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By Frederick V. Lawrence

Broadly speaking, fluxes are substances which promote wetting and spreading or enhance the fluidity and manipulative properties of materials in joining, fusion, and smelting operations. The term most strictly applies to substances used to facilitate soldering and brazing; but in the discussion which follows, the definition will be broadened to include materials used to promote fusion in arc welding and which aid in the smelting of metals. In each of the mentioned applications, the role of flux and its composition differs considerably; consequently in the discussion which follows, fluxes for soldering, brazing, arc welding, and smelting applications will be considered separately. Soldering and Brazing Fluxes Soldering and brazing are metallurgical joining processes in which a joint is formed using a filler metal of composition dissimilar to that of the joined pieces (base metal). The filler metal, solder or braze, is always of lower melting point than the base metal. Consequently with these processes there is no melting of the base metal. The successful creation of the joint depends upon the wetting and spreading of the solder or braze around or throughout the joint. The obstacles to successful soldering and brazing are contaminants and tenacious oxide films on the metal surfaces. In soldering and brazing applications, fluxes act to remove and exclude oxides and other impurities from the joint. There is no fundamental difference between soldering and brazing. The distinction between them is made on the basis of temperature. Join¬ing operations carried out at temperatures above 500° C are termed brazing. The higher temperatures used in brazing enable higher melting point filler metals to be used which generally provide stronger joints. The higher temperatures of brazing processes also require fluxes which are substantially different from those used in soldering and which will remain effective at high temperatures. Consequently the distinction between soldering and brazing can also be made on the basis of the fluxes used. Soldering Fluxes Even thoroughly cleaned and degreased, metal surfaces still possess tenacious oxide films which inhibit the soldering of the joint. The reactions which form these films increase with increasing temperature. The rate of oxide formation and the tenacity of the film varies with each base metal. Aluminum, magnesium, stainless and high alloy steels, aluminum and silicon bronzes when exposed to air form hard, adherent oxide films. These metals require highly active and corrosive fluxes to remove and prevent the reformation of oxide films during soldering. Metals such as copper and silver, on the contrary, form less tenacious films at a lower rate, so that mild fluxes are sufficient. Soldering fluxes must dissolve or remove oxides and promote rapid wetting and spreading of the solder. The flux removes the oxide film by loosening and floating it off into the main body of the flux. The oxide removal is often aided by the alloying of the solder with the base metal, undermining small areas of the oxide and detaching them (Anon., 1959). The flux coagulates and suspends the oxide particles which have been loosened. The flux forms a protective cover preventing the reformation of the oxides, permitting the spreading of the solder and the formation of a metallic bond between the solder and the base metal. Constituents of Soldering Fluxes: Soldering fluxes are commonly grouped into three categories: highly corrosive, intermediate, and noncorrosive. One normally would choose to use the least corrosive flux which will give satisfactory performance.

Jan 1, 1983

By E. W. Cawthorne, R. I. Jaffee, C. M. Craighead

SOLUTION of a solid metal or alloy in a molten metal bath is used daily in melting operations, extractive metallurgical processes, and in brazing. It is generally recognized that temperature, time, agitation, and the composition of the solute metal and the solvent bath all affect solution rate. However, there is little information available in the literature on the kinetics of the process or the relative effect that these variables have on solution rate. In connection with an aluminum brazing study, data on the solution of aluminum in an A1-Si* bath to promote rapid solidification. The chemical analyses were made on drillings taken from the cast plates. The results of this work are listed in Table I. The thermal-analysis data were obtained on 200 gram samples cooled at approximately 1.5" per min. A calibrated chromel-alumel couple was used. The thermal arrests were recorded autographically on a General Electric photoelectric potentiometer recorder. The instrument was calibrated to 22.5 pct. The thermal emf was bucked with a Leeds and Northrup semiprecision potentiometer so that 1 mv represented the full scale of the GE recorder. Referring to Table I, it will be noted that the analytical results tend to be lower than the intended compositions by about 0.3 pct Si in the higher ranges. In view of the known difficulties in obtaining accurate silicon determinations by wet analysis when the silicon content is high and in view of the care that was employed in weighing and preparing the alloys, the intended compositions are believed to be more accurate than the analyses. Furthermore, when the thermal-arrest data are plotted against the intended compositions, a smooth curve is obtained, as shown in Fig. 1. This is not the case when the data are plotted against the analytical results. It will be noted from Table I that the 12.5 pct Si alloy (melt 4) showed a primary arrest at 577.6"C and the eutectic at 576.l°C. The metallographic examination of this chill-cast plate sample showed a small amount of primary silicon. These results, Fig. 1, place the eutectic at slightly less than 12.5 pct Si and are in rather good agreement with the unpublished Hanford data. In all of the subsequent work, the composition of the A1-Si dipping baths was determined by thermal analysis (spread between the primary arrest and the eutectic temperature) employing 12.5 pct Si and 577.2 °C as the composition and temperature of the eutectic. Material Preparation and Selection of the Techniques: At the beginning of this work, it was anticipated that, owing to oxide film present on the surface of the aluminum, difficulty would be encountered in obtaining rapid uniform wetting of aluminum specimens dipped in the A1-Si bath. The following etchants were investigated as possible methods of providing a thin uniform oxide film on the specimen surface: 1—phosphoric acid (H³O4), 2—fluoboric acid (HBFI), 3—sodium hydroxide (NaOH), and 4—hydrofluoric acid (HF). Tests with sheet .specimens (2x½x0.06 in.) of 2s aluminum prepared with these etchants indicated that the fast uniform wetting required for this work could not be obtained if any oxide film existed on the specimen surface. Tests were then conducted by dipping similar specimens etched in 5 pct NaOH and given a thin

Jan 1, 1956

By Thomas W. Wälde

BACKGROUND Foreign investment has been a major factor in bringing about the substantial mining industries of Chile, Peru, Bolivia, Venezuela, Brasil and Guyana. But economic nationalism and sentiment against foreiqn domination of vital national industries grew in the 1960s and most major mining projects were transferred into state owner ship. Among the state mining enterprises formed were CODELCO - Chile, MINERO-PERU/ CENTRCMIN - Peru, CCMIBOL - Bolivia (in 1952), Hierro-PERU, GUY-BAU/BIDCO - Guyana, etc. New investment during that time was discouraged because it was subject to the restrictive conditions of the investment regulations of the Andean-Pact, a grouping of Chile, Bolivia, Peru, Ecuador, Venezuela and Colombia. The philisophy was that mineral resources were to be developed exclusively by national enterprises. Essential foreign inputs had to be acquired "depackaged" as separate purchases of equipment and technical assistance services. As a result of the worldwide economic recession which hit the mining industries in 1980-1982, many projects that were viable in 1970 were not developed by the new state enterprises due to lack of capital, managerial and technical abilities and due to problems with marketing. As a consequence of the long-term decline of metal prices, governments experienced difficulty in getting investment organized through national or foreign enterprises and have had to face up to the trade-offs between national control and active mineral development. A change has since taken place in governmental policies. The 1981 Peruvian mining law, the 1982 mining law of Uruguay, the 1979/1980 mineral promotion laws of Argentina, all witness the gradual shifting of emphasis from restriction to promotion. The investment rules of the Andean Pact have been progressively softened through national regulation and today are more or less irrelevant. Nationalizations and forced renegotiations have not occurred in the last few years. Countries have gone to great lengths (without much success) to re-attract foreign investment on terms that accommodate the political sensitivities of the South American countries and the practical requirements of investors and financiers. For this analysis, three contracts have been selected which reflect this accommodation in three South American countries, where miner a1 production plays a major role in the national economy. These con tracts reflect both the attitudes and traditions of the individual countries, but also mark the shift in mineral investment policies that has taken place. EL INDIO AGREEMENT The 1977 investment agreement between Chile and St. Joe Minerals marked a dramatic relationship between Chile and foreign mining investor s. In Chile, mining of copper has played a major role in the country's history. Large scale copper mining was initiated and developed by Kennecott and Anaconda. The nationalization of these two companies under the Allende government in July 1971 started a wave of nationalizations of foreign-held mining and petroleum operations since then in many parts of the world. The military government supported the new Chilean state mining companies ((30DELCO and ENMI) , but it also attempted to accelerate mineral development by prom ting foreign private investment, thus reversing the nationalistic policies followed by the Allende and the preceding Frei government. The new policy by the military government is expressed in Decreto-Ley 600 (1974) which governs foreign investment in Chile. Decreto-Ley 600 is

Jan 1, 1985

By C. Perez-Rosales

A statistical method for determining simultaneously some of the basic geometrical characteristics of porous media such as porsity, specific surface* mean pore width, mean grain thickness and absolute permeability is presented. The proposed method is characterized by its simplicity and the minimum amount of laboratory equipment that it requires. The experimental procedure used to evaluate the various geometrical characteristics is based 'pan the 'surface analysis Of a a In view of this fact the app1icability Of the method is limited to homogeneous and isotropic materials. INTRODUCTION The behavior of a fluid flowing through a porous medium depends, among other things, upon the internal geometry of the medium; hence the importance of developing efficient methods to determine the geometrical properties of porous materials. This paper describes a statistical method to determine simultaneously some of the basic geometrical properties of porous materials such as porosity, specific surface, mean pore width, mean grain thickness and absolute permeability. The mathematical formulation has been developed that the data required to calculate the various geometrical characteristics of a sample can be easily measured by analyzing a section of the sample with an evenly spaced grid. THEORY A simple way of obtaining information about the internal geometry of a porous material is to throw a point at random over a cross-section of a sample. l-Through this procedure the porosity can be detemined.l,2 By considering that the material is homogeneous and isotropic, and that the point is dropped many times, the porosity 4 is given by where N is the total number of times the point is thrown and n is he number of times the point falls within pore areas. Another simple manner of analyzing the structural characteristics of a porous material is to superimpose an arbitrarily long line on a cross-section so that its length is evenly distributed over the surface area. Through this procedure the porosity can also be determined. If L is the total length of the line, and 1 is the sum of the lengths of the line segments within void spaces, the porosity is given by 4 = —.1.............. (2) The advantage of this type of analysis is that geometrical characteristics other than porosity can be obtained. Thus, if c represents the number of intersections between the line and the perimeter of pores, it can be shown3 that the specific surface, defined as he surface area of pores per unit bulk volume, is given by To give a proper description of the internal geometry of a porous medium, it is necessary to define quantities that characterize the notions of pore size and grain size. Unfortunately, because of the complexity of porous materials, it is difficult to give exact geometrical definitions of what is meant by the ConCePtS of "poresl' and "grains", especially when dealing with consolidated materials. Never theless, one often talks about the "size of pores" and the "size of grains" without defining accurately the terms. A possible solution to this problem follows. Assume that an arbitrarily long line is placed on a section of a sample so that the line is evenly distributed over the surface area (see Fig. 1). 1n a system like this, each line segment within a void space will be, by definition, the pore width in a given location and direction. Consequently, if the

Jan 1, 1970

By Leendert de Witte, Fred J. Radd

In many areas caring failures can be directly related to electrical currents observed in the casings. It is the thesis of this paper that the observed casing currents are mainly due to electrochemical potentials of the type in evidence on spontaneous potential curves of electrical logs. The general nature of these potentials are discussed and an equivalent circuit is given for current and potential distributions around open holes. The casing forms a short circuit to these potentials and tends to average the effects of local cells. The case of casing corrosion opposite the Dakota water sands in the salt-mud area of Kansas is discussed anil used us a qualitative, illustration of the relation between SP's and casing currents. A method of quantitative derivation of casing current distribution frorn electric log SP curves, using linear transform theory, is described and results are compared with a measured current profile. The effects of hydrogen over-potentials at the cathodic portions of the pipe are considered and some laboratory data are given in support of conclusions regarding the over-1.01tuge.s. INTRODUCTION To date an appreciable amount of work has been done on the measurement of oil well casing currents and on the correlation of the anodic portions of the current profiles with corrosive casing failures. Speculations on the origin of the casing currents have, however, remained rather vague; and although almost every plausible cause has been mentioned, there is to the writers' knowledge no clear-cut expose' on the details of the causes of the corrosive currents in the literature. A study of current surveys and casing failures in the N.W. Burnett field, Ellis County. Kan.. indicated the probability that concentration cell emf's between the Wellington salt section and the relatively fresh waters in the Dakota sands were a major cause of the corrosion currents. A more general concept evolved upon analysis of the severe corrosive conditions in the Pleistocene sands in the Ventura Avenue and San Miguelito fields in California. In this area no major variations in the salt content of the formation waters occur and yet large casing currents are observed. An explanation is found in the fact that the local spontaneous potentials which are set up due to concentration contrast between the drilling fluid and the connate water are short circuited when casing is set. The very conductive path through the casing increases the magnitude of the currents and has the tendency to average local sources over fairly large intervals. Current will flow between the sections that are predominently shaly and the sections that are mostly sandy. At the places where the current leaves the pipe, corrosive attack will occur. This same phenomenon will be present wherever unprotected pipe is set through sections that show large SP kicks on the electric logs over reasonably thick interval~. GENERAL- NATURE OF THE SPONTANEOUS POTENTIALS When a sequence of sedimentary rocks is penetrated by a drill hole filled with a mud which has a different salt concentration from that in the formation waters, various types of electrochemical potentials are established between the formations and different parts of the mud column. Opposite clean sand sections. a simple liquid-liquid junction potential will be observed; while opposite argillaccous formations, a membrane potential, often referred to as shale potential, will be established. The first quantitative analysis of these emf's in terms of liquid junction and membrane potentials is due to Wyllie.1

Jan 1, 1956

By R. E. Carter, C. Wagner, F. D. Richardson

By means of inert markers of radio-platinum, it has been shown that cobalt metal oxidizes by out-ward diffusion of cobalt atoms through the oxide. Oxidation rates have been measured at various temperatures and oxygen pressures and have been found to agree with the rates calculated from the Wagner equation and the authors' values for the diffusion coefficient of cobalt in the oxide. The distribution of radio-cobalt in growing oxide loyers has been accurately measured and found to be different from that predicted from the Wagner oxidation theory. Attempts have been made to measure the change of lattice parameter of the oxide with composition. SEVERAL investigators have shown that cobalt metal oxidizes according to the parabolic law,1-3 but no detailed study has been made of the oxidation mechanism. Cobaltous oxide has a metal-deficient lattice, but the defect concentration which is dependent on the oxygen pressure is only approximately known.' From the similarities in the structures of "CoO" and "FeO" and the rate laws governing the oxidation of cobalt and iron, Gulbransen- as suggested that cobalt, like iron," oxidizes by diffusion of cobaltous ions through the oxide layer. To substantiate this hypothesis, he has attempted to measure the oxidation rate of cobalt as a function of the oxygen pressure but has been able to report only that the rate depends on a "small" power of the pressure. On the other hand, Preece," Valensi,' and Arkharov' all have suggested from indirect evidence that oxygen diffuses through the COO to the metal-oxide interface. The present authors, in a previous paper,' have shown that the rate of diffusion of cobalt in cobaltous oxide is dependent on the oxygen pressure. In that investigation, they also found that cobaltous oxide disks made by complete oxidation of cobalt metal were porous at their centers (Fig. 5L, ref. 4). Both these facts strongly suggest that oxidation of the metal proceeds via outward diffusion of cations. In order to establish the mechanism unequivocally, oxidation experiments were made with inert radioactive platinum markers, and the dependence of oxidation rate on oxygen pressure was measured. In addition, an attempt was made to determine the form of the cation vacancy gradient, which the marker experiment showed must exist across a growing oxide layer. This was done by depositing radioactive Co on the surface of a cobalt disk and then measuring the tracer distribution across the oxide layer produced by partial oxidation of the metal. Finally, an X-ray examination was made in an attempt to find the expected change of lattice parameter of COO with oxygen pressure. Experimental The apparatus and materials used were substantially the same as those previously described by the authors.4 Marker Studies: The use of inert markers to follow oxidation reactions was first attempted by Pfeil" in 1929, and radioactive markers have recently been used by Davies et al.' In the investigation reported here, the markers were applied as an (NH4)2PtCI6 slurry in several thin streaks across both faces of four disks of cobalt metal 1 mm thick and 14 mm in diameter. The disks were then oxidized almost to completion at 1200°C in pure oxygen. After oxidation, they were mounted and sectioned and auto-radiographs were taken to locate the markers. Oxidation Rate: The oxidation rate of cobalt was measured at 1148°C at oxygen pressures ranging from 0.0055 to 1.0 atm and at 1000°, 1148", and 1350°C under 1 atm of oxygen. The rate was deter-

Jan 1, 1956

By Kehsin Kuo

DIE steel with 1.47 pct C, 0.42 pct Mn, and 8.22 pct W contains Fe,C and WC in the annealed state and WC embedded in a martensitic matrix in the hardened state (quenched from 800°C). The presence of a large amount of undissolved angular WC carbide particles makes this steel extremely wear-resistant. However, the WC carbide begins to dissolve in the austenite when the heating temperature is raised above 1000°C, but this solution process is still not complete at 1250°C although partial melting has already taken place at the austenite grain boundaries. At 1325 C, this steel contains austenite and liquid metal but no WC carbide, Fig. 1. On quenching into brine, the liquid metal solidifies into a constituent which etches differently from the austenite-martensite matrix. This constituent appears lighter than the matrix at the 1250°C stage when etched with 2 pct nital but darker in Fig. 1 when etched with Murakami's reagent. Such a constituent has also been found in burnt tungsten high speed steels. This constituent has been isolated from the matrix by anodic dissolution in a 5 pct HC1 electrolyte and was found by the X-ray powder method to be iso-morphous with &manganese, Table I. The agreement in line intensity between these two phases indicates that there is no ordering in this new phase. The calculated cube edge of this phase is 6.395A, somewhat larger than that of ß-manganese (6.30A). Besides this phase, the anodic residue also contains free carbon from the matrix and amorphous WO,, although the X-ray powder pattern of the residue shows the presence of only this phase. This makes it impossible to determine directly the composition of this phase from the residue. Attempts to prepare an alloy containing only this phase have hitherto been fruitless. The following experiments serve to show that this phase can only be obtained by drastic quenching from the liquid state and that its tungsten and carbon contents must be lower than those in the Fe,W,C carbide. On air cooling from 1325oC, the liquid metal solidifies into a eutectic consisting of austenite and the Fe3W3C carbide. The nature of this dark-etching Fe3W3C has also been ascertained by X-rays. This eutectic becomes coarser on furnace cooling. The solidification of a specimen cooled for 5 min from 1325" to 1200°C and water quenched is still not complete and the fine eutectic is formed during the quenching. Since this new phase can be replaced by a eutectic of austenite and the Fe,W,C carbide, its composition must lie somewhere between the latter two phases. The special features of this phase are: 1—it can only form directly from the liquid state by drastic quenching and 2—it is a ternary phase of iron, tungsten, and carbon. The ß-manganese structure of this phase is also interesting. In the Periodic Table, iron and tungsten lie on opposite sides of manganese; a certain combination of these two elements, in the presence of carbon, may have average properties similar to those of manganese. It has already been established that the x phase, a ternary one of iron, chromium, and molybdenum, has the a-manganese structure."' A similar phase has also been found in the ternary system Fe-Cr-W and in the following binary systems: Re-Cb, Re-Ta, Re-Mo, and Re-W.6 References 1 G. D. Preston: Philosovhical Magazine 11928) 5. 7th Series, p. 1207. - K. W. Andres: Nature (1949) 164, p. 1015. 35. G. McMullin, S. F. Reiter, and D. G. Eberling: Trans. ASM 11954) 46, p. 799. ' J. S. Kasuer: Acta Metallurgica (19541 2, p. 456. • H. J. Goldschmidt: Trans. ASM (19541 46, p. 807. P. Greenfield and P. A. Beck: Private communication.

Jan 1, 1957

By Irwin R. Higgins

CONTENTS A. Introduction B. System Description C. Uranium Pilot Plant Programs D. Summary INTRODUCTION The Chem-Seps Continuous Countercurrent Ion Exchange (CCIX) contactor was first conceived of in 1951 at the Oak Ridge National Laboratory. In the 27 years that have passed, there has been a steady stream of pilot plant process development studies on a variety of processes far too numerous to mention. These have been in the area of water and waste treatment, chemical processing, ore leach treatment, and many others. Many successful production systems have been installed and operated in a variety of applications. A few of these are described herein together with a description of the system and its operational characteristics. SYSTEM DESCRIPTION Chem-Seps Continuous Countercurrent Ion Exchange* is a single loop in which various sections are separated by valves to isolate the sections performing different functions simultaneously. (Refer to Figure 1). To explain the working of a typical unit, let us use a simple configuration used in water softening or demineralization. The resin is moved in small increments by the hydraulic ram action. All solution flows are countercurrent to the flow of resin. The contaminants are removed in the process cycle and the resin is moved in the pulse cycle. A controller in the effluent stream from the treatment section senses the proper limit permissible in the effluent. In the process cycle, the influent enters through a set of distributors, moves downward and leaves through a set of collectors. Simultaneously the regenerant enters through valve RE and leaves through valve WA. The rinse enters through valve RI and its duration is controlled by an interface controller. In the process cycle, valves B, C, and D are closed, isolating all the sections. The duration of the process cycle is 4-10 minutes depending on the contaminants to be removed and is controlled either by a timer if the contaminants are fixed, or a controller in the effluent stream, if the contaminants fluctuate at short intervals. Valve A is open and resin is dropped to the pulse section simultaneously with the removal of contaminants in the treatment section, regeneration of loaded resin in the strip section, and rinsing of regenerated resin in the rinse section. As the resin drops through the valve A, it is backwashed to remove the suspended solids or resin fines. Removal of these fine particles is important to avoid the unnecessary pressure drop in the bed and plugging of the distributors. At the end of process cycle, all flows going into the unit and out of unit are automatically shut off. The valve A closes and valves B, C, and D open in proper sequence. A slug of water enters through valve PU, a predetermined incremental volume of resin moves into the regeneration section, an equal volume of regenerated and rinsed resin enters the bottom of the treatment section, and an equal volume of the loaded resin leaves the top of the treatment section and goes into the resin reservoir section. (The resin movement is plug flow with the Reynold's number being in the laminar region of the curve, and no fluidization occurs during the pulse cycle.) The total time required for proper sequencing of valves and the movement of resin is 20-30 seconds. At the end of this period, the valves B, C, and D close and valve A opens. The solution valves open and normal steady state operation begins. All valves are interlocked and properly sequenced. The resin movement is precisely controlled by sonic devices. Special Features of Chem-Seps CIIX "Downflow"*: The raw feed in the treatment section moves downward and the resin moves upward in the treatment section. The "downflow" of feed overcomes the handicap encountered in "upflow" systems. The "upflow" of feed requires a certain minimum flux during process cycle to lift the bed and keep it

Jan 1, 1979

By Reuel A. Cochrane, Harry H. Angst

The successful exploitation by opencut methods of the low-grade porphyry copper deposits is due to the economical handling of large tonnages. Large tonnages are possible only if the rock material is broken so that the large power shovels can operate with minimum delays. This is particularly true at the New Cornelia mine, where the dense, hard, tough rock material creates problems not encountered in most of the porphyry copper mines. The introduction of churn drills at the New Cornelia for primary drilling, in 1936, necessitated a complete change in the methods of breaking ground as formerly air drills had been used. The blasting operations are of particular interest because of the handling of great quantities of high explosives in safely and efficiently fragmenting the hard rock material. Rock Formations At the New Cornelia mine the rocks are quartz monzonite with a diorite border facies intruding a rhyolitic series. Overlying these formations is a fanglomerate formation composed of boulders of monzonite, diorite, rhyolite, and other types of rock of unknown derivation. (The word "fanglomerate" is used in this paper in referring to the local conglomerate type of rock formations.) The ore body is approximately 4800 ft. long and 2800 ft. wide, and is of the disseminated type. Mineralization occurs principally in the quartz monzonite and to some extent in the adjacent diorite and rhyolite. The principal ore minerals are chalcopyrite, bornite, and a small amount of chalcocite. Over a considerable area the quartz monzonite is extremely hard and siliceous in character, owing to pegmatitic zones of alteration. The hardness of the ground depends on the intensity of the silicification. In a small area in the pit, the monzonite contains an abundance of pyrite accompanied by sericitization and is soft and easily fragmented. This is true also in the remaining oxidized portion of the ore body. The diorite and rhyolite formations, like the monzonite, vary from extremely hard to very soft material, but on the whole are easier to fragment than the monzonite. Jointing is prevalent in all the rock formations and plays an important role in the blasting efficiencies. In the fanglomerate formation, numerous well-defined joints, widely spaced, tend to make the ground blocky when blasted. This is a deterrent to good fragmentation. In the other rocks the joints are more numerous and are closely spaced, except in localized areas where the formations are extremely hard. These descriptions indicate that the lowest blasting efficiency will be obtained in the harder formations, from which the major portion of the mine production is obtained; namely, the monzonite and rhyolite. All rock formations mined at the New Cornelia pit are so hard that excavation

Jan 1, 1943

By M. R. Pickus, I. W. Pickus

Ordinarily age-hardening is thought of as being associated with a limited solubility of one metal in another. Much less has been written about the type of age-hardening that attends the formation of superstructures. Solid solutions generally have a disordered or random arrangement of atoms; that is to say, in a unit cell, such as that of the face-centered cubic lattice, there is no distinction between atomic sites. Atoms of a given metal may occupy cube corners or face centers. Under certain conditions, however, some alloys develop what is known as an ordered structure. In this case, cube corners would be occupied by only one type of atom and face centers by another type. Associated with this ordering process are many interesting changes in physical and electrical properties. Moreover, in many instances the alloys become susceptible to age-hardening. From the evidence now to be described, it appears that age-hardening in 14-carat gold alloys is due to the formation of both a superstructure and a precipitate. Alloys of the metals gold, silver and copper were known in antiquity. The available knowledge regarding their constitution has been ably summarized and extended by Sterner-Rainer,' Jänecke,2 Carter,3 Wise,4 and Coleman.5 Despite the long familiarity with these alloys and the numerous investigations of their properties that have been made, there is still much that remains unexplained. It has been known for a long time that the hardness of these alloys is closely related to the rate of cooling. Similar changes have been observed in the binary gold-copper systemI6 one alloy of which corresponding to the formula CU³AU, has been the subject of a careful and competent report by the English investigators, Sykes and Evans.7 They have established the fact that the shift of atoms from the ordered to the disordered condition takes place in some critical temperature range. At temperatures above the critical range the structure is random, and at temperatures below it the structure is ordered. No difference between these two structures is revealed by the microscope. Both have a face-centered cubic lattice and complete solubility, so that there is no evidence to suggest that the changes in properties are associated with a phase change. The more slowly the alloy is cooled, the higher is the degree to which the ordering process proceeds and the more marked is the increase in hardness. As experimental data were accumulated on I4-carat gold alloys, several contradictions arose. Certain observations tended to confirm the existence of a superstructure, while other observations seemed to be inconsistent with such a transformation. Present Investigation As a focal point about which to develop this subject, it is expedient to consider first

Jan 1, 1943

By Gray L. L., Max Littlefield, Godbold A. C.

The West Edmond pool of Central Oklahoma, a limestone reservoir, has an area in excess of 29,000 acres and as of Sept. 15, 1946, had produced 53 million barrels of oil from 731 wells at an average depth of 6900 ft. Water has encroached into the reservoir along the west side of the pool and although the area of water invasion is large the net volume of water influx is small, because encroachment has been primarily into a fracture system. The most significant part of this study concerns the character of the Hunton reservoir. Geological study of cores of the producing section was made to supplement core-analysis data. It was determined that approximately 90 pct of the pore volume was contained in intergranular or sand-like porosity and 10 pct in fractures (intermediate porosity). The porous limestone is divided into blocks by the fractures, although in the strongly dolomitic parts of the producing section, fractures are less well developed. The low-permeability intergranular porosity, largely subsidiary to the high-permeability fractures, will produce oil into the fractures by evolution of solution gas. The fractures in effect serve as drainage channels for production of oil from the inter-granular porosity. Because of such a large difference in permeabilities of the two com-ponents, a high degree of by-passing will occur, and, accordingly, the economics involved in undertaking full-scale high pressure gas injection operations have been seriously questioned. Introduction The West Edmond Hunton pool, which covers portions of Canadian, Logan, Oklahoma, and Kingfisher Counties in Central Oklahoma, is the largest reservoir producing oil from a limestone in the state. The total area of the pool comprises about 29,240 acres and development is considered to be essentially complete. In all, 731 producing wells have been completed in the Hunton reservoir at an average depth of approximately 6900 ft, and have yielded a cumulative oil production in excess of 53 million barrels as of Sept. 15, 1946. In addition to wells completed in the Hunton limestone, 21 wells have been completed in the Bartlesville sand at a depth of approximately 6500 ft, which have produced a total of 730,000 bbl of oil. One small producer has been completed in the Cleveland sand at a depth of 5700 ft. However, a study of only the Hunton limestone reservoir will be presented in this paper. The most significant phase of this study concerns the special type of geological core examination that was made in an effort to ascertain the type and degree of porosity in the rock in accordance with lithologic types. Results of this geological study showed the west Edmond pool to be of such a complex nature as to appreciably affect the behavior normally associated with homogeneous reservoirs. Recognition of this condition in the

Jan 1, 1948

By M. N. Dunlap

Tries article summarizes the successful incorporation of a flash-flooding stream into the tailing-disposal system at the St. Joseph Lead Company's Federal Division mill, in St. Francois County, Missouri. The mill was built in 1906, by the Federal Lead Co., as its No. 3 mill for the concentration of southeastern Missouri lead ores, and damming Davis Creek was first considered in 1908. Plans were made also in 1925 and in 1937. Dam layouts varied from a reinforced concrete structure to a barrier built of tailings alone. All were abandoned because of liability that would be incurred by flashflood rupturing of an incompleted dam. By 1942 mill capacity had reached 12,000 tons daily and increasing tailing-disposal costs again focused attention on the Davis Creek basin. This time the problem of riskless dam building was solved. Moreover, most of the items that appeared in the answer were materials that normally required wasting and the major portion of labor involved performed functions that it would normally have done, without constructive benefit, elsewhere. The new layout also made possible advantageous changes in mill-water supply pumping; static head being reduced from 514 ft to 95 ft, friction head from 4900 ft to 2860 ft, and pumping can be done now at periods of low power demand. The following facts about the Davis Creek watershed explain the 36-year reluctance to reach these, and other, benefits. Size: 3600 acres. Outline: roughly pear-shaped, 2 1/2 by 3 miles at the largest dimensions. Topography: mostly hill land with steep valleys. Relief : 760 minimum to 1153 maximum. Maximum rainfall: 3.36 in. per hour. Permanent water: none natural. Now 2200 gpm discharged through 16-in. drill hole from mine pumps underground. Geology: the 17 acres near dam centerline is Bonne Terre dolomite covered with sand and gravel eroded from Pleistocene beds that cap some of the hills. The remainder of the pond basin is on Davis shale. Soil cover: mostly second-growth timber with some abandoned fields; all subject to careless burning, which reduces water-retaining ability. Flood history: flash-flooding that had taken at least one life. Downstream values: two railroad bridges before creek intersection with Flat River. Immediately below confluence, a highway bridge, a low-water crossing, a few business establishments and several blocks of residences. In July 1942 the following segments of an ingenious plan were put into operation. A ditch 270 ft long, 16 ft wide and 5 1/2 ft deep was excavated to bedrock in the gravelly soil along the proposed dam's centerline. This excavation, which exposed many gravel-filled channels, was run full of slimes drawn from a riser set in the top of an adjacent tailings-disposal

Jan 1, 1947

By J. M. Flaitz, A. S. Parks

OF the various methods of sampling gas-condensate wells, a method that secures a continuous representative sample of the well stream is desirable. Such a method, consisting of a sampling tube introduced into the well tubing, has proved satisfactory. The method is sufficiently accurate for operating and engineering problems. A portable testing apparatus can be used with the sampling tube to obtain data useful in studying the economic and technical aspects of the development and operation of gas-condensate properties. INTRODUCTION The recent discovery and development of gas reserves that contain hydrocarbons that condense with reduction of temperature or pressure, or both, to form a product known as condensate, has brought many new problems to the oil and gas industries. With further discovery of deep, high-pressure fields it is presumable that many more gas fields of this type will be added to the steadily increasing number. Such gas reserves are found either associated with oil as a gas cap or in separate formations. There seems to be no positive correlation between the physical or geological nature of the reservoir, and the chemical composition or phase characteristics of its contents. Knowledge of the chemical make-up and phase behavior of gas-condensate reserves are needed to cope with many problems. A knowledge of the chemical composition and phase characteristics of the reservoir material is necessary to properly design a gasoline or recycling plant, to estimate natural gas and condensate reserves, to enable the operator to study the economic and technical aspects of various methods of operation and development, and to carry out the plan of operating subsurface and surface lease equipment. This information is often useful in questions of mineral ownership, proration, legal position, and taxation. It is the purpose of this paper to discuss methods used by the writers to determine the chemical composition and phase characteristics of the fluids produced from a condensate well. The scope of the paper includes a discussion and description of the method of sampling, the results of tests on the accuracy of the sampling method, a description of a portable testing apparatus used to examine the phase characteristics, typical results of tests on wells from several condensate fields, and some of the applications of these data to production problems. References to previous work on this subject are cited at the end of the paper. THE PROBLEM At reservoir conditions of temperature and pressure, the fluids produced from a condensate well exist in a homogeneous vaporous condition. The consequent reduction of temperature and pressure that occurs as this gas enters and flows up the well tube results in condensation of some of the hydrocarbon material to form a liquid. The relative amount of liquid condensed at any point in the flowing system

Jan 1, 1941

By M. R. Pickus, I. W. Pickus

Ordinarily age-hardening is thought of as being associated with a limited solubility of one metal in another. Much less has been written about the type of age-hardening that attends the formation of superstructures. Solid solutions generally have a disordered or random arrangement of atoms; that is to say, in a unit cell, such as that of the face-centered cubic lattice, there is no distinction between atomic sites. Atoms of a given metal may occupy cube corners or face centers. Under certain conditions, however, some alloys develop what is known as an ordered structure. In this case, cube corners would be occupied by only one type of atom and face centers by another type. Associated with this ordering process are many interesting changes in physical and electrical properties. Moreover, in many instances the alloys become susceptible to age-hardening. From the evidence now to be described, it appears that age-hardening in 14-carat gold alloys is due to the formation of both a superstructure and a precipitate. Alloys of the metals gold, silver and copper were known in antiquity. The available knowledge regarding their constitution has been ably summarized and extended by Sterner-Rainer,' Jänecke,2 Carter,3 Wise,4 and Coleman.5 Despite the long familiarity with these alloys and the numerous investigations of their properties that have been made, there is still much that remains unexplained. It has been known for a long time that the hardness of these alloys is closely related to the rate of cooling. Similar changes have been observed in the binary gold-copper systemI6 one alloy of which corresponding to the formula CU³AU, has been the subject of a careful and competent report by the English investigators, Sykes and Evans.7 They have established the fact that the shift of atoms from the ordered to the disordered condition takes place in some critical temperature range. At temperatures above the critical range the structure is random, and at temperatures below it the structure is ordered. No difference between these two structures is revealed by the microscope. Both have a face-centered cubic lattice and complete solubility, so that there is no evidence to suggest that the changes in properties are associated with a phase change. The more slowly the alloy is cooled, the higher is the degree to which the ordering process proceeds and the more marked is the increase in hardness. As experimental data were accumulated on I4-carat gold alloys, several contradictions arose. Certain observations tended to confirm the existence of a superstructure, while other observations seemed to be inconsistent with such a transformation. Present Investigation As a focal point about which to develop this subject, it is expedient to consider first

Jan 1, 1943

By Max Littlefield, Godbold A. C., Gray L. L.

The West Edmond pool of Central Oklahoma, a limestone reservoir, has an area in excess of 29,000 acres and as of Sept. 15, 1946, had produced 53 million barrels of oil from 731 wells at an average depth of 6900 ft. Water has encroached into the reservoir along the west side of the pool and although the area of water invasion is large the net volume of water influx is small, because encroachment has been primarily into a fracture system. The most significant part of this study concerns the character of the Hunton reservoir. Geological study of cores of the producing section was made to supplement core-analysis data. It was determined that approximately 90 pct of the pore volume was contained in intergranular or sand-like porosity and 10 pct in fractures (intermediate porosity). The porous limestone is divided into blocks by the fractures, although in the strongly dolomitic parts of the producing section, fractures are less well developed. The low-permeability intergranular porosity, largely subsidiary to the high-permeability fractures, will produce oil into the fractures by evolution of solution gas. The fractures in effect serve as drainage channels for production of oil from the inter-granular porosity. Because of such a large difference in permeabilities of the two com-ponents, a high degree of by-passing will occur, and, accordingly, the economics involved in undertaking full-scale high pressure gas injection operations have been seriously questioned. Introduction The West Edmond Hunton pool, which covers portions of Canadian, Logan, Oklahoma, and Kingfisher Counties in Central Oklahoma, is the largest reservoir producing oil from a limestone in the state. The total area of the pool comprises about 29,240 acres and development is considered to be essentially complete. In all, 731 producing wells have been completed in the Hunton reservoir at an average depth of approximately 6900 ft, and have yielded a cumulative oil production in excess of 53 million barrels as of Sept. 15, 1946. In addition to wells completed in the Hunton limestone, 21 wells have been completed in the Bartlesville sand at a depth of approximately 6500 ft, which have produced a total of 730,000 bbl of oil. One small producer has been completed in the Cleveland sand at a depth of 5700 ft. However, a study of only the Hunton limestone reservoir will be presented in this paper. The most significant phase of this study concerns the special type of geological core examination that was made in an effort to ascertain the type and degree of porosity in the rock in accordance with lithologic types. Results of this geological study showed the west Edmond pool to be of such a complex nature as to appreciably affect the behavior normally associated with homogeneous reservoirs. Recognition of this condition in the

Jan 1, 1948

By Harry H. Angst, Reuel A. Cochrane

The successful exploitation by opencut methods of the low-grade porphyry copper deposits is due to the economical handling of large tonnages. Large tonnages are possible only if the rock material is broken so that the large power shovels can operate with minimum delays. This is particularly true at the New Cornelia mine, where the dense, hard, tough rock material creates problems not encountered in most of the porphyry copper mines. The introduction of churn drills at the New Cornelia for primary drilling, in 1936, necessitated a complete change in the methods of breaking ground as formerly air drills had been used. The blasting operations are of particular interest because of the handling of great quantities of high explosives in safely and efficiently fragmenting the hard rock material. Rock Formations At the New Cornelia mine the rocks are quartz monzonite with a diorite border facies intruding a rhyolitic series. Overlying these formations is a fanglomerate formation composed of boulders of monzonite, diorite, rhyolite, and other types of rock of unknown derivation. (The word "fanglomerate" is used in this paper in referring to the local conglomerate type of rock formations.) The ore body is approximately 4800 ft. long and 2800 ft. wide, and is of the disseminated type. Mineralization occurs principally in the quartz monzonite and to some extent in the adjacent diorite and rhyolite. The principal ore minerals are chalcopyrite, bornite, and a small amount of chalcocite. Over a considerable area the quartz monzonite is extremely hard and siliceous in character, owing to pegmatitic zones of alteration. The hardness of the ground depends on the intensity of the silicification. In a small area in the pit, the monzonite contains an abundance of pyrite accompanied by sericitization and is soft and easily fragmented. This is true also in the remaining oxidized portion of the ore body. The diorite and rhyolite formations, like the monzonite, vary from extremely hard to very soft material, but on the whole are easier to fragment than the monzonite. Jointing is prevalent in all the rock formations and plays an important role in the blasting efficiencies. In the fanglomerate formation, numerous well-defined joints, widely spaced, tend to make the ground blocky when blasted. This is a deterrent to good fragmentation. In the other rocks the joints are more numerous and are closely spaced, except in localized areas where the formations are extremely hard. These descriptions indicate that the lowest blasting efficiency will be obtained in the harder formations, from which the major portion of the mine production is obtained; namely, the monzonite and rhyolite. All rock formations mined at the New Cornelia pit are so hard that excavation

Jan 1, 1943

By Harry H. Angst, Reuel A. Cochrane

THE successful exploitation by opencut methods of the low-grade porphyry copper deposits is due to the economical handling of large tonnages. Large tonnages are possible only if the rock material is broken so that the large power shovels can operate with minimum delays. This is particularly true at the New Cornelia mine, where the dense, hard, tough rock material creates problems not encountered in most of the porphyry copper mines. The introduction of churn drills at the New Cornelia for primary drilling, in 1936, necessitated a complete change in the methods of breaking ground as formerly air drills had been used. The blasting operations are of particular interest because of the handling of great quantities of high explosives in safely and efficiently fragmenting the hard rock material. ROCK FORMATIONS At the New Cornelia mine the rocks are quartz monzonite with a diorite border facies intruding a rhyolitic series. Overlying these formations is a fanglomerate formation composed of boulders of monzonite, diorite, rhyolite, and other types of rock of unknown derivation. (The word "fanglomerate" is used in this paper in referring to the local conglomerate type of rock formations.) The ore body is approximately 4800 ft. long and 2800 ft. wide, and is of the disseminated type. Mineralization occurs principally the quartz monzonite and to some extent in the adjacent diorite and rhyolite. The principal ore minerals are chalcopyrite, bornite, and a small amount of chalcocite. Over a considerable area the quartz monzonite is extremely hard and siliceous in character, owing to pegmatitic zones of alteration. The hardness of the ground depends on the intensity of the silicification. In a small area in-the pit, the monzonite contains an abundance of pyrite accompanied by sericitization and is soft and easily fragmented. This is true also in the remaining oxidized portion of the ore body. The diorite and rhyolite formations, like the monzonite, vary from extremely hard to very soft material, but on the whole are easier to fragment than the monzonite. jointing is prevalent in all the rock formations and plays an important role in the blasting efficiencies. In the fanglomerate formation, numerous well-defined joints, widely spaced, tend to make the ground blocky when blasted. This is a deterrent to good fragmentation. In the other rocks the joints are more numerous and are closely spaced, except in localized areas where the formations are extremely hard. These descriptions indicate that the lowest blasting efficiency will be obtained in the harder formations, from which the major portion of the mine production is obtained; namely, the monzonite and rhyolite. All rock formations mined at the New Cornelia pit are so hard that excavation

Jan 1, 1941

By R. F. Mehl, B. Lustman

The formation of intermediate phase layers in cementation processes has been subjected to extensive qualitative investigation though to relatively little quantitative study; this work has recently been fully summarized by F. N. Rhines.' It is necessary here only to cnumerate the general conclusions drawn concerning the kinetic laws governing the growth of intermediate layers and to state what is known concerning the structural changes accompanying the generation of phase layers. I. When the intermediate phase is protective in type—i.e., when its density is less than that of the base metal, so that a continuous coating is formed and maintained—the isothermal growth of the phase follows a simple parabolic equation: X2 = kt [i] where X is the thickness of the alloy layer, k thc reaction rate constant, and t the time. The applicability of this equation to diffusion processes is tested by plotting the square of the thickness versus time, or by plotting the thickness versus the square root of time; the resultant achievement of a straight line in such a plot has been considered sufficient proof of the validity of this equation. Exceptions have been found where liquid phases are involved in the reaction, where the diffusion layer is cracked,2 and where thin semimetallic oxide and sulphide coatings are formed on metals.$ In the first two cases the thickness increases linearly with time, and in the latter it is a logarithmic function of time. 2. The rate of thickening varics with temperature according to the Arrhenius equation: k = Ae-Q/RT [2] where k is the parabolic rate constant of Eq. I, or some other rate-descriptive function, A is the action constant, e the base of natural logarithms, Q the heat of activation, R the gas constant, and T absolute temperature. This equation has been found to be generally valid except when transformations occur during reaction in either the base metal or in the reaction layer; in such instances Eq. 2 is still applicable with different values for the constants A and Q above and below the transformation temperature. 3. Ali phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two components. In some cases certain of the phases may be too thin to be observed and identified easily. Nonequilibrium phases have never been noted in thick reaction layers; i.e., layers of a thickness that may be discerned microscopically. The relative thickness of each phase in a diffusion layer is proportional to the concentration gradient and to the rate of diffusion in that phase.4 The reaction layers tend to have a

Jan 1, 1942

By Otto H. Henry, J. J. Cordiano

Though powder metallurgy is one of the oldest of metallurgical processes, it is in its infancy as a branch of the modern field of metallurgy. As early as 3000 B.C., the ancients produced implements and weapons of iron by reducing iron ore in a charcoal fire and forging the resultant sponge while still hot into the desired shape. Melting and casting soon superseded the powder metallurgy practice, and it was not until the turn of the twentieth century that powder metallurgy was applied to the commercial manufacture of tungsten lamp filaments. From this beginning, the use of the powder metallurgy process spread" to the manufacture of porous oil-impregnated bearings, cemented carbide tools, contact points, diamond grinding wheels, clutch facings, starter brushes, resin-bonded radio cores, magnets, metallic filters, and other parts. More recently, and particularly during the present war, there has been a definite trend toward the manufacture of machine parts by this process in competition with the more conventional fabricating methods. Notwithstanding these many developments, scientific progress has been slow. While many articles on powder metallurgy have appeared in the press and various publications, there have been too few contributions to our technical societies, with the result that there is a dearth of the type of information necessary for the full development of this science. It is of primary importance that the results of research and development be freely disseminated if powder metallurgy is to realize its fullest potentialities. Purpose of Investigation Excluding the refractory metal field, all commercial powder metallurgical products made by a cold compressing and sintering operation contain voids. These voids can be substantially eliminated by subsequent severe working and heat-treatment, but ' such practice has not proved economical in most applications. By applying heat during the compressing operation, plastic deformation of the powder particles is substantially increased, and the resultant compact or briquette is practically free of voids. However, hot-pressing has many attendant problems, which at present preclude its use in the manufacture of precision parts. The more important of these are to devise: 1. A die steel capable of withstanding high pressures at elevated temperatures. 2. A high-temperature lubricant capable of preventing excessive die wear and welding of the compact to the die walls. 3. A method of retaining a neutral or reducing atmosphere in the compacting zone of the die assembly. 4. A means of ejecting the hot-pressed specimen into a neutral atmosphere until reasonably cold.

Jan 1, 1946

By M. C. Udy, C. H. Lorig

THROUGH the years much interest has been centered in attempting to develop a direct method of iron-ore reduction, to replace or supplement the present indirect blast-furnace process. It would not be difficult to produce a list of more than 500 patents dealing with the direct production of iron and steel, but the few of this type of process that have proved successful do not produce in competition with the blast furnace; they produce special products. A survey of the literature reveals that the equilibrium conditions for the reduction reactions (iron oxides with carbon monoxide and with hydrogen) have been fairly well established but that data on the rate of reaction are discordant, although the general effects of the variables are known. This dissertation deals with the rate of reduction of a magnetite concentrate with hydrogen. The following variables have been studied: bed depth, gas velocity, particle size and temperature. The behavior of a single particle was also studied. LITERATURE Two general factors should be considered in a study of reduction of iron oxide: (I) equilibrium relations, and (2) rate of reaction. The first factor, equilibrium, has received the attention of many investigators and the equilibria Fe304-FeO-H2-H20, Fe3O4-FeO-CO-CO2, FeO-Fe-H2-H20, FeO¬Fe-CO-C02 are fairly well established. Of the second factor, the rate of reaction, much less is known. Data are comparatively scarce and there is very little concordance. The discordance probably results from the large number of variables influencing the reactions. However, the general effect of the variables is known. Among these variables are temperature, gas velocity, particle size, porosity, gas composition (distance from equilibrium), presence of impurities, greater or less prevalence of side reactions, and even design of the apparatus itself. Wetherill and Furnas1 published an excellent paper in 1934. They point out that any one or more of five processes (the chemical reaction, diffusion of the reactant through the gas film, diffusion of the reactant through the solid phase, diffusion of the reaction product through the solid phase, or diffusion of the reaction product through the gas film) may be the slow process, and thus the rate-controlling process. It is regretted that the work of these authors was limited to experiments at one temperature, and that the range of gas compositions was limited. Langmuir2 has shown that heterogeneous reactions take place at phase boundaries.

Jan 1, 1942