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By Paul W. Zimmer, Carl E. Dutton

Iron ore in the Menominee district is mined from two iron-formations of middle Precambrian age. The older formation is present in the northeastern part; is composed mainly of hematite, magnetite, quartz, and minor silicates; and contains about 34 per cent iron. The rock has been so coarsened by meta- morphism that concentration of magnetite and hematite is feasib!e, and pellets containing more than 60 per cent iron are being produced. The older formation is also present in the southeastern part where it has 1:een only slightly metamorphosed. Ore containing more than 50 per cent iron was formerly mined from local residual concentrations of iron oxides from which silica had been sufficiently leached, or replaced by iron oxide, or affected by combinations of these processes. The younger iron-formation occurs in the western part of the district and, if unaltered, is interlayered siderite and chert. The ore in this area also contains more than 50 per cent iron and formed as local residual concentrations but in two stages. The siderite was converted to iron oxides (hematite and "limonite"), and silica was contemporaneously or subsequently removed by leaching, or replacement, or combinations of these processes.

Jan 1, 1968

By O. D. Gonzalez, R. A. Oriani

The migration of hydrogen and of deuterium dissolved in a iron and in nickel induced by an applied electrical potential has been measured over a range of temperature. In all cases the intevstitial solute migrates to the cathode. The deduced charges of transport are positive, independent of or slightly dependent on temperature, and markedly larger for the beavier mass. These results are interpreted as showing predominating momenlum transfer between electron holes and the acticated complex of the elementary diffusion act. THE migration of components of a metallic system under the action of an applied electrical potential is called electromigration or electratransport. This phenomenon has been known since 1861 and is becoming of increasing interest to metal scientists because of the opportunity it offers to explore the connections between mass transport and electron transport. Until recently, reliable data have been very scarce because of the difficulties inherent in the measurements. In addition, theoretical understanding has been either nonexistent or rudimentary and at present this situation is only moderately improved. Whereas the prevalent notion had been (and is still widely held) that electromigration directly reflects the state of ionization of a component in its equilibrium state in the metal, it is now becoming clear that the major, if not the sole, factor is the momentum transfer between the charge carriers, themselves in motion because of the applied field, and the metallic components in their activated state. It becomes important therefore to obtain reliable data over a range of temperature on electrornigration in systems where only one component moves, that is, either in pure metals (vacancy motion) or in interstitial solid solutions. Our choice of systems was dictated by our measurements' of the Soret effect in solid solutions of hydrogen and deuterium in iron and nickel. Indeed, the main reason for making measurements on electromigration at all is that we suspected a mechanistic connection between thermal diffusion and electromigration. In our former paper' we proposed that what is common to both phenomena is the momentum transfer between the charge carriers in the metal and the atom as it jumps from one equilibrium position to another. In Soret diffusion, however, there is in addition the dissipation of the energy of the jumping atom via pho-nons. We have since found that similar ideas for this interconnection have been developed by Fiks.2 In the present paper we will discuss in more detail our understanding of the mechanism of electromigration itself, but we turn first to a presentation of the experiments and results. EXPERIMENTS AND RESULTS Let us consider a metallic system in which only one component, m , can diffuse at the temperature in question, and to which are applied simultaneously an electrical potential gradient, grad cp, and a chemical potential gradient, grad p,. One may write3 for the material flux Jm and the electronic charge flux Je by applying the condition, grad = 0, to Eq. [I] and evaluating grad(um/T) for the isothermal case and for activity coefficient independent of composition over the relevant composition range. ere, c is the concentration and D the diffusivity of the mobile component. The experimental technique that we have used to measure Z* for the isotopes of hydrogen individually dissolved in each of two transition metals has been developed from a method used by Wagner and Heller.4 (A somewhat similar method was also used by Herold.5) A wire or thin rod of the metal under study connects two volumes of gaseous hydrogen at identical pressures; hence grad um = 0. A direct current is made to pass through the specimen, serving to maintain the specimen at the desired temperature and also to produce the electromigration of the hydrogen dissolved in the metal in equilibrium with the gaseous hydrogen. Under these conditions, the flux of hydrogen from one volume to the other is given, from Eq. [I] for grad( um/T) =0by

Jan 1, 1968

By H. T. Kennedy, J. E. Little

An empirical equation for the prediction of the viscosity of several pure paraffin hydrocarbons and nitrogen is presented. It involves temperature, pressure and six constants of the material, and it applies reliably to both liquids and gases. The equation is similar in form to van der Waal's equation of state. For the paraffin hydrocarbons methane through r-hexane and nitrogen, an average absolute deviation of 1.9 percent was obtained on 1,006 data points described in the literature by 14 authors. When this equation is extended to complex, liquid hydrocarbon mixtures, a correlation was obtained with an average absolute deviation of 9.9 percent. INTRODUCTION Equations describing the flow of gas and liquid through porous media contain the viscosity coefficient of the fluid. If other pertinent variables remain constant, the volume rate of flow is inversely proportional to this coefficient. In dealing with condensate fluids and volatile oils, however, the compositional effects resulting from changing pressure materially affect the viscosity. The effect of compositional changes also may be significant in certain secondary recovery or pressure maintenance processes, notably miscible displacement or gas injection. Early attempts to describe the performance of reservoirs utilized a volumetric material balance method wherein gas and liquid in the reservoir were identified as produced gas and liquid at the surface. This method of analysis proved adequate for reservoirs at moderate temperature and pressure that contained gas with moderately low amounts of condensable materials. The volumetric material balance procedures for "black oil" reservoirs leave much to be desired when applied to condensate and volatile oil reservoirs because phase behavior and compositional changes are relatively more important in these cases. The alternative is a compositional material balance, which in turn, requires a correlation of properties of the reservoir fluid with composition. This paper supplies this correlation in regard to viscosity, for reservoir crude oils. REVIEW OF LITERATURE The literature contains many empirical equations describing the effects of composition, temperature and pressure on the viscosities of pure liquids and binary liquid mixtures. However, the applicability of a majority of these equations is limited to very low pressures and to a small number of systems. Most of them, when applied to complex hydrocarbon systems, are of little value. The lack of utility of the majority of equations results from the fact that they were developed to show the separate effect of temperature, pressure or composition on viscosity, but not to predict the viscosity as a function of all three variables. And with the few exceptions noted below, they were developed to apply to much simpler systems than hydrocarbon mixtures. Eakin1 developed an equation for the viscosity of pure light hydrocarbons applicable in the gas, liquid and dense fluid regions, and in its most general form is written as µ - µo =A(ebP - e-cpk) The pure component viscosity at atmospheric pressure and temperature T, µo, was calculated using the Sutherland equation: µo = BT3/2/T + S The constants in Eakin's equation permitted the term e-CPk to become quite small at high densities (above 0.215 gm/cc), and the general equation would simplify to

Jan 1, 1969

By R. E. Hurst, D. E. Ramsey, J. M. Moore

The "frac" method of well stimulation has been applied successfully to all producing formations in the Permian Basin area. During the five years since its development, many changes and improvements have been made in treating materials. procedures, and equipie11t. A number of fluid carrying agents, having different physica1 and chemical properties, have been developed to meet variorus well requirements. The current trend is toward larger gallonage treatments, employing higher injection rates. The use of "down-the-casing" techniques has greatly reduced high surface working pressures, attributable to friction losses resulting from injection throrugh tubing. Petrographic studies of various Permian Basin formations, coordinated with laboratory and well log data, have been found a valuable guide in planning frac treat111o1t.s. A knowledge of the extent (and orientation of naturally occurring fractures and planes of weakness in the formation, aid in predicting the ultimate drainage pattern resulting from the frac treatment. INTRODUCTION The South Permian Basin covers an area in Wcst Texas and New Mexico about onc-half the size of the state of Texas, This vast region has been called the "Permian Basin" for so long that the term will he used here. It includes an area south of the Matador Arch. approximately 250 miles wide and 300 miles long. Structural features of importance within the basin are the Northwest Shelf, Eastern Platform, Midland Basin, Central Basin Platform, and Delaware Basin. The principal producing formations include sand, limestone and dolo-mite, with lesser amounts of shale, anhydrite. chert. and various silicates. All of the producing formations in the Permian Basin have responded to some type of frac treatment. Essentially, a frac treatment may be defined as the injection, into a formation. of a fluid carrying agent containing a particulated solid (usually sand), for the purpose of increasing production. The application of this method of well stimulation to many differing Permian Basin reservoirs has necessitated numerous changes and improvements in carrying agents, solids, service equipment. well equipment. and treating techniques. CARRYING AGENTS A number of different types of fluid carrying agents have been developed since the introduction of the frac method of well stimulation. These agents have different physical and chemical properties, and in many cases the extent of production increase derived from the frac treatment depends on the choice of fluid carrier. Unfortunately, due to many different systems of nomenclature used in the oil field, these differences are not always recognized by the oil Operator. In general, carving agents may he divided into the following broad classi-

Jan 1, 1956

By F. S. Crawford

IRON and copper are mined in the Lake Superior district. The iron mines of the district have the best safety record for that industry in the country as a whole, while the copper mines of the district rank second in two of the four years recorded (Table 1). In Utah copper comes mainly from open-pit mines, which enables that state to lead easily in safety. All of the Michigan production comes from deep underground workings. About 60 per cent of the iron miners in St. Louis County, Minnesota, are employed at open-pit mines; this favorably affects the combined open-pit and underground accident-frequency rate, as this county provides most of the Minnesota-mined iron ore. In Michigan, however, there are few open-pit mines, the bulk of the production coming from underground mines, while all of the Wisconsin production, just across the state line from Michigan, is from underground mines. In spite of the fact that fewer mines in Michigan use the safer open-pit method, the iron-mining industry of that state maintained a consistently low record from 1931 to 1934; however, it was many points behind its nearest competitor, Minnesota, with its much greater production from open-pit mines.

Jan 1, 1939

By J. F. Radavich

Many heats of steel of low carbon value have been known to produce brittle pieces of steel. The brittleness is believed to be due to the impurities located within the grain boundaries. Such brittle steels have been examined with an optical microscope to ascertain the nature and the amount of the impurities present at the grain boundaries. Due to the relatively low resolving power of the optical microscope, the impurities are not visible in fine detail. The writer obtained some sheet steel and proceeded to determine the location of the impurities and to show the application of the electron microscope to the study of grain boundaries. One sample was known to be capable of becoming embrittled, whereas another sample was believed to be much less susceptible to embrittlement. Treatment of Specimens The specimens were embrittled by annealing above the A3 point under mildly oxidizing conditions. One piece of ingot iron could not withstand a 90" bend, whereas another piece of ingot iron was not affected and could withstand a 90" bend. The brittle piece was then annealed at a high temperature in a hydrogen atmosphere. The annealed ingot iron was termed cured and could withstand a 90" bend very easily. The three specimens examined will be designated as brittle, good. and cured in the discussion that follows. Procedure The sizes of the specimens were as follows: one piece of brittle ingot iron-3/8 by 35 in.; one piece of good ingot iron-96 by 1/8 in.; one piece of cured ingot iron-36 by 54 in. The specimens were too small to be polished by hand and therefore were mounted in bakelite. The polishing procedure was carried out in the conventional manner with the use of 1/0 through 3/0 papers, and the final polish was done with alumina on a billiard cloth. The specimens were then etched in a 4 pct solution of picral in alcohol, and then they were examined through an optical microscope. An area was chosen that showed distinct grain boundaries, and an effort was made to keep near this area when pulling the replicas REPLICA TECHNIQIJE The replica technique used in the preparation of the replicas for examination under the electron microscope is described in Electron Metallography.' It consists essentially of the following steps: 1. Obtaining a suitably etched specimen. 2. Applying a swab of ethylene di-chloride on the surface. 3. Applying a formvar solution on the surface. 4. Placing a screen on any desired spot. 5. Breathing on the fornivar layer. 6. Applying scotch tape on the screen and film. 7. Pulling the film and the screen up with the Scotch tape. 8. Separating the screen from the Scotch tape. This replica technique is very similar to the one described by Harker and Shaefer. However, with the added step, the percentage of replicas removed is very much higher regardless of the length of the time from the etching of the specimen to the actual pulling of the replica. The replicas were then shadow cast with manganese at a filament height to replica distance ratio of 1 1/2:7. This produced a very high contrast replica for use in the electron microscope. One of the dificulties encountered with this study was the restricted area of the specimen. The width of the specimens was the same as that of the 200 mesh nickel supporting screen. In order to increase the effective area, the screens were cut down as shown in Fig 1. The arrow indicates the direction in which the replica was pulled. This operation made it possible to obtain a large percentage of good replicas. Fig 3 shows an electron micrograph of a brittle piece of ingot iron and a grain boundary that was polished mechanically. The surface is very rough probably due to the incomplete removal of the flowed layer by the picral etchant. The grain boundary does show evidence of impurities. It was decided to electropolish the specimens to obtain a much smoother surface than the one obtained by mechanical polishing. ELECTROPOLISHING The specimens were cut in half to expose the metal on the back side. The exposed metal had sufficient area to make good electrical contact and electropolishing was carried out easily. The conditions for electropolishing were 0.9 amp, 35 volts, and 25 sec. in an electrolyte composed of 850 cc of ethyl alcohol, 100 cc distilled water, and 50 cc of perchloric acid. The polished specimens were then etched in the 4 pct picral solution for a shorter time than was necessary for

Jan 1, 1950

By Fred C. Bond

MOST investigators are aware of the present unsatisfactory state of information concerning the fundamentals of crushing and grinding. Considerable scattered empirical data exist, which are useful for predicting machine performance and give, acceptable accuracy when the installations and materials compared are quite similar. However, there is no widely accepted unifying principle or theory that can explain satisfactorily the actual energy input necessary in commercial installations, or can greatly extend the range of empirical comparisons. Two mutually contradictory theories have long existed' in the literature, the Rittinger and Kick. They were derived from different viewpoints and logically lead to different results. The Rittinger theory is the older and more widely accepted. In its first form, as stated by P. R. Rittinger, it postulates that the useful work done in crushing and grinding is directly proportional to the new surface area produced and hence inversely proportional to the product diameter. In its second form it has been amplified and enlarged to include .the concept of surface energy; in this form it was precisely stated by A. M. Gaudin2 as follows: "The efficiency of a comminution operation is the ratio of the surface energy produced to the kinetic energy expended. According to the theory in its second form, measurements of the surface areas of the feed and product and determinations of the surface energy per unit of new surface area produced give the useful work accomplished. Computations using the best values of surface energy obtainable indicate that perhaps, 99 pct of the work input in crushing and grinding is wasted. However, no method of comminution has yet been devised which results in a reasonably high mechanical efficiency under this definition. Laboratory tests have been reported' that support the theory in its first form by indicating that the new surface produced in. different grinds is proportional to the work input. However, most of these tests employ an unnatural feed consisting either of screened particles of one sieve size or a scalped feed which has had the fines removed. In these cases the proportion of work" done on. the finer product particles is greatly increased and distorted beyond that to be expected with a normal feed containing the natural fines. Tests on pure crystallized quartz are likely to be misleading since it does not follow the regular breakage pattern of most materials but is relatively harder to grind at the finer sizes, as will be shown later. This theory appears to be indefensible mathematically, since work is the product of force multiplied by distance, and the distance factor (particle deformation before breakage) is ignored. The Kick theory' is based primarily upon the stress-strain diagram of cubes under compression, or the deformation factor. It states that the work required is proportional to the reduction in volume of the particles concerned. Where F represents the diameter of the feed particles and P is the diameter of the product particles, the reduction ratio Rr is F/P, and according to Kick the work input required for reduction to different sizes is proportional to log Rr/log 2.5 The Kick theory is mathematically more tenable than the Rittinger when cubes under compression are considered, but it obviously fails to assign a sufficient proportion of the total work in. reduction to the production of fine particles. According to the Rittinger theory as demonstrated by the theoretical breakage of cubes the new surface produced, and consequently the useful work input, is proportional to Rr-1.5 If a given reduction takes place in two or more stages, the overall reduction ratio is the product of the Rr values for each stage, and the sum of the work accomplished in all stages is proportional to the sum of each Rr-1 value multiplied by the relative surface area before each reduction stage. It appears that neither the Rittinger theory, which is concerned only with surface, nor the Kick theory, which is concerned only with volume, can be completely correct. Crushing and grinding are concerned both with surface and volume; the absorption of evenly applied stresses is proportional to the volume concerned, but breakage starts with a crack tip, usually on the surface, and the concentration of stresses on the surface motivates the formation of the crack tips. The evaluation of grinding results in terms of surface tons per kw-hr, based upon screen analysis, involves an assumption of the surface area of the subsieve product, which may cause important errors. The'evaluation in terms of kw-hr per net ton of 200 mesh produced often leads to erroneous results when grinds of appreciably different fineness are compared, since the amount of -200 mesh material produced varies with the size distribution characteristics of the feed. This paper is concerned primarily with the development, proof, and application of a new Third Theory, which should eliminate the objections to the two old theories and serve as a practical unifying principle for comminution in all size ranges. Both of the old theories have been remarkably barren of practical results when applied to actual crushing and grinding installations. The need for a new satisfactory theory is more acute than those not directly concerned, with crushing and grinding calculations can realize. In developing a new theory it is first necessary to re-examine critically the assumptions underlying

Jan 1, 1952

By Charles H. Eldridge, Robert J. Anderson

When a metal or alloy is poured into a mold, internal stresses are set up by the cont,raction in volume on passing from the liquid state at the temperature of pouring to the solid state at the ordinary temperature. It is assumed by the writers that all castings are internally stressed. That any casting is internally stressed is shown by its warping or distortion on maturing at the ordinary temperature, by warping or cracking on heating, or by cracking or distortion on machining. In the investigation made by the writers, the internal stresses in cast non-ferrous alloys were studied with a view to examining the effects of heat treatment (i.e., simple anneal) on the release of such stresses. Data have been obtained that show quantitatively that internal stresses can be removed by appropriate heat treatment. The investigation was limited to a study of the effect of heat treatment on stress release in cast rings of the 87:7:5:1 copper-tin-zinc-lead alloy. The writers are indebted to E. G. Fahlman for the method used for inducing stress in cast rings; to M. E. Boyd for microscopic examination and for other aid; and to G. B. Dalrymple for the chemical analyses. General Information While casting stresses have been discussed considerably, they have usually been treated in a general way, and so far as the writers know no measurements of the magnitude of internal stresses in castings have been reported. It has been suggested by many investigators, particularly in the case of steel castings, that castings are internally stressed, and that these stresses can be removed by annealing. In a casting, the internal

Jan 1, 1923

By Robert J. Anderson, Charles H. Eldridge

When a metal or alloy is poured into a mold, internal stresses are set up by the cont,raction in volume on passing from the liquid state at the temperature of pouring to the solid state at the ordinary temperature. It is assumed by the writers that all castings are internally stressed. That any casting is internally stressed is shown by its warping or distortion on maturing at the ordinary temperature, by warping or cracking on heating, or by cracking or distortion on machining. In the investigation made by the writers, the internal stresses in cast non-ferrous alloys were studied with a view to examining the effects of heat treatment (i.e., simple anneal) on the release of such stresses. Data have been obtained that show quantitatively that internal stresses can be removed by appropriate heat treatment. The investigation was limited to a study of the effect of heat treatment on stress release in cast rings of the 87:7:5:1 copper-tin-zinc-lead alloy. The writers are indebted to E. G. Fahlman for the method used for inducing stress in cast rings; to M. E. Boyd for microscopic examination and for other aid; and to G. B. Dalrymple for the chemical analyses. General Information While casting stresses have been discussed considerably, they have usually been treated in a general way, and so far as the writers know no measurements of the magnitude of internal stresses in castings have been reported. It has been suggested by many investigators, particularly in the case of steel castings, that castings are internally stressed, and that these stresses can be removed by annealing. In a casting, the internal

Jan 1, 1923

By Earle E. Schumacher, W. C. Ellis

For the purpose of developing combinations of higher strength and conductivity than are obtainable by heat treatment alone in the age-hardening copper alloys, an investigation has been made of the effects of combinations of heat treatment and strain hardening on the properties in question. The investigation was limited to a study of the alloys containing nickel and silicon; nickel, silicon and cadmium; and cobalt and silicon. The experiments made in the course of the study arc described in this paper in three groups: 1. The effect of hard drawing subsequent to heat trcatment on the mechanical and electrical properties of the alloys. 2. The effect of low-temperature aging on the properties of heat-treat,ed and hard-drawn alloys. 3. The effect of strain on the rate of aging of quenched nickel-silicon-copper alloys. Preparation and Compositions or the Alloys The alloys were prepared by melting cathode copper in an electric resistance furnace and adding sufficient of the hardening elements to bring the compositions to the desired values. The purities of the hardening elements were as high as could be obtained in commercial practice. The metals were what are designated in the trade as electrolytic nickel, cobalt rondelles, commercial stick cadmium and fused silicon. The alloys

Jan 1, 1931

By L. W. Bahney

(Cleveland Meeting, October, 1912.) THE photograph, Fig. 1, shows the apparatus a little less than half size, consisting of a filtering-flask fitted with rubber stopper, through which passes a bent glass tube, and an extraction-thimble fitted with rubber stopper through which passes a glass tube of 0.2-5-inch bore. Both tubes are connected by a short piece of rubber tubing. A section of a thimble is shown in the photograph; the tube extends to within in. of the tapered end. The object of using the thimble is to remove the acid from the beaker after all the copper has been precipitated. Time is saved, the copper is not exposed to the acid alone, and there are none of the losses attending ordinary filtration. I have accomplished these results by means of a piece of perforated platinum fastened in the end of a 0.25-in. bore glass tube and a filter-mat of asbestos, but after my supply of proper length fiber became exhausted I could not replenish it even after purchasing 14 lots from four different dealers. The above apparatus may be used to remove at least seven-eighths of a supernatant liquid from a settled precipitate without disturbing the latter. The application of the thimble is best shown by partly out-lining the assay for copper, as follows: Dilute the acid solution of copper and other sulphates to 150 cc. in a 200-cc. Jena beaker, place on a hot plate, add 2 drops of concentrated HC1, then place a strip of aluminum in the beaker (this may be bent or straight, as desired). Connect the apparatus, as shown in Fig. 1, with a filter-pump having a, strong suction. When the copper is precipitated, remove the beaker from tine hot plate and insert the extraction-thimble alongside the strip of aluminum. The acid solution will be drawn through the porous tube. Wish the upper end of the aluminum strip with a jet of hot water, wash down the sides of

Nov 1, 1912

"Acta Metallurgical, C E Birchenall, Dec '58 Alfred Noble Joint Prize Committee F B Foley, Dec '61 American Association for the Advancement of Science J T MacKenzie, Dec '58, 0 B J Fraser, Dec '57 American Geological Institute Charles F Park, Oct '58, Arthur Montgomery, Oct '59 Committee on Government Relations American Power Conference J P Weir, T D Hess American Standards Association , Mining Standards Board E R Borcherdt, Jan '59, Otto Herres, '59, J K Richardson, Dec '58, Alternate E W Bullard

Jan 1, 1958

By G. P. Marino

The "conductivity ", Kr, of a spherical void in a linear temperature gradient due to radiation is calculated by integration of the general expression for diffuse radiation between two gray surfaces of arbitrary orientation. The spherical geometry allows an exact evaluation of the phenomenon without resorting to up-proximate expressions for the radiant heat flux. The resulting expression for Kr is three quarters of the approximate value obtained by Loeb. IN the determination of the thermal conductivity of porous materials such as sintered UO2 and ThO2 fuel pellets, the magnitude of the thermal conductivity in the pores due to radiative heat transfer across the pore, Kr, may be important in assessing the total conductivity of the pellets. Loeb' has calculated Kr for various pore geometries by approximating the net flux of heat between two surfaces of temperature difference AT as 4eT~AT and obtained: K,=4yoet3odp [1] where a is the Stefan-Boltzmann constant, E is the emissivity of the radiating surface, To is the average absolute temperature of the region across which radiation occurs, dp is the largest dimension of the gap in the direction of heat flow, and y is a geometric factor. That is: y = 1 for laminar pores and cylindrical pores with axes parallel to the heat flow direction, y = 2/3 for spherical pores, y = /4 for cylindrical pores with axes perpendicular to heat flow direction. It was the purpose of this work to obtain an exact expression for K, in spherical pores by integration of the general expression for the net heat transfer between two incremental areas on the surface of a spherical pore. This procedure yields a value of Kr 3/4 of that obtained by Loeb. I) CALCULATION OF Kr Fig. 1 illustrates the general geometry which defines the problem. The total emissive power for a gray body is given by: E = EoT4 [2] where E is the radiated energy per unit area of the radiation surface per unit time, T is the absolute temperature, o is the Stefan-Boltzmann constant (o = 5.67 X lo- '' watt per sq cm-"K1), and E is the emissivity of the surface. Although Eq. [2] gives the exact expression for the total emissive power of any gray body, all practical problems involve the net exchange of thermal radiation between a body and surrounding bodies. The two major considerations in the solution of such problems are a) shape and relative position of the surfaces and b) the emissivities of the surfaces. In this work it shall be assumed that all incremental areas on a pore have the same emissivity and, further, that little or no reflection occurs (i.e., the radiation hitting a surface is either absorbed or transmitted). Thus, the solution of the stated problem requires only that consideration a be satisfied. Consider two incremental surface areas dA 1 and dA2 of the same material in a general orientation to one another. Let dAl be at temperature TI and dAz be at T2. Fig. 2 illustrates the geometrical parameters involved. That is, 71, is the normal of dA, n2 the normal of dA2, r the line connecting the centers of each area, 81 the angle between nl and r, and Q2 the angle between 7,2 and r. Using Eq. [2] and the Lambert cosine law of diffuse radiation it is easily shown that:293 WdAf- dA, = ecr T*------^fpi------" dAidA2 [ 3a 1 and

Jan 1, 1970

By Lawrence Addicks

Discussion of the paper of LAWRENCE ADDICKS, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 104, August, 1915, pp. 1471 to 1484. L. D. RICKETTS, New York, N. Y.--In the Southwest we have stored up millions of tons of tailings in which the copper exists partly as sulphide and partly in an oxidized condition. Mr. Addicks' first paper suggests a, likely process for the treatment of such material. His second paper 1 deals with the recovery of copper from clear solutions of notable strength, and such solutions may come from the sulphating roast or direct from the leaching of completely oxidized copper ores of which vast deposits are known to exist. What strikes me particularly about the latter paper is the keen perception shown and the clear manner in which the writer has attacked the fundamental principles of the process. He calls your attention to the fact that ferrous sulphate is necessary in the electrolyte and is an ideal depolarizer; that sulphurous acid must be, used to reduce the ferric sulphate produced and thus prevent re-solution of copper at the cathode; that mechanical agitation in the cell, in order to bring the ferrous sulphate in contact with the anode and the copper in contact with the cathode, is essential to efficient work; that lead anodes are

Jan 12, 1915

By R. I. Jaffee, C. M. Craighead, G. A. Lenning

THERE has been considerable discussion among A metallurgists and others interested in the development of titanium alloys as to the nature of the fine line markings which appear in the microstruc-tures of unalloyed titanium and a titanium alloys. These markings have been variously called x phase, etching pits, and twins. Figs. 1 to 3 show typical examples of the line markings as they appear, respectively, in high purity iodide titanium, commercial purity titanium rod, and a high purity a alloy containing 0.2 pct N. The commercial purity titanium sample, shown in Fig. 2, contains both line markings and some spheroidal retained-ß phase. The ß phase seen in this micrograph should not be confused with the line marking, since it originates from the iron present as an impurity in the sponge metal. It will be noted that the line markings seem to have a definite orientation pattern with respect to the grains and in titanium noticeably resemble the precipitation occurring in artificially aged high purity Al-Cu alloys. This similarity led to the hypothesis that the line markings observed in titanium and a titanium alloys resulted from precipitation of some unknown phase. With the work of Hägg1 and McQuillan2 as background, there was little reason to suspect hydrogen of being responsible for the line markings. Hagg reported that up to 33 atomic pct H was soluble in a titanium, and McQuillan reported an a solubility of up to 8 atomic pct. Furthermore, McQuillan examined metallographically a 5.1 atomic pct H alloy quenched from 300°C and stated that the structure appeared to be a single-phase a solid solution. Line markings have been observed frequently and were first noted by Jaffee and Campbell3 in 1949. They did not observe them in vacuum-annealed titanium and a Ti-O and Ti-N alloys, but did observe them in Ti-H alloys containing 0.25, 0.5, and 1 atomic pct H. They stated that it was doubtful that the markings were a second phase based on hydrogen, because 1 atomic pct was far from the accepted solid solubility of hydrogen in titanium. Finlay, Resketo, and Vordahl,4 in 1950, concluded that the markings were a true second phase as a result of observations on their etching characteristics. Anderson5 Commenting on these markings in titanium was inclined to associate them with hydrogen, but was loath to call them titanium hydride, because of the reported high solubility of hydrogen. Work at Battelle Memorial Institute for the Navy Bureau of Aeronautics," done concurrently with the work described in this paper, provided information on the experiment converse to that described by Jaffee and Campbell in 1949. This work showed that the amount of line markings in unalloyed titanium could be decreased by vacuum annealing at elevated temperature. It was suggested that this was the result of removal of hydrogen; previously, the data of Jaffee and Campbell9 howed that the markings appeared when hydrogen was added. Recent work at Battelle for the Ordnance Corps, Department of the Army, which is described here, now establishes the identity of the markings as a titanium hydride phase. A sample of high-purity titanium rod 1/4 in. diam, 0.009±0.001 wt pct H (0.43 atomic pct), Fig. 1, was resistance heated in a 0.05 micron vacuum for 41/2 hr at 1500°C. During the early states of heating, the pressure increased to 150 microns, indicating that gases were being evolved. After cooling in vacuum, the iodide titanium rod was analyzed for hydrogen. Vacuum-fusion analysis showed 0.0006 ±0.0003 wt pct H (0.03 atomic pct) to be present.* Metallographic examination of the vacuum-annealed rod showed only a transformed ß structure. There was no evidence of fine line markings, Fig. 4. A section of this vacuum-annealed rod was cold rolled to 0.040 in. thick sheet and annealed for 1 hr

Jan 1, 1953

By E. C. Rudolphy, M. E. Potter, J. R. Mitchell

The effects of 0.006 to 0.20 pet Sn ml the hot workability and the annealed mechanical properties were investigated for Types 302, 410, and 430 stainless steel. The hot workability of these steels was not significantly affected by their tin content within the range studied, although some effects on mechanical properties were noted. Apart from the effect of tin, optimum hot-working temperatures and V-notch Charpy impact transition temperatures for these grades were determined. HIGH tin residuals in some heats of stainless steel have been blamed for the poor hot workability, particularly during secondary mill rolling. However, very little quantitative information has been available. Previous work1"6 with carbon steels indicates that tin increases tensile strength and hardness but de- creases tensile and impact ductility. Halley,7 in reviewing the sources and effects of residual elements in carbon and alloy steels, concluded that much of the surface checking (hot shortness) encountered in rolling was caused by copper, and that tin, arsenic, and antimony combined with copper to form low-melting constituents which further increase the steel's sensitivity to hot shortness. These elements had little effect in the absence of copper. A more recent paper by Langenberg and Johnson8 concluded that tin reduces hot workability but that researchers disagree concerning the amounts which will cause trouble. They state that laboratory investigations with small ingots seem to indicate a higher tolerable level of tin than do statistical studies of mill data, and also that statistical analysis of mill data indicate that small amounts of residual tin are detrimental to the surface quality of stainless sheet. The accumulative increase in the general level of tin and other tramp elements in steelmaking materials will present greater problems to steelmakers in the future. The purpose of the present study was to obtain quantitative information on the specific effects of tin on the hot workability and mechanical properties of such common stainless steels as Types 302, 410, and 430.

Jan 1, 1962

By R. O. Harma

Introduction Wet autogenous grinding is utilized in three iron ore concentrating plants operated by the Cleveland-Cliffs Iron Company (CCI). This paper will trace some of the development in converting from the use of metal grinding mill liners to the use of rubber and will update the current performance of rubber liners in these applications. The Cleveland-Cliffs Iron Company is a natural resources firm with major interests in iron ore mining and processing and oil and gas contract drilling. The company also has interests in oil shale, uranium, forest products, and Great Lakes shipping. The three operations discussed in this paper are the Empire and Tilden Mines on the Marquette Iron Range in Michigan's Upper Peninsula and the Sherman Mine in northern Ontario, Canada. The Empire Iron Mining Partnership is managed by The Cleveland-Cliffs Iron Company and is owned by Inland Steel, McLouth Steel, The Cleveland-Cliffs Iron Company, and International Harvester. The Tilden Iron Mining Partnership is also managed by The Cleveland-Cliffs Iron Company and is owned by Algoma Steel Corporation, Ltd., Jones & Laughlin Steel Corporation, The Cleveland-Cliffs Iron Company, Steel Company of Canada, Wheeling-Pittsburgh, and Sharon Steel Corporation. The Sherman Mine is a joint venture managed by Cliffs of Canada, Ltd. and owned by Dominion Foundries and Steel Company, Ltd. and Tetapaga Mining Company, a wholly owned subsidiary of The Cleveland-Cliffs Iron Company. The concentrators at all three mines utilize two stage autogenous grinding. Empire and Sherman process magnetic iron ores (Table 1) and utilize magnetic, hydraulic, and flotation concentration methods. Tilden processes an oxidized iron ore (martite, goethite, and hematite) and utilizes a selective-flocculation desliming and flotation concentration flowsheet. Final grind particle sizes are 90% -325M (43k) at Sherman, 90% -500M (25,u ) at Empire and 85% -500M (25 µ) at Tilden. Developmental History The success of using rubber mill linings in Scandinavia led to the first rubber mill lining used by CCI. It was installed in a conventional primary ball mill at Republic Mine in 1964 as reported by Lindroos (1970). This was followed by additional rubber liners for both primary and regrind ball mills. Generally these rubber linings provided about twice the service life as compared to the Type I Ni-hard liners previously used. Grinding efficiency of rubber was found to

Jan 1, 1982

By G. W. Healy, J. C. Schottmiller

Molten silicates were found to exist in the Cr-Si-0 system at temperatures above 1450°C. one atom of oxygen is readily removed from CrzOs in the presence of Si02 at 1700°C, forming a silicate melt. Steam-hydrogen ratio measurements made at this temperature indicate that the free energy of the reaction: Cr20s(c) + Hz = 2CrO (in Si02 -saturated melt) + H20 is approximately 5600 * 1500 cal. A deep-blue chromous silicate, probably Cr2Si04, forms from these melts at about 1400" to 1500°C, and is characterized by.its distinctive X-ray diffraction pattern and optical properties—distinct pleochroism and high refractive indices. THE question of the state of oxidation of chromium in slags has vexed metallurgists for many years The experiments of Koerber and Oelsenl suggested the probable presence of divalent chromium in silica-saturated slags equilibrated with high-chromium melts. Hilty and coworkers2 had also found chromium at lower valency, as Cr304, in inclusions formed from oxygen-saturated Fe-Cr melts with as little as 10 pct Cr. In both cases, disproportiona-tion of the lower oxide to CraO3 and chromium was found to occur to a greater or lesser extent, depending upon the rate of cooling from the high temperature. The work on Cr304 was sufficiently detailed for chipmans to derive its thermodynamic properties, but Oelsen's experiments in the silicate system were not extensive enough since most of his runs were made with slags containing large amounts of manganese oxide in addition to iron and chrome oxide and silica. The present study describes experiments carried out to map out an approximate liquidus diagram in the CrzOs, "CrO", SiOa portion of the Cr-Si-0 system, and to measure the partial free energy of solution of oxygen in the system. EXPERIMENTAL 1) Approximate Melting-Point Determinations. Preliminary trials showed that when an equimolar mixture of Cr20s and SiOa was treated with hydrogen in the temperature range 1500" to 1600°C, copious amounts of steam were evolved, and a low-melting liquid formed which could be quenched to a blue, crystalline, material having a distinctive X-ray diffraction pattern. It was found that the identical material could be produced by heating intimately mixed, finely divided Cra03, Cr, and SiOa, held in a tungsten crucible, under purified argon. Thus, it was possible to prepare mixtures containing any desired proportions of chromium, silicon, and oxygen, pel-letize them, heat to temperature in the furnace shown in Fig. 1, and observe, after cooling, whether the pellet remained unchanged or showed signs of incipient, partial, or complete melting. 2) Free Energy of Solution of Oxygen. This was studied by measurement of steam-hydrogen ratios for the reaction: H20 (gas) + O (dissolved in charge) + Ha (gas) The experimental method chosen was to prepare a

Jan 1, 1964

By H. Dykstra

Calculated wellbore pressures were obtained for parameters of radilcs ratio and permeability. In all cases bur two, after-production was allowed to occur for one day. The calculated pressure build-up data were compared with actual pressure build-up data from a condensate well. The paper discusses the comparison, gives reasons for, inability to match calculated (2nd actual data, and presents conc1usions derived from the comparison. INTRODUCTION Considerable information has been published on the decline in wellbore pressure for oil and gas fields resulting from production of fluids. Considerable information also has been published on pressure build-up for oil fields, but relatively little has been published for gas and condensate fields. Perrine' summarized the equations derived for pressure build-up in oil wells and showed how the different methods could be applied. On the other hand, very little theoretical information has been published on pressure build-up in gas or gas-condensate wells.2-4 Tracy,' by pointing out the similarity between the equation describing oil wellbore pressure decline and the equation describing gas wellbore pressure decline, showed how methods of pressure build-up analysis could be applied to a gas well. In analyzing pressure build-up data for gas or gas-condensate wells, it would be very desirable to compare actual pressure build-up data with calculated pressure build-up data. Such a comparison would lead to a better feeling for the quantitative picture of gas-well build-up curves and would help to establish a degree of confidence in a given build-up curve. This paper discusses the comparison and presents conclusions made from it. Calculated wellbore pressures are given for parameters of radius ratio and permeability. In all cases but two, after-production was allowed to occur for one day. The work was done in an attempt to evaluate the reserves of a gas-condensate field. As will be discussed later, it was not possible to make an evaluation. METHOD OF CALCULATION The method used for solving the depletion and pressure build-up behavior for a gas-condensate well was that developed by West, Garvin and Sheldon.5 or the IBM 704 computer program used, it was assumed that liquid condensing out of solution would have only a minor effect on the flow behavior. Therefore, the field was treated as having single-phase flow, with the gas saturation S, remaining constant at unity minus the connate-water saturation Sw. As will be discussed later, this may not have been a good assumption. It also was assumed that oil production could be considered as equivalent gas production by using a conversion factor based on an analysis of the liquid produced. An outer boundary condition of no-flow was assumed. BASIC DATA The data required for the study were reservoir properties, fluid properties and production data. Reservoir properties included the following: thickness h, 179 ft; porosity, 0.194; connate-water saturation, 0.43; gas saturation, 0.57; permeabilities k, 1.0, 0.5, 0.25 and 0.15 md; radius ratios re/rw, 800, 1,000 and 2,000; wellbore radius rw, 5 in.; initial reservoir pressure P, 6,529 psia; and reservoir temperature, 272°F. The selection of permeabilities was based on core-analysis data showing an average air permeability of about 2 md. With a relatively high connate-water saturation, the average effective gas permeability would be about one-half, or less, of the air permeability. The selection of radius ratios was based partly on the observed rapid decline in wellbore pressure during production and partly on the fact that the well was believed to be located in a relatively small fault block. Reservoir fluid properties were obtained from a reservoir fluid study on a recombined sample of gas and condensate. Gas formation-volume factors were calculated from pressure-volume measurements made at reservoir temperature. Gas viscosities were calculated by the method of Carr, et al,G from an analysis of the re-combined sample. These data are shown as a function of pressure in Table 1. The production schedule from the gas-condensate

By A. J. Shaler

The subject of the mechanism of sintering has received much attention in the past few years, particularly since the beginning of the series of AIME seminars in powder metallurgy of which this paper introduces the fourth. In the first of these, F. N. Rhines1 brought together and discussed the available experimental data on the sintering of pure metallic powder, and succeeded in bringing to a sharp focus the attention of workers in this field on the established observations which a satisfactory theory must explain. Several other authors3,5,6 have, in the last few years, studied the phenomena that occur when cold metallic powders, loose or in the form of compacts, are first brought to elevated temperatures. Some workers' in the field of friction have recently studied the adhesion of solid metal surfaces when they are brought into close contact. These researches have indicated that several separate mechanisms operate simultaneously, at least during the first part of the sintering process. Some of them have been called transient mechanisms4 because they are in general not absolutely necessary to sintering. Powders may be so prepared and so treated that these transient phenomena do not take place during subsequent sintering. This does not mean, of course, that their industrial and scientific importance is any less than that of the steady-state phenomena. The latter are changes that go on during sintering no matter how the powders are made or treated; they cannot be divorced from sintering. One way to analyze the process of sintering into its component parts is perhaps to distinguish between these transient and steady-state phenomena. Some of the transient phenomena have been studied in the past few years. Huttig3 has shown that, when the temperature of metallic powder is slowly raised, the following events generally occur in order: (1) physically adsorbed gases are desorbed; (2) there is an atomic rearrangement of the surface, a sort of two-dimensional "surface-reciystallization"; (3) there is a breakdown of chemically adsorbed surface compounds; (4) there is a recrystalliza-tion in the volume of the metal. All these changes are shown by Huttig and his coworkers to be completed fairly rapidly at lower temperatures than those generally used in sintering and are therefore not a part of the mechanism whereby the density of a mass of powder continues to change after long heating at an elevated temperature. But the first and third of these changes release gases in quantities which may or may not help to control the steady-state mechanisms, depending on when the voids become isolated from the outside of the compact. Among the phenomena studied by Steinberg and Wulff,8 there is the effect on sintering of residual stresses arising from the pressing operation. They found that the lateral surfaces of a green compact of iron are under a longitudinal residual tension-stress of the order of magnitude of half the yield-point for solid iron. If the outside surface is in tension, the core must be under longitudinal compression. When the compact is heated, the surface residual stress is thermally relieved first, and the compact therefore initially expands in the direction of its axis. This is a transient phenomenon, if for no other reason than the possibility of sintering unpressed powders, as demonstrated by Delisle,9 Libsch, Volterra and Wulff10 and others.1 The subject of recrystallization is dealt with further in a separate section, in view of its prominent place in sintering literature. It, too. is one of these transient phenomena. Among the steady-state parts there may be distinguished the attraction between particles and its consequences, the spheroidization of voids in the compacts, and the densification or swelling of the compact. There is considerable evidence4,7 showing that cold metallic surfaces, when brought to within a few interatomic distances of one another, are attracted to each other by forces of the order of many thousands of pounds per square inch. A calculation, discussed in greater detail in another section, shows that this force changes but slightly when the temperature of the surfaces approaches the melting point. Actual measurements of forces of adhesion of this magnitude have been made by Bradley12 on some nonmetals, but none has yet been made on cold or hot metals. This force is of sufficient magnitude to cause some plastic deformation in powder compacts, as will be shown below. A second force of steady-state nature is due to the surface tension, which probably has the same origin as the force of attraction between surfaces.164 A paper by Udin, Shaler, and Wulff1,3 gives the results of precise direct measurements of its value for solid copper. The demonstration of the tendency for the surface tension to shrink a pore was long ago given by Gibbs.17 He showed that its effect on a curved surface between two phases is equivalent to a pressure perpendicular to that

Jan 1, 1950