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By Nicholas J. Grant, Ulf Kalling, John Chipman

THE operation of a blast furnace is dependent to an important extent upon the sulphur content of materials charged and the desired limit of sulphur in the product. It has long been known that the blast furnace is the most efficient tool for desulphurization in common use and that this efficiency is associated with the strongly reducing conditions of the hearth and is enhanced by increased basicity and fluidity of the slag. The chemical reactions of desulphurization may be studied from the viewpoint of the ratio of the process or of the final equilibrium conditions. Both kinds of studies contribute to an understanding of the process and both are included here. A simple measure of the desulphurization power of a slag is given by the ratio: Pct sulphur in slag (Pet S) Pct sulphur in metal [Pct S] This ratio was used by Holbrook and Joseph',' to measure relative desulphurizing powers under controlled laboratory conditions. It was also used by Hatch and Chipman3 as a measure of the equilibrium distribution. For the latter purpose it would be preferable to employ thermodynamic activities rather than percentages, but until very recently this has been impossible for lack of data. Now, thanks to the work of Morris and Williams and Morris and Buehl," the effects of carbon and silicon upon the activity of sulphur in the metal are known. The confirmation of this work and its extension to include the effects of other elements by Sherman and Chipman and by Rosenqvist and Cox' make it possible to calculate the activity of sulphur in pig iron of any composition. Hence it is now possible to use data on the equilibrium distribution of sulphur to find its activity in the liquid slag and to approach an ultimate solution of the thermodynamic aspects of the problem. The rate of transfer of sulphur from metal to slag is the problem of major industrial importance and indeed the principal need for equilibrium data has been as a necessary adjunct to the kinetic studies. The rate of approach to equilibrium under laboratory conditions seems slow compared to the requirements of industrial practice, and it is clear that further laboratory studies of rates are needed. In the research reported below, the items which were investigated were the following: I—The role of mechanical stirring on the approach to equilibrium. 2—The role of MgO in desulphurization as compared to CaO. 3—The role of MnO in desulphurization. 4— The limiting reactions which constitute the slow steps in desulphurization. Experimental Procedure The experimental set-up and procedure previously described by Hatch and Chipman" were essentially followed with several small modifications. The graphite crucible containing the slag and metal charge was altered to provide considerably more active stirring and mixing of the slag and metal in the carbon monoxide atmosphere. For this purpose the crucible was machined to provide two deep cylindrical wells which were interconnected at top and bottom as shown in Fig. 1. A graphite screw with a flat thread and of shallow pitch (4 threads per in.) spinning at 600 to 800 rpm was used to lift the slag and metal over the partition between the two wells and throw them over into the second well, where the metal settled through the slag into the reservoir at the bottom. It was possible to see actual particles of slag and metal being thrown over the partition. In this respect, the stirring was more vigorous than used in the work of Hatch and Chipman. A charge of 400 g of wash metal was first melted, and 20 g of FeS was then added to yield a bath containing 1.65 pct S. Immediately 400 g of slag (as pure mixed oxides) was added and fused. The slag was generally fused in 1 hr * 10 min. Within 30 to 45 min after melting, the temperature was adjusted to 1525"C, and the first slag and metal samples were taken. The slag was picked up on the end of a cold Armco iron rod, whereas the metal was sucked into a silica tube. The wash metal composition was (in percent): 4.29 C; 0.022 S; 0.021 P; 0.38 Si. The slags used were of four fixed starting compositions covering a wide range of acid-base ratios shown in Table I. Deliberate variations in MgO were made in these slags to check the role of MgO in blast-furnace desulphurization. Changes due to additions and reactions were followed by analysis of samples. Additions of Mn and MnO were made to most of the heats to note the role of Mn and MnO on desulphurization. Three heats (62 through 64) were made in an open pot induction crucible (graphite) using a

Jan 1, 1952

By J. W. Downey, M. V. Nevitt

The phase boundaries for the 950" isothermal sections in the ternary systems Zr-Co-0 and `Zr-Ni-0 have been determined for the composition range from 50 to 100 at. pct Zr. The two systems show very similar phase relations, having no extensive solid solution phase fields. Each contains a ternary phase. These phases are apparently isostructural, but their structure has not been determined. Some aspects of the phase relations are discussed in terms of the alloying behavior of transition metals. THE work described in this paper is the outgrowth of a recent study of the occurrence of phases having the Ti2Ni-type structure (structure-type E9,) in certain ternary systems involving Ti, Zr, or Hf with another transition metal and O.", In the Zr-CO-0 and Zr-Ni-0 systems no Ti2Ni-type phases were found to occur. However, there are several interesting aspects of the phase relations in the two systems which have significance from the point of view of the alloying behavior of transition metals. The results of this investigation may also have some importance in studies of the oxidation of Zr-Co and Zr-Ni alloys. In both the Zr-Co-0 and Zr-Ni-0 systems only the 950" isothermal sections were investigated and, as a further restriction, the study was limited to the composition range from 50 to 100 at. pct Zr. A tentative Zr-Co binary diagram has been published by Larsen, Williams, and Pehin. In the composition range pertinent to the present work they report a eutectic at 980°C and 75.9 at. pct Zr, the products of which are the terminal solid solution based on /3 Zr and the compound Zr2Co, and a eutectic at 1080" and 64.8 at. pct Zr whose products are Zr,Co and ZrCo. The solid solution based on /3 Zr is shown to decompose eutectoidally at 826°C into a Zr and Zr2Co. The limits of solubility of Co in a and /3 Zr have not been established. The structure of Zr2Co is not identified in the publication just cited. Dwight has reported that ZrCo has the CsC1-type strcture. The Zr-rich portion of the Zr-Ni diagram has been determined by Hayes, Roberson, and Paasche." The phase relations are very similar to those of the ZrCo system. A eutectic reaction whose products are /3 Zr containing 2.9 at. pct Ni and Zr,Ni occurs at 961°c, and a eutectic between Zr,Ni and ZrNi is found at 985". The solid solution based on /3 Zr decomposes eutectoidally at 808°C. The solubility of Ni in a Zr is not known accurately but is believed to be very small. Smith, Kirkpatrick, Bailey, and Williams7 have found that Zr2Ni has a tetragonal structure of the A1,Cu-type and that ZrNi is orthorhombic. Domagala and McPherson8 have published a constitution diagram for the system Zr-ZrO,. At 950" their diagram indicates that the solid solution of 0 in 0 Zr is stable from 0 to 0.5 at. pct while the phase field of 0 in a Zr extends from 6 to 29 at. pct. These solubility limits were adopted in the present study and no binary Zr-0 alloys were made. No previous data on the phase diagrams of the ternary systems are known to exist. EXPERIMENTAL PROCEDURE The experimental details involved in the preparation of alloys in this laboratory by arc melting have been described in several previous papers"3 and they will not be repeated here. Information concerning the purity of the metals used is given in Table I. Oxygen was added in the form of reagent grade ZrO,. All of the cast specimens in both alloy systems were annealed in air-atmosphere tube furnaces at 950 3' for 72 hr and water quenched. The specimens were protected from oxidation by wrapping them in Mo foil and sealing them in quartz tubes that had been evacuated at room temperature to a pressure of 1 x 10B mm of Hg. The phase boundaries were determined by metallography, and identification of the phases was accomplished primarily by X-ray diffraction methods which employed a powder camera having a diameter of 114.6 mm. The diffraction techniques which are in use in this laboratory have been previously described.' An etchant that proved satisfactory for most of the alloys consisted of 5 pct by vol of AgNO

Jan 1, 1962

By D. V. Edmonds, C. J. Beevers

Tensile tests were carried out on a! titanium containing 850, 1250, and 2700 ppm 0, and up to -500 ppm H. The tests were performed at -196", -78", 20°, 150°, and 300°C at a strain rate of -1.0 x 10??3 sec-1. Increasing oxygen content, increasing grain size, and decreasing test temperature resulted in enhanced embrittlement of the a titanium by the hydrogen additions. Metallographic observations showed that this can be correlated with the influence of these parameters on the introduction of cracks into the a! titanium by fracture of titanium hydride precipitates. CRAIGHEAD et al.1 reported that the hydrogen content normally found in commercial-purity a! titanium (60 to 100 ppm) was sufficient to cause a substantial lowering of the impact strength, and they attributed this embrittling effect of hydrogen to the precipitation of titanium hydride. Lenning et al.&apos; found that in commercial-purity a titanium there is an almost complete loss of impact strength at about 200 pprn H, which is approximately half the value needed to eliminate the impact strength of high-purity a titanium. They also showed that the presence of 3000 ppm hydrogen reduces the room-temperature tensile ductility of commercial-purity material to a value of the order of 10 pct; the corresponding hydrogen concentration for high-purity titanium is over 9000 ppm. It thus appears that the detrimental effect of hydrogen on the mechanical properties of commercial-purity titanium becomes evident at much lower hydrogen contents than for high-purity titanium. The main difference between the two types of a titanium might be expected to be the higher level of interstitial impurity in the commercial-purity grade. Jaffee et a1.3 studied the influence of temperature and strain rate on the hydrogen embrittlement of high-purity and commercial-purity ! titanium. In general, the behavior was the same for both materials; embrittlement was enhanced by decreasing temperature and increasing strain rate. Recent results from tests on commercial-purity a titanium containing 850 ppm O and varying amounts of hydrogen up to -500 ppm showed that the degree of embrittlement by hydrogen is intimately related to the fracture characteristics of titanium hydride precipitates.4 The present paper considers the interrelationship between the mechanical properties and micro-structural features of commercial-purity a! titanium containing 850, 1250, and 2700 ppm 0 and varying amounts of hydrogen up to -500 ppm. 1. EXPERIMENTAL PROCEDURE Three types of commercial-purity titanium supplied by IMI* were used in the investigation, and for the *Address: Witton, Birmingham 6, United Kingdom. purpose of this paper are designated Ti 115, Ti 130, and Ti 160. The principal impurity elements are given in Table I. The material was received in the form of 12.7 mm diam bars having a fully recrystallized structure. Tensile specimens with a round cross-section of 4.5 mm diam and a gage length of 15.2 mm were machined from the bars. In order to develop the same grain size (mean linear intercept of grain boundaries) in each of the three types the specimens were annealed under a dynamic vacuum of <10?5 mm Hg, Table 11. Specimen hydriding was carried out in a modified Sieverts apparatus;&apos; hydrogen was taken into solution at 450°C and after holding the specimens at this temperature for 24 hr they were furnace-cooled to room temperature at an average rate of -100 C deg per hr. By this method nominal hydrogen contents of 0, 50, 100, 250, and 500 ppm were introduced into specimens of Ti 115, Ti 130, and Ti 160 (100 ppm (wt) -0.5 at. pct). The actual hydrogen contents were calculated from the weight differences obtained by weighing the specimens before and after the hydriding treatment. Tensile tests were carried out at temperatures of -196", -78", 20°, 150°, and 300°C on a 10,000 kg In-stron machine at a nominal strain rate of -1.0 x 10-3 sec-1. Fractured specimens were sectioned in planes parallel to the tensile axis, mechanically polished to 0.25 µm grade of diamond paste, and then attack polished using a solution containing by volume 99 parts H2O, 1 part HF, and 1 part HNO3. Although the latter treatment unavoidably opened out cracks and voids visible after mechanical polishing, it did reveal the grain structure, titanium hydride morphology, and deformation twinning structure.

Jan 1, 1970

By James H. Courtright, Kenyon Richard

SILVER Bell is situated 35 airline miles northwest of Tucson, Ariz., in a small, rugged range rising above the extensive alluvial plains of this desert region. Its geographical relation to other porphyry copper deposits of the Southwest is shown on the inset map in the lower left corner of Fig. 1. The climate is semi-arid. Altitudes range within 2000 and 4000 ft. Opening of the Boot mine, later known as the Mammoth, in 1865 was the first event of note in the district&apos;s history. Oxidized copper ores containing minor silver-lead values were mined from replacement deposits in garnetized limestone and treated in local smelters. Copper production had approached 45 million pounds by 1909 when the disseminated copper possibilities in igneous rocks were recognized. Extensive churn drill exploration carried out during the next three years resulted in partial delineation of two copper sulphide deposits, the Oxide and El Tiro. Although the then submarginal tenor discouraged exploitation of these disseminated deposits, selective mining of orebodies in the sedimentary rocks continued intermittently until 1930, providing a production total of about 100 million pounds of copper. The American Smelting & Refining Co. began exploratory and check drilling in 1948 and subsequently made plans for mining and milling the Oxide and El Tiro orebodies at the rate of 7500 tons per day. Production began in 1954 at a rate of about 18,000 tons of copper annually. Formations ranging in age from Pre-Cambrian to Recent are exposed in the Silver Bell vicinity. The more erosion-resistant of these, Paleozoic limestone and Tertiary volcanics, predominate in the scattered peaks and ridges comprising the Silver Bell mountains. The porphyry copper deposits are located along the southwest flank of these mountains in hydrothermally altered igneous rocks. These are principally intrusives which cut Cretaceous and older sediments and are considered to be components of the Laramide Revolution. For three-fourths of its length the zone of alteration strikes west-northwest, Fig. 1. There now is no single structure that accounts for this alignment. However, indirect evidence suggests that a fault representing a line of profound structural weakness existed in this position prior to the advent of Laramide intrusive activity. This line will be referred to as the major structure. It was obliterated by the Laramide intrusive bodies but exerted a degree of control on their emplacement, as evidenced by their shapes and positions. The influence of fault structures on the shapes of intrusives in other porphyry copper districts has been noted by Butler and Wilson&apos; and by others. As shown on the inset map on Fig. 2, a fault of parallel trend and considerable displacement lies to the north. This fault is now marked by a line of small Laramide intrusive bodies. To the south is a third fault of large displacement. Evidence of its age in relation to the Laramide intrusions and mineralization is not recognized, but its conformance in strike with the other two major faults is significant. These three breaks establish a pronounced trend of regional faulting. They are high-angle, and the southerly one may be reverse, Stratigraphic separations on these faults are of the order of several thousand feet. The local Paleozoic section is about 4000 ft thick. It is composed predominantly of limestone with a basal quartzite member. The Cretaceous section appears to exceed 5000 ft. Conglomerates, red shales, and arkosic sandstones (the youngest) characterize the three principal members. Intrusion of alaskite marked the beginning of Laramide igneous activity. It was emplaced as an elongate stock with one side closely conforming to the major structure line throughout a distance of nearly 4 miles. The alaskite was at one time regarded as a thrust block of pre-Cambrian rock&apos;; however, its intrusive relationship and consequent post-Paleozoic age has been established by inclusions of limestone found in outcrops north of El Tiro. The next event was the intrusion of a large stock of dacite porphyry into Paleozoic sediments and alaskite. The stock was some 3 miles wide and at least 6 miles long in a northwesterly direction. It was sharply confined along its southwest side by the major structure line. A number of large pendants of moderately folded Paleozoic sediments occur within and along its southwest edge. Thus the inferred, original major fault between Paleozoic and Cretaceous sediments became a contact between alaskite and Paleozoic sediments and then a contact between dacite porphyry and alaskite. Andesite porphyry may have been intruded later than the dacite porphyry, but relationships are not clear; it may be simply a facies of the latter. The intrusive activity was at this stage interrupted by an interval of erosion. The erosion surface probably was rugged, as there were local accumulations of coarse, angular conglomerate. Subsequently a series of volcanic flows and pyroclastics several thousand feet thick was deposited. A similar unconformity has been recognized elsewhere in the Southwest, particularly in the Patagonia Mountains near the Flux mine some 75 miles southeasterly. Here, as at Silver Bell, volcanics were deposited on an erosion surface cut in Cretaceous and older sediments which had been intruded by alaskite. Though no evidence is offered that closely defines the age of this unconformity, and proper analysis of the problem is beyond the scope of this paper, it is

Jan 1, 1955

By A. Spilners, M. Simnad

The rates of formation of the different oxides on molybdenum in pure oxygen at 1 atm pressure have been determined in the temperature range 500° to 770°C. The rate of vaporization of MOO, is linear with time, and the energy of activation for its vaporization is 53,000 cal per mol below 650°C and 89,600 cal per mol at temperatures above 650°C. The ratio Mo03(vapor.lzing)/MoOS3(suriace) increases in a complicated manner with time and temperature. There is a maximum in the total rate of oxidation at 6W°C. At temperatures below 600°C, an activation energy of 48,900 cal per mol for the formation of total MOO, on molybdenum has been evaluated. The suboxide Moo2 does not increase beyond a very small critical thickness. At temperatures above 725°C, catastrophic oxidation of an autocatalytic nature was encountered. Pronounced pitting of the metal was found to occur in the temperature range 550° to 650°C. Marker movement experiments indicate that the oxides on molybdenum grow almost entirely by diffusion of oxygen anions. USEFUL life of molybdenum in air at elevated temperatures is limited by the unprotective nature of its oxide which begins to volatilize at moderate temperatures. Although the oxide/metal volume ratio is greater than one, the protective nature of the oxide film is very limited. Gulbransen and Hickman&apos; have shown, by means of electron diffraction studies, that the oxides formed during the oxidation of molybdenum are MOO, and MOO,. The dioxide is the one present next to the metal surface and the trioxide is formed by the oxidation of the dioxide. Molybdenum dioxide is a brownish-black oxide which can be reduced by hydrogen at about 500°C. Molybdenum trioxide has a colorless transparent rhombic crystal structure when sublimed, but on the metal surface it has a yellowish-white fibrous structure. It is reported to be volatile at temperatures above 500" and melts at 795°C. It is soluble in ammonia, which does not affect the dioxide or the metal. In his extensive and classic investigations of the oxidation of metals, Gulbransen2 has studied the formation of thin oxide films on molybdenum in the temperature range 250" to 523°C. These experiments were carried out in a vacuum microbalance, and the effect of pressure (in the range 10-6 yo 76 mm Hg), surface preparation, concentration of inert gas in the lattice, cycling procedures in temperature, and vacuum effect were studied. The oxidation was found to follow the parabolic law from 250" to 450°C and deviations started to occur at 450 °C. The rates of evaporation of a thick oxide film were also studied at temperatures of 474" to 523°C. In vacua of the order of 10- km Hg and at elevated temperatures, an oxidation process was observed, since the oxide that formed at these low pressures consisted of MOO, which has a protective action to further reaction in vacua at temperatures up to 1000°C. Electron diffraction studies showed that, as the film thickened in the low temperature range, MOO8 became predominant on the surface. Above 400°C MOO, was no longer observed, MOO, being the only oxide detected. The failure to detect MOO, on the surface of the film formed at the higher temperatures does not militate against the formation of this oxide, since according to free energy data MOO3, is stable up to much higher temperatures. At the low pressures employed, this oxide would volatilize off as soon as it was formed. Its vapor pressure is relatively high and is given by the equations" log p(mm iig) = -16,140 T-1 -5.53 log T + 30.69 (25°C—melting point) log p(mm He) = -14,560 T-1 -7.04 log T+1 + 34.07 (melting-boiling point). Lustman4 has reported some results on the scaling of molybdenum in air which indicate a discontinuity at the melting point of MOO, (795°C). Above the melting point of MOO,, oxidation is accompanied by loss of weight, since the oxide formed flows off the surface as soon as it is formed.5,6 Qathenau and Meijering7 point out that the eutectic MOO2-MOO3 melts at 778C, and they ascribe the catastrophic oxidation of alloys of high molybdenum content to the formation of low melting point eutectics of MOO3 with the oxides of the melts present. Fontana and Leslie -explain the same phenomenon in terms of the volatility of MOO,, which leads to the formation of a porous scale. Recent unpublished work by Speiser9 n the oxidation of molybdenum in air at temperatures between 480" and 960°C shows that the rate of weight change of molybdenum is controlled by the relationship between the rates of formation and evaporation of MOO,. They have measured the rates of evaporation of Moo3 in air at different temperatures and estimated an activation energy of 46,900 cal. This compares with the value of 50,800 cal per mol obtained by Gulbransen for the rate of sublimation of MOO, into a vacuum.

Jan 1, 1956

By Ming-Kao Yen

A considerable amount of work has been reported in the literature in regard to the texture and earing behavior of copper strip. The rolling texture of copper has been confirmed as (110) [112] and (112) [111], which yields ears of a drawn cup at the position 45" from the rolling direction.1-3 The recrystallization texture has been established as the cubic or (100) [001] texture, where the earing positions are at 0" and 90" to the rolling direction.4-8 It has also been reported that in the development of cubically aligned grains of copper strips, the percentage of this cubic texture increased with an increase of final reduction and final annealing temperature.8,9 A comprehensive study on H.C. copper (British commercial copper of high-conductivity quality = Cu 99.95 pct, O2 0.03 pct, Ag 0.003 pct, Fe 0.005 pct and Pb < 0.001 pct) was made by Cook and Richards.6 They concluded that the recrystallization textures could be described as one or more of the following textures: (1) a single texture (100) 10011, (2) a twin texture (110) [112] and (3) a random orientation, depending upon the previous history of the specimen concerned. The effect of various alloying additions in copper was reported by Dahl and Pawlek.10 They found that certain alloying additions, such as 5 pct Zn, 1 pct Sn, 4 pct Al, 0.5 pct Be, 0.5 pct Cd, or 0.05 pct P suppressed the formation of cubic texture. Brick, Martin and Angierll reported that the cold rolled textures due to various additions fitted a rather simple pattern. However, the recrystallization textures were subject to very considerable variations. In the discussion of this paper, Baldwin stated that deoxidized copper containing 0.02 pct P gave a complicated recrystallization texture at lower temperature. When this copper was annealed at high temperature, a single texture appeared which was described as (110) [ill] but. according to a pri- vate communication from Baldwin, this orientation reported was in error and should have been reported as (110)[112]. He also reported that the earing positions of drawn cups were at 60" to the rolling direction.12 Recently, Howald, in his discussion on the paper by Hibbard and Yen,13 reported that the rolling texture of phosphorus deoxidized copper, containing from 0.006 to 0.020 pct phosphorus, was of the pure copper type. When these coppers were annealed at lower temperatures, they exhibited a random orientation, and when they were annealed at higher temperatures they had a mixed (111)[110] and (100)[001] texture, depending on the severity of the final reduction and annealing temperature. However, the specific influence of phosphorus and other impurities on the recrystallization textures and the deep drawing properties of copper strip has not been thoroughly reported. Therefore, an attempt has been made in the present work to determine the rolling and recrystallization textures and also the earing behavior of five types of commercial copper and thereby to evaluate the effect of phosphorus and some other significant impurities on the development of texture for cold reductions of about 87 to 89 pct. Materials Used The five types of copper employed in the present investigation were two phosphorus deoxidized coppers of different phosphorus content (0.007 and 0.013 pct P), an oxygen-free copper (OFHC), an electrolytic tough-pitch copper, and a fire-refined tough-pitch copper. These materials were subjected to a thorough spectroscopic and chemical analysis. The designations and the chemical compositions were as shown in Table 1. The coppers, FA1, FA2 and FA3. were hot-forged from 3-in. billets into a ½ X 6-in. plate and cold rolled to the ready-to-finish gauge indicated below. FA4 and FA5 were hot rolled and scalped to ready-to-finish gauge. The grain size of all the materials in the ready-to-finish condition was about 0.030 to 0.045 mm. Table 2 shows the last stage of the production schedule for each copper strip used. Experimental Procedure ANNEALING, GRAIN SIZE AND HARDNESS DETERMINATIONS Specimens of each type of copper were finally annealed in air for periods of one hour at temperatures ranging from 300 to 1600°F and were subsequently cooled in air. The average grain diameter of the annealed specimen was estimated by comparing with a standard grain size chart. Hardness was determined on the Rockwell 15 T scale. CUPPING TESTS Cups were made in a blanking and drawing set, in which blanks of 2-in. diam were drawn to a cup of 1.25-in. diam with an average depth of about 0.75 in. The clearance between the punch and die was about 0.032 in. The ears of the cup were measured with a special fixture which read the height of ears to one-thousandth of an inch on every ten-degree interval along the circumference of the cup. POLE FIGURES The usual transmission diffraction method with unfiltered copper radiation was employed to determine the pole-figures of the specimens cold-rolled or annealed at 900°F. All the pole-figures were derived from the positions of intensity maxima on 111 diffraction rings of the X ray photo-grams taken at 10 rotation of a

Jan 1, 1950

By D. H. Thompson, A. W. Tracy

Season-cracking is a type of failure of brass that results from the simultaneous effect of stress and certain corrodants. The object of this paper is to present data that will aid in a more complete understanding of the mechanism of season-cracking and related phenomena. Results presented show that certain high copper alloys are susceptible to season-cracking or stress-corrosion cracking, and possible explanations are discussed. Starting at least as far back as 1906, many papers have been devoted to this subject but the symposium1 held in Philadelphia in 1944 is the richest source of information. In order to study season-cracking, several of the many variables were held constant so as to learn the effects of others. Season-cracking is generally understood to refer to the corrosion cracking of brass having internal stresses;²,³ it is a special case of the general stress-corrosion cracking. Inasmuch as applied stresses are more readily produced and controlled, they were used exclusively in this research and the resulting phenomenon must he called stress-corrosion cracking.²,³ Only constant tensile stresses were used. The agents believed to be most frequently responsible for season-cracking are ammonia. amines and compounds containing then]. Both moisture and oxygen also appear to he necessary. Therefore, an atmosphere containing ammonia, water-vapor and air was selected for these tests. Briefly, the work consisted of exposing sheet metal specimens, having a reduced section ¼ by 0.050 in., of copper-base alloys to the effect of static tensile stresses between 5,000 and 20,000 psi and simultaneous contact with a. continuously renewed atmosphere containing 80 pct air, 16 pct ammonia and 4 pct water vapor at 35°C. The gas mixture and the speci- mens were maintained above the dew-point. The time-to-failure in minutes was the primary measure of results. In order to limit the experiment to finite time, it was considered that a specimen which had neither failed nor undergone microscopically detectable cracking in 40,000 min. (4 weeks) while under a stress of 10,000 psi or more could be considered immune to cracking. This is merely a convenient limit and is not to be considered proof of immunity. Supplementary tests in the absence of stress using weight loss or microscopical appearance as measures of attack were made. Apparatus The apparatus used in this research is shown in Fig 1. To facilitate the description it may conveniently be divided into six parts: stress-producing units, test chamber, gas train, electrical controls, timers and gas analysis device. A stress-producing unit is shown in an exploded view at the left in Fig 2. At the right is an assembled unit with a specimen in place in the lower portion; it is this part that remains in the ammonia atmosphere during a test. The upper part contains a spring, a central threaded rod, a large nut and necessary washers, pins, and so forth. Stress is produced in the specimen by screwing down the top nut against the spring, thus putting a tensile load on the central rod and so on the specimen. The wrench that turns the nut by extending through the upper cap, is seen at the upper right of the figure. The magnitude of the load is gauged by measuring from the pin that extends through the side of the tube, to a fixed point on the large flange. Measurement is made with a vernier beam caliper, shown at the right of the figure. The necessary spring compression to give a desired stress is calculated from the calibration curve of the spring and the dimensions of the specimen. The test chamber, center Fig 1, consists of a thermally insulated steel box 32 in. long by 10 in. high by 7 in. wide. A horizontal baffle reaching nearly to each end divides the chamber equally. Below this baffle are inlets for air and ammonia, a heating coil and a fan. Thus the gases are warmed and mixed in the lower level and flow past the specimens in the upper level. A thermo-regulator and thermometer project into the upper space. The top is pierced by 12 ports flanked by 3/8 in. threaded studs. A test starts when a port is opened and a unit containing a stressed specimen is thrust through it and bolted down against a neoprene gasket. The test chamber is held at 35°C. The gas train, right rear Fig 1, carries ammonia and air continuously to the test chamber. Tank ammonia passes through two reducing valves, a needle valve, a flow meter and into the test chamber. The air from either the plant compressor or a small laboratory compressor passes through wool towers and flow controls to the flow-meter. It then bubbles through water at 34°C and through a heated line to the test chamber. Electrical controls, left rear, Fig 1, provide rectifiers and mercury relays for the test-chamber and humidifier-heating-control circuits and outlets for

Jan 1, 1950

By E. Breinan, M. Salkind

Al3Ni whiskers were chemically extracted from unidirectionally solidified Al-A13Ni eutectic ingots, bent into loops, and heated for 0.1 to 10 hr at 320°, 415", and 510°C. The initial strains ranged from 0.003 to 0.055. In all cases, permanent plastic deformation was noted after heat treatment. The deformation consisted of relatively uniform bending at low stresses and temperatures and short times and kinking followed by fracture at high stresses and temperatures and long times. After kinking, the whisker segments adjacent to the kinks were found to have straightened, which is evidence of a dislocation condensation mechanism. The range of temperatures and strains at which time dependent plastic deformation was found indicates that creep of whiskers probably plays a role in the creep of A13Ni whisker-reinforced aluminum. WHISKERS may be defined as nearly perfect single crystals which exhibit high strength. Because they can support high stresses at relatively low strains, they have been successfully employed in reinforcing metals at both ambient and elevated temperatures. In studying the creep behavior of A13Ni whisker-reinforced aluminum at elevated temperatures,1,2 it was noted that the composites exhibited measurable creep deformation. This investigation of the creep relaxation of individual A13Ni whiskel, extracted chemically from the composite was initiated to determine if creep of whiskers could con. "bute to the overall creep of the composite material. Many observations of plastic deformation of metal and halide whiskers have been made. Brenner3-8 noted that copper, silver, and iron whiskers exhibited heterogeneous plastic deformation at room temperature when strained beyond their yield points. Gyulai9 and Gordon10 observed plastic deformation of relatively large (>3 µ) NaCl and KC1 whiskers, although the smallest, most perfect whiskers were completely elastic. Eisner" noted plastic deformation and microcreep of iron and silicon whiskers at room temperature after straining beyond the yield point. Whiskers reported to exhibit creep at stresses below the yield point were zinc1&apos;-" and Silicon.15 Cabrera and price" observed some zinc whiskers which crept at room temperature after a short incubation period but then stopped creeping after a short time. Because some of their specimens exhibited no creep, they concluded that those whiskers that crept were relatively imperfect. Pearson, Reed, and Feldman15 observed similar creep behavior of silicon whiskers at 800°C. They also concluded that creep of the whiskers was a result of imperfections in their crystals. Brenner16 observed delayed failure of A12O3 whiskers at elevated temperatures but found no evidence of plastic deformation up to 2030°C (99 pct of E.EREINAN and M.SALKIND,JuniorMembers AIME,are Research Scientist and Chief, respectively, Advanced Metallurgy Section, United Aircraft Research Laboratories, East Hartford, Conn. Maunscript submitted April 5, 1968. IMD the melting temperature). Brenner also noted7 that some copper and iron whiskers exhibited delayed kinking above 350°C while others did not. One can conclude from these observations that small relatively perfect whiskers could exhibit completely elastic behavior during sustained elevated-temperature loading of composites. Since A13Ni whiskers tested in both bending and tension were found to exhibit no evidence of plastic deformation at room temperature&apos;7&apos;18 this study was initiated to determine whether or not creep of A13Ni whiskers occurred at the elevated temperatures at which creep in the composites was observed. Whiskers were chemically extracted from ingots of unidirectionally solidified A1-A13Ni eutectic, constrained in bending to various elastic strains and heat-treated. The bending constraints were removed after heat treatment and the amount of permanent set was taken as a measure of the time-dependent plastic deformation. EXPERIMENTAL PROCEDURES Ingots of eutectic Al-A13Ni containing nominally 6.2 wt pet Ni were unidirectionally solidified at approximately 11 cm per hr using a process described elsewhere.19,20 The starting materials were 99.99 pct pure. Cylindrical sections cut from the center of each ingot were placed in a 3 pct aqueous solution of hydrochloric acid and the whiskers were extracted as described previously.17 The whiskers nearest the surface were blackened somewhat due to overexposure to the acid while the center of the ingot was being dissolved These partially attacked whiskers were discarded. An intermediate zone of silver-gray-colored whiskers was collected and stored in methanol for use in relaxation experiments. Individual long pieces of A13Ni whiskers were placed on Fisher Precleaned Microscope Slides. These normally straight whiskers were bent elastically into arcs or loops of varying radii by manipulating their ends with a slender probe. The mass attraction between the whisker and the probe was sufficient to cause the whisker to follow the probe. The whiskers were retained in the elastic bend by the surface tension of a fine residual film on the slides. By using long whiskers, the action of the surface tension on the unlooped ends of the whisker allowed high elastic strains to be maintained in the loops. After each whisker was bent, a photomicrograph was taken for use in measuring the bending strain. The range of strains studied was 0.003 to 0.055. The bent whiskers were then encapsulated in Pyrex tubes at pressures between 10"6 and 5 x 10"6 mm of mercury and heat-treated at 320°, 415°, and 510°C (respectively 53, 61, and 70 pct of the peritectic decomposition temperature). After each heat treatment, the liquid film on the slides was found to have dried, but the whiskers were held in their original shapes by a residue on the slide. The minimum radius of curvature of each bent whisker was measured before and

Jan 1, 1969

By H. W. Reinhardt, J. W. Dally

A dynamic photoelastic analysis of stress waves interacting with a free surface is described. The free surface is that of a bench with a fixed bottom so common in quarry applications. The stress waves are generated by line charges of lead azide (Pb N,). Four models of identical geometry are investigated with the direction of detonation of the line charge varied between the four models. Dynamic photoelastic patterns are recorded and analyzed to indicate which method of detonating the line charge produced the largest magnitude of tension at the free surface. The mechanics of rock breakage by means of explosives has received considerable treatment by many investigators including Duvall, Obert, Broberg, Rinehart, and Langefors1-11 over the past two decades. Indeed in more recent years several texts12-15 have been written on the topic, treating a wide variety of subjects which are logically related to the modern technique of rock blasting. In rock blasting the chemical energy of a concentrated explosive contained in a relatively small diameter borehole is utilized to fragment the rock. The explosive is transformed into a gas with enormous pressures which exceed 10-5 bars18 This high pressure shatters the rock in the area adjacent to the borehole and produces dilatational and distortional stress waves which propagate radially away from the borehole. The state of stress associated with these outgoing waves produces a system of cracks which extend for a few feet from the borehole. The breakage produced in this manner is limited as the dynamic stress in the pulse attenuates markedly with distance. In the absence of a free surface, the stress wave propagates away from the source without further fracture. With a free face of rock near the drill hole, another mode of breakage occurs which is due to scabbing failure of the layer of rock adjacent to the free face. These scabbing failures are produced by the reflection of the incident waves and the conversion of compressive stresses into tensile stresses sufficiently large to fracture the rock. The detailed nature of the interaction of the stress waves with the free surface is complex and difficult to treat analytically. However, dynamic photoelasticity offers an experimental approach which gives a fullfield visual display of propagating stress waves and the reflection process. Applications of static photoelasticity to solution of problems related to mining technology have become relatively common (see, for instance, Refs. 17 and 18) with a plastic model loaded to produce a state of stress representative of that occurring in the workings of a mine. The application of dynamic photoelasticity is ex tremely limited. Tandanand and Hartman19 have used a multiple spark camera to study fracture in glass and plastic plates impacted by a chisel-shaped tool. This paper describes a dynamic photoelastic analysis of stress waves interacting with a free surface. The free surface is that of a bench with a fixed bottom so common in quarry applications. The stress waves are generated by line charges of lead azide (Pb-N6). Four models of identical geometry are investigated with the direction of detonation of the line charge varied between the four models. Dynamic photoelastic patterns are recorded and analyzed to indicate which method of detonating the line charge produced the largest magnitude of tension at the free surface. Experimental Procedure The model illustrated in [Fig. 1] was fabricated from a sheet of Columbia Resin CR-39 to represent a bench with a fixed bottom. Properties of the CR-39 pertaining to these dynamic experiments are listed in [Table 1]. Scribe lines on 1-in. centers are used to identify locations along the bench face. The bench height was 8 in., the burden was 3 in., and the overall dimensions of the sheet, 16 and 18 in., were large enough to eliminate reflections from nonessential boundaries during the period of observation of the dynamic event. To simulate a charge in a borehole, a groove 0.062 in. wide and 0.080 in. deep groove was cut into the sheet from one side. The lower end of the groove was 1 in. or 1/3 the burden distance below the bottom of the bench. The upper end of the groove was 3 in. or one times the burden distance below the upper level of the bench. The groove was packed with 60 mg of Pb No per in. of length, and ignited with a bridge wire detonator. Four different ignition procedures were used to examine the effects of detonation direction on the stress wave interaction with the free face of the bench. In Test 1 the line charge was ignited at the top and the line charge detonated downward. In Test 2 the line charge was ignited at the bottom and the charge burned upward. In Test 3 the charge was ignited in the center with the top half burning upward and the bottom half burning downward. Finally in Test 4 the line charge was ignited at both ends simultaneously. Sixteen high-speed photographs of the photoelastic fringe patterns representing the stress wave propagation were recorded for each of the tests. A Cranz-Schardin multiple spark gap camera 20,21 was operated at framing rates which were systematically varied from 110,000 to 250,000 frames per sec during each test.

Jan 1, 1972

By Linda Lee, R. E. Reed-Hill, C. R. Smeal

Four fcc metal surfaces, etched to make them responsive to polarized light, have been studied with an electron microscope. Jones&apos;prediction that these surfaces are grooved has been verified. Optical-goniometer measurements made on commercially pure nickel indicate that the groove walls are poorly defined (100) facets. Surface mientations close to either 4001 or {ill).- show no extinctions on the polam&apos;zid-light microscope. An explanation is offered for this orientation dependence. It has also been deduced that polarized-light extinctions on a grooved cubic-metal surface should not be used directly in crystallographic-orientation determinations. The nature of the etching solutions that produce these surfaces is considered. A cubic-metal surface may be made responsive to polarized light in two basic ways."&apos; In one, an anodic film, believed anisotropic, is formed on the surface. A plane-polarized-light beam, at normal incidence, should be reflected from this type of film with an ellipticity that varies with grain orientation. Under crossed polarizers of a polarized-light microscope, each grain may be distinguished from its neighbors by a difference in reflected-light intensity. An alternate treatment,&apos; more generally applicable to cubic metals and of principal concern here, involves etching of grain surfaces. The characteristic features of this surface were first deduced by Jones3 from light-microscope observations. She concluded that, in general, grain surfaces were furrowed so that light was reflected from two parallel sets of etched facets. A grooved surface produces elliptical polarization of a plane-polarized beam because the beam does not strike groove walls at normal incidence. Jones also observed that the furrows must have faces inclined to each other by approximately 90 deg, since the light returns along the incident path, and that a grooved surface should show four maxima and minima of reflected-light intensity during a 360-deg stage rotation of the polarizing microscope. Positions of maximum extinction were predicted to occur when groove axes were parallel to either polarizer or analyzer vibration directions. Because of the limited resolving power of Jones&apos; optical microscope, her deductions were primarily indirect. Proof of the correctness of her conclu-sions, as demonstrated by the electron microscope, will be given as well as evidence concerning the crystallographic nature of the etch furrows and the types of etching solutions that produce them. EXPERIMENTAL PROCEDURE During a comprehensive study of hot plastic deformation in nickel and nickel alloys, an etch was evolved that produced a surface with an excellent polarized-light response on Nickel 200 ("A" Nickel). The etching solution and associated metal-lographic procedures are given in Table I. In evaluating this etch, a study was made of the topological features of the etched surface and their relation to the underlying crystalline structure. As part of this investigation, large crystals (2 mm average diameter) were grown in a 1-cm-sq Nickel 200 specimen. After the surface was etched, the crystallographic orientations of ten grains were determined by the standard back-reflection Laue technique of Gren-inger.4 Maximum extinction positions during a microscope stage rotation were also measured for the ten grains. Groove-wall positions on the surfaces of the ten grains were measured with a two-circle optical goniometer. The technique was essentially that of Barrett and Levenson.5 Several grain surfaces were photographed with a Philips Model 100A electron microscope. All specimens were replicated with collodion, or collodion backed with formvar and chromium shadowed at 18 to 20 deg. The basic material was Nickel 200. However, an electron-micrographic study was also made of surfaces developed by polarized-light etches on other fcc metals (90-10 a brass, Monel 400, and lead). All etching procedures are given in Tables I and 11. EXPERIMENTAL RESULTS Fig. 1 shows typical electron micrographs of three different fcc metal specimens and an optical micrograph of a fourth. All photographs show a grooved structure corresponding closely to Jones&apos;3 predictions. Also, as noted by Jones, extinctions were always observed when groove axes were either parallel or perpendicular to the microscopes&apos; vertical cross hair. The symmetry of the grooves, with respect to the twin boundaries in Fig. 1, implies that furrows have a crystallographic basis. The coarse-grained Nickel 200 specimen was used to study this basis. Facet Orientation. The poles of the ten Nickel 200

Jan 1, 1964

By J. G. Richardson, J. W. Graham

The purpose of this paper is to present the results of theoretical and experimental studies of water imbibition. The imbibition processes are involved in recovery of oil from stratified and fractured-matrix formations in natural water drives and water flooding. An understanding of the role of inhibition in implementing the recovery of oil from such formations is deemed essential to proper control of these reservoirs to achieve maximum recovery. The theoretical studies involved development of the differential equations which describe the spontaneous imbibition of water by an oil-saturated rock. The dependence of the rate of water intake by the rock on the permeability, interfacial tension, contact angles, fluid viscosities and fluid saturatiorls is discussed. A few experiments were performed using core samples to determine the effects of core length and presence of a free gas suturation. The role of water imbibition in recovery of oil from a fractured-matrix reservoir by water flooding was investigated by use of a laboratory model. This model was scaled to represent one element of a frac-tured-matrix formation. Water floods were made at various rates with several fracture widths. Interpretations were made of the behavior expected in a system containing many matrix blocks. The presence of a free gas sntu.ration was found to reduce the rate of water imbibition. In the reservoir prototype of the fractured-matrix model, water imbibition rather than direct displacement by water was the dominant mechanism in the recovery of oil at low rates. INTRODUCTION Imbibition may be defined as the spontaneous taking up of a liquid by a porous solid. The spontaneous process of imbibition occurs when the fuid-filled solid is immersed or brought in contact with another fluid which preferentially wets the solid. In the process of wetting and flowing into the solid, the imbibing fluid displaces the non-wetting resident fluid. Common examples of this phenomenon are dry bricks soaking up water and expelling air, a blotter soaking up ink and expelling air and reservoir rock soaking up water and expelling oil. As increasingly better lithological descriptions have been made of the characteristics of petroleum-bearing formations, it has become obvious that imbibition phenomena which were once considered laboratory curiosities are of practical importance. For instance, in reservoirs composed of water-wet sand strata of different permeability in intimate contact, the tendency of water to channel through the more permeable stratum is offset by the tendency for water to imbibe into the tight sand and expel oil into the coarse sand. Also, in fractured-matrix formations the tendency of water to channel through the fractures is offset by water-wet matrix blocks. As some imbibition of the water into the of the largest fields in the world are fractured-matrix reservoirs, it has become increasingly important to understand all the factors involved in the imbibition process. Examples of fractured-matrix reservoirs are the Spraberry field in West Texas which produces from a fractured sandstone&apos;, the giant Kirkuk field in Iran&apos;, the Dukhan field in Qatar, Persian Gulf2, and the Masjid-I-Sula-main and the Haft-Kel fields in Southwestern Iran, which produce from fissured limestone3. Research into recovery of oil from fractured-matrix formations was stimulated by the rapid decline of oil productivity of wells in the Spraberry formation. One result of this research was the water imbibition process developed by the Atlantic Refining Co.4 Another idea was that much of the Spraberry oil could be recovered by conventional water-flooding procedures5. Subsequently, pilot floods were conducted in this field to test the feasibility of these ideas. It was felt that an understanding of the role played by imbibition processes in displacement of oil from a fractured-matrix reservoir could not be obtained from field data alone because of the many complicating factors and uncertainties involved. Therefore, theoretical and laboratory studies were undertaken to provide this understanding. Study of the equations which describe the linear, countercurrent imbibition process provided an insight into the role of various factors in the process, such as the permeability of rock and inter-facial tension. In addition to the theoretical studies, imbibition experiments were conducted with core samples to determine the effect on the rate of imbibition of such variables as core length and free gas saturation. The principal experimental studies were conducted by water flooding a scaled model of an clement of a frac-tu red-matrix reservoir to evaluate

By E. S. Bumps, M. Baeyert, W. F. Craig

SOME time ago during a study of impact properties of tempered martensite,1 it was postulated that the consistently good ductility of tempered martensite might be caused by its relatively small and peculiarly shaped ferrite grains. The fer-rite grains of tempered martensite have approximately the same size and shape as the martensite "needles." Thus they form an interlocking mass of needle-shaped grains quite different from equiaxed or lamellar ferrite grain structures. When the common mechanical test methods are applied to steel, variations are often observed in the ductility of specimens that have closely similar hardness and tensile strength values. The ductility so measured appears to be structure dependent. When steel from the same heat has been heat treated to produce different structures with the same hardness, the elongation and reduction of area values from the tensile test and the transition temperature determined by the notched-bar impact test vary according to whether pearlite, tempered martensite, or other structural constituents were produced by the heat treatment. It has been widely recognized that tempered martensite gives a consistently good performance, when tempered to the same hardness as many other structures with which it has been compared. In recent years the isothermal transformation of austenite to specific structural products and the quantitative evaluation of the character of these products with respect to their nature and response to deformation has received considerable attention. The objective of the present study was to pursue somewhat further the dependence of ductility upon structure; specifically, it was desired to ascertain whether ferrite grain structure, including both shape and size of the grains, can account for the consistently good performance of tempered martensite in the notched-bar impact test. It was thought that a simple experiment would indicate whether the ferrite grain structure plays any part in the good ductility exhibited by tempered martensite in contrast to other steel structures with different types of ferrite grains. By determining the impact transition temperature, it was proposed to compare spheroidites having similar carbide particle size and spacing but obtained in such a manner that their ferrite grain structures would be very different. Spheroidite obtained by tempering martensite, with its small, needle-shaped grains, was to be compared with spheroidite from pearlite. If the latter is produced by sub-critical annealing, the ferrite grains correspond to the pearlite colonies. Thus, if the pearlite was not too coarse, the ferrite grains of spheroidite from pearlite are equiaxed in contrast to the needle-shaped grains of spheroidite from martensite. It was thought that the ferrite grain structure of spheroidite from martensite might depend to some extent upon the grain size of the prior austenite. The austenite grain boundaries limit the maximum attainable size of the martensite needles and thus of the ferrite grains in the derived spheroidite. In order to evaluate any possible influence of prior austehite grain size, spheroidites were to be prepared from martensites that had been formed from fine-grain austenite and also from coarsened austenite. As the carbide particle size and distribution were to be essentially alike in the various spheroidites, the difference would be in the ferrite grain size and shape. Thus any marked difference in transition temperature could be attributable to the character of the ferrite grain structure. There are certain considerations in assuming that these spheroidites would be equivalent in all respects except ferrite grain structure, and an attempt was made to take them into account. One of the considerations was the choice of the carbon content of the steel. An approximately eutectoid steel was selected for two reasons. First, the pearlitic structure would contain no proeutectoid ferrite which might complicate the picture by producing a non-uniform ferrite grain structure in the resulting spheroidite. Then, too, the high-carbon content would inhibit ferrite grain growth during the sub-critical treatment. Another factor to be taken into account was the choice of an alloying element to assure a martensitic structure throughout on quenching the impact specimens. Nickel was chosen, because it is a common alloying element and resides in the ferrite both upon its formation from austenite and throughout tempering. The formation of alloy carbides, or even a large solubility of the alloying element in cementite, would have complicated the interpretation by changing the composition of the ferrite .during spheroid-ization. The possibility of temper brittleness was minimized insofar as possible by using a tempering temperature as high as consistent with the 1 pct of nickel in the steel, namely, 1150°F. While it certainly is not claimed that no difference other than ferrite grain structure could exist between the spheroidites, nevertheless, reasonable precaution has been exercised within the limits of steel metallurgy. It is believed that any large difference in transition temperatures would reflect the difference in ferrite grain structure and that relatively good ductility in the spheroidites from mar-

Jan 1, 1951

By G. Sachs, B. B. Muvdi, E. P. Klier

IT is now generally i-ecognized that hydrogen is responsible for delayed failures encountered in high-strength steels,&apos;.&apos; and the hydrogen responsible for the embrittlement is introduced in the cathodic cleaning and plating operations to which these steels are subjected. Numerous test methods have been used in the past for the determination of brittleness in embrittled parts, namely tension? = notch-tension:&apos; impact,&apos; stress-rupture: a and bend tests.% * Several of these tests are not suitable for routine testing.

Jan 1, 1958

By Pradeep K. Rohatgi, Clyde M. Adams

Structures obtained on freezing of several hypo-and hypereutectic Al-Cu alloys over a range of solidification rates have been examined. Dendrite spacing, L, increases linearly with solute concentration and with the square root of the inverse freezing rate. The relationship for hypoeutectic alloys is: where rate of change of fraction solid with time, is freezing rate, C is solute concentration, (pct Cu)=1. Mass transport in inter dendritic liquid during solidification is analyzed; the experimental observations suggest maximum concentration differences and constitutional supercooling in the inter dendritic liquid increase with an increase in the solute concentration. The dendrite morphology changes with freezing rate and alloy composition. The dendrites of the a phase are parallel, uniformly spaced plates with slow freezing and rods with rapid freezing. Nonor-thogonal side branching has been observed in phases with cubic and tetragonal structures. Side branches in a dendrites are orthogonal with slow freezing and at 60 deg with rapid freezing. Formation of second-phase envelopes around the Primary phase is also discussed. DENDRITIC structure is characteristic of many types of phase transformation. The most extensively studied so far has been solidification of liquid solutions. chalmersl and coworkers have interpreted the formation of dendrites in terms of the breakdown of a planar interface. Most of the work done concerns itself with the development of an instability at the interface. Little theoretical work has been done quantitatively to relate the parameters of dendritic structure to mass transport in the liquid phase. A few empirical relations based on the experimental2&apos;3 observations exist in the literature. Several workers2 including Brown and Adams1 have studied dendrite spacing in A1-Cu system as a function of solidification variables. In most cases, dendrite spacing has been found to increase linearly with the square root of some parameter proportional to the freezing time. The effect of solute concentration is not clear; some workers report the dendrite spacing increases with solute concentration4 whereas others report vice versa.&apos;&apos;&apos; ~ohatgi&apos; has observed an increase in the spacing between ice dendrites with an increase in solute concentration in water. Tiller has also suggested that dendrite spacing should increase with solute concentration. In the present work dendrite spacing and morphology have been examined as a function of solute concentration and freezing rate. The freezing rate is defined as the fraction of liquid solidified per unit time, dfs/dß?, where f, is the fraction solid and 8 the time. The fastest freezing rate studied was 4550 times the slowest freezing rate. THEORETICAL CONSIDERATIONS It is of interest to analyze the concentration distribution in the liquid phase between growing dendrites during solidification, Fig. 1. Since this distribution is a direct consequence of the rejection of solute by the growing solid, a diffusional process, the concentration gradients increase with the freezing rate. However, when solidification rate is the only variable in a series of experiments, the interdendritic liquid regions become smaller (i.e., the dendrites become more closely spaced) with an increase in freezing rate. The main purpose of the analytical treatment of interdendritic liquid diffusion will be to reveal a tendency for dendrite spacing to decrease with increasing solidification rate in just such a way that the maximum concentration differences developed in the liquid phase are remarkably independent of freezing rate. Two rather different analyses are set forth, one pertaining to the one-dimensional diffusion which obtains in the interdendritic liquid between parallel plate-shaped dendrites, and the other to the cylindrically symmetrical diffusion around rod-shaped dendrites during early stages of solidification. The results of the two analyses are quantitatively similar, correlating dendrite spacing, maximum concentration difference, and freezing rate. First consider the simpler one-dimensional case. Two parallel plate-shaped dendrites are separated by a distance, L, between centers, Fig. 1. Solidification takes place by the thickening of these plates, with solute being rejected into the liquid. It is assumed there is no diffusion in the solid. This thickening process is slow enough and the dendrite spacing small enough that the concentration differences which develop, although interesting and important, are very small (an important assumption which is verified ex-

Jan 1, 1968

By D. A. Elgillani, S. Atak, D. A. Rice, M. C. Fuerstenau, R. B. Bhappu

Quartz and feldspar cannot be floated with sulfonate at any pH; spodumene floats over a narrow acid pH range, while beryl responds moderately over a broad pH range. After wet-grinding in a steel mill, beryl, quartz, and spodumene float well with sulfonate below about pH 7, whereas the improvement in the response of feldspar is not so marked. A mechanism by which iron can be adsorbed on these minerals is presented. Also, the responses of leached, natural, and wet-ground beryl to amine, sulfonate, and oleate flotation are shown and related to the measured zero-points-of-charge of these materials. Earlier work with leached beryl showed that good flotation could be obtained with alkyl aryl sulfonate over a rather wide pH range using a Fagergren flotation cell.&apos; When a similar response was observed with leached quartz, it was decided that unintentional activation was being obtained from the metallic components of the Fagergren cell. To obviate this difficulty, a microflotation cell was designed, and an experimental technique was devised. These have been described elsewhere. Experiments conducted with the small cell showed that leached quartz could not be floated at any pH with any sulfonate addition,3 which is in agreement with the observations of Kraeber and Boppel.4 Similarly, it was also found that leached beryl responded to sulfonate flotation only over a narrow pH range rather than the broad range reported earlier.1 This early work,1 however, revealed the important effect that wet-grinding in a steel mill has on the flotation response of certain silicates. That is, it was found that quartz and especially beryl floated well over an unusually wide pH range after wet-grinding in a steel mill. Microcline, however, floated poorly below pH 4, even though wet-ground under the same conditions. The work of Eigeles6 on adsorption of oleic acid on leached quartz and iron-contaminated quartz at constant pH is in agreement with these flotation data. Other research has shown that ferric iron, added as a salt to the system, functions as an activator in the narrow pH range in which Fe +++ iron hydrolyzes to its hydroxy complexes.3,5 These phenomena indicate that iron functions differently in flotation systems depending on its method of introduction. The object of this paper is to determine the mechanism by which iron is adsorbed on certain minerals, the mechanism of collector adsorption after iron abstraction, and the role that Fe++ and Fe+++ assume in the selective separation of these minerals. EXPERIMENTAL MATERIALS AND METHODS Sodium alkyl aryl sulfonate, mol wt 450,7 pure potassium oleate, and pure dodecylamine were used as collectors. All other chemicals were reagent grade in quality, i.e., n-amyl alcohol as frother; HC1, H2SO4, and KOH for pH adjustment; and ferric chloride as activator. Conductivity water, made by passing distilled water through an ion exchange column, was used in the experimental work. All minerals used in the investigation were hand-picked specimens. Sample Preparation: Each of the minerals was crushed through 8 mesh, and the product was divided into two groups, one to be ground dry and the other wet. Dry grinding was accomplished with an alumina mortar and pestle. The product was dry-screened to 48 x 150 mesh, cleaned magnetically, deslimed in conductivity water, and dried. Preparation of the samples by wet-grinding involved grinding a 200-g charge of the mineral (-8 mesh) at 60% solids with natural water in a mild steel rod mill for four minutes. This charge was then wet-screened immediately with natural water to 48 x 150 mesh, dried, and cleaned magnetically. Some experiments were also conducted with leached beryl and quartz. These products were prepared by leaching the sized sample (48 x 150 mesh) with concentrated HC1 with a percolation technique until no iron could be detected in the leach liquor. Following this step, the sample was rinsed with conductivity

Jan 1, 1967

By E. A. Cisney

The formula for calculating the crystallographic angles of a tetragonal lattice is: C°S =where $ is the angle between planes (HKL) and (hkl). The angles in Table I have been calculated for indium

Jan 1, 1960

By D. L. McCain

Slurry transportation of coarse coal from the mining face to the preparation plant has proved successful in a West Virginia underground mine. Coal has been pumped from the mining section for several months. The system is currently being provided with the flexible link to the face to allow for continuous transportation. Some future plans for coal mines and projections for broader applications of the transportation method are given.

Jan 1, 1976

By James W. Neill

Bituminous coal has for many years been used for the smelting of iron-ores in the blast-furnace. In some districts in Scotland it is used alone, in others it is used mixed with coke. The similar use of certain bituminous coals in the United States has been repeatedly mentioned in the Transactions. (See, for instance, as to the Hocking Valley coal, the papers of Dr. T. Sterry Hunt, Trans., ii., 275, and vii., 313; and as to Indiana "block-coal," the paper of Mr. J. S. Alexander, Trans., i., 225.) Phillips (Elements of Metallurgy, p. 250) says: " Raw coal for blast-furnace use must be of a non-cokiog kind, and, when of suitable quality, is perhaps the most advantageous fuel." In the first

Jan 1, 1892

By K. V. S. Sastry

This paper summarizes recent research on the kinetic aspects and process behavior of agglomeration in balling circuits. The physical concepts underlying agglomeration, the mechanisms responsible for size changes during agglomeration, and a generalized population balance model for agglomeration systems are summarized. Experimental techniques for investigating the batch balling behavior and for simulating the balling- circuit operations are reviewed. Further, the effect of such operating variables as feed moisture, bentonite content, and the rate of feed addition are discussed. An approach to the computer simulation of the agglomerating circuits is shown and the importance of such models in process engineering is discussed.

Jan 1, 1977

By V. P. Yashin

Modern trends in the use of autogenous grinding of minerals have been investigated by Mekhanobr Institute. The conclusions drawn are based on experimental and theoretical investigations by the author and his coworkers. A method is suggested for determining the efficiency of converting from ball milling to autogenous grinding. A qualitative interpretation is given for comminution theory using both methods. This interpretation is used as a basis for considering both the principal trends in increasing use of primary autogenous grinding and the results of such in industrial application. Data are given from testing some ores from USSR deposits for the effect of the ore Preparation step on subsequent metallurgical treatment. Autogenous grinding is shown to be widely used in various USSR industries.

Jan 1, 1980