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By R. W. Smith

Many industries such as the cement industry handle large quantities of limestone and clay slurries. However, at present very little is known about the flow properties, such as friction loss due to flow of slurries in pipelines. This lack of knowledge has made it often very difficult to calculate the total dynamic head of a proposed slurry handling system, and therefore has often made the selection of correct size slurry handling equipment difficult. Because of lack of knowledge about slurry flow a study of slurry flow theory has been made at the Portland Cement Association's Research and Development Laboratory with the idea of developing a method whereby friction losses due to slurry flow may be predicted for any size pipeline. The flow equations developed have been checked by pilot plant size equipment. DERIVATION OF FLOW EQUATIONS It has been known for some time that limestone and clay slurries handled in cement plants do not flow in the same manner as a Newtonian fluid such as water. When a Newtonian fluid flows the shear stress at any flow velocity is proportional to the rate of shear. This phenomenon can be illustrated by a line (Figure 1). The viscosity of the fluid is the slope of the curve. Thus, the flow properties of the material may be characterized by a single materials constant: viscosity. When a non-Newtonian fluid with the type of characteristics exhibited by limestone and clay slurr-ries flow, a similar curve can be constructed (Figure 2). This graph is a shear diagram of a Bingham plastic non-Newtonian fluid. It should be noted that with the Bingham(1) plastic type of flow viscosity, the slope of the curve, is still an important materials constant. In addition, however, there is another materials constant, namely the yield stress of the material. One way to visualize this constant is to consider it as the amount of energy that must be put into a Bingham plastic material to start it flowing.

Jan 1, 1961

EDMUND NEWTON, Minneapolis, Minn. (communication to the Secretary?).-In discussing the question of the deoxidation of steel and material suitable for performing this function at the end of the heat, it would seem logical also to include the question of prevention of oxidation in the steel or the formation of iron oxide, FeO. I refer to the use of manganese in the basic open-hearth and basic Bessemer processes. The advantages of high manganese in pig iron for these processes have evidently been clearly understood in Germany for a number of years, although little has been written in regard to the exact manner in which the benefits are obtained. In this country, while we make no steel by the basic Bessemer process, our basic open-hearth process is becoming more and more important. Until 10 years ago, in this country, manganese in the pig iron for this process was considered of little value and by many writers it was spoken of as a disadvantage. During the past 10 years, however, in certain parts of the United States, higher contents of manganese in basic pig have been used with considerable success, although there is apparently nothing in our technical literature to show the reasons for this trend. A German book, "The Basic Open-Hearth Steel Process" by Carl Dichmann does, however, offer an explanation. Dichmann says that if the charge for either of the above-mentioned processes contains 3 per cent. of manganese or above, satisfactory steel.

Jan 6, 1917

By Charles H. Thurman

THE data given herein were first included in a paper read before San Francisco Section, A.I.M.E., in October 1940, and are applicable to conditions existing until the gold-dredging industry was temporarily suspended by Order L-208 of the War Production Board in the fall of 1942. There is no doubt that gold dredging will be resumed at some future time, and on a scale equivalent to that of the recent past, but the cost data given herein will be affected to some extent by conditions existing at that time, and by labor rates and prices for materials then prevailing. DRAGLINE VS. BUCKET-LINE Dragline dredges should not be considered for mining large areas of low-grade placer gravel. In such deposits a dragline operator with a 5-cu. yd. dragline would be doing well to maintain an operating cost of 6¢ per cu. yd., while a bucket-line dredge with buckets no smaller than 7 cu. ft. each could be operated for less than 4¢ per cu. yd. By operating costs, I mean only field charges such as direct operating and overhead, which includes pay roll, power or fuel, repairs and maintenance, insurance, land clearing and general expenses, but not including such items as prospecting, depletion, depreciation of equipment, State Franchise Tax, or Federal Income Tax. It is not to be inferred that a dragline dredge cannot make a profit in small low-grade deposits, where the extent of a given property is too small to justify the use of the more costly bucket-line dredge. Consider small deposits of 10¢ gravel. It is obvious that a deposit of 5,000,000 cu. yd. of such gravel could not be mined profitably with a new, 7-cu. ft. bucket-line dredge, costing upward of $250,000, and with operation costs at 4¢ per cu. yd., paying for land or royalties out of earnings; nor could a new combination 5-cu. yd. dragline and washing plant, worth upward of $125,000 and working at 6¢ per cu. yd., make a profit. These comparisons are made because the hourly capacity of both types of dredges is nearly the same. The bucket-line dredge averages 93 per cent operating time in 24 hr., as against about 80 per cent or less for the dragline dredge. These percentages of operating time are important factors in making a comparison of this kind. The bucket-line dredge has greater efficiency in cleaning soft bedrock, usually characteristic of dredging deposits, and a 7-cu. ft. bucket-line dredge can be efficient to a total digging depth of 80 ft. (65 ft. below water, 15 ft. above). A 5-cu. yd. dragline dredge is limited to about 30 ft. of efficient digging depth, 5 ft. of which could be above water. In small areas of gravel not over 30 ft. deep, a 5-cu. yd. dragline dredge could make a profit where a bucket-line dredge could not do so. As an example: compare the dredging of 3,000,000 cu. yd. of 10¢ gravel 28 ft. deep with bucket line, costing 4¢ per cu. yd., and with a 5-cu. yd. dragline dredge operating at 6¢ per cu. yd. Because of small yardage, new equipment is not warranted, therefore we can assume that the dredges of both types are used equipment, fully depreciated. Dismantling, mov-

Jan 1, 1945

By L. T. Stanley

A method is described whereby the behavior of the front is approximated when gas is injected into a thick reservoir having reasonably homogeneous properties. The method is applied to the Abqaiq field of Saudi Arabia. The producing member is the Arab-D, a high-permeability calcarenite which has no continuous betlding planes. Field performance indicates the injected gas to be partially miscible with the reservoir oil because gas volume factors experienced are lower than those predicted by the gas law. Eqlrilibril~m calculations confirnz ihis and also show that the volume factor may vary appreciably, depending on the relative quantities of oil and gas in contact in the reservoir; consequently, volutnetric balances are made for the purpose of determining the behavior of the gas volume factor during injection history. The effect of gravity segregation on position and shape of the gas front is approximated by dividing the producing section into three zones vertically and tracing the movement of the average interface in each zone, with counterflow of oil and gas taking place betweell zones behind the front. This results in a gas front that advances more rapidly along the top of [he formation than along the base, producing an "umbrella" effect in cross section that becomes more pronounced as the front progresses. The calculations cover the gas-injection period of Abqaiq field history through 1958, and the position of the gas front is plotted at one-year intervals. Finally, some comparisotls between the calcrlated fronial position and the gas-oil contact as Measured by neutron logs are made. INTRODUCTION Fig. 1 is a structure contour map of the Abqaiq field. For analytical purpcses, the field has been divided into two areas designated A and B, as shown on the map. Gas injection into Area A was begun in early 1954 into two wells located near the crest of the structure on the north-south axis of the anticline. During the period covered by this paper, the average injection rate has been 122 MMscf/D with a maximum sustained rate of 160 MMscf/D. The reservoir pressure has been maintained at 2,450 psig since start of gas injection. The reservoir originally was undersaturated but, prior to pressure maintenance, the pressure was drawn below the bubble point in most of the Area A section, creating an in-place free-gas saturation of 8 per cent at the crest of the structure. The average critical gas saturation is 13 per cent established by laboratcry core tests. That the entire reservoir remained below critical gas saturation prior to gas injection is borne out by the fact that none of the crestal wells have exhibited high gas-oil ratios during production history. The Area A reservoir is a carbonate section about 200-ft thick having average porosity and permeability of the order of 22 per cent and 500 md, respectively. The productive horizon is the Arab-D member of Jurassic age and is encountered at an average depth of

By William E. Ford, Edward Salisbury Dana

The Nitrates being largely soluble in water play but an unimportant r81e i~ Mineralogy. SODA NITER. Rhombohedral. Axis c = 0.8276; rr" 1071 A 7101 = 73' 30'. Homeo- morphous with calcite. Usually massive form, as an incrustation or in beds. Cleavage: r (1011) perfect. Fracture conchoidal, seldom observable. Rather sectile. H. = 1.5-2. G. = 2'262.29. Luster vitreous. Color white; also reddish brown, gray and lemon-yellow. Transparent. Taste cooling. Optically -. w = 1'5874, e = 1'3361. Camp. - Sodium nitrate, NaN03 = Nitrogen pentoxide 63'5, soda 36'5 = 100.

Jan 1, 1922

By J. B. Morrow, D. H. Davis

THERE are two general approaches to the problem of increasing profits from an operation. One is to lower expense; the other is to raise income. Mechanical preparation of coal may be used for either purpose but a prudent consideration of many details must precede any decision lest the results be negative instead of positive. It is quite possible that any net gain will result from a combination of the two. Since mechanically prepared coal invariably is a better product qualitatively than a hand-picked coal from the same mine, it is a reason- able expectation that the customer will be willing to increase the producer's income by paying a higher price. Or there may be the possibility that a combination of mechanical mining plus mechanical cleaning will give a lower over-all production cost for the coal in the railroad car. More likely, there will be found a combination of these two factors. From the customer's point of view, the competitive delivered cost per B.t.u. considered in relation to such incidental factors as dust nuisance, handling properties, ash disposal, and ash fusibility determines what he will pay. In a bulk tonnage product such as coal, freight is a very considerable part of the delivered fuel cost, and obviously freight paid on incombustible ash has no economic attractions. INCENTIVE FOR CLEANING Coal is prepared in four major ways: 1 (I) by screening or sizing, (a) by mixing or blending, (3) by cleaning, including hand picking and mechanical cleaning, (4) by dustless treatment. By a combination of any or all of these methods, coal can be prepared to standard specifications. It is easily possible to have good cleaning and still get a poor final product because of faulty screening or mixing,

Jan 1, 1943

By Fred P. Peters

T. D. Yensen.*—As my information is of a negative nature, I think it belongs under this paper. We are particularly interested in magnetic materials and we would like very much on occasions to make use of powder metallurgy. We have tried repeatedly to use powder metallurgy in preparing our nickel alloys but always. with negative results; that is, we cannot get as good magnetic properties by powder metallurgy as we can by starting with a molten material. We have tried by all possible means to make materials' like 50 per cent iron-nickel alloys by powder metallurgy. The compacts can be regularly lorged and rolled but no matter what we do in the way of annealing, the magnetic properties come out very much poorer than if we start with molten material. F. V. Lenel. †—I want to mention one characteristic of articles made from metal powders which distinguishes them from die castings; that is, their wear resistance. Die castings usually are made from zinc or aluminum alloys and a few copper-zinc alloys; all of them are comparatively soft and not very wear resistant. I know of a number of cases where powder metallurgy rather than the die-casting method was used for producing a certain part because higher wear resistance was needed than could be attained in die castings. A, J. LanghammeR.*—The subject of powder metallurgy is somewhat difficult to discuss, and portray, in the time that his been allotted. Most of you would rightly be bored if we went into details. However, I will cite one incident that possibly will help illustrate some of the potentials. Last summer I was in Washington and met Navy officials for the purpose of studying the possibility of making a certain part by powder metallurgy. The part is highly intricate and I happened to remark that the material cost would be high; that is, the cost on one raw material. Promptly a high-ranking Navy officer said: "Mr. Langhammer, if you must pay x dollars a pound for the raw material, but achieve the desired results, the cost of the finished part would still be low."

Jan 1, 1945

By G. Derge, Lo Ching Chang

The chemical and physical propertties of slag systems are of special interest to metallurgists, for nearly all metals are in contact with molten slags during the primary reduction from their ores and then during the subsequent refining and alloying processes that determine their ultimate use. These processes are carried out at high temperatures and involve such complex chemical systems that funda-mental scientific knowledge of the Properties and behavior of these slags is inadequate. Various hypotheses have been Proposed to explain known slag characteristics. The commonest of these regard the molten slag as constituted of compounds that are dissociated in varying degrees into their constituent oxides, as illustrated by Schenckl and the recent Papers of Chipman and co-authors. Another proposal is that these compounds dissociate by com-plete6 or partial ionization, the evidence for which has been reviewed by Martin and Derge.? whatever hypothesis is favored, the exact formulation of these compounds is incomplete. It is based on three principal types of information: 1. Studies of solidified 51% samples by X ray diffraction, petrography, and similar methods that can be used at room temperature. The correlation of this information with the high-temperature properties of the molten slag is uncertain. 2. Studies of slag-metal equilibria, which have the advantage of providing observations on the molten slag at high temperature. However, even these data present problems of interpretation because they require a complete knowledge of the metal phase. 3. Direct measurements of properties of molten slag at the temperature of greatest metallurgical interest. Viscosity, electrical conductivity, specific heats, and similar properties have been measured, but the data of this type are widely scattered and frequently difficult to interpret. Additional direct measurements of properties of molten slag that can be interpreted in terms of chemical behavior are required, and this paper shows that the standard physical-chemical measurement of reversible electrode potentials, which measure the activity of specific constituents, is a fruitful source of such information. The purpose of this investigation, therefore, was to find an electrode combination that would yield reversible electromotive force measurements when dipped into the molten slag to be studied. Slags of the systems cao-sio2 and cao-120,-SiO2 were chosen for study because graphite containers could be used and the data could be correlated with those for viscosity, conductivity, and other proper-

Jan 1, 1948

By G. Derge

The chemical and physical propertties of slag systems are of special interest to metallurgists, for nearly all metals are in contact with molten slags during the primary reduction from their ores and then during the subsequent refining and alloying processes that determine their ultimate use. These processes are carried out at high temperatures and involve such complex chemical systems that funda-mental scientific knowledge of the Properties and behavior of these slags is inadequate. Various hypotheses have been Proposed to explain known slag characteristics. The commonest of these regard the molten slag as constituted of compounds that are dissociated in varying degrees into their constituent oxides, as illustrated by Schenckl and the recent Papers of Chipman and co-authors. Another proposal is that these compounds dissociate by com-plete6 or partial ionization, the evidence for which has been reviewed by Martin and Derge.? whatever hypothesis is favored, the exact formulation of these compounds is incomplete. It is based on three principal types of information: 1. Studies of solidified 51% samples by X ray diffraction, petrography, and similar methods that can be used at room temperature. The correlation of this information with the high-temperature properties of the molten slag is uncertain. 2. Studies of slag-metal equilibria, which have the advantage of providing observations on the molten slag at high temperature. However, even these data present problems of interpretation because they require a complete knowledge of the metal phase. 3. Direct measurements of properties of molten slag at the temperature of greatest metallurgical interest. Viscosity, electrical conductivity, specific heats, and similar properties have been measured, but the data of this type are widely scattered and frequently difficult to interpret. Additional direct measurements of properties of molten slag that can be interpreted in terms of chemical behavior are required, and this paper shows that the standard physical-chemical measurement of reversible electrode potentials, which measure the activity of specific constituents, is a fruitful source of such information. The purpose of this investigation, therefore, was to find an electrode combination that would yield reversible electromotive force measurements when dipped into the molten slag to be studied. Slags of the systems cao-sio2 and cao-120,-SiO2 were chosen for study because graphite containers could be used and the data could be correlated with those for viscosity, conductivity, and other proper-

Jan 1, 1948

By E. W. Lithgow, E. G. Williams, R. R. Holbrook, B. R. Wilson

The mineralogy and geochemistry of Pennsylvanian shales and underclays were studied to determine their suitability for lightweight aggregate and refractory ladle brick. Eighty percent of the variation in bloating of shales and clays was explained by the variation of Si02, A1203, and fluxes (Fe203, MgO, CaO, Na20, and K20); 60% by variation in quartz, kaolinite, illite, and chlorite. The best bloating was exhibited by marine shales, whereas freshwater shales and underclays experienced little or no expansion. Regional paleogeographic maps o f Pottsville and Allegheny shales permit bloating to be geographically predicted. It was found that clays meeting the specifications for refractory ladle bricks were obtained from underclays having over 34.5% mica, over 40% kaolinite and less than 15% quartz. Underclays of this composition are confined to the lower Allegheney outcropping along the near-margins of the coal basin. The best clay is that underlying the Lower Kittanning coal. Porosity of the first fired brick was found to be inversely correlated with reheat expansion.

Jan 1, 1975

By H. Fechtig, R. H. Buck, A. G. Guy

MULTIPHASE diffusion has been studied for many years in two-component systems1,2 and many of the experimental aspects are now fairly well understood.314 Although by no means all of the problems connected with the two-component case have been solved,' attention has recently been directed to the more complex situation involving three components. The pioneer work of Clark and Rhines6 yielded a qualitative picture of the types of behavior that can occur, and Clark7 has suggested conventions for describing the various phenomena. Kirkaldy and co-workers8,9 have made quantitative studies in several ternary systems and have offered explanations of the occurrence of isolated and nonisolated precipitates. At present, however, there is no comprehensive theory for the variety of phenomena observed in ternary, multiphase diffusion. By analogy with several studies that have been made of multiphase diffusion in the binary Cu-Zn system,2'10'11 a similar exploratory study was made of Cu-Zn-Ni alloys lying along the line in the ternary diagram from the point 80 Cu-20 Ni to the zinc corner of the diagram, Fig. 1. A principal question to be answered was whether initially plane interfaces would remain plane during the course of one-dimensional diffusion. The diffusion specimens studied are described in Table I. The five separate alloys from which they were made were melted in evacuated Vycor capsules from 99.9 pct purity copper, zinc, and nickel. Since some of the alloys were too brittle to be swaged, all of the alloys were used in the cast condition. To facilitate later homogenization, the molten alloys were solidified by plunging the capsule in water. Homogenization heat treatment was done at 720°C for 20 hr. The five nominal compositions in weight percent zinc and nickel, respectively, were: 37.5, 12.5; 44.0, 11.2; 50.0, 10.0; 55.0, 9.0; 65.0, 7.0. Ln Table I the alloys are identified only by their zinc content. Sandwich-type diffusion specimens were prepared by pressure welding disk specimens, each about 3 mm high by 10 mm in diameter. Welding was done in a special threaded vise which was heated at 500°C for about an hour in an atmosphere of flowing hydrogen. A measurement of the separation of the phase interfaces was made on a polished flat on the welded specimen, and then the specimen was sealed in an evacuated capsule and given the diffusion treatment shown in Table I. The diffused specimen was sectioned longitudinally

Jan 1, 1965

By P. C. Johnson, B. A. Stein

This paper describes a study of the effects of combined heat treatment and explosive loading on the mechanical properties of high-strength steels. nis program investigated two distinct areas: 1) the effect of shock waves, without gross irreversible defmmution, on a 3-Cr steel at various stages of heat treatment; and 2) the effect of rapid deformation (explosive forming) on H-11 and D6-AC steels in the metastable austenitic state. The mechanical properties of these steels were improved, in some cases markedly, as a result of these treatments. ,AUSFORMWG, which requires the plastic deformation of metastable austenite, is a process which can appreciably improve the properties of selected alloy stee1s.l,2 The Ausform process significantly increases the strength of these steels without decreasing their ductility. The properties at high temperatures are also improved through a change in the response of the steels to tempering. Although the mechanism by which ausforming alters the properties of these steels is not fully understood, it appears that the dislocation arrays produced by deformation of the metastable austenite influence the structure of the martensite on subsequent transformation. This, in turn, affects the strength, ductility, and tempering response of the martensite. This research used chemical explosives to deform steels at various stages in their heat treatment in order to improve the properties of these steels. The explosive energy is used in two ways; 1) high-pressure shock waves are propagated through the steel to produce extensive microscopic shear strain without causing a large irreversible change in shape, and 2) explosive energy is used to cause extensive macroscopic plastic strain in the metastable austenitic state (explosive forming). I) AUSFORMING WITH INTENSE SHOCK WAVES The steel used in this phase of the research was an alloy having a nominal composition 0.43 pct C, 3.0 pct Cr, 1.5 pct Ni, and 1.5 pct Si. The steel was subjected to intense shock waves in three conditions: 1) in the metastable austenitic state, 2) in the tempered mar tens itic state, and 3) in the tempered martensitic state after ausforming by conventional techniques. The specimens were in the form of disks 2.75 in. in diam and 5/16 in. thick. These were incorporated into a specimen assembly consisting of two disks pressed into a 5 by 5 by 1 in. block of stainless steel, Fig. 1. Spalling (or scabbing) is confined to the front disk. The specimen is protected from oxidation and decarburization by the surrounding metal. The temperature of the assembly is monitored by a thermocouple inserted into one side of the stainless steel block. The assembly is positioned over an oil reservoir which serves both as a means of catching the disks and as quenching medium for the disks shocked under ausforming conditions. Plane shock waves are introduced into the assembly by a metal driver plate impacting the top surface of the block. The driver plate is accelerated by a chemical explosive sheet supplied by E. I. du Pont de Nemours & Co. All the specimens were subjected to plane shock waves having a peak pressure of approximately 430 kbar. The pressure is that quoted by G. E. Dieter for the plane wave generator used in this work.' The driver plate used was 1/4 in. thick, so that the initial pulse was essentially a l/2-in.-wide square wave. The attenuation of the peak pressure during the subsequent 1/4 in. is estimated to be less than 5 pct. The shock front induces a temperature rise, a portion of which is irreversible. Rough estimates (+25 pct) of this temperature rise have been made for iron shocked at room temperature.4 For a 500-kbar shock wave, the temperature rise in the shock front is about 700°F, and is held for a time of the order of microseconds. The irreversible temperature rise, which remains after the shock wave passes, is about 450°F.4 The disks are quenched to room temperature within a few seconds of the shock treatment. It should be emphasized that the temperature rises given above are estimates for pure iron at room temperature, and are not necessarily true for the tests made in this work. The disks shocked at temperatures in the metastable austenitic range were austenitized in the stainless steel assembly in a furnace protected from the firing area. The assembly was removed from the furnace and placed over the recovery reservoir. The plane wave generator was then positioned and

Jan 1, 1963

By J. W. Givens, P. B. Crawford

A potentiometric model study has been made of the effect of vertical fractures existing in the matrix of the reservoir on the flooding or cycling performance. Fractures can have unusual flow characteristics. Fluid entering one side of a fracture can emerge on either the same or opposite side of the fracture, depending on the particular streamline. Fracture orientation has a great influence on the sweep efficiency. However, sustained fluid injection may still permit large areas to be swept. INTRODUCTION One can find considerable information available in the literature on the effect of fractures originating at the wellbore on sweep efficiencies of water-flooding or gas cycling programs.1-5 However, there arc few, if any, quantitative data reported in the literature on the effect of vertical or horizontal fractures existing out in the reservoir matrix on secondary recovery performance. Several papers have been presented on the effect of vertical and horizontal fractures on the productivity or conductivity of waterflood and gas injection patterns, but in all cases the fractures initiated at the well and simulated commercial fractures.6,7 It is believed that natural fractures may exist out in the reservoir matrix and would effect the displacement performance. The purpose of this report was to study the effect of a few isolated vertical fractures existing out in the reservoir matrix on the performance of waterflood or gas injection patterns. DESCRIPTION AND EQUIPMENT Since the potentiometric model was described by Lee8 it has been widely used to study numerous types of fluid displacement problems. The potentio- metric model can be used for fluid displacement studies when the following assumptions are valid: (a) steady-state conditions exist; (b) the mobilicy ratio is one; and (c) the capillary and gravitational effects can be neglected. Five-spot and direct line drive square patterns were studied using a copper strip of the desired length and orientation to simulate a vertical fracture in the reservoir matrix. The 20 x 20-in. model was considered to represent only one element of an infinite array of similar patterns. DISCUSSION AND RESULTS FIVE-SPOT PATTERN — ONE FRACTURE BETWEEN INJECTION AND PRODUCING WELLS Fig. 1 shows a quadrant of a five-spot pattem with the vertical fracture existing out in the matrix along a line connecting the injection and producing wells. Length of the fracture was equal to 35.4 per cent of the distance between injection and producing wells. In this particular pattern it is noted that fluid breaks through from the injection well to the producing well when the dimensionless time is equivalent to 26.9. Dimensionless time is defined as volume of fluid injected divided by the volume of displaceable fluid in the pattem expressed as a per cent. The cross-hatched areas of this

Jan 1, 1967

By O. P. Arora, M. Metzger, G. R. Ramagopal

The rates of grain boundary and general corrosion were surveyed by an approximate method. Quantitative differences between their variations with the strength or cupric ion content of the acid yielded large variations in their ratio, highly selective intergranular attack being observed only under specific chemical conditions. The boundary corrosion rate increased with the copper content of the aluminum; this was attributed to an autocatalytic effect similar to the one shown for general corrosion. High- purity aluminum in hydrochloric acid exhibits striking intergranular corrosion and other structure-dependent corrosion phenomena of fundamental interest. The behavior is highly sensitive to the metallurgical and chemical conditions, the significance of many of which has not been established. The features of the intergranular-corrosion phenomenon, first described by Rohrman,l are summarized in the remainder of this paragraph. Strong attack normally occurs only at high-angle grain boundaries.' Usually 15 to 25 pctHCl is used to obtain a high rate, but this has also been obtained with weaker (7 to 15 pct) acid either by adding cupric or ferric ion to the acid3-5 or by passing an anodic current (-0.1 ma per sq cm).2,3,5,6 The two latter corrosion conditions produce strong attack of low-angle boundaries after certain heat treatments 2-4,5,7 The susceptibility of high-angle boundaries is influenced by the grain-boundary segregation of iron atoms; this increases the slow (µ per month) attack in 10 pct HCl8 but diminishes the rapid (mm per month) attack in 20 pct Hc14 (the present and most previous investigations deal with rapid attack). That segregation of elements other than iron affects intergranular corrosion has not been demonstrated, although analysis of data for iron alloys indicated that at least one other element must be considered.9 Intergranular attack occurs over a wide range of purity although it begins to become obscured above several hundred parts per million (ppm) total im- purities by the severe general corrosion which accompanies the higher iron contents and which is associated with the presence of a second phase or an inhomogeneous distribution of the dissolved iron.4,6,10 The variation of intergranular-corrosion rate with heat treatment1'3-6'"10 can be explained in some cases in terms of the distribution of the iron impurity but is not in general adequately understood. The present work dealt with two questions not previously considered in detail. The first proceeded from the view that the extent to which a special behavior is associated with the boundaries is indicated not by the intergranular corrosion rate alone but by the ratio of the intergranular to the general corrosion rate. A comparison of the two rates was therefore made for one lot of aluminum in acids of varying strength and metallic ion content. The second question was the effect of the copper content of the aluminum. For general corrosion, it has long been known that copper ions introduced into the acid by corrosion of the solid solution are reduced on the aluminum as patches of elemental copper which enhance the corrosion rate by providing cathodes of lower hydrogen overvoltage than were originally present.''-'3 Since the copper patches remain themselves unchanged, their action is "catalytic", and since they are products of corrosion, the effect is "autocatalytic." This phenomenon is significant at copper levels much lower than previously suspected, even at those typical of high-purity aluminum, as the authors have shown in a previous paper.l4 The present work shows that copper content affects intergranular corrosion. With polycrystalline specimens, truly quantitative rate measurernents are not readily made for intergranular corrosion or for general corrosion in the presence of rapid intergranular attack, and previous work in this field has tended to be qualitative. The present study made use of a simple procedure which provided fair approximations to the quantitative corrosion rates and fitted the purpose of surveying the behavior over % wide range of conditions and displaying certain large effects. The approximations involved in this work were usually outweighed by the experimental scatter, which tends to be substantial in a system as sensitive as this one. I) EXPERIMENTAL A. Material. The material procured, Table I, represented three low copper (1 to 3 ppm) lots, two of "normal" copper content (21 and 22 ppm), and two

Jan 1, 1962

By Charles H. Fulton

There are comparatively few accurate data on the melting-or the freezing-point temperature of metallurgical slags, or on related physical phenomena, such as fluidity near the melting-point, specific heat, latent heat, etc. With the exception of the work of H. 0. Hofman,' and some older work by R. Akerman, P. Gredt, and H. M. Howe, no information is available that is of direct interest to the metallurgist. Hofman's valuable work is the only one that refers to slags produced in the metallurgy of copper and lead. The classic work of J. H. L. Vogt,2 who views slags from the standpoint of physical mixtures (solutions in which the entities are minerals), has opened up a new field in the study of slags, and has placed the investigation of such properties as melting-temperatures, etc., on a rational basis. The recent work of A. L. Day, E. T. Allen, and W. I?. White, of the Carnegie Institution, at Washington, and of European investigators3 on certain systems of silicate minerals confirms the value of the investigation of silicate series from this standpoint, and it is my aim to apply this method to metallurgical slags, in order to gain exact data of value in metallurgy. The work recorded in the present paper is the result of an investigation of reverberatory-furnace slags made for a Western smelting company to determine exactly the influence of change in composition, within comparatively narrow limits, on the melting-point. For a general discussion concerning the mineralogical character of slags and the principles on which this investigation is based, reference should be made to other work: for the subject is too large to be stated in this paper, except very briefly in the following outline:

Jan 1, 1913

By John T. Norton

N order to attempt to arrive at a better under-Jl standing of the whole basic problem of sintering, these remarks will serve as an introduction for discussion that is included and will, perhaps, help to isolate specific questions which need to be answered or to suggest some definite avenues of investigation which should be followed. To bring some sort of logical order into the presentation, I will consider the various types of interaction between the metal to be sintered and the atmosphere which surrounds it, depending upon whether the phenomena are essentially chemical or physical in nature. For example, when the only necessary criterion for the satisfactory sintering of a certain powder is the removal of an oxide skin, then the problem of choosing a suitable atmosphere is primarily chemical; however, if a special surface condition as a consequence of the oxide skin removal is necessary for particularly effective sintering, then the problem becomes a physical one. Of course, the two aspects overlap considerably, but it may be possible to make a distinction in principle if not in practice. The chemical characteristics of the phenomena will be emphasized, since these are the better known. Metal-gas reactions involved in sintering are controlled primarily by the thermodynamics of the processes involved. In which direction will a reaction go and how far before it stops? The answer is to be found in the magnitude of the free energy change associated with the reaction. If a constituent is to be removed from the specimen as completely as possible or if a constituent is to be formed in the specimen as completely as possible, then one chooses conditions which are far from equilibrium so that the reaction is driven toward completion. On the other hand, if the composition is to be maintained at a desired value, then conditions are adjusted as closely as possible to the equilibrium point. This aspect of the problem is susceptible to quite precise analysis, provided, of course, that the significant reactions can be recognized and the required thermodynamic data are available. Conversely, if one asks how fast the reaction goes or how far it proceeds in a given time, the answer is frequently much more difficult to answer in quantitative terms. Yet the rate-con trolling factors of the reactions may be of primary importance in the success of a particular operation, especially where competing processes are at work. Both equilibrium and rate factors must be understood if a clear picture is to be obtained. For instance, in a process for carburizing titanium dioxide, is the difficulty of obtaining a stoichiometric Tic due to a true limitation of the equilibrium or simply to a very slow rate of reaction? An example of this appears in the work of Kalish and Mazza.' They showed that the oxygen content of sintered iron compacts was lower when sintered in pure hydrogen than in the case where the hydrogen was diluted with either argon or nitrogen. The equilibrium oxygen content of the iron would be the same in the two cases, since it is determined by the ratio of the partial pressures of water vapor and hydrogen and this pressure ratio is unchanged by dilution. The rate of oxygen removal, however, under the conditions of a constantly replaced furnace atmosphere, depends upon diffusion and thus upon the concentration of hydrogen in the furnace atmosphere. Possibly the clearest way to illustrate the interplay of these two factors is to consider in more detail some of the typical metal-gas reactions. Adsorbed Gases It is common experience that fine metal powders with their very large surface areas often contain large quantities of gas. This gas, which results from exposure to air or perhaps from some step in the

Jan 1, 1957

By J. C. Humbert, J. F. Elliott

The solubility of nitrogen in liquid pure Fe, Cr, and Ni, in liquid Fe-Ni, Fe-Cr, and Ni-Cr alloys and Fe-Cr-Ni alloys, has been measured by the Sieverts' type apparatus between 1500° and 1800°C. Tabulations and graphs of the solubility data and activity coefficients are shown. Heats of solution are reported. Interaction coefficients of the several elements in Fe. Cr, and Ni ave also reported. THE solubility of a gas in a liquid metal is usually measured by either the quenching technique or the so-called Sieverts' method. In the quenching method, 1-3 the melt is equilibrated at the desired temperature and pressure with the gas phase having a known fugacity of the gas being studied. The melt is sampled and the sample is quenched and analyzed chemically for its gas content. In Sieverts' method the melt is contained in a closed chamber. The apparent volume of this chamber, i.e. the "hot volume," is usually determined by introducing a known quantity of an inert gas having very closely the same physical characteristics as does the experimental gas. Alternatively, the experimental gas is used with an inert specimen having the same general physical characteristics as does the experimental melt. Subsequently, the experimental melt is equilibrated with the experimental gas by introducing a known quantity of the gas into the calibrated chamber. The solubility of the gas is obtained from P-V-T relationships. The quenching method suffers from' the limitation that some gas may be gained (as in the case of Cr-Fe alloys) or lost (as in the case of Fe-Ni alloys) during solidification and cooling of the sample. With Sieverts' method sampling and analysis are unnecessary. However, errors can result from the difficulty of determining accurately the "hot volume,"

Jan 1, 1961

G. M. TAYLOR,* Colorado Springs, Colo.-The ore treated at the United Eastern is primarily a gold one and is cyanided-the counter-current decantation method being employed. One of our employees visited this plant a few months ago and, on his return, reported that the moisture in the tailing was carrying 20 c. per ton, which would appear to be somewhat high. As this type of plant has been advocated by one of the recognized cyaniding engineering firms in the country, and a number of these plants are in successful operation, it does not seem to me that the dissolved loss could be so high, and I would like to know if any one can give any definite information on this point? J. V. N. DORR, New York, N. Y.-I am very glad that Mr. Taylor has raised this question. When I first read Mr. North's paper and saw his statement, that they had an actual dissolved loss of 21.5 c. per ton, I was very much puzzled at this high loss which appeared avoidable by another decantation or the addition of a rotary filter. Reading it again, however, I noted that the actual dissolved loss of 21.5 c. given was evi-dently obtained by multiplying the assay of solution discharged from Z. thickener by the tonnage. On the basis of 283 tons milled per clay, this means $56.54 going to the clam. He states, however, that he returns from. the dam into the system, 70 tons daily assaying 40 c. per ton or $28 per day, so it would seem reasonable, unless I have overlooked something to regard the actual dissolved loss as $56.54 less $28 or $28.54, equaling 10.8 c. per ton. Even this loss, however, is much higher than good practice elsewhere, and can be accounted for largely by the tonnage being handled, which I believe is 30 per cent. above the capacity planned.

Jan 12, 1919

By R. W. Armstrong, P. C. Jindal

The hardness dependence on grain size for polycrys-talline cartridge brass and a leaded brass has been measured by Brine11 and Rockwell B testing. In each case, the hardness, H, depends on the average grain diameter, 1, according to: H =Ho + kHl-1/2 where Ho and kH are experimental constants. Diamond pyramid hardness values have also been measured as a function of the indentation size and grain size to give additional information on the nature of the hardness test and the dependence of hardness on micro-structure. The hardness of polycrystalline brass depends on its grain size. Bassett and Davis' demonstrated this as early as 1919 by making Brinell hardness measurements on cartridge brass. Since then, the hardness of this type of material has been measured as a function of grain size by making Rockwell,2'3 Vickers,4 and Brinell5 tests. he hardness dependence on grain size has also been measured for other materials. Angus and summers6 investigated the grain size dependence of the Brinell hardness of polycrystalline copper and a Cu-4.5 pct Sn bronze. In other studies, nickel,? Armco iron,Big an Fe-0.07 pct C alloy,I0 and an 0.39 pct C-12.45 pct Cr stainless steel" have been investigated. In some of the preceding cases, the hardness results have been analyzed to show that the hardness varies with the average grain diameter, 1, according to an l-l\4, l-1/4 or I-2 dependence,11-13 The studies of the influence of grain size on hardness have not been based on any theoretical model. This may be because the hardness of a material is itself a complicated property. However, attempts have been made to correlate, experimentally and theoretically, the hardness of a material with its unidirectional stress-strain behavior.14-l6 On this basis, Hall" proposed that the polycrystal hardness dependence on grain size might follow directly from the Hall-Petch18,19 relation for the grain size dependence of the yield stress. Thus, the hardness-grain size relation was given as: H = Ho + kHl-1/2 [1] where Ho and kH were taken as experimental constants. The relation was applied to the measurements on brass,' copper,6 bronze,= and Armco iron.' More recently, this relation was shown by Armstrong and jindal20 to adequately describe the measurements on cartridge brass made by Bassett and Davis' and Babyak and Rhines.5 In this case, the relationship was taken a step further by independently relating the values of Ho and kH to the values of oyand ky, previously reported by Armstrong, Codd, Douthwaite, and petch21 from measurements of the yield stress dependence on grain size for this type of material. In the present investigation, new Brinell and Rockwell B hardness measurements have been made as a function of grain size for a cartridge brass and a leaded brass. In addition, diamond pyramid hardness values were measured as a function of the indentation size. All these results are applied to a further analysis of the hardness dependence on grain size. MATERIALS AND EXPERIMENTAL METHODS Cartridge brass and a leaded brass were selected for this investigation for two main reasons: it was anticipated 1) that these materials could be cold-worked and recrystallized to a wide range in grain size and 2) that the results to be obtained on these typical industrial materials could be usefully compared with previous investigations. The chemical analyses of the actual materials which were employed are given in Table I. The as-received 1/2- and 3/4-in.-thick plates were given various reductions in thickness by cold rolling. The rolled material was heat-treated at various temperatures between 330" and 850°C for differing time periods from 5 min to 9 hr to achieve a variation in the average grain diameter between 0.0339 and 0.000543 cm.22 During heat treatment, the brass was protected from zinc loss by packing it in chips or foils of the same composition material. Reasonably equi-axed grain structures were obtained in each case. The metallurgical grain sizes of the specimens were determined from measurements of the average linear intercept on a random line. Annealing twin interfaces were not counted along with grain boundaries. The

Jan 1, 1970

THE first session, on alloys, took place on Feb. 20, Mr. Hibbard presiding in Mr. Campbell's absence. The session covered papers on manganese, chrom-ium, and silicon-iron systems. The paper by Mr. Wohr-man was presented by title. This paper showed that manganese produced many of the effects generally at-tributed to carbon and indicated that our ideas on manganese-bearing carbon steels will have to be modi-fied. Mr. Krivobok discussed this paper at length, the gist of the discussion being that Mr. Wohrman had not taken sufficient precautions in carrying out some of his work, particularly as to the effect of silicon content. Mr. O'Neill's paper was also submitted by title and no discussion was presented. Mr. Kinzel showed an accu-rate determination of .the carbon-free chromium-iron loop obtained by means of a specially constructed tele-scopic dilatometer. The loop ends at 12.2 per cent chromium and the A-3 line at 900° is unaffected by chromium content. The A-4 line runs from 1400° to 900° at 12.2 per cent chromium as an oblique hyperbola. Mr. Armstrong noted that the brittleness in high chromium alloys is often attributed to the gamma trans-formation and, according to Mr. Kinzel's diagram, this was impossible, as the alloys contain a great deal more than 12 per cent chromium. Mr. Kinzel pointed out that the presence of carbon in the commercial alloys caused the elongation of the loop and made possible local austenite transformation. Mr. Styri discussed the relations of the coefficients of expansion as shown in Mr. Kinzel's diagram. Mr. Corson presented the iron-silicon diagram as he has worked it out, showing a pre-viously unknown intermetallic compound, Fe3Si, to-gether with characteristic martensitic microstructure varying with the heat treatment. This compound formation is the real cause of brittleness in certain re-gions of the iron silicon system. Dr. Hoyt believed some of the evidence presented by Mr. Corson to be in contradiction to the phase rule. Mr. Corson, however, explained that true equilibrium does not exist under the conditions at hand so that the diagram was accurate in spite of the discrepancies. The meetings of the subcommittee on the physical chemistry of steel making were interspersed through-out the day. Mr. Feild presided and a program of future activities was outlined. This includes plans for a symposium at the next annual meeting and methods for interesting physical chemists, particularly those in the universities, in the steel man's problems. This committee has been newly formed and bids fair to be especially active. The Iron and Steel Committee met at lunch at the Engineers' Club at noon, with Dr. Mathews presiding. After disposing of the food the report of the Nominat-ing Committee was called for, and the following were elected as officers for 1928: R. H. Sweetser, chairman; F. C. Langenberg and W. J. Priestley, vice-chairmen; and T. T. Read, secretary. The report of the commit-tee appointed at the last meeting to consider publica-tion and general policy for the committee was then called for and freely discussed, after which it was unanimously voted to instruct the new chairman to se-cure from the Board of Directors the necessary author-ization for the Committee to recognize as a Division. This action was reported to the Board at its meeting the following night and the authority granted.

Jan 3, 1928