Search Documents

By F. E. Jaumot, A. Sawatzky

IT as long been recognized that there is a need for accurate systematic data on diffusion in solids. Originally, such data were needed to check existing theories but, more recently, it would appear that it could be used most advantageously as a guide to, or a check for, much needed extensions of the theory of diffusion. The awareness of the conditions which are important to experimental accuracy, the availability of the materials for accurate experiments, and the techniques have improved to the extent that it would now seem to an experimentalist that, unless extensions of the theory are made which take into account the fundamental parameters of the atoms, the electrons, and the lattice in some detail, the field of diffusion will rapidly become an empirical or semi-empirical field. The present series of experiments was designed to provide accurate data on the diffusion of the elements of the IB and IIB subgroups in silver; that is, to provide data on the diffusion in silver of three face-centered-cubic elements with roughly similar chemical properties, but with different atomic or ionic sizes and, similarly, for three noncubic elements. The elements of these two subgroups have different valences, so that the data will not give any significant information on differences due to the crystal structure of the solute. The present paper reports data on the diffusion of copper and mercury in single crystals of silver; the data for the other elements of the IB and IIB subgroups were reported previously by the authors1'2 and by Tomizuka and Slifkin.8 Experiment The general technique used was identical to that previously described1,2 and will not be repeated here. In all cases, the sectioning technique and high specific activity isotopes" were used. The short half-life of Cu64 made decay corrections more important than for the other isotopes, and necessitated around the clock shifts while data were being taken. Each section was counted at least twice (as was true for all longer half-life isotopes) and a monitor was counted along with each sample. Data for the diffusion of mercury in silver are presented at a greater number of temperatures than for the other solutes. This is a result of two circumstances. First, six (of 30) samples had to be discarded because of pitting or recrystallization which occurred during the diffusion runs, even though the samples had sustained high temperature prediffusion anneals. Either of these was a very rare phenomenon in the other experiments, and their occurrence in this case is considered in more detail below. Second, the curves of the logarithm of the activity of the sections vs the square of the penetration deptht were, in general, quite good, but frequently seemed to show one point to have high activity and the next point to have slightly low activity in terms of the best straight line. When this occurred, there was remarkable regularity of the high-low sequence. In any event, the results, as far as diffusion coefficients are concerned, were not affected by this amalgam effect. In fact, the mercury data had the highest internal consistency of any of the data. Results Diffusion of Copper in Silver—-Diffusion runs were made at eight temperatures In the temperature range from 700° to 950°C, for times ranging from 5 to 45 hr. A linear curve of the logarithm or the activity vs the square of the penetration depth was obtained for all samples. Table I summarizes the results for individual samples and Fig. 1 gives a plot 02 the logarithm of the diffusion coefficients as

Jan 1, 1958

By E. Furubayashi, T. Taoka, S. Takeuchi

Recrystallization textures developed from artificial nucleation around indentations were compared with spontaneously recrystallized textures in two rolled 3 pet Si-Fe single crystals with (111)[112] and (100) [011] orientations. Orientation of individual grains in some stages of their growth was also directly determined by a microetch-pit method. In both the crystals, the recrystallization texture was characteristic of each orientation regardless of any nucleation conditions, artificial or spontaneous, though artificially nucleated grains were more randomly oriented in finer stage. These results support the concept that the process of selection of growing grains controls the formation of the prejerred recrystallization texture. Discussion is given on the factors controlling the mobility of grain boundaries. Recrystallization textures are formed through a number of stages which are customarily called by the terms recovery, nucleation, and grain growth. Many experiments have been done to clarify the mech- anism of formation of recrystallization texture but no fully successful explanation has been proposed. The texture consists of oriented grains which nucleate at many sites of the deformed matrix and grow at the expense of the matrix during annealing. The current theories on the formation of recrystallization texture are based on the following two extreme hypotheses: 1) the oriented nucleation theory by Burgers et al.;1, 2 2) the oriented growth theory by Beck et al.3-5

Jan 1, 1968

By D. A. Woodford

In a constant-load creep test, if the density of nlobile dislocations is assumed constant for strains exceeding that corvesponding to the minimum creep rate, it is shown that the creep rate may be approximated by the equation where E is the nominal strain, o0. is the initial stress, and a' the stress fov unit dislocation velocity. The constant C contains the mean density of mobile dislocations and n is a measure of the stress sensitivity of dislocation celocity. This equation is shoum to be applicable to published data on an alloy steel and on nickel. The degree of plastic instability and hence the creep ductility is dependent on the calue of n for these materials. When instability becomes gross and local macroscopic necking occurs, the assumptions are no longer valid. On the basis of this equation, and the strain-time relation derived from it, a method of predicting the creep behavior at different stresses is suggested. MOst analyses of creep data have been concerned with time-dependent transient creep or time-independ- ent secondary creep in constant-stress tests. The far more widely used constant-load test has been neglected in terms of a mechanistic approach. In general, since the strains involved are usually small, the same laws for transient creep may be applied to both types of tests. However, there is no steady-state creep in a constant-load test since the stress increases continuously. Any apparent steady state observed on a strain-time plot is either fortuitous or illusory, and is generally revealed as a continuously varying creep rate on a carefully constructed strain rate vs time plot.* Transient creep may be understood in terms of a simple differential equation representing the change in mobile dislocation density with time:' where p is the density of mobile dislocations. The first term on the right is related to first-order kinetics of dislocation multiDlication and the second to second-order kinetics of exhaustion. On the basis of this equation, several authors2-4 have found good agreement with experimental transient creep curves for a number of materials. When k1p = k2p2, a steady-state creep

Jan 1, 1968

By T. R. A. Gokcen

THE possibilities of separating and purifying metals by high vacuum distillation were examined by Kroll.1 He suggested vacuum treatment for the removal of zinc from the lead produced after Parkes desilverizing. The St. Joseph Lead Co. developed the first commercial vacuum dezincing process at their Herculaneum refinery, as described by Isbell.² The Broken Hill Associated Smelters at Port Pirie, Australia, has, after several years of pilot plant operations and fundamental investigations, developed a continuous process, which will be described briefly in a forthcoming publication." As the full-scale continuous vacuum dezincing plant at Port Pirie is still experimental, publication of full practical details of the plant will be deferred until the unit is operating as a normal part of the continuous refinery. This paper deals only with theoretical aspects of vacuum distillation processes, with particular reference to vacuum dezincing. The method of mathematical analysis is of general interest as it may be applicable to other metallurgical separations which have been investigated recently.4-6 Evaporation Processes At about atmospheric pressure, or higher, most liquids possess a boiling point—a temperature at which any heat put into the liquid is absorbed only as latent heat, not as specific heat. If a steady heat input is supplied, the liquid's temperature rises to this value, then remains constant while bubbles of vapor form beneath the surface. The rate of evaporation is determined solely by the rate of heat transfer to the liquid; the temperature of boiling is determined by the partial pressures of the volatile constituents in the liquid, and the total pressure above the surface. If the rate of heat transfer to the liquid is increased, the temperature remains constant, and the rate of boiling increases. When evaporating metals under vacuum, however, the partial pressures concerned are generally so small that boiling does not occur, because at even a fraction of a millimeter below the surface the hydrostatic pressure is usually too great to permit the formation of a pocket of vapor. In addition, the high thermal conductivity of metals tends to prevent the local superheating which is necessary for bubble formation.' Although this effect is doubtless also exerted when boiling metals at higher pressures, the magnitude will be less because the degree of superheat required to form bubbles is very much less at the higher temperatures involved. Under vacuum, therefore, evaporation of volatile constituents takes place only from the exposed surface, and the rate of evaporation depends upon the surface area, the surface concentration of volatile constituents, the surface temperature, and the partial pressures of volatile constituents immediately above the surface. If the heat input is raised above a certain level, the effect is not to increase the evaporation rate at constant temperature, but to raise the temperature of the liquid until at some higher level an increased rate of evaporation (and thus of latent heat absorption) again balances the heat input rate.? Many substances (including metals) have a very large intrinsic evaporation rate at quite low temperatures—far below their normal boiling points. However, at atmospheric pressure, the large numbers of atoms evaporated are almost completely deflected back into the liquid (or solid) surface by air molecules. Thus the back condensation rate is practically equal to the gross evaporation rate, and the net evaporation rate is practically zero. It can therefore be seen that an overall distillation rate depends not only upon the intrinsic evaporation rate, but also upon the ability of the volatile atoms to move away from the evaporating surface. This movement is facilitated by the provision of a condensing surface close by. Vacuum Distillation: The function of the vacuum above the evaporating surface is to remove foreign molecules, so that the chances of deflection of an evaporated atom back into its source are reduced. When the residual gas pressure is reduced so far that the evaporated atoms have a high probability of reaching a nearby condensing surface without suffering collision with a foreign molecule, the state of affairs is termed "molecular distillation." This process is practiced commercially today for the purification of numerous organic chemical products of high unit value, but not, to the writer's knowledge, for any metallurgical separation. When the degree of vacuum produced in a still is not sufficient to promote molecular distillation, then the evaporated molecules must diffuse through the

Jan 1, 1954

By H. Habenicht, J. J. Scott

An experimental method is described to compare strain data for rock and rock bolts when exposed to shock waves released by blastings. Static and dynamic strains were measured. Bolt gage response indicated a static decay of the bolt anchorage coupled with a reaction due to blasting vibrations. A distinct loss of bolt tension was indicated during vibrations and this was accompanied by a smaller but steady loss of tension due to static loading. The strain losses were found to relate to the shock source distance and the vibrational amplitude in the rock and bolts. Millions of roof bolts are used each year to stabilize mine openings and prevent their failure. Frequently, bolts become loose and lose their effectiveness as reinforcement to the mine structure. Many attempts have been made to determine the cause of loosening, including observation of the bolt tension or bolt torque through the use of torque wrenches, compression pads, and load cells. Pull tests have been used extensively to determine anchorage characteristics.102 These investigations have shown that even when bolts are loaded below the nominal anchorage capacity of the rock under 'static' conditions they exhibit a decay of load through adjustments and slippage at the bolt anchor. Since bolts are quite often found with the plate hanging loose from the rock surface, this condition suggests that some additional mechanism may have played a part in loosening the anchorage. Vibration from blasting or shock loading have been suggested as one cause in this type of anchorage deterioration. This paper gives the results of an investigation carried on at the University of Missouri at Rolla to determine the influence of shock waves on rock-bolt anchorage stability. ROCK BOLT ANCHORAGE UNDER DYNAMIC LOADING CONDITIONS In this report dynamic loading conditions are defined as conditions under which rock and bolts are exposed to vibrations occurring as a consequence of blasting, machine vibrations, earthquakes, rock bursts, etc. Whatever the location of the shock source, the waves created suffer extensive alterations along their travel paths, depending upon the vibrational properties and geometric parameters of the transmitting media. Together with reflection, refraction and diffraction at material boundaries, waves suffer changes in their nature to form tensile, compressive and shear waves. They become polarized, retracted, accelerated, dispersed, so that the waves incident at a point in the material can be the result of either one or a combination of this wide range of processes. A certain fraction of the wave energy will be lost due to friction, deformation, and material failure at the anchor-rock contact. Thus, the physical nature of wave propagation is such that it inhibits an exact analytical solution. For this reason this investigation should be considered qualitative rather than quantitative even though numerical data have been used as a base. CONCEPT OF THE INVESTIGATION Experiments were designed to find, from a series of rock bolts installed in natural mine rock, whether or not, and to what extent, bolt tensions would be influenced when bolts were exposed repeatedly to shock waves such as those produced by blasting. Electronic instrumentation available in the rock mechanics laboratory of the University of Missouri at Rolla was used to observe wave development in the rock and vibrational reactions in the bolts. EXPERIMENTAL PROCEDURE Fig. 1 illustrates schematically the experimental equipment. Electric resistance wire strain gages were used as sensors for the strain response of the rock and the bolts. Bolts were 5 ft long and 5/8 in. in diam, equipped with two-leaf type expansion shells for 1 3/8 in. boreholes. The bolt gages were mounted by use of Du Pont Household Cement, covered with an epoxy insulation and then enclosed in a copper foil for electronic shielding. For details of placement and the wiring diagram see Fig. 2 and 3. The output of both the rock gages and the bolt gages was fed into cathode ray oscilloscopes from which the vibrational traces could be photographed. A static strain indicator was also used to read the output of all gages.

Jan 1, 1968

By Oren C. Baptist, Eliot J. White

Samples of four reservoir sands having different degrees of water sensitivity were subjected to several laboratory tests to determine differences in capillary behavior attributable to clay-mineral effects. The degree of water sensitivity was estimated by the difference between gas and water permeability. Unsaturated pore volumes determined with mercury injection were comparable to irreducible water saturations determined with the semipermeable bar-rier method only for the non-sensitive sands that contained small amounts of non-swelling clay minerals. Irreducible saturations were independent of salinity of the water, which suggests that most residual water is adsorbed 0.7 a film over solid surfaces and that internal retention by clay minerals is relatively insignificant. The water-sensitive sands imbibed water to higher saturations than did non-sensitive sands, and this result is believed to be a combination of the effects of clay minerals and preferential wettability; however, the relative importance of each of these effects is riot determinable. Thus it is concluded that the semipermeable barrier method is the best of the laborafory methods used for estimating formntion water .saturations in the sands studied. INTRODUCTION This investigation is a continuation of studies of the role of clay minerals in petroleum production in the Rocky Mountain area. Previous work has shown large differences in gas and water permeability in numerous reservoir sands; these water-sensitivity effects observed in the laboratory have been correlated with well behavior in the field, and the degree of water sensitivity imparted to reservoirs by the various clay minerals has been determined.'.' The effect of interstitial clay minerals on formation water3 saturations is not so well known. It has been reported that formation water saturations probably are higher in clayey than clean sands,' but this effect has not been evaluated in the laboratory, and the relative effect of the various types of clay minerals on formation water saturation has not been determined. The clay-mineral groups of most importance to this study and to petroleum production in general are kaolinite, illite, and montmorillonite. The minute layers of montmorillonite are loosely bound to one another so that water enters between them, causing great expansion of the particles. Kaolinite and illite do not exhibit interlayer hydration, but they do immobilize considerable amounts of water owing to their large surface areas, which are of the order of 15 to 97 m2/gm of clay.5 The four Wyoming sands used in this study were selected to represent a wide range of water sensitivities. These sands, with the number of wells and fields from which the samples were obtained, are: Second Frontier, five wells in two fields; Newcastle, six wells in one field; Tensleep, two wells in two fields; and Lower Muddy, five wells in one field. EXPERIMENTAL METHODS AND PROCEDURES Water-displacement data were obtained by the semipermeable barrier method," using both fresh water and brines having either 16,500 ppm sodium chloride or calcium chloride. A displacement pressure of 35 psi was found to be sufficient to obtain the practical irreducible water or brine saturation (IWS, IBS) in most samples. Mercury-injection data were ob-tained with equipment and pro-cedures similar to those described by Purcell.7 Exceedingly high pressures are required to attain complete mercury saturation by this method; however, since saturations in most samples change very little with large pressure increases above 1,000 psia, the maximum pressure used was 1,400 psia. To facilitate comparison of mercury-injection and water-displacement results, it is convenient to express mercury-injection data in terms of unsaturated pore volume. The abbreviation, (100 - SHg)min, is used to denote the pore volume unsaturated by mercury at 1,400 psia injection pressure. Gas permeabilities, ki, were deter-mined by the method proposed by Klinkenberg.8 Methods of determining types and amounts of clay minerals by X-ray diffraction analyses, as well as methods of determining water permeability, have been described previously.' The imbibition characteristics of

Jan 1, 1958

By W. W. Mein

IN March 1949 the Calaveras Cement Co. was sued by five landowners whose properties are located in the vicinity of the plant. These landowners—all of them cattle ranchers—sued for dust damages of $120,338 and for an injunction preventing the company from casting dust upon their properties in injurious quantities. The issue was split, the jury deciding the amount of damages and the court handling the injunction features. The action came to trial before a jury in April of that year and resulted in damages being awarded in the amount of $7,508. A month later the court issued its injunction requiring recovery of stack dust to an 87 pct minimum. The Calaveras plant, shown in Fig. 1, is located three miles from San Andreas in the heart of the Mother Lode country, about 45 miles east of Stockton, Calif. Since it is in a small town, the company's responsibilities to its employees and to the community are different from those of plants located in large centers of population. Construction of the plant was begun in 1925, and production was started the following year. Standard gray Portland cement as well as several specialty cements are produced. Production facilities have been continually enlarged so that the present capacity is more than double what it was 25 years, ago. The most important item in the company's expansion program was the purchase in 1945 of an 11 ft 3 in. x 360 ft Allis-Chalmers kiln which had been declared surplus by the Defense Plant Corp. The company is now able to produce about 2,500,000 bbl of cement a year, and employment at the plant is approximately 300. The production of cement has always involved a dust problem, solution of which has been attempted in a number of different ways. By far the most efficient method of catching dust discharge is electric precipitation. Soon after the company went into production in the 1920's, the landowners near the plant began complaining about dust discharge. The company settled the matter by paying them a total of $27,000 for dust damages incurred during the period from 1929 to 1938. In the latter year the two-unit Cot-trell Electric Precipitator shown in Fig. 2 was installed and collected over 85 pct of the dust resulting from operation of the two 11 ft 3 in. x 10 ft x 240 in. kilns. From 1938 until 1946 the landowners registered no objection and were apparently satisfied with that dust recovery. In 1946, however, the substantially higher production resulting from operation of the new kiln immediately overtaxed the facilities of the existing two-unit precipitator. In a short time claims for dust damages were again received from the landowners. The company informed them that because of postwar shortages it would take several years to install a new precipitator. The company stated that it intended to purchase an additional precipitator and offered in the meanwhile to pay the landowners a fair amount to cover their damages. This offer was rejected and the landowners filed suit in the Superior Court of Calaveras County asking for total damages of $120,-338 and for the injunction outlined above. Case for the Ranchers The attorneys for the plaintiffs produced three different types of witnesses: first, the landowners themselves and members of their families; second, other cattle raisers who were sympathetic to the plaintiffs; and third, several types of technical experts: veterinarians, soil chemists, and an aerial photographer. The testimony of these witnesses was designed to establish that the flue dust from the plant had not only damaged the land and the forage, but had also caused fluorine poisoning to their animals. By a combination of these causes, the plaintiffs attempted to prove substantial loss of profits.

Jan 1, 1952

By Michael J. Messel

OF the various minerals that occur in fibrous form known as asbestos, chryso-tile is the variety most in demand for commercial uses, and, last year, over 683,000 tons of the various grades were produced in Canada and United States, exclusive of African and Russian production, which figures are uncertain. Production has not been able to keep up with the increased demand, and an acute shortage exists. Canada, Russia, and Africa are still the most important producers. However, Russia consumes most of its production at home and exports very little. The United States consumes over 60 pct of the total production and produces only about 4 pct of the total from deposits in Vermont and small quantities from Arizona. This paper will review mainly, some of the more recent developments concerned with the extraction and processing of this fibrous mineral for various industrial uses, such as textiles, insulation, building materials and brake linings. Four of the more important factors that have influenced recent developments are: 1. The lack of discovering and developing new deposits of any important size to supply the increased demand. 2. Rapid postwar expansion of industrial uses, especially in asbestos cement products, together with in-rreased manufacturing facilities. Euro-peal) countries are again back on the market with their demand. 3. The ability of manufacturers to develop their technique of blending fibers and obtaining more utility value out of each ton of fiber, together with the utilization of shorter grades of fiber to obtain equally as good products. In the past, many manufacturers were wasteful in their use of fibers. 4. The struggle for reduced operating costs, in face of increased wages and prices of supplies, together with the necessity, at some mines, to change the method of mining from open quarry to underground. Most of the recent capital invested in the asbestos mining industry has gone into more efficient extraction of the fibers from the existing ore, especially in the recovery of the shorter grades. There has been very little new plant expansion. Progress in the utilization of shorter fibers has been so far reaching that some of the mining companies are retreating present tailings as they leave the mill, and others are considering retreating of the old tailing dumps for recovery of fibers that, until recently, were not saleable and were discarded as part of the tailing. Many of these dumps contain much valuable fiber from days when milling was very inefficient. It might be appropriate to mention here that the present known asbestos reserves of proved commercial value (excluding Russia) are being depleted at an alarmingly rapid rate, about 10,000,000 tons of ore is being mined annually. No new deposits have come into production during the last 15 years, with the exception of certain deposits in Africa, which are the most promising, and minor developments in Canada, Venezuela, Cyprus, Australia, and Brazil. The African deposits are the only ones that hold promise of developing large reserves. Unless new deposits are developed, in twenty years or maybe sooner, the supply picture will not be a very bright one. Stimulated by the acute shortage, increasing fiber prices and technical developments, many new areas are being prospected in Canada, United States, New Zealand, Newfoundland, South America, Europe, Africa, and China. From information now available, it appears that no real progress has been made in duplicating this rare development of nature by producing synthetic asbestos. The most promising experiments were carried out at the University of Leipzig, but they seem far from practical. There has been marked progress in fiber glass manufacture, but so far, it has replaced asbestos only in very few instances for minor uses. Asbestos ore and the fiber it yields are different in some respect at each mine and vary usually in the following: 1. Percentage of fiber content by weight to the gangue. 2. Variations in proportions of long and short fibers, some deposits being predominantly long fiber and others short fiber. 3. The hardness of the rock in which the fiber occurs. 4. The nature of the fiber, as to

Jan 1, 1950

By C. H. Li, S. H. Bendel, J. A. Sartell

Small additions of Mg to a 62 Cu-38 Ni alloy reduce the oxidation yates drastically between 500° and 850°C. Metallographic examination of the oxide scale disclosed a continuous network, identified by X-ray diffraction as (Ni, Mg)O solid solutions, located along the former alloy grain boundaries. This network acts as a barrier to diffusion. It is thought to result from the segregation of mg to the alloy grain boundaries. Oxidation occurs preferentially in these regions because of the presence of this more active element. To substantiate these ideas, homogenized alloys ulere oxidized. No oxide network was produced and oxidation rates were the same as for the parent 62 Cu-38 Ni alloy. An interesting aspect of the oxidation of the 62 Cu-38 Ni alloy previously described by the present authors, is the relationship between oxidation kinetics and changes in the microstructure of the oxide.' The oxide scale on these alloys consists of two layers: a thin layer of CuO outside a much thicker layer of Cu20 in which particles of NiO are dispersed. In addition, immediately beneath the oxide-metal interface there is an internally oxidized zone in which NiO particles are dispersed in a copper-rich alloy matrix. Experimental observations on the growth of the individual layers under isothermal conditions have led to the conclusion that the rate-determining step in the oxidation of this alloy is the diffusion of anions through the Cu20 layer. It has been found that this diffusion rate is increased by the recrystallization of the outer CuO layer. Willardson and Gorton have reported that the addition of magnesium to the 62 Cu-38 Ni alloy causes a decrease in the oxidation rate.2 The present investigation was undertaken in order to determine the mechanism by which magnesium additions improve the oxidation resistance of the 62 Cu-38 Ni alloy. EXPERIMENTAL PROCEDURE Fifty-gram ingots of Cu-Ni alloys were prepared by vacuum melting materials of 99.999+ pct purity. These ingots were then remelted in a He atmos- phere and magnesium added in the form of a previously prepared and analyzed Cu-Mg master alloy. This procedure was necessitated by the high reactivity of pure magnesium at high temperatures. The proportion of the alloying elements was adjusted so as to obtain alloys with the desired magnesium content while maintaining a Cu-Ni ratio of 62 :38 by weight. (All alloy compositions will be given in weight percent.) Since it was considered desirable to study the oxidation of only single-phase, solid-solution alloys, it was necessary first to determine the approximate limit of solid solubility of magnesium in the 62 Cu-38 Ni alloy. A series of melts with various magnesium contents was made, homogenized by annealing for 48 hr at 975OC, then cooled in the furnace. Metallographic samples were prepared, etched in a potassium dichromate solution and examined at XI500 for the presence of a second phase. The alloys were then chemically analyzed and it was found that the approximate limit of solid solubility of magnesium in the 62 Cu-38 Ni alloy was 1 pct Mg. The ingots containing less than 1 pct Mg (0.19, 0.29, 0.58, and 0.87 pct Mg) were cold-rolled down to thicknesses suitable for oxidation experiments and specimens for gravimetric studies were cut to dimensions of 3.0 by 1.5 by 0.05 cm, specimens for inert marker studies, 0.6 by 0.6 by 0.17 cm. These were heat-treated in a protective atmosphere at a temperature (975" C) well above the oxidation temperatures and furnace-cooled to insure structural stability of the alloy during oxidation. Immediately prior to oxidation, the specimens were chemically cleaned by immersion for 1 min in a solution of 2 parts nitric acid, 1 part acetic

Jan 1, 1961

By M. C. Fuerstenau, A. M. Gaudin

A homogeneous suspension is viewed by X-rays. The radiation density seen, affords a measure of the extra absorption due to the solids contained. This radiation density, at a predetermined depth, varies with time. The chart of this relationship gives the desired determination. s it is frequently necessary to know the distribu-rt tion of particle sizes in various products used in industrial applications, a number of means have been devised for these determinations. Some of them include direct microscopic measurement, screening of product, extraction of samples from a settling slurry, air and liquid elutriation, adsorption of gases and liquids, and light absorption. The absorption of light as a means for particle size analysis has been known and employed for some time. X-ray absorption has not received the attention that light has enjoyed primarily because of the complex and costly instrumentation involved with X-rays. In 1954, Brown and Skrebowskil suggested the use of X-rays for this type of determination but did not supplement their suggestion with experiment. In 1958, the authors conducted size analysis experiments on suspensions of quartz with the Trans-viewer: an X-ray unit specifically adapted for sedimentation research, and Rossa conducted experiments in a similar manner in 1959 with a stable gamma emitter, AmZ4l, on suspensions of uranium oxide. To illustrate the applicability of X-ray absorption for analyzing particle size distributions, an essentially mono-energetic and well collimated X-ray beam was used as a source. The beam was made mono-energetic by placing a zirconium filter before the counting window together with feeding the pulses from the proportional counter into a reverter, a device capable of discriminating against pulses of various heights. The sketch in Fig. 1 shows the collimation arrangement in more detail. As shown, the X-ray beam was collimated by inserting a 3/8-in. ID pipe into one of the ports of the X-ray tube and further by two small steel plates with slits 3/32-in. wide and 1/2-in. long placed in front of the window of the Geiger-Mueller (G-M) tube. One of the plates was located 1/2 in. and the other 2 1/2 in. from the window of the counter; both plates were contained in an aluminum holder mounted on the box containing the G-M tube. This type and degree of collimation should eliminate any intensity due to scattered radiation; the transmitted intensity would then be solely a functior. of the absorption by the suspension at that level. Experimentally, homogeneous suspensions of finely ground quartz were prepared, Daxad (a sulfo-nated compound made from wood) was added as dis-persant, and the transmitted X-ray intensity measured as a function of time at a fixed depth in the suspension. In more detail, the experimental procedure involved the following: 1) measuring the transmitted X-ray intensity through the Daxad solution at a predetermined position or settling depth in the absence of solids, 2) placing a known amount of dry solids into the vessel and agitating thoroughly, 3) measuring the transmitted X-ray intensity at time zero (i.e., immediately upon cessation of stirring), and 4) measuring the transmitted X-ray intensity as a function of time (a 10-sec counting interval being chosen and counting being started 5 sec before the desired time). Since a linear relationship exists between percentage solid in a slurry and the logarithm of transmitted intensity for a homogeneous material, the cumu-

Jan 1, 1961

By Elton A. Youngberg

The Holden mine operated by the Chelan Division of the Howe Sound Co. is on the east slope of the Cascade Range in north central Washington on the south slope of Railroad Creek valley at an elevation of 3500 ft. The mine may be reached by a 40 mile boat trip from the town of Chelan which is at the southern tip of Lake Chelan, to Lucerne at the mouth of Railroad Creek and an 11. mile bus ride up Railroad Creek to Holden. A11 freight and concentrate is moved over this route to Chelan Falls on the Columbia River which is on the railroad four miles below the town of Chelan. The mine is now producing 2000 tons of gold, copper, and zinc ore per day which is treated in the Holden mill. Gold-copper and zinc concentrates are made, the first of which is shipped to Tacoma, Wash., and the latter to Kellogg, Idaho, for smelting. Ore is broken by long-hole blasting using the Noranda system which has been modified to meet local conditions. Until recently, blastholes have been drilled by diamond drills. Now a partial substitution of percussion drill holes, drilled with tungsten carbide insert bits, is being made. Geology The ore body occurs as a replacement deposit in a highly metamorphosed series of sedimentary rocks, mainly gneiss and schists, in a shear zone several hundred feet in width and of undetermined length. Commercial ore has been found in mineable widths of 25 to 100 ft for approximately 2500 ft along its strike. The commercial minerals are chalcopyrite, sphalerite, and gold. During the period of mineralization considerable silicifica-tion took place giving the ore an abrasive drilling characteristic. Following the period of mineralization, numerous dikes were introduced into the ore body. The earlier ones were of granite composition having a width of a few inches up to 80 ft. These were followed by much younger, fine grained basic dikes which usually do not exceed 2 ft in width. Development of Percussion Blasthole Drilling Equipment Test work with the 1½-in. tungsten carbide bit was carried on in development headings for several months early in 1947. The short life of the bits, because of gauge loss caused by the abrasive nature of the rock, prevented its adoption for this use. However fast drilling speed and ability to drill a long uniform hole suggested its use for drilling blastholes in competition with diamond drills as diamond costs were steadily increasing and exper-ienced drillers were difficult to obtain. The 1½-in. bit was the largest available at the time initial test work was started with sectional steel. The 1½-in. hole limited the diameter of the steel thread and coupling which could be used. Type F couplings were first used but because of the small thread section excessive breakage of the steel was experienced. Type H couplings were tried next. In order to use this coupling which is 15/8 in. in outside diameter, it was reduced to 1 3/8 in. giving 1/8 in. clearance between the coupling and the hole. Rod breakage at the thread was substantially reduced but some coupling breakage was experienced, however the overall performance was considered satisfactory (see Fig 1 for illustration of coupling and thread). Early test work with the 1½ in. bit indicated machines of piston diameters larger than 255 in. would cause inserts to loosen or break. It was found however that the additional weight of the sectional steel cushioned the blow enough to prevent bit failures when 3-in. Leyners were used. Rods used with the 1½-in. bits were 7/8 in. q. o. for sectional steel and 1 in. q. o. for all chuck pieces. In May 1948, 2-in. tungsten carbide bits became available and test work was immediately started. The 2-in. hole approximated the AX (1 15/16 in.) diamond drill hole which was being used exclusively for blastholes and permitted their substitution for diamond drill holes in a ring without alteration of pattern, burden, or explosives. The 2-in. bit also gave room in the hole for larger couplings and permitted the use of heavier rods and 3½-in. machines, increasing the

Jan 1, 1950

By Ihor A. Kunasz

Introduction Lithium minerals occur predominantly in pegmatites which contain mineral assemblages derived from the crystallization of postmagmatic fluids or from the metasomatic action by residual pegmatitic fluids. They have been the traditional sources of raw materials for ceramic and chemical industries. With the discovery of Searles Lake, brines became new sources of lithium. Indeed, the 1960s may well be referred to as the "brine decade" because several brine bodies of significant economic importance were discovered. In the United States, the brines of Clayton Valley, Nevada, are presently exploited by Foote Mineral Co. The brines of the Great Salt Lake of Utah, the Smackover formation, and the Imperial Valley geothermal field, have been defined as important resources of lithium. In South America, new occurrences have been identified in Bolivia and Argentina. At the Salar de Atacama, Chile, new production capacity is scheduled for 1984. Following the termination of the AEC purchase program in 1959, several companies such as Maywood Chemical Co., American Lithium Chemicals, and Quebec Lithium Corp. were forced to close their operations. Nevertheless, with the development of new applications in glass ceramics, air conditioning systems, synthetic rubber, and metallurgy (aluminum potlines), the lithium industry grew steadily, and with the potential application of lithium metal in batteries and nuclear reactors, a healthy growth can be foreseen. New products and new applications are likely to stimulate exploration for expanded, reserves as well as the search for new sources from which lithium could be extracted economically. Geochemistry of Lithium Lithium is the third element in the periodic table. It is the lightest of all the metals, having an atomic weight of 6.938, an ionic radius of 0.68Å and a charge of +1. The geochemistry of lithium has been extensively studied and has been summarized by Rankama and Sahama (1950), Goldschmidt (1937), and Hortsman (1957). The distribution of lithium in igneous rocks is controlled by its size and its charge, and by the (MgO+FeO) / Li2O ratio. In the early stages of crystallization of a magma, that ratio is very large. Consequently, both magnesium and iron are removed by ferromagnesian minerals in preference to lithium which is then concentrated in the residual magma. This results in an enrichment of lithium in silicic rocks and pegmatites (Strock, 1936). Pegmatites are coarse-grained igneous rocks formed by the crystallization of postmagmatic fluids. Minerals within pegmatites may also form by metasomatism (Jahns, 1955). Genetically, the pegmatites are associated with neighboring intrusives. Mineralogically, granitic pegmatites contain feldspar, quartz, and mica as the main constituents and a variety of exotic elements such as lithium, beryllium, tantalum, tin, and cesium, which may or may not occur in economically significant concentrations. Detailed studies by numerous investigators (Cameron et al., 1949, 1954; Hanley et al., 1950; Jahns, 1953, 1955; Page et al., 1953) indicate that pegmatites often exhibit an internal zonal arrangement, with each zone containing a specific suite of minerals. The lithium minerals are usually found in the intermediate zones, and although as many as 13 zones have been recognized by Cameron, et al. (1949), a complete zonal arrangement is rarely found. Zoning of pegmatite bodies has also been observed on a regional basis. The regionally zoned pegmatite sequences exhibit mineral assemblages and complexity according to their re-

Jan 1, 1983

By C. Perez-Rosales

A statistical method for determining simultaneously some of the basic geometrical characteristics of porous media such as porsity, specific surface* mean pore width, mean grain thickness and absolute permeability is presented. The proposed method is characterized by its simplicity and the minimum amount of laboratory equipment that it requires. The experimental procedure used to evaluate the various geometrical characteristics is based 'pan the 'surface analysis Of a a In view of this fact the app1icability Of the method is limited to homogeneous and isotropic materials. INTRODUCTION The behavior of a fluid flowing through a porous medium depends, among other things, upon the internal geometry of the medium; hence the importance of developing efficient methods to determine the geometrical properties of porous materials. This paper describes a statistical method to determine simultaneously some of the basic geometrical properties of porous materials such as porosity, specific surface, mean pore width, mean grain thickness and absolute permeability. The mathematical formulation has been developed that the data required to calculate the various geometrical characteristics of a sample can be easily measured by analyzing a section of the sample with an evenly spaced grid. THEORY A simple way of obtaining information about the internal geometry of a porous material is to throw a point at random over a cross-section of a sample. l-Through this procedure the porosity can be detemined.l,2 By considering that the material is homogeneous and isotropic, and that the point is dropped many times, the porosity 4 is given by where N is the total number of times the point is thrown and n is he number of times the point falls within pore areas. Another simple manner of analyzing the structural characteristics of a porous material is to superimpose an arbitrarily long line on a cross-section so that its length is evenly distributed over the surface area. Through this procedure the porosity can also be determined. If L is the total length of the line, and 1 is the sum of the lengths of the line segments within void spaces, the porosity is given by 4 = —.1.............. (2) The advantage of this type of analysis is that geometrical characteristics other than porosity can be obtained. Thus, if c represents the number of intersections between the line and the perimeter of pores, it can be shown3 that the specific surface, defined as he surface area of pores per unit bulk volume, is given by To give a proper description of the internal geometry of a porous medium, it is necessary to define quantities that characterize the notions of pore size and grain size. Unfortunately, because of the complexity of porous materials, it is difficult to give exact geometrical definitions of what is meant by the ConCePtS of "poresl' and "grains", especially when dealing with consolidated materials. Never theless, one often talks about the "size of pores" and the "size of grains" without defining accurately the terms. A possible solution to this problem follows. Assume that an arbitrarily long line is placed on a section of a sample so that the line is evenly distributed over the surface area (see Fig. 1). 1n a system like this, each line segment within a void space will be, by definition, the pore width in a given location and direction. Consequently, if the

Jan 1, 1970

By Donald E. Grimes

In conjunction with Inland Steel&apos;s development of lead-bearing steels possessing improved machin-ability because of tellurium and/or selenium additions, it was decided to determine liquidus and solidus temperatures in the Pb-PbTe-PbSe sub-ternary system. With the exception of alloys in the PbTe-PbSe system, it is believed that no previous study of this subternary has been performed. Thermal analysis was employed in a general survey of the subternary. In addition to PbTe, PbSe, and pure lead, ten ternary compositions were selected at intervals of ten at. pct. Sixty-gram alloys were prepared by sealing an appropriate mixture of the elements in quartz crucibles with a central thermocouple-well under a vacuum of less than 10 p. All three elements were 99.999+ pct pure with only trace impurities detected by spectroscopic examination. After the alloys had been heated at least 20°C above the liquidus in a Kanthal furnace, cooling and heating curves were obtained. Two or more cooling curves were employed both for the determination of each alloy liquidus and for the solidus of those al- loys containing greater than 50 at. pct Pb. Cooling rates were 0.5° to 3.5°C per min during the 5 min immediately prior to the start or end of solidification. For those ternary alloys containing 50 at. pct Pb, the solidus was determined from heating curves. Temperatures were measured with a Pt/Pt-10 pct Rh thermocouple which was calibrated in the same apparatus against the freezing points of zinc (A. D. MacKay—99.999 pct), antimony (A. D. MacKay-99.999 pct), and copper (ASARCO—99.999+ pct) both before and after the experimentation. The only interruptions in the continuous strip-chart recording of the temperature occurred for brief periods at significant points of interest when direct readings were made with a Rubicon Type B potentiometer sensitive to * 1 µv. The average liquidus and solidus temperatures obtained in this investigation are listed in Table I together with probable errors based on the accuracy of the thermocouple calibration and the reproduci-bility of the data. No chemical analyses of the alloys were performed because the synthetic or as-charged compositions were felt to be reliable. The melting points obtained for PbTe (924.7° ± 0.7°C) and PbSe (1084.0° ± 0.6°C) compare favorably with recent findings of other investigators.&apos;-&apos; As indicated in Table I, both the liquidus and solidus temperatures increase as selenium replaces tellurium for a constant atomic percent lead. As a result, the ternary liquidus and solidus temperatures for a given percent lead lie between the corresponding binary temperatures published in the literature. It should be noted that those ternary alloys containing 50 at. pct Pb exhibit a relatively narrow liquid-plus-solid region (<80°C) when compared with alloys containing greater than 50 at. pct Pb. Alloys with 60, 70, or 80 at. pct Pb not only have a much wider liquid-plus-solid region (>500°C) but also exhibit considerably lower and approximately constant solidus temperatures which thus form a virtually isothermal solidus "plane" slightly below the melting point of pure lead (327.3°C). For these alloys

Jan 1, 1965

By G. C. Wallick, W. R. Foster, J. G. Savins

A comprehensive review of the salient features of the differentiation method of rheological analysis in Poiseuille flow from its inception circa 1928 is presented. Here no initial assumptions regarding the nature of the function relating rheological parameters to observed kinematical and dynamical parameters are required in the data-analysis process. In contrast, the integration method involves interpreting flow properties in terms of a particular ideal model. It is shown that, although both methods represent modes of solution of the same integral equation, being relatively bias-free, the differentiation method offers a more discriminating procedure for rheological analysis. The application to problems involving plane Poiseuille flow is also described. INTRODUCTION In most instances, the approach to the problem of interpreting the rheological properties of various compositions as they are affected by changes in chemical or physical environment, assaying the characteristics of a particular constituent of a suspension, analyzing flow behavior in terms of interactions between components in a system, to cite but a few examples, has been in terms of what Hersey1 terms the integration method. Briefly, it consists of interpreting flow properties in terms of a particular ideal model. The usual practice of the integration method is to choose a model with a minimum number of parameters because, other things being equal, it is desirable to use the simplest model which will describe the behavior of a real material and yet be mathematically tractable for the requirements of data analysis. This expression is then substituted into an equation which relates observed kinematical and dynamical quantities, such as volume flux Q and pressure gradient ], and angular velocity and torque T, in a capillary and concentric cylinder apparatus, respectively. The rheological parameters appear on integrating, in an expression relating the pairs of observable quantities such as those just given. In many instances a particular model provides a good representation of rheological behavior over a reasonable range of compositional and environmental changes. Just as often, however, it is obvious that the interpretation of rheological changes by the integration method is not providing realistic information about changes in flow behavior. A more general method of interpreting rheological data for a given material is to make no initial assumptions regarding the nature of the function relating rheological parameters to observed kinematical and dynamical quantities, e.g., flow rate and pressure drop in capillary flow or angular velocity and torque in a rotational viscometer. This general method Hersey1 terms the differentia-ation method. Instead of integrating, one differentiates the integral equation with respect to one of the limits, i.e., one of the boundary conditions; the resulting expression contains the same observable quantities just given, their derivatives, and the rheological function evaluated at that boundary. By obtaining these derivatives from experimental data, graphically or by a computer routine, they can be substituted into the differential equation and a graphical form of the function derived. THEORY OF THE DIFFERENTIATION METHOD FOR POISEUILLE-TYPE FLOWS In this introductory paper, two flow cases which are important in viscometry are considered (one for the first time) from the differentiation method of analysis, flow in a cylindrical tube and flow between fixed parallel surfaces of infinite extent, the basic integral equations being formulated in a manner analogous to the way they originally appeared in the literature. In addition, the following ideal conditions will be assumed: (1) an absence of anomalous wall effects, (2) isotropic behavior everywhere, and (3) steady laminar flow conditions. Before proceeding it would seem appropriate to preface the analysis of these flow geometries with the comment that the basic philosophy of the differentiation method could be said to stem directly from the efforts of Herzog and weissenberg2 to indicate systematically the various ways of using

By H. R. Brannon, R. J. Robinson, G. W. Kattawar

Accurate prediction of storm wave characteristics are needed for design of offshore structures. Statistical methods of random noise analysis provide techniques for predicting required wave properties. These techniques have been used to analyze and characterize storm wave profiles from Gulf of Mexico recording installations in 34, 65 and .98 ft of water. Correlations based on the results can be used to predict wave crest probabilities and wave shapes for a range of Gulf water depths and storm conditions. Example predictions of wave crest probability as a function of water depth for a particular set of storm conditions are given. INTRODUCTION Accurate predictions of wave crests and wave shapes are needed for design of offshore structures. With predictions of wave crests, platform deck elevations giving adequate protection from exposure to storm waves can be selected. Use of hydro-dynamic wave theories with the wave crest and wave shape predictions permits an estimate of the wave forces an offshore structure must withstand. Observation of ocean waves suggests use of statistical analysis for studying wave characteristics for water depths beyond the breaking wave zone; recent wave generation theories lend support to this approach. l-3 One of the most powerful methods of statistically analyzing wave profiles was introduced by Cartwright and Longuet-Higgins; most of the basic relations used were developed by Rice5.6 in studies of random noise theory. This method predicts wave crest elevation probabilities from two parameters characterizing a wave profile. The statistical approach also provides a means for predicting wave shapes. In the random noise model of a wave profile, surface elevation is represented as an infinite sum of sine waves with closely spaced frequencies and random phase angles. Power density is proportional to the sum of the squares of the amplitudes of sine waves having frequencies within a narrow band, and the distribution of power density as a function of frequency is called the power density spectrum, or power spectrum. The power spectrum characterizes an irregular sea, and hence finds use in motion studies of ships, barges and semisubmersible drilling platforms. From the power spectrum, a wave profile of any duration of time can, in principle, be calculated; this long wave profile depicts the many wave shapes to which a structure may be exposed. Thus, the statistical methods of wave analysis provide an approach to selecting wave shapes as well as wave crest elevations needed for design of offshore structures. For practical application of these techniques, power spectra and related quantities must be predicted from storm properties. Barber and Tucker 7 have reviewed correlations of wave properties and storm conditions. Their review summarizes work of Darbyshire,8 among others, in which a correlation of power spectra with wind intensity of the North Atlantic was developed. These results, plus more recent work by Pierson and Moskowitz and Kitaigorodskii,10 establish feasibility of correlation, but there is no theoretical basis for modifications extending the relations to other areas as remote as the Gulf of Mexico. Hence, to predict characteristics of Gulf of Mexico waves, a study of local observations is needed. This paper presents (1) a practical approach to computing wave profiles hat depict shapes of waves for use in force calculations, (2) a summary of relations for predicting probabilities of wave crest elevations, (3) correlations of parameters needed to apply these methods in the Gulf of Mexico and (4) examples of application of the techniques. THEORETICAL BACKGROUND The following sections summarize relations needed to calculate wave profiles and to estimate wave crest probabilities. These relations also identify quantities that must be related to storm

By D. T. Novick, M. B. Bever, B. Roessler

Ordered and disordered specimens of the alloy CusAu were cold worked and then annealed at 2880, 310°, and 340°C, together with disordered unworked specimens. me resistivity decreased during annealing mainly as a result of ordering; the resistivity measurements suggest that in cold-worked specimens the growth of antiphase domains is impeded. The strength properties increased during annealing at 288 "C; in cold-worked specimens this increase was lo a level above that for cold-worked specimens which had not been annealed. X-ray diffraction showed that after annealing for a few hours at 288ºC, the long-range order increased to a constant value; additional annealing at 288ºC resulted in the growth of antiphase domains in which the degree of order was constant. Changes in peak breadth and particle size confirmed that in cold-worked specimens the major effects of cold work were not eliminated during annealing at 288 "C, although a slight recovery process occurred. When a specimen of the alloy Cu3Au is heated to a temperature below the critical temperature (388ºC), long-range ordering tends to occur in a specimen containing less than the equilibrium amount of order characteristic of that temperature Ideally, a specimen of Cu3Au contains no long-range order if it has been quenched from above the critical temperature. Long-range order is reduced by cold work. If cold-worked specimens are heated, restoration processes such as recovery and recrystallization may occur,

Jan 1, 1963

By Fred H. Poettmann

The vaporization characteristics of carbon dioxide in a League City natural gas - Billings crude oil system were studied at three temperatures, 38°. 120°, and 202°F and for pressures ranging from 600 to 8,500 psi. Variation of carbon dioxide concentration up to 12 mole per cent in the composite showed no effect on the equilibrium vaporization ratios (K values) of the hydrocarbon constituents or on the K value of carbon dioxide itself. It was shown that carbon dioxide is more soluble in crudes than in distillates which is contrary to the behavior of methane. A working chart of carbon dioxide K values is presented. INTRODUCTION The study of the equilibrium vaporization ratios of mixtures of paraffin hydrocarbons has been rather thorough.2,6,7,8,9 In the past few years considerable attention has been paid to the vaporization characteristics of the so-called noncondensable gases such as nitrogen, carbon dioxide, and hydrogen sulfide in mixtures of hydrocarbons. since they usually occur to some extent in most crude oils and natural gases.1,3,4,5 Knowledge of this behavior is useful to both the production and refining phases of the petroleum industry. This paper reports the equilibrium vaporization ratios (K&apos;s) of carbon dioxide in a mixture of League City natural gas and Billings crude oil, and compares them to those obtained in a natural gas-distillate system. The equilibrium vaporization ratios for the hydrocarbon components in this system had previously been studied by Roland.&apos; In addition to the determination of the K values for carbon dioxide, the K values for methane and ethane were also determined in order to observe what effect, if any, the presence of carbon dioxide had on these K values. The concentration of carbon dioxide was also varied in order to observe the effect of this variable on the carbon dioxide K values. EXPERIMENTAL PROCEDURE The apparatus used in this study cotlsisted of a stainless steel equilibrium cell of about 2 liters capacity. The cell was mounted on trunions permitting rocking in a thermostatically controlled oil bath. Two high pressure valves fitted with steel tubing were mounted on the top of the cell. one was used for sampling the equilibrium gas phase and the other for sampling the equilibrium liquid phase by means of an induction tube within the cell. Stainless steel tubing from the bottom of the cell led to a mercury reservoir and manifold which was connected to a free-piston type pressure gauge manufac- lured by the American Instrunlent Ctr. and to a volumetric. putrip. The temperature of the oil bath was measured by means of a ralibrated mercury-in-glass thermometer. The recorded temperatures are believed to be accurate to ±0.5 °F. The pressures are correct to 22 psi. The crude oil used in this study was stock tank oil obtained from the Wilcox formation in the Billings Field, Noble County. Okla. The natural gas was obtained from the League City Field. Galveston County, Tex. The oil was treated with anhydrous calcium sulfate in order to remove the last traces of water. To insure a supply of constant composition gas at room temperature the cylinders of League City gas were cooled to about 30°F, inverted, and the condensed liquid was allowed to drain from the cylinders. The analysis of the gas and crude are tabulated in Table I. The carbon dioxide came from Pure Carbonic, Inc., and was .stated to have a purity of 99.5 per cent or better. The procedure used to obtain samples of the equilibrium liquid and vapor was similar to that employed by others making use of the rocking type equilibrium cell.6,7,8 The equilibrium cell was evacuated and calculated quantities of carbon dioxide, natural gas, and crude oil were charged to the cell to the desired pressure. In charging the equilibrium cell an attempt was made to maintain the ratio of the natural gas to crude oil as close as possible to that employed by Roland. After the cell was charged, samples of

Jan 1, 1951

By R. J. Sherman, M. R. Achter

Creep rates have been measured for nickel at 1200°F in air and in vacuum, and related to the depth of surface cracks in the specimens tested in the two environments. The surface cracks were observed to grow faster in air than in vacuum in both short-time and long-time tests. Crack depths, however, could be correlated with creep rates only in the short-time tests. Although no cracks were observed in a relatively brittle Ni-Cr-A1 alloy creep tested at 1300°F, the appearance of alloy specimens fractured after interruption in creep indicated that there was a decrease of intergranular cohesion resulting from the diffusion of atmospheric gases into grain boundaries. PREVIOUS investigations1-3 have demonstrated that the effect of atmosphere on the high-temperature strength of nickel and nickel-base alloys may be reversed by changes in the stress or temperature of the test. At high stress and low temperature the creep-rupture life is longer in vacuum than in air, while at high temperature and low stress the relative strengths are reversed. A mechanism to explain this behavior was proposed based on two competing processes. Oxidation hardens and strengthens a metal, but adsorption of gas, by lowering surface energy, reduces the work required to propagate an intergranular crack. The controlling process is determined by temperature and stress. Basic to this mechanism is the concept that environment determines the ease of propagation of intergranular cracks and thus affects creep rate and rupture life. To explore the mechanism in greater detail, this investigation was undertaken to determine the effect of atmosphere on crack initiation and propagation rates in nickel1 and a relatively brittle Ni-Cr-A1 alloy.3 EXPERIMENTAL PROCEDURE The materials were the same as used previously. Nickel of 99.8 pct purity had the following impurity content: 0.02 pct Co, 0.03 pct Fe, 0.02 pct Mg, 0.03 pct Si, and 0.008 pct C. Rods were cold swaged from 1/2 in. to 3/8 in. in diam and machined into speci- mens with gage sections 1/4 in. in diam by 1-1/4 in. long. They were annealed in vacuum at 1600" F for 1 hr to achieve a grain size of 0.07 mm. The alloy was composed of 19.1 pct Cr, 3.6 pct Al, 1.7 pct Si, 0.57 pct Fe, 0.10 pct Mg, 0.027 pct C, 0.004 pct S, and the balance Ni. Sheet specimens of 0.500-in. width and 1.25-in. gage length were machined from 0.033-in.-thick strip and annealed in vacuum at 2000° F for 2 hr, resulting in a grain size of 0.036 mm. Large amounts of an intergranular phase were introduced as a result of the anneal. Creep tests on both materials, using equipment previously described by Shahinian; were conducted in air and in a vacuum of 1 x 10-5 mm Hg. They were continued to rupture and interrupted at various stages of the test. Although extensions were measured from dial gage readings of movement of the lever arm, it is considered that valid comparisons of creep rate may be made in this manner.l Two parameters were measured metallograph-ically* on longitudinal sections of nickel specimens interrupted during creep—the mean depth of surface cracks 2, and the density n as the number of cracks per unit length of surface. They were combined into one parameter by the relation p = n-d [1] As used here, p is equal to the total of crack depths per unit length of surface. RESULTS Nickel. It is well known that the incidence of intergranular cracking is increased with increasing rupture life. Indeed, it is evident in Tables I and I1

Jan 1, 1962

By J. C. Purcupile, R. L. Morris

Present methods of roof support require that first a hole must be drilled, and then a toggle belt or grouted resin bolt be set. Automating this system is very difficult. Therefore, we decided to develop a system which would insert pins into the roof in one step. We think that this type of system can be automated much easier. It would then speed up the roof bolting operation and eliminate the need for a man to work under unsupported roof, making roof bolting a much safer job. There are two ways that a pin can be inserted in a mine roof without drilling a hole. It can either be pushed in, using a very high, constant axial force; or it can be hammered in like a nail. The former method involves very high compressive stresses in the pin, and requires complicated machinery to prevent buckling. Since hammering the pin does not require high axial forces buckling is not as likely. Also, experiments have shown that there are no problems associated with getting the pin to go in straight. We chose to develop the second method. While investigating methods for hammering a pin into a mine roof, we learned that piles were being driven 10 times faster than by conventional methods with a method called "orboresonance." We decided to turn the pile driver upside down, and drive pins up into the mine roof. Sonic Pin Setting Machine The machine consists of a steel bar supported at the nodal points of its first mode of transverse vibration (Fig. 1). A mechanical oscillator, driven by a hydraulic motor, is attached to one end of the bar. This provides the forcing function for the vibrations in the bar. The hydraulic power is supplied by a portable unit. When the forcing function is near the natural frequency of the bar, large amplitudes of vibration occur and require little power input. An anvil is attached to the bar at a point of maximum deflection, providing a means for striking the pin. Since the bar is being driven near its natural frequency, it takes little energy to accelerate the bar back and forth between each hit. This means that most of the power being put into the bar is going into driving the pin. This is unlike conventional pile drivers which use most of their power to accelerate the hammer back and forth between hits. The resonant frequency of the bar we used is about 250 Hz, which is in the audible range, hence the term "sonic pin setting machine." The system benefits are: (1) elimination of the two-step drilling and pin-setting roof bolt operation, (2) increased speed, (3) more intimate contact between the formation and bolts, (4) less expensive roof bolts, (5) higher integrity, (6) potential for automatic operation. Modifications During the months from Oct. to Dec. 12, 1974, under U.S. Bureau of Mines grant No. 00144104, "Projects on Coal Extraction," six members of the senior class at Carnegie Mellon University designed and built the experimental machine. They drove three pins into the Safety Research coal mine at Bruceton, Pa., and determined that the project was worth continuing. In January 1975 we began making modifications and repairs in preparation for a more extensive program of testing at Bruceton. The major items were: 1) Design and build a collapsible pin guide to keep the pin parallel with the line of travel of the lift table. 2) Move the anvil to the center of the bar. 3) Refinish the nodal holes and install new node pins and bushings. 4) Realign the bar in its frame. 5) Install a relief valve on the lift unit to control the upward force. The upward force that we exert on the pin is relatively small, so there is no tendency for it to buckle. This means that all we need to do is hold the pin straight during its initial penetration. This allows the bushing to travel up and down in a straight line. At the beginning of penetration, the bushing

Jan 1, 1977