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By H. O. McLeod, J. M. Campbell

Data analysis of pentane and hexane adsorption from natural gas in a fixed bed of silica gel shows that constant length mass transfer zones form, the curvature of the adsorption isotherm controls the growth of the mass transfer zone and surface diffusion of molecules inside the silica gel particle controls the mass transfer rate. Curvature of the hexane isothem is more than the curvature of the pentane isotherm. Because of this curvature the hexane adsorption zones reached a constant length. In contrast, the pentane adsorption zones were always increasing in length during each run. A procedure was developed to obtain correct mass transfer coefficients using effluent curve slopes. These transfer roefficients increase with the amount of hydrocarbon adsorbed on the silica gel particle. The characteristic shape of the hexane effluent curves also show that molecular diffusion inside the silica gel particle controls the adsorption rate of pentane and hexane. INTRODUCTION The purpose of this study was to determine the mechanisms that control the dynamic adsorption of hydrocarbons from a natural gas onto silica gel. Before one can deal effectively with multicomponent adsorption, the transfer mechanisms by which a single hydrocarbon component is adsorbed from the gas stream must be defined. Two principal investigations of this system have been published ' and indicate that diffusion through the gas around the particle controls the adsorption rate. Some of the experimental observations in each study either do not support this transfer mechanism or are inconsistent with the mathematical model used in analysis. In this study surface diffusion of molecules inside the particle controls the mass transfer rate of pentane and hexane. This mechanism is indicated by the effluent curve shape for a constant length transfer zone and by the variation of the mass transfer coefficient with concentration of the adsorbed hydrocarbon. THEORY AND DEFINITIONS — MATHEMATICAL MODELS Mathematical solutions for the isothermal adsorption of a trace component from a carrier gas are derived from three relationships: the mass balance or continuity equation, the equilibrium relationship between the gas and solid phases, and a mass transfer rate equation. The transfer rate is proportional to the adsorbate concentration gradient within either the gas or solid phase. Mathematical solutions of these equations usually give the adsorbate concentration as a function of time and distance from the bed inlet. That part of the bed in which the adsorbate concentration changes from a maximum to a minimum value is called the transfer zone. This transfer zone is directly related to a plot of the effluent concentration vs time which has a characteristic S-shape. This general shape is determined by the continuity equation and occurs in many processes of diffusional transfer.

Jan 1, 1967

By O. T. Berge

Development and production from open cut mines continued its vigorous growth trend during the year 1968. Material handling and transportation were again exposed to the use of larger equipment with shovels, trucks and front end loaders leading the way. Highlights of World Mining Activities Africa: The Anglo American Corp. opened a new high-grade copper mine in Zambia during the year. In Angola, the Companhia Minera do Lobita planned a 3 million ton iron ore production for 1968 from new mines which will ultimately produce 5 million tons per year. A feasibility study of Bethlehem Steel Co., for the development of large high- grade iron ore reserves in Gabon, was in final stages of completion this year and Pickands Mather and Co. continued its investigation of iron ore deposits along the Ivory Coast.

Jan 2, 1969

By Scott Turner

PRESIDENT SCOTT TURNER officiated as chairman of the opening session on mining methods, Monday morning, Feb. 15. The first paper was that of Max H. Barber on open-pit mining in the Lake Superior district, read by C. F. Jackson. W. L. Taylor stated that liquid-oxygen explosive had been tried but that the operators are satisfied with the explosives used; lb. of dynamite breaks one ton of rock. Although black powder is considered the most effective explosive, the factor of safety has decided in favor of high explosives. Lucien Eaton told of the Michigan Lime and Chemical Co.'s large L. 0. X. plant at Rogers City, Mich. Mr. Turner referred to this plant, also said that the Bureau of Mines is shortly to issue Bulletin 349 completely covering the use of L. 0. X. from its inception. W. D. B. Motter, Jr., gave some items concerning Chuquicamata, Chile. Twelve years ago the blasts moved 850,000 to 1,000,000 tons, but average shots now move 250,000 to 300,000 tons. One pound of L. 0. X. breaks 3.7 tons, against 3.1 tons by dynamite. Another speaker told of some large dynamite blasts in open pits, one of 360,000 Ib. in March, 1931, and another of 430,000 lb. to be shot in 1932. Tests have been made to determine the effect of large shots on the surrounding country. Mr. Taylor said that 4- and 5-yd. shovels were preferable to those of 8 yd.; their performance is better and cost is lower.

Jan 1, 1932

By J. M. GLEDHILL

(Washington Meeting, May, 1905.) A Discussion of Mr. J. M. Gledhill's paper, read by title at the Lake Superior meeting, but presented first at the New Yolk meeting of the Iron and Steel Institute (October, 1904), and here published under a mutual agreement. Between the two Institutes. Discussion. MR. E: WINDSOR RICHARDS, Past-President, said that at a recent meeting of the Institution of Mechanical Engineers a paper was read on tool steel, and he called the attention of the members to the high-speed tool steel at the Bethlehem Works. They would have the pleasure of seeing those wonderful works and would see 60, 70, 80 and 100 tons oil lathe with half-a-dozen of these high-speed tools running. PROP. H. M. HOWE (Columbia University) said that they all looked upon these high-speed tool steels as of very great importance, particularly to the machine shop. One point occurred to hire : Had it really been shown that Swedish steel is necessary, or better than equally pure steel that is not Swedish; and is cemented steel really necessary, and is there any advantage in using that, rather than equally pure open-hearth steel'! It might be well if the author could indicate the kind of evidence on which lie bases his assertion that it is necessary to have cemented Swedish steel. Many were hoping for the development of high-speed steels from elements which exist in great quantities, such as silicon, manganese and chromium, rather than from rarer metals like molybdenum, vanadium and tungsten, the supply of which is likely to be soon exhausted. If the high-cutting speed was to last more than a generation, it. seemed to him that they would have to draw upon the common ele¬ments and not upon the rare ones. MR. Tom WESTGARTH (Middlesbrough) said he fully appreci¬ated what had been said about the advantages of using high-speed steel, because great benefit had been derived from the

Mar 1, 1905

By Leo F. Reinartz

It was with humility that I accepted the invitation of the Board of Directors of our Institute to deliver the Twentieth Howe Memorial Lecture. Many previous lecturers could speak from personal experience of the great work done by Professor Howe. It was not my privilege to be one of his students but, indirectly, I came under the influence of his work many years ago. My mentor in Metallurgy at Carnegie Institute of Technology, Prof. Fred Crab tree, was an ardent admirer of Professor Howe and his work. Professor Crabtree taught me early to appreciate Professor Howe's love of truth and keen desire to find a scientific reason for every metallurgical phenomenon. In this early search, Professor Howe encountered many unexplainable facts. Nevertheless, in the classic text, "The Metallurgy of Steel," published in 1891, he indicated that he believed Research could light the way. Under the heading of "The Treachery of Steel" he said: "In the early use of Bessemer and Open Hearth Steel, many then unexplained and hence mysterious failures occurred. With our present knowledge, an easy explanation of most of them would probably have been seen. But even today certain unexplained and apparently inexpli- cable failures occur in steel; inexplicable in spite of full and intelligent investigation." Then Professor Howe continued to talk about "the trustworthiness of steel" in the following manner: First, the steel-maker has learned by experience. He knows today far better the effects of a high percentage of carbon or of phosphorus; of cracks, pipes and blow-holes; of segregation and imperfect mixing; of over-heating; of finishing too hot or too cold. Knowing, he guards against them more effectually, and keeps at home much steel that he would formerly have sent into the market. Those who would not, or could not learn and do, have been driven out of the business; the conditions necessary for producing good sound steel by the acid Bessemer and the acid Open Hearth processes have been mastered. By and by, the basic process came along with new conditions, new liabilities to unsoundness, a great hue and cry about mysterious fractures followed, and Lloyd's register provisionally forbade the use of basic steel. Much basic steel was irregular and brittle throughout; too much carbon, too much phosphorus, too cold teemings—imperfect mixing. Still there was little doubt that, with further experience, these difficulties of the basic process would be mastered as those of the acid process had been. This shows that Professor Howe could not take anything for granted. Believing that careful research would find the answer to all mysterious phenomena, he was several generations ahead of the practical acceptance and adoption of this principle.

Jan 1, 1943

By Leo F. Reinartz

It was with humility that I accepted the invitation of the Board of Directors of our Institute to deliver the Twentieth Howe Memorial Lecture. Many previous lecturers could speak from personal experience of the great work done by Professor Howe. It was not my privilege to be one of his students but, indirectly, I came under the influence of his work many years ago. My mentor in Metallurgy at Carnegie Institute of Technology, Prof. Fred Crab tree, was an ardent admirer of Professor Howe and his work. Professor Crabtree taught me early to appreciate Professor Howe's love of truth and keen desire to find a scientific reason for every metallurgical phenomenon. In this early search, Professor Howe encountered many unexplainable facts. Nevertheless, in the classic text, "The Metallurgy of Steel," published in 1891, he indicated that he believed Research could light the way. Under the heading of "The Treachery of Steel" he said: "In the early use of Bessemer and Open Hearth Steel, many then unexplained and hence mysterious failures occurred. With our present knowledge, an easy explanation of most of them would probably have been seen. But even today certain unexplained and apparently inexpli- cable failures occur in steel; inexplicable in spite of full and intelligent investigation." Then Professor Howe continued to talk about "the trustworthiness of steel" in the following manner: First, the steel-maker has learned by experience. He knows today far better the effects of a high percentage of carbon or of phosphorus; of cracks, pipes and blow-holes; of segregation and imperfect mixing; of over-heating; of finishing too hot or too cold. Knowing, he guards against them more effectually, and keeps at home much steel that he would formerly have sent into the market. Those who would not, or could not learn and do, have been driven out of the business; the conditions necessary for producing good sound steel by the acid Bessemer and the acid Open Hearth processes have been mastered. By and by, the basic process came along with new conditions, new liabilities to unsoundness, a great hue and cry about mysterious fractures followed, and Lloyd's register provisionally forbade the use of basic steel. Much basic steel was irregular and brittle throughout; too much carbon, too much phosphorus, too cold teemings—imperfect mixing. Still there was little doubt that, with further experience, these difficulties of the basic process would be mastered as those of the acid process had been. This shows that Professor Howe could not take anything for granted. Believing that careful research would find the answer to all mysterious phenomena, he was several generations ahead of the practical acceptance and adoption of this principle.

Jan 1, 1943

Annual Meeting,Wallace, Idaho, Nov. 15-16, 1913. The third annual meeting, which was also the eighth consecutive meeting and the second to be held in the Coeur d'Alène district, was held in Wallace, Idaho, Nov. 15-16, 1913, with side trips to Kellogg-Wardner, Larson, and Mullan, where several mills were visited. The meeting was held jointly with the Montana Section, about 50 members and guests being present. Headquarters were in the Samuels Hotel, sessions being held in the public library. The arrangements and program were in the hands of the following local committee: George W. Roddewig, W. Earl Greenough, H. M. Childs. At 2.30 p.m., Nov. 15, the first session was called to order by Prof. F. A. Thomson, member of the Executive Committee, adjournment being taken to the Mine Rescue car, where Mr. Anderson and his assistant entertained the visitors for nearly two hours by demonstrations of mine-rescue and, first-aid practice, after which the party visited the Hercules mill, mention of which was made in the report of last year when the Section visited the plant. There are, however, several important alterations and additions to the flow-sheet to be noted, such as substitution of Chilean and Hardinge mills for the Huntington mills in the regrinding department; rearrangement of the tables and slimers, with a noticeable addition of the later models of the Franz machines, and the installation of the Wyman flotation process, which has been tried out, or is being tested, with more than ordinary success, on the middlings in several of the mills of the district, the Green Hill Cleveland mill being provided with a 100-ton unit, partly described below

Jan 12, 1913

By William P. Shinn

IT seems proper to present in the Transactions of the Institute, from time to time, formal record of the advances made in the arts and sciences to which our organization is devoted-milestones in the highway of progress-from which our successors may measure what they in their turn have gained. The admirable address of the Hon. Abram S. Hewitt, then president elect of the Institute, on "A Century of Mining and Metallurgy in the United States," read at the opening of the meeting held in this hall in June, 1876, forms a point of departure, and the conclusion of the eighth decade of the nineteenth century and the end of the first five years of our country's second century seem to offer a fitting time for again making up our record. The period since 1875 has been marked by a degree of activity in mining and metallurgical industry never before equalled in our history, while the progress made in the science and art has been, if possible, still more noticeable. Whether we consider the mining of iron, ore, and coal, or of the precious metals,-the advances made in smelting the former and in reducing the latter, the extraordinary increase in the production of Bessemer steel, or the science of Thomas and. Gilchrist, which makes the hitherto rejected phosphorus the corner-stone of success,-the past five years are alike memorable for the progress they have shown and to some of the most marked features of this progress I will now oriefly call your attention. It may be of interest in this connection to note the following figures, showing the growth of the population of the United-States during the last three decades :

Jan 1, 1881

By AIME AIME

AT the Morenci branch of the Phelps Dodge Corporation, of which Frank Ayer is manager, several new types of machines that have been developed by Charles Mitchell, shop foreman in the drill steel shop, invite comment for their time and labor-saving qualities. Foremost of these is an adjustable gage-block and gaging device for attachment to drill-sharpening machines, developed and patent applied for by Mr. Mitchell. It replaces the blocks on the standard Ingersoll-Leyner drill steel sharpener No. 5. Features of the device are gage blocks with a flat surface which can readily be removed when worn and planed in any flat planer; blocks that can be adjusted with a templet to give a far more accurate gage than was formerly possible; and a center stop that is adjustable and can be accurately set to center any standard size drill steel.

Jan 1, 1930

By . M. Muskat

A THEORETICAL consideration of the mechanics of various water-flooding systems with the viewpoint of comparing their relative merits involves the study of two fundamental properties of such systems. On the one hand, it is important to determine the efficiency of the flood as measured by the percentage of the total area that is swept out by the encroaching water before water actually reaches the output wells. This is really a measure of the regional tendency of the water to "bypass" the oil. On the other hand, the various systems must be compared from the viewpoint of their resistances which determine the rate of fluid production obtainable for given pressures maintained at the water input wells. The first of these questions has been studied and very definite answers have been obtained by means of simple electrolytic models.1 These models showed that, in an ideal system, the percentages of the areas flooded out before water reaches the output wells are about 57 per cent for the direct line-drive flood (the input and output wells being equally spaced and placed in alternate parallel lines), 74 per cent for the regular five-spot network, and 79 per cent for the seven-spot network. With respect to the efficiency of the usual flooding arrangements, they are, therefore, given quite accurately by the above numbers. With regard to the resistances of the flooding networks, electrical conduction models have also been used successfully2 and are well adapted to the problem of determining experimentally the pressure distribution and streamlines, or over-all resistances of specific flooding networks. However, such models do not permit readily a study of the effect of changing dimensions or configuration within a network, since a new model must be made up for each set of dimensions considered.

Jan 1, 1933

By J. H. Brophy, M. H. Kamdar, J. Wulff

A constitutional diagram for the Ta-W-Re alloy system is presented. Rhenium dissolves in the complete range of solid solutions between tungsten and tantalum up to 48 wt pct in tantalum 'to about 30 wt pct in tungsten. Intermediate x and u phases only are found. X-ray diffraction and fluorescence, metallography and melting-point measurements were employed. THE constitution diagram of ternary alloys of tungsten, tantalum, and rhenium for temperatures above 1000°C is reported in this paper. Alloys in this system rich in tantalum and tungsten are of interest for high-temperature applications, and those rich in rhenium for electronic applications. No ternary phase diagram appears to be available in the literature. The three-component binary diagrams have been previously established1-3 and the present ternary data are consistent with these. EXPERIMENTAL TECHNIQUES Commercially pure tantalum (99.7 pct), rhenium (99.99 pet), and tungsten (99.9 or 99.95 pct) powders were purchased from Fansteel Metallurgical Corp., Chase Brass and Copper Co., and Fansteel or Westinghouse Electric Corp., respectively. These powders were pressed without binder and arc-melted under helium. The preparatory and analytical techniques employed were identical to those used for the Ta-Re system investigation carried out in this laboratory.324 These included X-ray diffraction and metallographic phase identification, X-ray fluorescent and wet chemical analyses, solidus determinations and heat treatments in a resistance-heated tantalum-filament vacuum furnace. For microstructural examinations standard mechanical polishing techniques were used through diamond laps. Polished speciments of all compositions were etched by swabbing with 4 parts HI?, 4 parts HNO3, and 1 part H20. Since the microstruc-tures of alloys containing one or two phases closely resembled their counterparts in the respective binary systems, typical examples are omitted in this presentation. In all the alloys examined, it was possible to observe the number of phases present. Particularly when there were small amounts of one phase involved, it was possible to identify it only by a combined conclusion based on X-ray diffraction, position of an alloy in a composition series, and the phase rule. A total of 100 different alloy compositions was arc-melted and studied in the as-cast condition metallographically and by X-ray diffraction. Specimens of each of these compositions were heat-treated at 2680, 2530, and 2020°C for 1, 2, and 4 hr, respectively. Those which were treated at 2020 were given a preliminary homogenization treatment at 2500°C for 1 hr. Specimens of 25 alloys were heat-treated at 1200o C for 168 hr. Solidus temperature measurements were made by the detection of incipient melting in eighteen alloy compositions. The metallographic and X-ray diffraction results are summarized in Table I. Graphically, this information appears in the isothermal plots of Figs. 2 and 3. Within the accuracy of the experimental methods, two such plots are sufficient to locate these data, since the results for 1200°C were similar to 2020 and those at 2530 resembled 2680

Jan 1, 1962

By J. R. Lucas, R. L. Frantz

Mine sealing programs for the alleviation of acid mine drainage were begun by the Federal Government in the '30's. As part of an acid mine research project to The Ohio State University, a field test was undertaken to determine the effectiveness of mine seals for reducing mine acid. Details of the tests made at the McDaniels mine show the feasibility of air-sealing and flooding an acid-producing drift coal mine. Work by the University continues. The Federal Government undertook in the early thirties an extensive mine sealing program for the alleviation of acid mine drainage. In the states of West Virginia, Ohio, and Pennsylvania many general summaries have been made on this program but no critical evaluation with supporting data has been found on the effectiveness of mine seals for reducing mine acid. Because of this it was decided to undertake a field testing program as part of an acid mine research project of the Engineering Experiment Station, The Ohio State University. The objective of this phase of the project was to develop and install a field research laboratory for acid mine drainage studies. Specifications for such a mine laboratory were developed and resulted from the following considerations: 1) Size and preservation—the test mine shou1d be of limited size to permit frequent and detailed examinations; it should be in a reasonably sound condition to permit safe entry. 2) Isolation—the mine should be physically separated from all other mines. 3) Openings—a minimum number would be desirable to reduce the sealing problem. 4) Structure—the mine especially near the openings should be structurally sound. 5) Acid production—the mine should be producing significant quantities of acid. After considerable searching, the McDaniels mine was selected in the Hocking coal field in Vinton County just above Lake Hope State Park in southeastern Ohio. The small drift mine in the middle Kittaning coal consisted of two small rooms with one mine opening about 6 ft above a seasonal stream bed. Before it was finally decided to seal the mine, a short study was made of the acid drainage over several months. Fig. 1 shows a plot of acidity (milligrams per liter), flow (gallons per minute), and acid production (pounds per day) vs time over the sampling period. Because the coal was overlain with a porous sandstone, the mine drainage was consistent the year around even though the mine was

Jan 1, 1961

By H. C. Schultz

CERTAIN local conditions were known to govern in large measure the successful adaptation of liquid-oxygen explosives to the large-scale blasting at Chuquicamata. The wide variation in hardness of the rock at this mine makes necessary the use of several types of explosives. A locally manufactured, relatively cheap black powder is used in blasting the softer waste and capping material, where a thorough displacement, breaks the ground sufficiently. Before the introduction of L. 0. X., an ammonia dynamite of about 65 per cent. strength was being used exclusively in the harder underlying orebody, where a strong disruptive as well as a displacement effect is required for breaking the ore. The L. 0. X., as developed for quarry work in the United States, has a practically pure carbon cartridge material, and the explosive has an extremely high rate of detonation, which should therefore cause it to usefully develop its full disruptive effect in hard ground. The individual blasts at Chuquicamata are large, black-powder shots which dislodge masses of rock averaging 250,000 tons each, and dynamite shots which dislodge masses averaging 80,000 tons each. It was desirable, therefore, to attempt to displace with L. 0. X. the faster, higher-cost ammonia dynamite used in the smaller blasts. It was not considered practical to attempt to displace the low-cost black powder with L. 0. X., as estimated costs showed no probable saving if this were accomplished. Since it was desirable to continue shooting relatively large blasts for effective operation, it was recognized that larger storage facilities than had been in use would be needed for the liquid oxygen. Because of the difficulty of transporting and discharging large storage containers of efficient design, the better plan appeared to be storage and discharge of the liquid at the place of manufacture, and transportation of the filled soaking boxes to the blast.

Jan 1, 1928

By L. J. Health

Synthetic rock with predictable porosity and permeability has been Prepared from mixtures of sand, cement and water. Three series of mixes were investigated primarily for the relation between porosity and permeability for certain grain sizes and proportions. Synthetic rock prepared of 65 per cent large grains, 27 per cent small grains and 8 per cent Portland cement, gave measurable results ranging in porosity from 22.5 to 40 per cent and in permeability from 0.1 darcies to 6 darcies. This variation in porosity and permeability was caused by varying the amount of blending water. Drainage-cycle relative permeability characteristics of the synthetic rock were similar to those of natural reservoir rock. INTRODUCTION The fundamental behavior characteristics of fluids flowing through porous media have been described in the literature. Practical application of these flow characteristics to field conditions is too complicated except where assumptions are overly simplified. The use of dimensionally scaled models to simulate oil reservoirs has been described in the literature. 1-3 These and other papers have presented the theoretical and experimental justification for model design. Others have presented elements of model construction and their operation. In most investigations the porous media have consisted of either u ncon soli da ted sand, glass beads, broken glass or plastic-impregnated granular substances—materials in which the flow behavior is not identical to that in natural reservoir rock. The relative permeability curves for unconsoli-dated sands differ from those for consolidated sandstone. The effect of saturation history on relative permeability measurements is discussed by Geffen, et a1.4 Wyga15 has shown quite conclusively that a process of artificial cementation can be used to render un consolidated packs into synthetic sandstones having properties similar to those of natural rock. Many theoretical and experimental studies have been made in attempts to determine the structure and properties of unconsolidated sand, the most notable being by Naar and Wygal.6 Others have theorized and experimented with the fundamental characteristics of reservoir rocks. This study was conducted to determine if some general relationship could be established between the size of sand grains and the porosity and permeability in consolidated binary packs. This paper presents the results obtained by changing some of the factors which affect the porosity and permeability of synthetically prepared sandstone. In addition, drainage relative permeability curves are presented. EXPERIMENTAL PROCEDURE Mixtures of Portland cement with water and aggregate generally are designed to have certain characteristics, but essentially all are planned to be impervious to water or other liquids. Synthetic sandstone simulating oil reservoir rock, however, must be designed to have a given permeability (sometimes several darcies), a porosity which is primarily the effective porosity but quantitatively similar to natural rock, and other characteristics comparable to reservoir rock, such as wettability, pore geometry, tortuosity, etc. Unconsolidated ternary mixtures of spheres gave both a theoretically computed and an experimentally observed minimum porosity of about 25 per cent.7 By using a particle-distribution system, one-size particle packs had reproducible porosities in the reproducible range of 35 to 37 per cent.6 For model reservoir studies of the prototype system, a synthetic rock having a porosity of 25 per cent or less and a permeability of 2 darcies was required. The rock had to be uniform and competent enough to handle. Synthetic sandstone cores were prepared utilizing the technique developed by Wygal.5 Some slight variations in the procedure were incorporated. The sand was sieved through U. S. Standard sieves. A 18-20 sand denotes that the sand passed the Number

Jan 1, 1966

By D. A. Elgillani, M. C. Fuerstenau, J. D. Miller

Adsorption of lead and ferric iron on quartz and alumina is presented as a function of pH. Only the hydrolyzed species of these metal ions, FeOH++ and PbOH+, adsorb significantly on each of these minerals. Zeta potentials of quartz were measured as a function of pH in the presence of various additions of aluminum, lead, and magnesium salts. Sign reversal occurs at the pH values where significant concentrations of hydroxy complexes are formed. Models of adsorption are presented in the absence and presence of collector. The mechanism of adsorption of metal and collector species in the activation of nonmetallic minerals is still the center of considerable discussion in spite of the extensive study given this system. Until recently, the view was widely held that hydrated metal ions were responsible for this phenomenon. This fact is surprising, since it had been shown that the pH range in which flotation is effected corresponds to that in which metal ion hydrolysis occurs.' Additional support of this concept was pro vided by the work of Wolstenholme and Schulman in another system.' Later work has shown that hydroxy complexes of metal ions are the active species. These studies have also indicated that basic aqueous complexes of metal-collector may be necessary for flotation.3-7 Depending on the molecular weight of the collector, formation of these complexes may occur before or after precipitation of the metal-collector salt has occurred. Ion pair formation can occur when low molecular weight collectors are involved because relatively high concentrations of metal hydroxy complex and collector can be present in solution before precipitation occurs. This is not the case when high molecular weight collectors are used. A model of aqueous complex adsorption has been presented6,7 in which it has been assumed that adsorption occurs by the formation of water from adsorbed hydroxyl and hydrogen of the hydroxyl contained in the complex. Other authors8 have suggested that hy-droxy complexes are involved in these systems but that collector adsorption occurs by replacement of the hydroxyl of the adsorbed metal hydroxy complex with a fatty acid anion. All of these investigations have involved mineral surfaces that were negatively charged so that it is not possible to state with certainty whether hydrated metal ions or hydroxy complexes are the active species in this system. Use of a positively charged mineral should be helpful, however, since the hydrated metal ion will be repelled from this surface. On the other hand, if the hydroxy complex adsorbs by splitting out water, surface charge should have no effect because of the free energy decrease that the system will experience when water is formed. In this regard, sapphire is well-suited for study, since its surface is positively charged until approximately pH 9. Electrokinetic studies of quartz in the presence of various metal ions should also be useful in establishing the mechanisms of adsorption in these systems. That is, if the hydroxy complexes adsorb by water formation, drastic changes in the zeta potential should occur in the pH range in which hydrolysis occurs. In this view, adsorption of ions of widely different hydrolysis characteristics on both sapphire and quartz was measured. In addition, zeta potentials of quartz were measured as a function of pH in the presence of various metal ions and compared with flotation responses obtained under similar conditions. Experimental Materials and Techniques Reagent-grade aluminum, ferric and magnesium chlorides, and lead nitrate were used in this investigation. Adjustments in pH were made with reagent-grade HCl or KOH. Conductivity water, made by passing distilled water through an ion exchange column, was used in all of the experiments.

Jan 1, 1971

By B. E. Warren

Jan 1, 1965

By J. Geertsma, F. de Klerk

During the hydraulic fracturing treatment of an oil or gas well the liquid pressure in the borehole is increased until tensile stress in the surrounding rock exceeds tensile strength. Once a tensile fracture is initiated, it is penetrated by liquid from the borehole and fracture propagation under continuous hydraulic action takes place. The fracturing liquid carries a propping agent to ensure a highly permeable flow channel after pressure release. Field results range from failure to obtain increased production to outstanding success. In all cases, however, it unfortunately remains uncertain whether the values chosen for the operational parameters, such as injection rate, pumping time and fluid viscosity, were in fact the ideal ones. Though experience provides a lead, a more satisfactory way to predict results would seem to be to subject the fracture propagation process to a theoretical analysis that (1) makes the maximum use of the relevant physical information and (2) so simplifies the resulting calculations that the field engineer gets practical data that he can handle comfortably. We are attempting here to do this in connection with the prediction of fracture width and areal extent before pressure release. What remains of the fracture afterwards depends on the distribution of the propping agent between the fracture walls, and that is a separate story. Idealization of the Problem To keep the problem tractable, a number of simplify- ing assumptions have had to be made: 1. The formation is homogeneous and isotropic as regards those of its properties that influence the fracture-propagation process. 2. The deformations of the formation during fracture propagation can be derived from linear elastic stress-strain relations. 3. The fracturing fluid behaves like a purely viscous liquid; i.e., any peculiar flow behavior due to the addition of gelling agents or other additives is neglected. Moreover, the effect of the propping agent distribution on the distribution of fluid viscosity in the fracture is not taken into account. 4. Fluid flow in the fracture is everywhere laminar. 5. Simple geometric fracture-extension patterns are assumed — either radially symmetrical propagation from a point source (Fig. 1A) or rectilinear propagation originating from a line source (Fig. 1B). In the first case the periphery of the fracture is circular, in the second case it is rectangular. 6. A rectilinear propagation mode can be accomplished only by injection over a large perforated interval, thus forming a line source. Such a rectilinear fracture must therefore be located in the vertical plane. A circular propagation mode might be expected from injection through a narrow band of perforations. This forms a point source. Because gravity effects are excluded from our considerations, the fracture propagation plane may in this case assume any angle with respect to the wellbore as far as the

Jan 1, 1970

By AIME AIME

EITHER the 2300 people who came to the Annual Meeting were in a better frame of mind or they were resigned to their fate, or it was a better meeting than usual. Whatever the reason, at the 1nstitute?s 148th meeting the attendance was better than ever before, things went more smoothly than in some previous years, and complaints appear to have been almost entirely absent. Patience was sometimes reauired but. almost without exception, it was forthcorning the well-known recession seems to have given many members enough leisure time to come to the meeting without depriving them of the tangible wherewithal to come.

Jan 1, 1938

By C. Feng, C. Elbaum

Knoop hardness measurements were carried out on large grains of iodide titanium containing different amounts of oxygen. For each oxygen content the hardness is recorded ainingas a function of the crystal orientation and of the angle 4 between the indenter diagonal and the projection of the C (hexad) axis in the surface. The results can be expressed by the following relation; hardness = n-k cos 2ø, where n and k are constants for a given oxygen content and crystal surface orientation. A NISOTROPY of hardness is a well-known phe-nomenon and has been reported for many metals.1-3 At the present time, however, such information is not available in the literature for titanium. Consequently, a systematic study of the simultaneous effects of oxygen content and crystallographic orientation on the hardness of titanium was undertaken in this laboratory. Evaluations of oxygen content in titanium are frequently carried out through hardness tests. Although such procedures may be justified in small grain specimens, the results of the present investigation indicate that the anisotropy of hardness should be taken into account in the case of coarsegrained specimens as well as in the case of pronounced preferred orientation. Materials and Experimental Procedures Iodide titanium, 99.99 pet pure and containing of the order of 0.002 wt pet O, was used throughout this investigation. The metal was arc melted in an argon atmosphere and cold rolled into strips 1/16 in. thick. These strips were subsequently recrystal-lized and strain annealed in vacuum (10" mm Hg or better) at 850°C in order to produce crystals varying in diameter from 10 to 25 mm. Oxygen was introduced into selected large crystals by heating at 700°C in an atmosphere of pure oxygen under an observed pressure of approximately 50 mm Hg. Each sample was subsequently annealed in vacuum at 850°C for 100 hr, in order to homogenize the oxygen content throughout the specimen. It was found that longer annealing was not necessary, for no change of surface hardness in a given direction was detected after prolonged annealing. The oxygen content was determined by the difference in weight of the specimens before and after the oxidation-annealing cycle. The accuracy of oxygen determination is within ±0.1 mg in samples weighing 0.5 to 1 g. A vacuum fusion analysis of oxygen was performed on several samples and gave results in good agreement with the ones obtained by the weight change. It should be emphasized that expected weight losses through evaporation of the metal in vacuum at 850°C' are many orders of magnitude lower than the precision of these measurements. Following the annealing treatment, both oxidized and unoxidized crystals were carefully polished. All detectable traces of surface cold working were removed by repeated polishing and etching. Laue back reflection X-ray patterns were taken for each crystal for the purpose of determining the orientation and ascertaining the absence of substructures detectable by this method. Hardness measurements, using a 1 kg load, were subsequently carried out on a Tukon hardness tester equipped with a Knoop indenter. The Knoop indenter was used throughout this work because indentations obtained by means of a Vickers indenter are considerably distorted due to the anisotropy of the elastic constants in titanium. Such distortions are much less pronounced in the case of Knoop indentations, although for some orientations a cer-

Jan 1, 1959

By John Nunes, Frank R. Larson

Temperature-dependent functions of various ten-sile flour stress and fracture parameters were investigated on iron and low composition alloys of Fe-C, Fe-Cr, Fe-Mn, and Fe-Ni. Data were obtained over a range of test temperatures from 200" to -196"C at an initial strain rate of 0.01 min". It was found that the strain-hardening exponent, n, for the Fe-Ni alloys increased significantly at very low testing temperatures with increased alloy addition. Also, the stress and strain at fracture followed a predictable transitional type of behavior. The flour stress-temperature dependence was evaluated employing the relation: M where it is shown that composition can strongly influence the constant M. An empirical formula describing this effect is as follows: M = MI (equivalent at. pct Ni)-'" Some preliminay, tests were run on several commercial steels to test the generality of this relationship. One of the phenomenological explanations of the ductile-to-brittle transition encountered in bcc metals is based upon the difference in the temperature dependence of the flow and fracture stresses.' It states simply that the fracture stress is relatively insensitive to temperature and that the yield or flow stress rises rapidly with decreasing temperature so that, when the flow stress reaches the fracture stress, brittle fracture occurs without appreciable plastic deformation. This behavior is illustrated schematically in Fig. 1 where the ductile-to-brittle transition is shown to occur at two possible temperatures. The lowest temperature, TB, represents essentially completely brittle behavior while the higher temperature, TN, represents "notch" brittle behavior. Support for this theory is obtained when it is observed that fcc metals, which do not commonly have a ductile-to-brittle transition, also do not commonly exhibit any strong temperature de- pendence of the yield stress. This relationship of yield or flow stress behavior with the ductile-to-brittle transition has been generally observed for most metals representative of these two crystallo-graphic structures. One exception to this generalization appears in the case of tantalum where no apparent ductile-to-brittle transition has been observed. However, this may simply be an indication that this type of behavior is not directly related to the flow stress and that some other mechanism such as twinning must also be operative. A comparison of the typical temperature dependence of the yield stress of some representative metals is shown in Fig. 2. In the study of the temperature dependence of the strength of metallic materials, considerable ef-

Jan 1, 1963