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Jan 1, 1963

By F. D. Richardson

STAFF: Editor, Gerhard Derge Carnegie lnstitute of Technology Schenley Park Pittsburgh, Pa. 15213 Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: Jack H. Scoff, President; Richard C. Cole, Past-President; Harold 0. Emerick, President-Elect; Ralph L. Hennebach, Treasurer; Robert W. Shearman, Secretary; Donald A. Parks, Assistant Secretary; Leslie S. Wilcoxson, Assistant Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: R. E. Lund, Chairman; T. E. Dancy, H. O. Emerick, P. R. Gouwens, R. E. Grace, J. H. Jackson, H. H. Johnson, A. E. Lee, Jr., R. R. Nosh, R. D. Pehlke, and Paul Queneau. Review and selection of manuscripts is under the supervision of the following Publications Committees: Extroctive Metallurgy Division: R. E. Grace, Choirmon; G. M. Bell, D. W. Bridges, J. M. Cigon, G. W. Heoly, T. A. Henrie, R. D. (Holli-doy, C. E. O'Neill, C. S. Somis, A. W. Schlech-ten, and Charles Shull. Iron and Steel Division: R. D. Pehlke, Choirmon; T. P. Floridis, Arnulf Muon, G. R. St. Pierre, E. T. Turkdogan, L. H.Von Vlock, and J. M. Uys. lnstitute of Metals Division: H. H. Johnson, Jr., Chairman; J. B. Clark, Vice Choirmon; M. R. Achter, G. F. Bolling. J. O. Brittoin, G. P. Conard, II, R. S. Davis, L. A. Girifolco, G. T. Hohn, J. P. Hirth, L. Himmel, G.T.horn, George Krauss, J. D. Livingston, R. D. Manning, H. M. Otte, S. V. Rodcliffe, R. E. Reed-Hill, H. C. Rogers, E. ScaIa, O. Sherby, M. T. Simnad, G. R. Speich, E. A. Steigerwald, R. A. Swolin, W. A. Tiller, W. R. Upthegrove, J. B. Wagner, Jr., Derek Wolton, H. W. Weart, W. W. Webb, and D. Published seven times yearly in February, March, April, June, August, October, and December by the American lnstitute of Mining, Metallurgical, and Petroleum Engineers, Inc., 345 East 47th Street New York, N. Y. 10017. Telephone PLAZA 2 -6800. Subscription $30 per year for non-AtME members m United States and North, South, and Central America; $32, foreign; $7.50 for AlME members Single copies, $6.00, single copier foreign, $6.50. The AiME is not responsible for any statement made or opinion expressed in its publications . . . Copyright 1964 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . . . Registered cable address, AiME New York Indexed in Engineering Index, Industrial Arts Index, and Chemical Abstracts. Second dost postaas poid ot New York, N. Y.,ond Ann Arbor, Mich. Volume 230, Number 6.

Jan 1, 1964

By James C. M. Li, J. Weertman

James C. M. Li (United States Steel Covp.)—The author has discovered a single analytical relation between the minimum, or the steady-state, creep rate and the applied stress confirming a statement made earlier by orn" that such relation should exist and should reduce to the power law at low-stress levels and to the exponential law at high-stress levels. However, as pointed out by the author, all the available theories of creep are not adequate to explain such a single relation. Inspired by such a statement, I have made a suggestion concerning a possible explanation13 of the new relation. This is based on the concept that the rate-controlling step is the cooperative motion of a short dislocation segment. The nature of and the reason for the cooperation have been discussed13 as well as the reason why the motion of the dislocation could be controlled by the mobility of the short segments. A natural short segment has been proposed13 to be the node formed at the intersection of two dislocations. The reason why the node may contain only a few atoms has not been discussed and the application of the proposed model to all the metals and alloys reported in this paper has not been attempted. It seems appropriate to include these in this discussion. The model was partly inspired by the substructure recently observed in the electron microscope on creep specimens. One such example is shown in Fig. 48 in Darken's Campbell Memorial Lecture. The substructure is a collection of dislocation intersections and irregular networks. No pileups have ever been observed in such specimens. A closer look at the network indicates that one set of dislocations is more straight than the other set sug- gesting that the other set may be mobile in the plane of the net. Since, for the network to survive the creep deformation, some dislocation reaction has to take place at the intersection of the two sets of dislocations, the mobile dislocation, even if it can slip in the plane of the net, will have difficulty in moving at these intersections. To illustrate, an idealized network is shown in Fig. 9. The thin lines represent the set of dislocations which are mobile and can slip in the plane of the net except at the nodes which are formed at the intersection of the two sets of dislocations. The other set of dislocations, represented by the thick lines, may have a Burgers vector which is not parallel to the plane of the net, and therefore may be immobile. Because of this nonparallel Burgers vector, the Burgers vector of the node, which is avectorial sum of the Burgers vectors of the two sets of dislocations, will also be nonparallel to the plane of the net. Therefore, the node cannot slip in the plane of the net and the set of mobile dislocations will have to drag the node along as indicated in Fig. 9. Now the problem is how many atoms could be involved in the nodes. Exact calculation of the length of the node is a difficult task especially since the length should be a steady-state length and not an equilibrium length. An estimate of the equilibrium length can be made by balancing the line tension of all the dislocations. The results would be a small fraction of the length 1 between nodes as shown in Fig. 10. In some instances such a calculation shows that the node will not be formed. But, since the calculation is only approximate, it does not rule out the possibility of the formation of a short node. In other instances the equilibrium length of the node is an appreciable fraction of I. Such a node would

Jan 1, 1963

By E. Northcott, F. N. Oberg

By electrostatic separation, course Florida pebble phosphate, too lou-grade to find a ready market, can be upgraded to a satisfactory saleable product. Pebble running from 60 pct bone phosphate of time may be upgraded to 73 to 77 pct BPL depending on the mineralogical. structure of the pebble and the nature of the silica innpurity. High-grade concentrates from Florida pebble phosphate deposits have long been recovered by wet methods. When work was begun in the field, only the coarse pebble (generally +1 mm) was re- covered. In the 1920's a froth flotation process was developed to separate quartz from the finer phosphate fractions, but this method proved unsatisfactory for treating the intermediate fraction (—1 mm +35 mesh). Consequently various other processes were adapted, including agglomerate tabling and spiral separation of reagentized feed. Today the three processes are used—washing and screening for coarse pebble, tabling or spiraling for intermediate sizes, and flotation for —35 mesh material.

Jan 1, 1959

By W. H. Bassett, C. H. Davis

In the commercial annealing of cartridge brass there are four points regarding which definite data are essential. They have to do with the correct interpretation of grain count in its relation to annealing temperature and, incidentally, to Brinell hardness. These points are: 1. The comparison of the grain sizes of two cartridge-brass mixtures: 69 copper, 31 zinc, 0.376-in. (9.5-mm.) gage; and 68 copper, 32 zinc, 0.130-in. (3.3-mm.) gage 2. The comparison of the grain sizes of annealed metal that had previously been reduced by rolling varying amounts; for instance, 20.0, 36.6, 50.9, and 59.1 per cent. 3. The determination of standards for grain sizes on annealed brass of the composition 68 per cent. copper, 32 per cent. zinc and 69 copper, 31 zinc. 4. The comparison of grain size with Brinell hardness on identical samples of annealed metal. In their comprehensive and thorough investigation of the recrystal-lization of cold-worked alpha brass on annealing,l Mathewson and Phillips have discussed the relations between temperature of anneal, degree of deformation, and structural alteration in alpha brass. They have also shown certain comparisons between the ordinary physical properties and the grain size of annealed brass. The purpose of the present investigation is mainly concerned with the grain size of cartridge brass, its relation to Brinell hardness, and the publication of sufficient data to enable those engaged in the inspection of such material to have a correct foundation upon which to work. The first alloy was taken from regular mill stock that had been rolled from 0.580 in. to 0.376 in. (14.7 mm. to 9.5 mm.) gage, a reduction of 35.1 per cent. This bar (No. 1) had the following composition: Copper, 69.20 per cent.; zinc, 30.76 per cent.; lead, 0.02 per cent.; iron, 0.02 per cent. The second alloy was also taken from mill stock of 0.325 in. (8.25 mm.) gage and was rolled as shown in Table 1, in order to get four bars reduced two, four, six, and eight B. & 5. numbers respectively. This second alloy

Jan 1, 1919

By G. M. Schwartz

THERE has been considerable controversy regarding the structure and mineral constituents produced when iron ore is sintered. This investigation was undertaken in order to establish the fundamental reactions that take place in the sintering process by determining the nature of the resulting minerals. The writer's immediate interest in the subject arose mainly from the request of E. W. Davis for information based on a microscopic study of sinter submitted by him in May, 1926. In the author's preliminary work, samples of iron-ore sinter were secured from the Minnesota School of Mines Experiment Station and from commercial plants. These were polished by the usual methods for polishing opaque ores. In order to study these surfaces satisfactorily, it is necessary to magnify them rather highly, a range from 100 to 1000 dia. being used. For the higher magnifications oil-immersion lenses and an intense source of light are necessary. After the preliminary study had shown the problems involved, a series of small samples were sintered under carefully controlled conditions and with analyzed materials. Variations in the relative amounts of ore, coal and water were made in order to study the effect of each constituent. The attempt has been to arrive at a clearer understanding of the sintering process and the reactions involved without reference to any preconceived notion as to sinter. It is clear that the study of polished surfaces has yielded results not possible with thin sections alone. The thin sections made in this work were found unsatisfactory at magnification greater than 75, whereas magnifications of 1000 were easily studied with reflected light on carefully polished surfaces. A rather complete statement of observed facts is made so that the reader may form his own conclusions. The writer's interpretations are suggested.

Jan 1, 1929

By R. G. Vardiman, M. R. Achter

Observations of dislocation structure in niobium are presented using two techniques. Triangular pits developed by electroetching are confined to orientations in the stereographic triangle between the (111) pole and planes of the (1ll) zone and require the presence of carbon. Some unusual electroetching phenomena at other orientations are noted. A chemical etch of dislocations decorated by the addition of carbon to 50 ppm reveals the complete dislocation line structure in a surface layer up to 30 p deep, with a resolution of less than 1 p. This effect is independent of surface orientation. The structure of subboundary nets may be resolved for misorientations up to about 1'. Dislocation structures found in strain anneal grown crystals, such as helices, prismatic loops, and high-density areas, are observed. The measurement of dislocation density is discussed and values obtained in different ways are compared. IN the course of some work on the response of refractory metals to thermal-mechanical treatments, it was desired to examine the defect structure of relatively low dislocation density crystals of niobium in bulk form. Surface and bulk methods for the observation of dislocations have been reviewed by ~melinckx,' and include etch pitting, decoration, and various X-ray techniques. The dislocation line structure has been developed by decoration in a few metals, although observations were limited to certain orientations, or by the coarseness and nonselectivity of the precipitate. The most commonly used technique is etch pitting. In niobium, etch pits have been developed chemically'0," in material of high impurity content and electrolyti-cally'' in relatively pure material. In this paper, etch pits developed electrolytically, and the dislocation line structure of a surface layer developed by decoration and chemical etching, are examined, and observations are presented from both techniques. EXPERIMENTAL METHODS Our starting material was electron-beam-melted niobium, swaged to 4 or -in.-diam rod. Chemical analysis is given in Table I. Single crystals were grown by a strain anneal technique using 1 to 2.5 pct of strain and growth temperatures of 1700" to 2300"~.'~ Some crystals grown by zone melting were also examined. The desired surface orientation was exposed either by spark machining or by sectioning with a cut-off wheel and prepared for etching by electro-polishing.

Jan 1, 1969

By R. Schuhmann

Jan 1, 1965

By C. E. Sims

THE following presentation is more a summation of observations made and conclusions drawn over a period of three to four years than a report of experiments made with a definite objective. Tests were made, of course, to verify hypotheses, but the large mass of data was collected incidental to other work. Lack of space forbids the presentation of more than a few of those data. On the other hand, it is unfortunate that some of the most illustrative examples are not available. The work is admit¬tedly incomplete but is presented in the hope that it will stimulate further work along a similar line. The answers to many of the questions left unanswered by this paper will be found only after long and painstaking study, such as is scarcely possible in a commercial laboratory where problems of immediate importance consume most of the time. It is also hoped that this study will in some measure throw light on some of the dark spots of steelmaking, and help to clarify some of the annoyingly vague references to "good practice." Only cast steel was studied and the conclusions apply to cast steel, but it is the authors' opinion that the quality of rolled or forged steel is largely dependent on the quality of the ingot, which is a casting. Although this discussion deals almost entirely with inclusions, it is important that the reader understand that only those natural inclusions which owe their origin to the solubility of certain materials in steel and to the chemical reactions of steelmaking are considered. Accidental inclusions, such as entrapped particles of slag, nozzle, runner, or mold are outside its province and are not considered. Such accidental inclusions are always dangerous and should be carefully avoided.

Jan 1, 1932

By R. L. Whiting, H. J. Ramey

The basic study from which this paper was prepared was started as the result of the growing need throughout the world for increasing quantities of energy in all forms. Quite obviously, natural forms of energy that are readily available at low development cost are those in greatest demand. The underdeveloped countries — and particularly those having little or no petroleum resources — are the countries in which the most interest is being shown in the newer energy sources. One of the least expensive energy sources is natural geothermal steam.'-* Although this form of energy has been recognized for centuries, it has been only during the past 20 years that serious efforts have been made to harness it. Natural geothermal steam energy in Italy, New Zealand, Mexico, Japan, and California is now being produced through wells to drive turbines and generate electricity. Further, active exploration for natural geothermal steam is being conducted in Hawaii, Fiji, Taiwan, Chile, Russia, Greece, and Katanga. It is surprising to find that most geothermal steam exploration is in the "steam seep" stage. That is, surface studies are made and exploratory wells are drilled in the general area of steam seeps. However, in the larger geothermal steam areas, there have been efforts to apply the most modern geological and reservoir engineering principles in order to define the reservoir parameters, particularly those relating to estimates of reserves and future productivity. This paper is concerned with the development of appropriate equations and techniques to facilitate these estimates. Production of natural steam or hot water presents problems different from those experienced in the production of oil and gas. For example, steam or hot water systems may be essentially single-component systems, while hydrocarbon systems are most frequently multicomponent fluid systems. Heat effects are much larger for water than for hydrocarbon systems; and the natural steam production may or may not be isothermal, while production of petroleum reservoirs is considered normally to be isothermal. Petroleum reservoir engineering principles may be applied to natural steam or hot water reservoirs if the inherent differences in the systems are considered. The basic considerations involved in geothermal steam reservoir engineering are: thermodynamics, physical and thermal properties of water, materials and energy balances, fluid influx, and performance matching and predicting. Thermodynamics Fig. 1 is a pressure-temperature diagram for the liquid-vapor region for pure water, showing the critical point and five other points representing possible initial conditions for a geothermal steam reservoir. To generate a physical appreciation for the mechanics of natural steam production, it is helpful to consider

Jan 1, 1970

By B. P. Nutter, M. Lebourg, J. A. McAlister

The Multi-Flow Evaluator (MFE) is a new system of tools providing an original approach in drill-stem testing. It improves control during the testing operation and gives a more accurate evaluation of the fluid recovered while providing additional pressure information for reservoir analysis. The tools are operated entirely by up and down motion of the drill stem. This up and down operation provides a positive means of control and offers easily observed surface indications of tool operating position. An unlimited number of shut-in and flow periods may be taken with this tool while in the hole. The key to the success of the MFE system of tools is the safety seal packer. Until this development, operation of the tools by up and down motion only had proven unreliable. The success ratio of the MFE now exceeds the ratio achieved by conventional tools. The equipment includes a 2,750-cc chamber in which a representative sample of the flowing formation fluid is trapped at the end of the last flow period and brought to the surface under pressure. The sample can be evaluated at the wellsite or transferred under pressure for laboratory analysis. The sampling feature of the tool allows a sample to be obtained from a reservoir which has suffered minimum influence from production. A representative sample can be obtained for laboratory or empirical analysis by employing a testing technique to minimize drawdown during flow periods. Interpretation methods to take advantage of this additional information are presented and supported by actual field examples. INTRODUCTlON The Multi-Flow Evaluator (MFE) represents the most recent technical advance in formation testing. Drill-stem testing techniques prior to the MFE have been limited in three areas—(1) operaiion, (2) recovery analysis, and (3) reservoir analysis. The tools in the MFE system allow maximum control during testing and provide test information superior to that obtainable with conventional tools. The system of tools and the operation procedures are described to illustrate the mechanical advantages over present tools. Methods of pressure build-up and fluid

Jan 1, 1966

By C. S. Samis, D. P. Seraphim

In the presence of oxygen, galena is oxidized in an aqueous medium containing ammonium acetate in accordance with the following reaction: PbS + 1/2 0, + 2 NH~Ac -» PbAc, + So + 2 NH: + H2O. This reaction was studied in an autoclave under oxygen pressure by polarographic measurement of the concentration of lead ion in solution. Oxidation rate is parabolic. The reaction products are lead acetote and elemental sulfur, the latter forming a film on the galena crystal. Reaction kinetics appear to be determined by the diffusion of lead from the galena phase to the solution interface through the film of sulfur. RECENT applications of pressure leaching on a commercial scale have emphasized the metallurgical importance of the oxidation of sulfide minerals in aqueous media by oxygen under pressure. Research experience has shown that sulfates, thio-nates, and metal oxides are the products of humid oxidation of sulfide minerals in basic solutions. The metal oxides may be solubilized in the presence of a complexing ion.' Certain oxide minerals are also amenable to treatment by this type of oxidation.' Several kinetic studies have been made of reactions of this type. Stenhouse' found that pyrite (FeS?) oxidized in a sodium hydroxide solution to produce a soluble sulfate and an insoluble layer of iron oxide and that the kinetics of the reaction were controlled by oxygen diffusion through the oxide layer. Andersen' studied the oxidation of galena (PbS) in a sodium hydroxide solution under oxygen pressure. He found the lead and sulfur to be simultaneously oxidized to produce plum bite ions and sulfate ions, and that the reaction rate was proportional to the surface area of the galena. The kinetics appeared to be determined by the reaction of oxygen and water with the galena surface. In each of the above reactions the metal and sulfur components of the mineral were oxidized simultaneously and at equal rates. In the present study the alkaline medium has been replaced by an approximately neutral solution of ammonium acetate in which lead sulfate is soluble. Under the conditions no sulfate was produced and no sulfur could be detected in the solution. The metal component of the mineral was solubilized and the liberated sulfur remained as a film of elemental sulfur on the surface of the galena crystal. A kinetic study of this reaction was undertaken to establish the kinetic mechanism and to determine the rate controlling step. Specific reaction rates were determined by oxidizing crystals of galena of measured surface areas in an autoclave maintained at the desired temperature and oxygen pressure. The rate of reaction was followed by measuring the concentration of lead in the ammonium acetate solution with a cathode ray polarograph, employing stationary platinum electrodes incorporated in the autoclave. Experimental Materials and Equipment Crystals of galena obtained from Violamac Mines, Retallack, B. C., were selected for oxidation because

Jan 1, 1957

By F. W. Jessen, C. C. Patton

Adsorbed films were formed on polished stainless steel specimens from dilute benzene solutions of two crude oil distillation residua. Although the two residua were extremely dissimilar in composition, contact angle measurements showed that the two films increased the wettability of the steel specimens to oil by equal amounts. Furthermore, the wettability of the films was essentially unaffected by the desorption techniques used. Paraffin deposits were formed from heptane-wax solutions on the same stainless steel specimens. These deposits definitely adhered to the surface. Presence of an adsorbed crude oil film on the metal surface increased its free surface energy and resulted in increased deposition of paraffin. The addition to the heptane - wax solution of small amounts of the same distillation residua that were used to form the adsorbed films resulted in decreased cohesive strength in the deposits formed, which resulted in decreased deposition. The presence of a crude oil fraction both in the solution and as a preadsorbed film eliminated the adherence of a deposit of any kind. A mechanism of deposition is proposed which explains the results obtained. INTRODUCTION The natural formation of any predominantly organic accumulation in oilwell tubing, surface flow lines or other production and storage facilities is called a paraffin deposit. These deposits restrict the production of crude oil, causing a substantial increase in production costs because of decreased flow capacity, expense for periodic deposit removal and unproductive downtime. The conditions under which such deposits form, their physical characteristics and the nature and severity of the problem created are extremely varied. Over the past several years, much progress has been made in developing and utilizing methods to remove accumulated paraffin deposition. However, like so many other problems, the basic stumbling block appears to be a lack of understanding of the fundamental mechanism involved in the formation of such deposits. Crude petroleum is known to contain considerable quantities of polar, surface active substances which Doddl has shown to be present at the oil-water interface. Denekas, Mattax and Davis2 observed that the wettability of reservoir rocks was drastically altered by exposure to crude oil fractions; and Zisman, et a1.3 showed that the nature of the compounds adsorbed on a surface would determine its wettability characteristics. Cole and Jessen4 and Ehrig5showed that surface wettability can have a profound effect on the magnitude of paraffin deposition, and Parks6 demonstrated chat the presence of certain adsorbed films on a metal surface would reduce the adherence of paraffin to that surface. Zisman7 has since advanced the theory that the conditions for adhesion are the same as for wetting. Therefore, it was felt that there was adequate evidence to support the supposition that adsorption of compounds from a crude oil might play an important part in paraffin deposition. ADSORPTION-WETTABILITY EXPERIMENTS Initial experiments were conducted to determine the effects of adsorption from solution of crude oil residua on the wettability of a polished stainless steel surface. Distillation residua with initial atmospheric boiling points of 700F were used in preference to the whole crudes in order to concentrate on the molecular weight range of interest, and to eliminate the possibility of composition change due to evaporation of the light ends. Also, these high boiling materials would be expected to be adsorbed from the whole oil in preference to similar compounds of lower molecular weight.

Jan 1, 1966

By A. Roberts

This paper reviews progress in equipment design and in the techniques applied to mine lighting in Great Britain. The incidence of the disease miner's nystagmus, which was a major source of concern only a few years ago, has now diminished, largely owing to improvements in standards of lighting in mines. The reorganisation of the coal mining industry, involving increasing mech-anisation, together with new safety legislation, has brought about the widespread use of mains electric lighting underground. An account is given of some of the results of research to determine the lighting conditions needed for compliance with the compulsory legal requirement of "sufficient and suitable" general lighting at specific localities in British mines. Some details are given of the techniques applied and the results of recent research in the problem of glare from miners' cap lamps. Of the various factors in the working environment of the miner, it is true to say that lighting is seldom given attention comparable with that devoted to other factors, such as dust, heat and humidity, or atmospheric gas content. No doubt one reason for this lies in the ability of the human eye to adapt itself to low brightness levels. Be that as it may, the fact is that at the turn of the 20th century the miner's working light improved little throughout the centuries during which mining technology has developed. Indeed, in coal mines which encounter a methane explosion hazard, flame safety lamps, with a luminous intensity less than one candle power, were virtually the sole means of lighting during almost the whole of the 19th century. The 20th century has witnessed a substantial improvement in lighting techniques underground in coal and metalliferous mining. In Great Britain the general pattern has been one of standards periodically raised by the implementation of Statutory Regulations imposed under successive hlines Acts, but it is fair to add that the more progressive mining companies usually anticipated the Statutory Regulations, which when they have been put into effect have served to turn into general practice what was already being done at the better mines. In earlier years, official requirements were limited to the specification of approved lamp designs, with stipulated minimum values of luminous intensity and light output, but more recently the necessity of satisfactory maintenance of standards during service has been recognized, and the current regulations not only require that a maintenance organisation should exist, but also specify a maximum permissible depreciation below initial approval standards.'

Jan 1, 1961

By A Guinier

RECIPITATION in alloys is undoubtedly one of the most essential phase transformations in metallurgy and, besides, it is a phenomenon of great interest to physicists. It seems then that it can be chosen as a topic for an Annual IMD Lecture. Of course, the subject is a very wide one and I shall discuss here only a very restricted part of it. I should like to show why it is now considered that there is, at the beginning of the process, a stage distinct from the real precipitation, which is the pre-precipitation. We shall be chiefly interested in the atomic structure of the metal in this preprecipi-tation stage. Numerous reviews on this subject have been published recently.', ' The latest was given by H. K. Hardyh t the last meeting of the Institute of Metals in London. One of the most complete articles has been written by the late Dr. Geisler." I should like, at the beginning of this lecture, to pay a tribute to the memory of our friend Arthur Geisler. Some of the ideas which will be developed here are different from those advocated by him. But everybody knows the considerable progress in experiment and in theory which we owe to him and, personally, I deeply feel how fruitful have been the long discussions which we have had during many years. Experimental Basis of the Precipitation Problems Let us recall the essential facts pertaining to the problem of the precipitation. The starting point and the final one are well known. The initial stage is the supersaturated solid solution before quenching. The dissolved atoms replace some of the atoms of the solvent at the points of a definite lattice. It is generally considered that the distribution of the atoms is completely random, and that the lattice distortions are relatively weak. These assumptions are only an approximation. It has now beenproven", that, in some cases, the dissolved atoms have a tendency to segregate to form very small nuclei. These fluctuations of composition are greater than the normal statistical fluctuations in a purely random alloy. We shall see the role played by these nuclei later. The final state is obtained by a very long annealing at such a temperature that an equilibrium is reached in a reasonable time. The alloy is then composed of a matrix which is a saturated solid solution, much poorer than the initial one. Imbedded

Jan 1, 1957

By L. E. Lynd

Ilmenite concentrates prepared from beach and dune sands of Florida, India, Australia, and other localities deviate to varying degrees from the theoretical composition of pure ilmenite, and generally contain more TiO2 than the formula FeTi03 would indicate, and some Fe2O3. This variation in composition is due to different amounts of altered ilmenite in the concentrates. (') The alteration has been shown to take place by oxidation and leaching of the iron in ilmenite, to yield residual products consisting of amaphous or very finely crystalline titanium dioxide and ferric oxide. Other studies(2) have stressed that ilmenite may alter first to an amorphous titanium-iron oxide, or to an amorphous mixture of titanium and iron oxides, with later alteration to crystalline titanium dioxide. There has been some speculation as to whether alteration of ilmenite is usually caused by weathering or by hydrothermal pr0cesses.(3,4,5 Three main methods of approach were used to study the mechanism and rate of ilmenite weathering. (1) Etch tests were used to learn the relationship between crystallographic orientation and the rate of chemical attack on ilmenite. (2) Altered ilmenites in New Jersey sands were compared with ilmenite in rocks of the area from which the sands were probably derived. (3) Experiments were carried out to determine at what rate, and by what agents, originally fresh ilmenite could be altered in the laboratory under simulated weathering conditions. ETCH FIGURES ON ILMENITE CRYSTAL PLANES A rather large ilmenite crystal from Sannidal, Norway, about 11/2 x 11/2 x 2 inches, bearing a few natural faces with imperfect surfaces, was prepared for etching by grinding and polishing crystal planes whose Bravais-Miller indices (referred to hexagonal axes) had been determined by X-ray methods to be 00.1, 10.0, and 10.2. Metallographic examination showed that the crystal was homogeneous, and uniform in orientation, except for the presence of twin lamellae which were oriented with their broadest surfaces parallel to the 00.1 planes of the large crystal. Since ilmenite is rather inert to standard etch reagents, strong solutions of hot sulfuric acid and cold hydrofluoric acid were used. Preliminary tests established that better etch figures were obtained using HF than with H2So4 solutions. The etch figures produced on 00.1 and 01.0 planes of ilmenite by etching 3 to 5 minutes in cold concentrated HF solution are shown in Figures 1, 2, and 3. The figures on 00.1 are "etch hillocks", rather than pits, and according to Honess(6), this phenomenon

Jan 1, 1961

By L. W. Berger, and R. I. Jaffee, D. N. Williams

The effects of hydrogen on the properties of binary Ti-A1 alloys containing 2.5, 5, and 7 pct aluminum and ternary alloys of the same compositions with added interstitial elements oxygen, nihrogen, and carbon were stzdied. Aluminum increases the apparent hydrogen solubility of the a-phase, resulting in a marked increase in resistance to impact embrittlement. In the Ti-5Al and Ti-7Al alloys, for example, the addition of 180 and 305 ppm hydrogen, respectively, did not cause embrittlement, while unalloyed titanium was embrittled by as little as 75 ppm. The role of aluminum in increasing hydrogen solubility of the a-phase probably accounts for the excellent hydrogen tolerance of a-ß alloys containing considerable amounts of aluminum. There is some evidence that aluminum retards the rate of hydride precipitation. If so, these alloys may be susceptible to slow-strain embrittlement. UNALLOYED a-titanium is extremely sensitive to small amounts of added hydrogen in that there is a marked decrease in notch properties. For example, as little as 100 ppm hydrogen is sufficient to lower the room-temperature notch-impact strength from over 100 to less than 20 in.-lb.' This loss of impact Strength has been associated with the Presence of hydride phase in the microstructure. Hydrogen in the amounts encountered in commercial practice

Jan 1, 1959

Jan 1, 1965

By Karl A. Bauer, Cornelis Bezemer

The deposition of calcium carbonate scale on surface and subsurface production equipment creates an operation problem in many oil fields. The formation water in which the carbonate-scale-forming components are initially dissolved becomes supersaturated with calcium carbonate as a result of the drop in pressure during production. The continuous flow of a supersaturated solution through the production equipment results in the growth of a dense layer of calcium-carbonate crystals. For a scale layer to be built up, the supersaturated formation water should contact the walls of the production equipment. The tendency for scale to be deposited, therefore, will be low, if the crude has a low water cut and if the water is finely dispersed in the oil. A scale problem will occur, if at a high water cut part of the water is present as free water. The rate of scale deposition will then be approximately proportional to the rate of free water production. Depending upon where the formation water becomes supersaturated, scale may be deposited in the flow line only, in both flow line and tubing, and in some cases even in the perforations and in the formation near the wellbore. In the South Sumatran fields (Indonesia) the main difficulties encountered due to the deposition of calcium-carbonate scale have been restriction of flow through tubings and flow lines, wear and abrasion of plungers and liners, and stuck plungers or wellhead valves. So far, the only methods of combating the *Presently associated with Brunei Shell Petroleum Co., Ltd.. Seria. scale problem have been routine acidizing and additional well pulling. As for the pumping wells, it was estimated that some 50 percent of the total well-pulling effort was directly attributable to scale deposition. The most promising alternative was to prevent the deposition of calcium carbonate scale by means of chemicals. Inorganic polyphosphates such as sodium hexametaphosphate and trisodium polyphosphate are known to retard the formation of scale by the "threshold action". They are adsorbed on specific faces of the crystal nuclei and thus prevent crystal growth, thereby stabilizing supersaturation. Polyphosphates are effective at very low concentrations ( a few ppm), and far less than stoichiometric quantities are required to keep the scaling ions in solution. Recent investigations on barium sulfate scale1 have confirmed this mechanism. The types of polyphosphate mentioned can be applied as concentrated aqueous solutions either squeezed into the formation, lubricated down the annulus or injected via macaroni string. Several squeeze jobs with polyphosphate solutions have been carried out in the South Sumatran fields, however, with disappointing results. Lubrication down the annulus and injection through a macaroni string were not considered attractive in this area because of the kind of equipment and the degree of supervision these techniques require. Polyphosphates are also available in a granular, glassy form, which, in contrast with the readily soluble types already mentioned, show an extremely low

Jan 1, 1970

By M. A. Elliott

The technology of gasifying coal to produce synthesis and pipeline gas has advanced significantly in the Past 20 to 30 years. This period has seen the extensive use of oxygen in coal gasification, the development of suspension gasification processes and fluidized-bed gasifiers, the operation of various gasification processes at elevated pressures, and operation of gasifiers under slagging conditions. These developments are discussed, and their application to commercial and pilot plant gasifiers is reviewed. Typical processes for synthesis gas production are described, and operating results are compared. Pipeline or high-Btu gas may be produced from coal either by catalytic conversion of synthesis gas to methane, or by the direct reaction of coal with hydrogen (hydrogasification) to produce a methane-rich gas. Neither of these methods has been applied commercially, but developments pertaining to each of them are reviewed, and general processing schemes are discussed. The use of coal as a raw material for manufacturing gas has a long and distinguished history. In fact, the gas industry began in the early 1800's when William Murdock demonstrated that it was feasible to produce and distribute gas made by retorting coal. Coal was used exclusively for gas manufacture until the middle of the 19th centruy, when Lowe invented the carbureted water gas process. In that process, coke was one of the raw materials used, so coal was still an important factor in gas manufacture. However the availability and relatively low cost of natural gas in the United States, and its widespread distribution by long-distance pipelines in recent years, has virtually eliminated the use of coal as a raw material for gas manufacture in this country. It should not be inferred from the foregoing that the technology of coal gasification has remained static in the United States and abroad. In fact, in the past two decades many new concepts have been developed in both the science and the technology of gasification. This progress has been a result of the considerable expansion in research on the fundamental chemistry and physics of gasification reactions, and in development work on gasification processes. This expansion in effort stems in part from increased interest in the use of gas as a raw material for the synthesis of chemicals and liquid fuels, and in part from the need to develop methods for gasifying coal and other solid fossil fuels to ensure a long-range supply of energy in the form of gaseous fuel. In these uses of gas, synthesis gas, a mixture of hydrogen and carbon monoxide in various proportions, is the starting material. It may be converted catalytically to gaseous and liquid hydrocarbons and other chemicals, or to hydrogen for use in hydrogenation or reduction reactions. Since coal is our most abundant fossil fuel, it is inevitable that one day it will regain its prominence as a raw material for gas manufacture. It is of interest, therefore, to consider the present status of gasification technology, directing attention particularly to advances made in recent years. Inasmuch as many comprehensive treatises l-3 and review4-7 of gasification technology are available, no attempt will be made in the present review to cover all processes in detail. Instead, the discussion will be concerned chiefly with typical processes embodying the advances that are most likely to be generally applied. ADVANCES IN GASIFICATION TECHNOLOGY For purposes of this discussion the starting point will be the conventional processes that were used for many years for the complete gasification of coal. These were: 1) carbonization in coke ovens followed by gasification of coke with air and steam in cyclic water-gas generators, and 2) fixed-bed air-blown producers. Both of these methods have obvious deficiencies when we consider that the ideal complete gasification process would be a single-stage, continuous

Jan 1, 1961