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By S. Yukawa, M. J. Sinott

The low solubility of bismuth in copper and its segregation at copper grain boundaries with resulting embrittlement is well known.1-3 The heterogeneous diffusion of liquid bismuth into polycrystalline copper has also been studied.4 This work presents some further observations on these phenomena using high-resolution auto radiography to detect the presence of bismuth in copper polycrystalline and bicrystal specimens. The auto radiographs were made by the stripping film technique which produces an autoradiograph that is intact with specimen surface and can be examined simultaneously with the under-lying microstructure. The details of the technique have been described previously.3 In one series of experiments, high-purity copper was alloyed with 0.02 to 0.03 wt pct radioactive bismuth obtained from the Oak Ridge National Laboratory. Melting and casting was done under a

Jan 1, 1960

By H. Baldauf, H. Schubert

The structure of flotation reagents is important for their adsorption on mineral surfaces and thus for their flotation effectiveness. The influence of the structure of organic depressants on the flotation of fluorite and barite with anionic and cationic collectors was investigated using a modified Hallimond microflotation cell. In addition, adsorption, desorption, and electrokinetic results were employed to further elucidate the role and the correlation of the structural parameters for adsorption and the depressing effect. As hydrophilic reagents, different aliphatic and aromatic compounds capable of forming chelates with alkaline earth materials were used. For the depressing effect, the kind, number, and position of the polar groups in the molecule, as well as the structure of the reagent films play decisive roles.

Jan 1, 1980

By J. S. Billheimer, B. H. Sage, W. N. Lacey

A restricted ternary system made up of n-pentane, tetralin, and a purified bitumen was investigated at 70, 160, and 220 °F. Most of the experimental observations were at atmospheric pressure or at 200 psi." However, some experimental measurements were carried out at a pressure of approximately 8000 psi. It was found that the purified bitumen was precipitated from its solution or dispersion in tetralin by the addition of n-pentane and that the separation occurred at lower weight fractions of n-pentane at the lower temperatures. The bitumen-tetralin solutions show some colloidal characteristics at temperatures below 160 °F when near compositions at which the bitumen separates as a solid phase. At states remote from the phase boundaries and at temperatures above 160 °F these characteristics become less evident. Under these latter circumstances the mixtures tend to follow the behavior of true solutions, particularly in regard to the approach to heterogeneous equilibrium. An increase in pressure appears to increase the solubility of bitumen in tet-ralin-n-pentane solutions. This effect is more pronounced at temperatures above 160 °F than at lower temperatures. INTRODUCTION Asphaltic phases of plastic or solid nature have appeared in numerous instances during the recovery of petroleum from underground reservoirs. Such depositions occurring underground appear to have caused adverse production histories for particular wells or zones. Because of this field experience, it is desirable to understand the factors which influence the formation or separation of the asphaltic phases from petroleum. The problem is unusually complex because the number of true components involved is very large and the details of the phase behavior encountered are difficult to ascertain experimentally. The literature relating to asphalts, asphaltines, and bitumen is voluminous and widespread.' Only those references which are directly pertinent to the work at hand are cited. The separation of an asphaltic phase, hereinafter called bitumen? from naturally occurring hydrocarbon mixtures has been the subject of several investigations.2'3'4'5'6 It has been found that as many as four phases4 may be produced from a crude oil by the solution of a natural gas and propane at a pressure of 1500 psi and a temperature of 70 °F. The separation of bitumen from such naturally occurring mixtures results in at least one liquid phase which is substantially free of high molecular weight components.³ The influence of the solution of lighter hydrocarbons on the separation of bitumen from a Santa Fe Springs crude oil has been investigated. The results indicate that in the case of the methane-crude oil system, the quantity of plastic or solid phase separated reaches a maximum between 0.14 and 0.19 weight fraction methane and then decreases until negligible at higher weight fractions of methane. Similiar behavior was encountered in the case of mixtures of ethane and crude oil. The decrease in the quantity of the solid phase with an increase in the weight fraction of the lighter component appears to result from the formation of an additional liquid phase6 in which the bitumen is relatively soluble. The formation of this additional phase probably occurs at a weight fraction of methane close to that at which the quantity of separated solid reaches a maximum. A comparison of the deposition of bitumen in the field with the separation of asphalts from lubrication oil has been made' and apparently the phenomena are similar. The phase behavior of bitumen also appears to be comparable to that of coal tar."' The chemical and physical characteristics of asphalts and bitumen have been the subject of extended investigations which have been reviewed in some detail by Katz.¹º The conclusion was reached that the dispersion of bitumen in a number of organic liquids was not entirely colloidal since it was impossible to isolate individual dispersed particles even with the electron microscope. However, the evidence appeared to indicate that at states close to phase boundaries the extent of the dispersion of the phases influenced the equilibrium to a greater extent than is encountered in many simpler systems. From earlier study of field samples it became apparent that the phase behavior of bitumen-hydrocarbon systems was unusually complex. It was difficult to characterize in detail the phase behavior involved in naturally occurring hydrocarbon systems, even after a relatively extended investigation. For this reason, the study of a somewhat simpler system which still behaved in a similar manner became desirable. Three major constituents were necessary as-follows: a bituminous solid, a liquid constituent which was a reasonably good solvent, and a constituent in which bitumen was largely insoluble. A sam-

Jan 1, 1949

By W. N. Lacey, B. H. Sage, J. S. Billheimer

A restricted ternary system made up of n-pentane, tetralin, and a purified bitumen was investigated at 70, 160, and 220 °F. Most of the experimental observations were at atmospheric pressure or at 200 psi." However, some experimental measurements were carried out at a pressure of approximately 8000 psi. It was found that the purified bitumen was precipitated from its solution or dispersion in tetralin by the addition of n-pentane and that the separation occurred at lower weight fractions of n-pentane at the lower temperatures. The bitumen-tetralin solutions show some colloidal characteristics at temperatures below 160 °F when near compositions at which the bitumen separates as a solid phase. At states remote from the phase boundaries and at temperatures above 160 °F these characteristics become less evident. Under these latter circumstances the mixtures tend to follow the behavior of true solutions, particularly in regard to the approach to heterogeneous equilibrium. An increase in pressure appears to increase the solubility of bitumen in tet-ralin-n-pentane solutions. This effect is more pronounced at temperatures above 160 °F than at lower temperatures. INTRODUCTION Asphaltic phases of plastic or solid nature have appeared in numerous instances during the recovery of petroleum from underground reservoirs. Such depositions occurring underground appear to have caused adverse production histories for particular wells or zones. Because of this field experience, it is desirable to understand the factors which influence the formation or separation of the asphaltic phases from petroleum. The problem is unusually complex because the number of true components involved is very large and the details of the phase behavior encountered are difficult to ascertain experimentally. The literature relating to asphalts, asphaltines, and bitumen is voluminous and widespread.' Only those references which are directly pertinent to the work at hand are cited. The separation of an asphaltic phase, hereinafter called bitumen? from naturally occurring hydrocarbon mixtures has been the subject of several investigations.2'3'4'5'6 It has been found that as many as four phases4 may be produced from a crude oil by the solution of a natural gas and propane at a pressure of 1500 psi and a temperature of 70 °F. The separation of bitumen from such naturally occurring mixtures results in at least one liquid phase which is substantially free of high molecular weight components.³ The influence of the solution of lighter hydrocarbons on the separation of bitumen from a Santa Fe Springs crude oil has been investigated. The results indicate that in the case of the methane-crude oil system, the quantity of plastic or solid phase separated reaches a maximum between 0.14 and 0.19 weight fraction methane and then decreases until negligible at higher weight fractions of methane. Similiar behavior was encountered in the case of mixtures of ethane and crude oil. The decrease in the quantity of the solid phase with an increase in the weight fraction of the lighter component appears to result from the formation of an additional liquid phase6 in which the bitumen is relatively soluble. The formation of this additional phase probably occurs at a weight fraction of methane close to that at which the quantity of separated solid reaches a maximum. A comparison of the deposition of bitumen in the field with the separation of asphalts from lubrication oil has been made' and apparently the phenomena are similar. The phase behavior of bitumen also appears to be comparable to that of coal tar."' The chemical and physical characteristics of asphalts and bitumen have been the subject of extended investigations which have been reviewed in some detail by Katz.¹º The conclusion was reached that the dispersion of bitumen in a number of organic liquids was not entirely colloidal since it was impossible to isolate individual dispersed particles even with the electron microscope. However, the evidence appeared to indicate that at states close to phase boundaries the extent of the dispersion of the phases influenced the equilibrium to a greater extent than is encountered in many simpler systems. From earlier study of field samples it became apparent that the phase behavior of bitumen-hydrocarbon systems was unusually complex. It was difficult to characterize in detail the phase behavior involved in naturally occurring hydrocarbon systems, even after a relatively extended investigation. For this reason, the study of a somewhat simpler system which still behaved in a similar manner became desirable. Three major constituents were necessary as-follows: a bituminous solid, a liquid constituent which was a reasonably good solvent, and a constituent in which bitumen was largely insoluble. A sam-

Jan 1, 1949

By Richard M. Foose

The year 1950 has been a fascinating and unusual one as far as industrial minerals are concerned because of the sudden development of a critical international situation in late June. The first half of the year was marked by thriving peacetime conditions.

Jan 2, 1951

Faulty rock dusting of the New Orient Mine at West Frankfort, Ill. was declared to have been the primary cause of the extent of the blast that killed 119 men on December 21. Walter Eadie, state director of mines and minerals, ascribed the explosion to the ignition of methane in a working place about a mile northwest of the shaft of the mine. The initiation of the combustion was either by a spark from electrical machinery or from men smoking in the mine. It was surmised that a train of empty cars stalled in a ventilation door, had caused sufficient disturbance in the ventilation system to permit accumulation of gases. The Federal Bureau of Mines said that the Illinois explosion was caused by an electrical spark that touched off the clouds of gas present because of the faulty ventilation equipment. The bureau report listed three conditions as primarily responsible: An inadequate ventilating system, operation of faulty electrical equipment and the presence of large accumulations of fine coal dust capable of exploding. "This coal dust, principally along roadways, was not removed from the mine or rendered inert by the application of sufficient rock dust," the report stated. Investigations showed that an even more disastrous blast was averted because the explosion eventually reached areas where it could expand into open workings and where enough rock dust had been applied to retard it.

Jan 1, 1952

By L. W. Page

PrEvious to the introduction of the motor vehicle the broken stone or macadam' road met the conditions of rural horse-drawn traffic better than any other type of road, but under fast motor traffic it has been proved to be quite unsatisfactory, and necessitates high maintenance charges. Such a road depends for its success upon the fact that the rock dust fills the voids between the stones and acts as a cement or binder. Under ideal conditions it should be constructed of rock so suited to the volume and character of horse traffic that only enough fine dust is worn from the stones of which the road is composed to take the place of that carried off by wind and rain; and when these conditions are met, the fine dust resulting from the wear of traffic forms with the stone a smooth, impervious shell, shedding the surface water and protecting the foundation. With increase in the number and speed of motor vehicles, however, it was soon found that the cost of maintenance also increased, until at the present day highway engineers consider the old method of constructing and maintaining broken-stone roads increasingly inadequate, and are introducing every known type of binding material other than rock dust to cement the stone together. Among the most prominent types of products in use are those produced from our various petroleums. That the value of modern methods of road preservation was appreciated in this country much earlier than we have been accustomed to believe is demonstrated by the recent revival of an old patent which was granted to one John Martineau, of Elbridge, N. Y., in 1834. Petroleum had, of course, not been discovered at that time, but he claims as his invention and improvement "The application of tar, turpentine, or any of that class of tenacious, cohesive substances, reduced before use to a fluid state, and that state used as a cement, to apply to, and combine with sand, gravel, pebbles, and pulverized stone, such as is used for a Mc-Adam road, or cobble stone, the interstices of coarser material being in all cases filled,'as well as may be, with sand and gravel and cemented with tar or turpentine, to form the wearing face or surface of streets,

Jan 1, 1915

By R. S. Schechter, T. R. Guilinger, P. Bobeck, J. G. Price, L. W. Lake

This paper presents the results of an experimental study on the rate of uranium and molybdenum extraction from a flow reactor. Specific variables tested are fluid throughput and flow rate, lixiviant cation, and injected pH and carbonate concentration. The ore tested was from the Felder mine in southern Texas. It contained substantial quantities of marcasite and molybdenum disulfide that competed with the uranium ore for oxidant. Flow studies showed the oxidation of molybdenum disulfide under field conditions is mass transfer controlled, whereas the uranium oxidation is limited by surface reaction rate. The rate of uranium oxidation decreased with decreasing pH. The total carbonate levels, on the other hand, were unimportant. Ammonium carbonate appears to greatly decrease, if not completely halt, the reaction of marcasite with the oxygen. This effect was not found using either sodium or potassium carbonate.

Jan 1, 1986

By F. Garofalo

It has been shown by various investigators that during constant stress creep the dependence of minimum creep rate, 6,, on stress, o, is given by em = A onat low stress levels, md by 6, = A' exp [ß s] at high stress levels. In these relations A, n, A', and ß are constant at constant temperature. A single relation has been found which satisfies conditions for both high and low stresses and agrees well with experimental results. This relation is 2, = AN (sinh a s)n, where A" is a constant at constunt temperature and a = p/n. This relation also satisfies the linear relation, 6, = k s, found at temperatures near the melting point at low stresses. EXPERIMENTAL creep results have led to a number of empirical relationships between minimum creep rate, 6,, and the applied stress, s. Under conditions of constant stress it is generally found that at low-stress levels,'-' the dependence of minimum creep rate is given by 6, = Asn. At high-stress levels'74 the experimental results fit the relation, 6, = A' exp [po l. In these relations A, n, A' and ß are constant at constant temperature. A model based on climb-of-edge dislocations from a pile-up array leads to a relation similar to that found experimentally at low stresses.' On the other hand. theories based on chemical-reaction rate,5 nonconservatively moving dislocation jogs, and jog migration and climb-of-edge dislocations4 lead to a relation similar to that found experimentally at high stresses. No difference in mechanism between low and high stress levels has been clearly defined; it is questionable whether such a difference really exists. In any event, the major argument usually given in substantiation of a change in mechanism from low to high stresses is that no single relation exists for defining the stress dependence of the creep rate over wide ranges in stress. However, such a relation has been found and is of the form, dm = A" (sinh a s)n, where A" is a constant at con- stant temperature and a = ß/n. This relation agrees well with experimental results over wide ranges in stress and temperature for copper, aluminum, an A1-3.1 pct Mg alloy, and an austenitic stainless steel. STRESS DEPENDENCE OF MINIMUM CREEP RATE At low stress levels the minimum creep rate, gm, depends on the stress, 0, under conditions of constant stress creep through the relation em=Aon [1] The quantities A and n have been defined previously. In the range in which this relation applies, a linear dependence is found in a log em,-log o plot. Above the stress range of application of relation [I], the minimum creep rate increases much mar; rapidly than predicted by relation [I]. This behavior is shown in Fig. 1 for a series of creep tests on copper4 at various temperatures ranging from 673 o to 973°K. Relation [I] is satisfied at the lower stresses, although the results at 973°K are quite limited. In all cases the transition beyond the applicable range of relation [I] is a gradual one indicating no abrupt change in mechanism. For all test temperatures, values of n have been determined from the results in Fig. 1. These are reported in Table I under Alog tm/hlog o. At high stress levels the stress dependence of minimum creep rate under conditions of constant stress is given by im = A' exp [ß a] 2] All factors have been defined previously. In a log em-0 plot, relation [2] predicts a linear function. Experimentally, a pronounced deviation from the prediction of relation [2] is found at lower stresses. As the stress is lowered, the minimum creep rate decreases more rapidly than predicted by relation [2]. This shown for copper in Fig. 2. Again it is found that the transition from high to low stresses is gradual and no really sharp change is found. Values of p determined from the high stress results are given in Table I. The dependence of minimum creep rate on stress at constant temperature for all ranges in stress

Jan 1, 1963

By Royal B. Jackman, Carle R. Hayward

Two comprehensive papers have appeared regarding the forms of copper that occur in smelter slags, one by Frank E. Lathe1 and the other by C. G. Maier and G. D. Van Arsdale.2 These authors comment on other published results and draw conclusions from their own investigations. The development of X-ray examination of minerals and improvement in high-power microscopic methods make it possible today to get additional evidence by means that were not available to earlier investigators. The present work was confined to reverberatory slags obtained from five different plants. Some definite conclusions were reached regarding the forms of copper present in these slags. In most cases these agree with some of the findings of Maier and Van Arsdale but new methods of attack were used in the investigation. Conclusions of Previous Investigators Various important conclusions reached by previous investigators are summarized in the following paragraphs, arranged chronologically. William A. Heywood:3 Slag losses increase with grade of matte but with the same grade of matte losses decrease as the acidity of the slag increases. Lewis T. Wright:' Slag losses are only partly due to prills of matte. It is suggested that part of the copper is dissolved in the slag. J. Parke Channing9 A considerable part of the copper enters the slag as silicate or oxide and not as sulfide. C. A. Grabill:6 Slag losses are both physical and chemical. Physical losses, due to poor settling, gas flotation and slight differences in specific gravity, are small under normal conditions. Chemical losses may- be due to formation of oxides or to solution of metals and sulfides. The last is considered the most important. John W. James:' The copper in converter slag is largely the oxide and as such enters the reverberatory slag when converter slag is added to the charge.

Jan 1, 1934

By R. N. Stevens

Any consideration of the errors involved in determination of ?gb by previous workers should discuss their experimental methods in terms of the appropriate theoretical equation; this the authors have not done in a number of cases. To facilitate the present

Jan 1, 1969

By Halbert Powers Gillette

In every chemical reaction heat is either developed or absorbed, and this plus or minus heat of formation is as definite in quantity as the weights of the reacting elements. In this paper I shall show that each chemical element and each chemical radical has its own definite heat-valency,—a fact which, so far as I know, has hitherto escaped the attention of investigators, but, I feel sure, will be admitted after the demonstration here given, and may lead to some practical conclusions of value. When Berthelotys " law of maximum work " was found to have so many inexplicable exceptions, the pendulum of a scientific theory swung away from a recognition of the truth underlying that proposition; and this reaction went so far that not only has thermal chemistry been relatively neglected by recent investigators, but it is not uncommon now to find textbooks on physical chemistry which practically ignore all that Thomsen, Berthelot and others have done. To this temporary tendency of thought I attribute the failure to recognize the principles herein announced and explained. Not long ago, while studying tables of the formation-heat of various salts, I noticed that in this respect all potassium salts in solution differ from the corresponding sodium salts by 9.3 cal.1 I found also that similar differences exist between other salts, not only when the basic radical is varied, while the acid radical remains constant, but also when the acid radical is the variable. Thus chlorine salts in solution differ from bromine salts in this respect by 10.9 cal. Upon further study, I found that Thomsen had noted similar constant differences, but, so far as I can ascertain, he appears to have attached no great significance thereto.

Jan 1, 1904

By H. W. Gillett

WE hear much in these days about "tailor-made" steels. Farseeing executives have sensed the demand for metals of improved and special properties, with those properties deliberately built into the steel in order to fit it for a particular use or group of uses. They have set their metal-lurgists at work to produce what the customer needs, even though the tonnage required may not, at least at first, be great. As the metal-lurgists bring out such metals, the products are advertised and the customer becomes increasingly conscious that he no longer has to take "ready-made" steel as the only thing available, whether it fits his needs or not, but that there are plenty of steelmakers ready to serve his specific needs with a tailor-made steel. Of course this is nothing new in the realm of rather highly alloyed steels to be heat-treated. The automotive industry demanded and got such steels long ago. Indeed, one could not design a modern car using only non-heat-treated carbon steel, since an engine of present horsepower would be so heavy that the gasoline required merely to lug the engine itself around would be absurd. Many different alloy steels and many different heat-treatments are required to produce the fine gradations of properties and the strength per unit weight that are needed in each particular part. Aircraft designers, of course, count a high strength-weight ratio in the materials used as Article I in their constitution, and they too, and in outstanding degree, require tailor-made alloys. Aircraft and automobiles may be considered as the tail coats and Tuxes of the metallurgical tailors. Nowadays there is also a demand for business suits, in the form of high-strength alloys to reduce dead load and so increase payload, all through the transportation industry. We hear most about weight-saving design and materials in respect to the railroads, with the spectacular new high-speed passenger trains and the prosaic freight car. The latter sounds especially sweet to steel-mill ears, because it means tonnage. While most of us think of these developments, and of the engineering acceptance of high-strength materials as "new," the fundamentals are of almost hoary antiquity. It is the widespread availability of a variety of materials and their general acceptance that are new.

Jan 1, 1936

ANYONE who wishes to make the patterns for statues in order to cast them later in bronze, even though he himself is the artificer who made them, must take many things into consideration: first, whether they are large or small, and whether they are wholly round or only in part; then of what material they are made, for the way that can be followed if they are of wax cannot be used if they are of clay, wood, marble, or even of plaster; likewise he must consider whether or not it has irons inside to support it. There is also a great difference in facility if the support is placed more in. one way than in another. Great consideration should be given to whether it is to be made hollow or solid. If you have not been the workman yourself, you must at least have been an active helper in this and in every other part in order to be able to observe everything without a fault. For if they are large it is necessary to make their moulds in pieces, with marks and measurements so that you can replace them-at will exactly in the same order and in the same places after they have been taken out. But if you are the artificer [as well as sculptor] the process is made easier. Taking the ordinary way and, over an iron, make out of well beaten moulding clay, compounded with cloth clippings a core exactly as the statue is to be or however large you wish the hollow to be. Dry and bake it. On top of this work the wax, thickening it all over as much as you wish the bronze to be and finish it completely, remembering to arrange that the base may come out solid with bronze so as to support the whole work. Then take some rods of hammered bronze one dito thick and one palmo long. Pass these throughs the thickness of the wax and fasten them in several places in the core of clay that you made. [81] Do it so that they, project out of the wax a good three or four dita. These are, put in so that when the wax is removed the core is held in the middle of the mould that forms the outer part, and this outer part is held by the inner part, namely the core, so that the mould may not move in any part from its place even when it is handled. This done, take some of that clay made with well-prepared cloth clippings as I taught you, and mix with it if you wish some wash ashes or

Jan 1, 1942

By Leonard Austin

WHAT Colonel Dwight says regarding the treat-ment of oxidized ores1 holds true also of the silver-lead smelting operations in Utah. The ore sought for was such as would, with appropriate fluxes, yield slag, and "lead bullion," as the lead reduced from the ore and carrying its gold and silver, was called. No matte, and probably little or no speiss, was yielded, and hence there was nothing to roast, either of ore or matte. But, by 1880, when I first took hold in smelting, there was quite a production of matte at the works of the Ger-mania Smelting and Refining Co., Utah, because, by that time, ores containing some pyrite and galena were being smelted. This was due, as at the Grant Works, Denver, to the more attractive price paid for the treatment of such ores. The matte, containing about 5 per cent. copper, was accordingly heap-roasted and returned to the blast furnace for the recovery of its contained metals. By this time there had been built a long-bedded, hand-rabbled reverber-atory roaster with a hearth of about 40 by 10 ft. in size, and in this matte and ore, crushed at the sampling mill, was treated. When, in 1892, I took control of this works, called& now the Germania Lead Works, three other roasters had been added, but the prac-tice of heap-roasting continued. This had the merit of needing no equipment, and of doing good work, because the pieces that were imperfectly roasted went back upon the next roast heap. At this time, when some suitable lump ore was obtainable, I roasted in heaps, in a satisfactory way. By 1892, the Bruckner cylinder roaster had been installed, which, compared with the reverberatory roaster, reduced labor. As such a cylinder revolves, a talus of ore is formed within it and at the same time fresh surfaces are exposed to the air, but the trouble was that the air did not reach to the bottom of the cylinder. This we corrected by placing a steam jet at the fire-box end, to project the air down-ward upon this stagnant ore, thus increasing the speed and completeness of roasting without at the same time increasing dust formation. The firing, if skilfully done, gave a somewhat sintered product, but with certain ores a slight access of heat over the normal would cause accretions to form within the cylinder near the fire end. These could be cut off by running back the fire box and barring off the crusts. It was in 1895 that the Bruckner cylinders at the Arkansas Valley plant, Leadville, were giving unsatis-factory service and I was called in to investigate. The steam jet was put in use as at the Germania Lead Works, but we found that, due to the altitude (10,500 ft.), combustion was feebler than at sea level or even at 4000 to 5000 ft. Later it appears, as Colonel Dwight states, that R. D. Rhodes and Mots sought to increase the air supply by admission through perforated tiles, but the trouble was due to the air itself.

Jan 8, 1922

By Richard Dunmore

Tests of the MRDE firedamp prediction method have been carried out in a number of longwall districts with different conditions. The method itself and its development have been described previously At many test sites the prediction has been good, i.e. the calculated gas emission levels have agreed with measured values, averaged over a period of many weeks, within a few percent. In other cases, where there have been larger discrepancies between calculation and measurement, investigations have shown that these may be attributed to particular conditions of mining or geology. Recognition of these conditions in advance of mining is clearly desirable to improve the accuracy of the initial prediction. It has been shown that variations in gas emission rates depend largely on coal production in terms of the weekly advance of the coal face. Although there appears to be a random element present, variations in gas emission levels calculated from changing face advances agree well with measurement. The accuracy of prediction therefore depends on how well face advance can be forecast and needs to be updated as the working proceeds in the light of the face performance actually achieved. Continuous monitoring of the mine environment provides the information necessary to compare actual gas emission with predicted levels, and computerised systems make it possible to carry this out in real time. Predictions can thus be adjusted to take account of emission levels measured in previous weeks These adjustments, whether they are made after the first few weeks or subsequently during the district life, would also be used to alert management to particular abnormalities or significant changes in gas emission.

Jan 1, 1982

By Horace Pops

Martensitic transformation has been studied during cooling and heating in ß-phase Cu-Zn alloys to which small additions have been made of Ni, Ag, Au, Cd, Ga, In, Si, Ge, Sn, and Sb. The start and finish of the martensitic reaction and the variation of transformation temperature with third-element content were determined by electrical-resistivity measurements from alloys which had either constant zinc contents or constant values of electron concentration. All of the third elements, except nickel, lowered the transformation temperature if the results were plotted along the lines of constant zinc contents in each ternary system. A significant difference in the rate of lowering of the transformation temperature per atomic percent of the third element was observed for elements which had the same nominal valence. No systematic variation of transformation temperature with the valence of the third element was observed. It is suggested that the observed increase in transformation temperature for nickel-bearing alloys is due to the transfer of electrons from the conduction band of the alloy to virtual bound states. However, electron concentration is not the most important factor controlling the instability of the 0 phase. The transformation temperatures of the ternary alloys can be predicted from the following approxilnate expression: Ms (°K) = +3280 - 80 Zn + 8 Ni - 30 Ag - 12 Au - 140 Cd -90 Ga- 145 In - 80 Ge -175 Sn - 120 Si - 150 Sb MOST binary ß -phase alloys based upon the noble metals copper, silver, and gold are unstable at low temperatures and transform spontaneously by a martensitic reaction. This transformation has been studied recently in the ordered bcc ß'-phase Cu-Zn binary al1oys1,2 where the transformation temperature is below the room temperature and decreases with an increase in zinc content. It has been reported that the transformation temperatures can be raised above room temperature by small additions of a third element such as silicon3,5 or gallium,4,5 but no quantitative study has been made. The transformation temperature of different binary alloys can be altered by third-element additions. For example, it was shown that nickel and copper may have a large effect on the Ms temperature of CU-Al6 and Au-cd7 alloys. The present investigation was made to determine systematically the influence of various third elements on the martensite-transformation temperature of Cu-Zn ß-phase alloys. Since these alloys have an electronic origin,' alloy compositions were chosen so that the transformation temperatures could be determined at constant zinc contents or at constant values of electron concentration. I) EXPERIMENTAL PROCEDURE Ten ternary alloy systems were obtained by adding nickel, the noble metals silver and gold, and some B-subgroup elements to a Cu-Zn matrix. These are arranged according to their rows and columns in the Period Table as follows: Each ternary alloy was prepared by melting and casting weighed quantities of high-purity metals (99.99+ pct) in sealed quartz tubes under a partial pressure of helium to make a 4-g ingot. The molten alloys were shaken vigorously and then quenched in water. Since the weight loss was negligible, the compositions of the ingots after casting and annealing were assumed to be the same as the nominal compositions. The ingots were homogenized after casting in helium-filled Vycor tubes for 24 hr at temperatures between 750" and 810 C and quenched into brine. Metallographic examination revealed that all alloys were homogeneous, poly crystalline ß-phase alloys, and that the grain size was in the range 1 to 5 mm. Electrical-resistivity measurements were made to determine transformation temperatures of the ternary alloys during continuous cooling or heating. Transformation temperatures of the ternary alloys can be determined by electrical-resistivity measurements since the resistance of the martensitic phase is much higher than that of the 0' phase. The technique has been described previously in connection with a study of Au-Zn alloys.9 The reproducibility of transformation temperature was approximately ±6°C. II)RESULTS A hysteresis was always observed in electrical-resistivity curves and was usually less than about 12°C.

Jan 1, 1967

By E. V. Potter, H. C. Lukens

THE volume of hydrogen released from electrolytic manganese at various temperatures and pressures was determined in a previous investigation1 as part of a study to determine the most practical procedure for removing the hydrogen from electrolytic manganese metal. No attempt was made to determine the absolute volume of gas in the metal at any temperature and pressure; the volume of gas released showed only the variation in solubility with temperature and pressure. The results were very similar to those obtained by Sieverts and Moritz.2 Both sets of data show a minimum solubility between 500° and 700°C., but they differ in certain respects; on cooling from 500°C., our results showed an increase in solubility of about 7 C.C. as compared with an increase of 34 C.C. per 100 grams shown by Sieverts. Furthermore, the transition temperatures, as indicated by sharp breaks in the solubility curves, did not agree well with Sieverts' data. This information was of secondary importance in the earlier investigations, and the solubility at low temperatures and the transition temperatures were subject to considerable error. There- fore, a subsequent investigation, reported in this paper, was made to measure the absolute solubility at temperatures from room temperature through the melting point and make more accurate observations of the transition temperatures. APPARATUS AND METHOD The apparatus and method were essentially the same as those described in the previous work,1 as shown in Fig, I. At high temperatures, the small tube containing the thermocouple in the sample container A frequently broke off, so for some of this work the thermocouple was placed outside the sample container and protected by a quartz tube of about the same wall thickness as the sample container. No significant difference was found in the transition temperatures obtained in the two ways. The automatic temperature controller was used in these tests in the regions where there was little change in solubility with temperature. In the neighborhood of the transition points a continuously variable autotransformer was used instead of the automatic controller, and the power input to the furnace was adjusted so that the temperature increased or decreased at a very slow, uniform rate through the transition range. This procedure was followed because the temperature oscillations produced by the controller were too great compared with the transition range, and the transition points determined under such conditions were less accurate. ABSOLUTE SOLUBILITY Procedure and Results The absolute solubility of hydrogen in manganese could be determined most

Jan 1, 1946

By N. Mungan

Formation damage, i.e.. reduclion in permeability, has been generally attribuled to clay minerals which expand or disperse upon contact with water that is less saline than the connate water. Luboratory, studies show that penneahility reduction can also occur in formalions containing only nonexpandable clays such as illite or kaolinite, and can be caused also by changes in pH. Furthermore, pH changes can damage even formations that are essentially free of clays. It is suggested that permeability reduction is due to the small passages being blocked by particles, which may be dispersed clays, cemenlion material or other fine parricles. These particles are dislodged by dispersion of clays due to changes in salinity or by dissolution of calcareous cement by acids, or of silicaceous cement by alkaline solutions. In working with reservoir cores, it was found that extracted cores damaged more easily and extensively than nonextracted cores. The extent of damage depended also on tenlperatltre. INTRODUCTION Permeability is an important property of porous media and has been the subject of many studies by engineers and geologists. Many of these studies are conccrned with formation damage, i.e., reduction in permeability, resulting from exposure of oil-producing formations to water substantially less saline than the connate water. This effect causes understandable concern since during drilling, completion and production phases formations are often exposed to fresh water. The damage resulting from contact with relatively fresh water has been attributed to expansion and dispersion oF clay minerals. During laboratory investigation of the use of NaOH as a wettability reversal agent to increase oil recovery from oil-wet reservoirs, several cores used in the displacement studies suffered loss in permeability. Despite the traditional usage of NaOH for conditioning aqueous mud systems, the role of the caustic filtrate in wellbore damage seems to have been overlooked. Browning2 as recently reported on the effects of NaOH in dispersing clay minerals but he was concerned only with complications that may arise in drilling massive shale beds. The following study was made to examine the role of pH and salinity changes in core damage. Where cores from reservoirs were used, tests were performed with extracted and nonextracted cores both at room and reser- voir temperatures, since it was felt that the test environment and core condition may affect the results. Because of its limited coverage and exploratory nature, this study is not intended to provide answers to field formation damage problems. It is hoped that it will encourage research into new aspects of the permeability reduction problems, particularly those allied to new recovery and production processes. PROCEDURE In all permeability tests, fluids were pumped through the cores at a constant volumetric rate. Only deaerated fluids and reagent grade chemicals were used. The fluids were passed through two ultrafine filters before injection to remove any entrained particles. The cores, with the exception of the unconsolidated cores, were mounted in Hassler holders. Water was used to transmit pressure to the sleeve. The inlet endpiece had two entry ports which permitted scavenging one fluid with another to avoid any mixing in the small holdup volume. The cores were flushed with CO2 gas, evacuated for 5 to 6 hours and saturated with the first liquid at a pressure of 1,000 psi for 24 hours to eliminate any free gas from the cores. Pressure differences up to 20 psi were measured by transducers, calibrated in inches of water and continuously recorded. For greater pressure drops, gauges were used. All reservoir cores were cleaned with a light refined mineral oil, then with heptane, and finally dried with CO2. Compatibility tests showed that no precipitates formed when mineral oil and the crudes were mixed. Some cores were extracted in Dean-Stark-type solvent extractors using xylene and trichloroethane and dried in a vacuum oven at 450F. Each test consisted of a sequence of water, test solution, and again water flow. RESULTS AND DISCUSSION STUDIES IN BEREA CORES Salinity Contrast Berea cores 2-in. in diameter and 12-in. long were cut from sandstone quarried in Cleveland, Ohio. The clay minerals were identified by X-ray diffraction to be chlorite, kaolinite, illite and incerlayered illite. Flow of fresh water or 30,000 ppm brinc does not cause any permeability reduction (Fig. 1). However, after injection of brine the core is readily damaged by fresh water. Damage starts almost instantly as the fresh water injection is begun, and at a cumulative injection of 1.2 PV fresh water, the permeability has dropped from 190 to 0.9 md. Upon continued injection, the effluent contains clay minerals dislodged from the core. The final core per-

Jan 1, 1966

By G. Broughton

For the past few years a great amount of work has been done on the viscosity characteristics and gelation of clay suspensions, much of which has been reported in papers published by the Institute.7,12,18,19,24 Impor-tant reviews have been made elsewhere by Evans and Reid,10 Marshall20 and Clews, Macey and Rigby,8 the last two on the general properties of clay. It is unnecessary, therefore, to recapitulate past work beyond recalling that three explanations for the high viscosity and gelation of clay suspensions have been put forward. For lack of more exact nomencla-ture, these may be called the water hull,16 mechanical interference" and attraction-repulsion" theories. The first pictures the clay particles as surrounded by relatively rigid water envelopes, which increase effective volume; the second emphasizes the mechanical interference of platy particles or their agglomerates; while in the third the particles are assumed to be held relatively rigidly at a distance from each other determined by the balance between the attractive (van der Waal's) forces and the elec-trical repulsions of the charges. 13,14 This article presents fresh data on clay suspensions, particularly on the influence of previous flow history of the suspensions, specific contra-ions, temperature, solvation and particle size, in an attempt to contribute to the solution of the problem.

Jan 1, 1938