ascertained in this manner, however, is useful to the production engineer only for comparisons of wells drilled in the same horizon, as permeabilities determined in the laboratory are measures of only the ability of a porous medium to transmit a single fluid. As a result of many investigations, it has been shown, however, that under actual reservoir conditions water is coexistent with the petroleum and that its presence greatly reduces the permeability of the sand to oil. Empirical relationships showing the effect of the presence of any immiscible fluid A (such as water) in a porous medium on the permeability of the medium to a fluid B (such as oil) have been established separately by Hassler,1 Dunlap,2 and the writer (Fig. I),3 so that the average specific or dry-core permeability as determined in the laboratory can be corrected to give the true measure of the ability of the horizon penetrated to transmit oil, provided the percentage of pore space occupied by connate water is known accurately.

Jan 1, 1942

By N. Van Wingen

EFFective sand permeabilities can be ascertained from core analysis if the laboratory data are compensated to allow for the presence of connate or residual water. Such adjustments can be made by applying empirically derived correction factors. Effective sand permeabilities can be estimated also from analytical studies of field depth-pressure measurements. In one method the time rate of pressure build-up after a well is shut in from steady-state flow is required, and in the other the direct measurement of a steady-state rate of flow and the corresponding equilibrium pressure. The results of the investigation discussed in this paper demonstrate that these methods for determining mean effective sand permeabilities can be correlated. Introduction In recent years many investigators have demonstrated the practical value of an accurate knowledge of the physical and dynamical characteristics of reservoir sands containing oil and gas. Of these factors, which serve to completely define a porous medium as a container or carrier of fluids, the dynamical characteristics are of particular interest to the production engineer because they afford a direct measure of the rate at which the oil or gas content of a reservoir will become available. The constant that defines dynamically the porous medium as the carrier of a homogeneous fluid in viscous motion is the "permeability." Coke-analysis Method The generally accepted practice in com-piling permeability data has been to analyze in the laboratory core samples taken in the course of drilling through the productive horizon, and to obtain the mean measure of the productive ability or permeability for the interval open to production by graphical integration of the permeability profile. An average permeability ascertained in this manner, however, is useful to the production engineer only for comparisons of wells drilled in the same horizon, as permeabilities determined in the laboratory are measures of only the ability of a porous medium to transmit a single fluid. As a result of many investigations, it has been shown, however, that under actual reservoir conditions water is coexistent with the petroleum and that its presence greatly reduces the permeability of the sand to oil. Empirical relationships showing the effect of the presence of any immiscible fluid A (such as water) in a porous medium on the permeability of the medium to a fluid B (such as oil) have been established separately by Hassler,1 Dunlap,2 and the writer (Fig. I),3 so that the average specific or dry-core permeability as determined in the laboratory can be corrected to give the true measure of the ability of the horizon penetrated to transmit oil, provided the percentage of pore space occupied by connate water is known accurately.

Jan 1, 1942

By G. R. Leverant, C. P. Sullivan

To evaluate the effect of a dispersion of nondeform-able, incoherent, second-phase particles on high-strain cyclic deformation and fracture, recrystallized TD-nickel (Ni-2ThO2) and a commercially pure nickel, Ni-200, were fatigued under strain control at total strain ranges varying from 0.009 to 0.036. Relative to the Ni-200, the slip at the surface of the TD-nickel was more wavy and discontinuous due to the presence of the thoria particles. This made crevice formation (incipient cracking) within slip bands more difficult in TD-nickel than in Ni-200. Both materials cyclically hardened to a constant (saturation) flow stress which increased with increasing plastic strain amplitude. Cellular substructures were developed in both materials during cycling. The cell size in TD-nickel was controlled by the thoria particle distribution and was independent of plastic strain amplitude over the range investigated. The cell size in Ni-ZOO was larger than that in TD-nickel at similar plastic strain amplitudes and was a function of plastic strain amplitude. These results, together with the cyclic stress-strain curves for both materials, are discussed in terms of a model for fatigue strain accommodation at saturation recently proposed by Feltner and Laird. NUMEROUS fatigue investigations have considered the interrelation of slip character, dislocation substructure, and cracking in pure metals and solid-solution alloys. However, except for the studies of the low-strain fatigue of internally oxidized copper alloys1 and cast, dispersion-strengthened lead,&apos; little is known about the effects which small, incoherent, nondeform-able, second-phase particles have on cyclic deformation and cracking processes. Effects due to the particles alone are often obscured by a dislocation substructure introduced during thermomechanical processing of dispersion-strengthened metals. In the present study, recrystallized TD-nickel and a commercially pure nickel, Ni-200, were employed to evaluate the effect of a thoria dispersion on high-strai fatigue deformation and cracking at room temperature. I) MATERIAL AND EXPERIMENTAL PROCEDURE The TD-nickel was supplied by DuPont as a 5/8-in.-thick stress-relieved plate which had been subjected to a proprietary schedule of thermomechanical treatments, and the Ni-200 as 3/4-in. bar which was subsequently annealed for 2 hr at 850°C in argon resulting in an average grain diameter of 0.05 mm. The compositions of these materials are given in Table I. The microstructure of the TD-nickel consisted of elongated grains parallel to the primary working direction with an average width of 0.16 mm, Fig. l(a). Many fine annealing twins were present indicating that the starting material was in a recrystallized condition; this supposition was confirmed by the absence of of any extensive dislocation substructure, Fig. l(b). Sheetlike stringers parallel to the rolling direction were occasionally seen both within grains and at grain boundaries. Some approximately spherical particles about 2 in diam, which may correspond to exceptionally large thoria particle aggregates, were also present. The average Young&apos;s modulus of the plate material in the rolling direction was 21.8 X 106 psi which is consistent with a {100}<001>recrystalliza-tion texture3&apos;* being prominent. In transmission microscopy, the 2.3 vol pct of thoria particles generally appeared to be uniformly distributed although some clusters, 0.1 to 0.3 in diam, of larger particles were observed as previously reported for TD-nickel sheet,5 and stringering of particles was present in some areas as welt. The average diameter of the thoria particles was 450A with a calculated mean planar center-to-center spacing of 2100A, as determined by quantitative metallographic analysis.= The 0.2 pct offset yield stress was 36,000 psi which agrees with the value predicted by the modified Orowan relation7 for edge dislocations bowing between thoria particles of the size and spacing observed in the present investigation. Fig. 2 illustrates the specimen design employed for the axial high-strain fatigue testing. Adapters were screwed onto the threaded portions of each specimen so that testing could be performed in the same manner as that reported for buttonhead specimens.8 Stressing was coincident with the working direction for both materials. The gage section of each specimen was electropolished and lightly etched prior to testing. The total strain was controlled, being varied between zero and a maximum tensile strain ranging from 0.009 to 0.036. In addition to these tests, a circum-ferentially notched TD-nickel specimen was cycled over a total strain range of 0.0075. The same strain

Jan 1, 1969

By A. Steiner, K. L. Komarek

Activities of aluminum in solid Ni-A1 alloys have been determined between 20 and 60 at. pet Al and 1200" and 1400°K by an isopiestic method in which nickel specimens, heated in a temperature gradient, are equilibrated with aluminum vabor in a closed all-alumina system. The activity of aluminum shows a strong negative deviation from Raoult&apos;s law at low concentrations but increases by three orders of magnitude within the ß(NiAl) phase. The partial molar enthalpy and entropy of mixing are negative. Using Wagner and Schottky&apos;s theory of ordered compounds, a degree of disorder of 4 x 10 -4 for NiAl and 1.25 X 10-2 for FeAl has been calculated THE Ni-A1 system has been studied by a great number of investigators, and the results, as far as the phase diagram is concerned, have been compiled by Hansen.1 The phase boundaries from 0 to 50 at. pet Ni are well-established. At higher nickel contents the boundaries are still in dispute and an additional phase, A12Ni3, has been reported.&apos; The phase diagram is dominated by a very stable high-melting compound, NiA1, with a relatively wide range of homogeneity. Heats of formation of solid alloys have been determined calorimetrically by Oelsen and Middel3 from 20 to 95 at. pet Ni and by Kubaschewski4 from 25 to 80 at. pet Ni. According to the most recent compilation5 no other thermodynamic investigations have been reported for the Ni-A1 system. Due to the corrosive nature and the low vapor pressure of aluminum, a method has been employed for determining activities of aluminum which was previously developed for the Fe-A1 system.= Nickel specimens, heated in a closed evacuated alumina system in a temperature gradient, were equilibrated with aluminum vapor from a source within the system kept at constant temperature. After complete equilibration the specimens were analyzed and activities calculated from the known vapor pressure of aluminum. APPARATUS AND EXPERIMENTAL PROCEDURE Materials. The nickel specimens were made from wafers of electrolytic nickel (International Nickel Corp.) of 99.99 pet purity which were rolled to a 0.001-in.-thick foil by Driver-Harris Co. and to a 0.005-in.-thick sheet in our laboratory. The aluminum (Aluminum Corp. of America) had a purity of 99.99+ pct. The alumina tubes and crucibles were made of impervious recrystallized alumina with an alumina content of 99.7 pet (Triangle RR, Mor-ganite Inc.). Experimental Procedure. Annular specimens were punched from the sheet, the punching burrs removed, and the specimens degreased in carbon tetrachloride and acetone and weighed on a micro-balance to within an accuracy of ±0.01 mg. The specimens were positioned with alumina spacers along an alumina tube, and the positions measured. Aluminum metal was machined into cylindrical shape, and placed into an alumina crucible. The tube with the specimens was then inserted into a hole drilled into the aluminum metal. An alumina tube with its closed end at the top was slipped over the specimens so that its lower end fitted snugly into the alumina crucible. The assembled reaction tube was inserted into a mullite tube with a water-cooled brass head which had an opening for a quartz thermocouple protection tube and a metal-to-glass connection to a conventional vacuum system. A Pt-Pt 10 pet Rh thermocouple could be raised and lowered in the quartz tube which was placed along the outside of the alumina reaction tube. The mullite tube was heated by two separately controlled resistance-tube furnaces so that in the experimental temperature range an over-all temperature gradient of approximately 150o to 250°C could be imposed on the reaction tube. The position of the mullite tube was adjusted so that the surface of the aluminum metal was always at the temperature minimum. The reaction tube was thoroughly evacuated before and during slowly heating the assembly up to the melting point of aluminum. A pressure of less than 2 µ (Hg) was maintained during an experiment. Once the aluminum had melted, it isolated the contents of the alumina tube from the surroundings. Several times during an experiment the temperature gradient was carefully measured. An experiment lasted from 3 to 6 weeks and it was terminated by air cooling the evacuated mullite tube. For further details of the experimental procedure the paper on the Fe-A1 system6 should be consulted.

Jan 1, 1964