Search Documents

By J. W. Spretnak, J. N. Cordea

The gain boundary relaxation in high-purity aluminum, nickel, copper, and silver was studied by means of a low-frequency torsion pendulum. Both internal friction and creep at constant stress tests were conducted. A lognormal distribution in relaxation times was found to account for the relatively wide experimental internal friction peaks and the gradual relaxation behavior during the creep tests. This distribution was separated further into a lognormal distribution of relaxation time constants and a normal distribution in activation energies. A spread of up to ±6 kcal per mole in the activation energies accounted for the major part of the distribution. A "double-peak" internal friction phenomenon was observed in silver. The activation energies in kcal per mole derived from the grain boundary relaxation phenomena are 34.5 for aluminum, 73.5 for nickel, 31.5 for copper, and 41.5 for silver. It was found that the rain boundary relaxation strength in these metals increases with the reported stacking-fault energy. GRAIN boundary relaxation phenomena have been observed in a large number of polycrystalline metals and alloys. Numerous investigations have been conducted to study the structure of the grain boundary through this relaxation process. One of the first investigators was Ke1-4 who observed that the activation energy for grain boundary relaxation in aluminum, a brass, and a iron was about the same as that for volume diffusion. He concluded that the grain boundary behaved as if it were a thin liquid layer with neighboring grains sliding over one another. Leak5 conducted experiments on iron of a higher purity and observed that the grain boundary activation energy is comparable with that of grain boundary diffusion. He suggested that, in metals where this relationship holds, the damping may be caused by a reversible migration of grain boundaries into adjoining grains. Nowick6 has presented an interesting view of inter-facial relaxation with his "sphere of relaxation" model. A relaxed interface is represented as one where the shear stress is greater than the normal value along the edges and zero in the interior of the interface. The region of the stress relaxation is pictured as a sphere surrounding the interface. From his calculations Nowick concluded that the slip along an interface is directly proportional to its length. Therefore, the time of relaxation, T, depends on the size of the relaxation interface. This means that in the Arrhenius relationship, t = TO exp[H/RT], valid for atom movements, the relaxation time T is predicted to be proportional to the grain diameter through the pre-exponential term, TO. Since the internal friction can be given as Q-1 = ?j wt/(1 + w2r2), where ?J is the relaxation strength and w is the angular frequency, an increase in grain size at a constant frequency will shift the peak to a higher temperature. A great deal of work has been done to determine the exact relationship between the internal friction and grain size.1,5,7,8 In metals, the grain boundary peaks are found to be lower and broader than predicted theoretically.' The above model can explain this by a distribution in the size of the interface areas, represented by a distribution in the parameter tO, and an overlap of spheres of relaxation, represented by a distribution in activation energies. Both these phenomena result in an over-all distribution in the relaxation time, which could affect the internal friction peak height, breadth, and also position. This relationship between the experimental data and theoretical calculations appears very promising in the study of interfacial relaxation mechanisms. THEORY A lognormal distribution in t can sometimes be used to adequately describe the spectrum of relaxation times governing an anelastic relaxation. wiechert9 originally suggested such a distribution to explain the elastic after-effect in solids. This choice is particularly applicable to grain boundary relaxation when considering Saltykov's work.'' He found a lognormal distribution in the grain sizes within a metal. Recently Nowick and Berry11 have introduced a log-normal distribution in T into the theoretical internal friction equations. The form of the distribution function is where z = In(r/rm), and Tm is the mean value of t. The parameter ß is a measure of the distribution and is the half-width of the distribution when is l/e of its maximum, IC/(O). Nowick and Berry have described the methods to obtain the parameters Tm, ß, and ?,J from experimental internal friction and creep test data. In the idealized case, where only one relaxation event occurs with one relaxation time, only ?J and T are necessary to completely describe the event, and 0 = 0. For the broader internal friction curves 6 is some positive number greater than zero. The larger the 6, the greater is the half-width of the distribution in In t.

Jan 1, 1967

By N. Mungan

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

Jan 1, 1966

By 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 H. D. Merchant

NUMEROUS publications have examined hot hardness of metals and alloys. Some have studied creep in long-time hardness tests, few of which, however, were tested under a spherical indentor. 1-3 The results of Mulhearn and Tabor&apos; indicate a parabolic-type creep for indium and lead, whereas Moore and Tabor2 how a logarithmic-type creep for indium. Similar semilog relationships between hardness and time have been found by Goffard and wheeler3 for magnesium, aluminum, and their alloys. In this note, the elevated-temperature hardness of some complex alloys, shown in Table I, was examined to discover whether any basic information about the deformation behavior of the alloys could be obtained. One of the alloys, H-13 alloy steel, was tested for short-time creep tests to examine the hardness-time relationship at various temperatures. A standard Brinell Hardness Tester, mounted with an appropriate furnace and 99 pct A12O3 poly-crystalline indentor, was employed for the purpose. The alloys were tested at temperatures from room to 1400°F for 30 sec under 1500-kg load. The creep studies were conducted for about 8500 sec at 7l°, 500°, 1000°, and 1200°F. For constants A and B, a relationship of the type H = Aexp(-BT) [ll was obtained for all alloys between hardness, H, and temperature, T. In the semilogarithmic plot, the data points for each alloy were arranged into two groups, each group on a straight line with a specific set of A and B values. These results are in agreement with many such observations on hot hardness, notably those of Westbrook for pure metals,4 The thermal softening coefficient, B, and transition temperature, Tt, for various alloys are shown in Table I. The change in slope around the transition temperature suggests an apparent change in the mechanism of deformation, probably from the shear (below Tt) to the diffusion type of mechanism. At the temperatures above Tt, for constants A&apos; and B, a relationship of the type was obtained between H and T, Fig. 1. The nature of the equation, where R is gas constant, suggests the possibility of a thermally activated mechanism of deformation above Tt. The constant B&apos; may hence be defined as the apparent activation energy of indentation. The B&apos; values of various alloys are shown in Table I. A plot of B vs B&apos; gives a curvilinear relation shown in Fig. 2. The indentation-creep data for H-13 alloy steel is shown in Fig. 3. At 71" and 500°F, the creep initially follows the logarithmic time law. However, the indentation size stabilizes after 7 sec at 71°F, and after 10 sec at 500°F. Further increase in loading time has no effect on indentation size. The creep of 1000° and 1200°F follows the logarithmic time law for the first 1000 sec, after which the

Jan 1, 1964

By Robert Glass Cleland

[George B. Agnew Cleveland H. Dodge James Douglas E. Hayward Ferry Francis L. Hine Arthur Curtiss James1908-1941 1908-1926 1908-1918 1908-1935 1908-1927 1908-1941]

Jan 1, 1952

By A. Stanley, J. C. Mead

E. H. ROSE*—You have wrapped up a great deal of new and interesting information in one quite compact package, and I wonder if it might not help the

Jan 1, 1950

By T. H. Weldon, L. V. Whiton, R. R. McNaughton, J. H. Hargrave

R. H. McNAUGHTON*—The Smelting Co. and Mr. Reid and his men at Selby are to be congratulated on the job they have done on sinter gas recircula-

Jan 1, 1950

By R. H. Frazier, J. M. Hodge, F. W. Boulger

This paper reports the results of studies of the impact properties of quenched and tempered alloy-steel plates as a function of sulfur content. It was found that the impact energy levels decreased continuously as the sulfur content increased and that there was a straight-line relationship between impact energy and sulfur content when plotted on logarithmic coordinates. Cross rolling raised the level of these Lines for transverse tests and lowered the level for logitudinal tests proportionately to the amount of cross rolling. ALTHOUGH it has been generally recognized that, for applications in which notch toughness is critical, the sulfur content of the steels used should be held to a low value, quantitative information on the effect of sulfur on notch toughness has not been available. For such applications, it is a common practice to specify minimum impact values, and in order that these may be met consistently it is important that the steel producer know quantitatively the effect of sulfur on notch toughness so that realistic sulfur content limits can be applied to the steels they produce. In many instances, particularly in flat-rolled products, impact properties are specified in the direction transverse to the principal rolling direction, so that the factors affecting the anisotropy or directionality of impact properties are also of concern to the steel producer. For some applications, furthermore, it is a common practice to increase the sulfur content of steels in order to improve their machinability, and, in such instances, the effect of this practice on notch toughness may often be of concern. This paper reports on an investigation, carried out at Battelle Memorial Institute, designed to furnish this quantitative information on the effect of sulfur on notch toughness and also to furnish further information on the factors affecting the anisotropy of impact properties in wrought heat-treated alloy steels. MATERIALS AND EXPERIMENTAL PROCEDURE The experimental steels were of intended base analysis: 0.30 pct C, 0.80 pct Mn, 0.25 pct Si, 2.5 pct Ni, 0.80 pct Cr, and 0.45 pct Mo. Steels were made with sulfur contents varying from 0.005 to 0.179 pct. The steels were prepared from 600-lb induction-furnace melts. Steels containing 0.020 pct or more sulfur (at meltdown) were melted from a charge of ingot iron (except for one heat): lower-sulfur steels were made from electrolytic iron. The charge consisted of ingot or electrolytic iron, ferrosilicon to give 0.10 pct Si, and ferromanganese to give 0.05 pct Mn. At meltdown, electrolytic nickel, ferromolybdenum, iron phosphide, and pyrite were added followed in sequence by ferrochromium, sili-comanganese, ferrosilicon, and ferromanganese. The slag was then removed and graphite added to give the desired carbon content. Bath temperature was adjusted to 2850°F and, when no other additions were to follow, 2 lb per ton of aluminum was added, immediately before tapping. Compositions of the experimental steels appear in Table I. Analyses are from single determinations, except sulfur which was analyzed in duplicate. A test sample (3 in. in diam by 6 in. long) and a 575-1b ingot were poured from each heat. The test sample was poured in a sand mold; the cooling rates of the test sample and the large ingot were approximately the same. Chemical analysis chips and metal lographic specimens were taken from the test samples. The ingot was 8 in. sq at the base and 9 in. sq at the top. A 5 X 5 X 6-in. sand mold hot top was completely filled in teeming the ingot. After solidification, the mold was stripped from the ingot which cooled to room temperature. Ingots were reheated to 2250"F and rolled to 1.9-in. slabs on a commercial mill. The slabs were box-cooled to room temperature. Sections of the 1.9-in. slabs were heated to 2250°F and rolled on a Battelle laboratory mill according to one of three schedules: 1) rolled straightaway to 0.5-in. plate; 2) rolled straightaway to 1.3-in. thickness, then cross rolled to 0.5-in. plate (29 pct cross rolling); or 3) cross rolled from 1.9-in. to 0.5-in.-thick plate (46 pct cross rolling). The 0.5-in.-straight- or cross-rolled plates were normalized at 1700°F for 1 hr and then water quenched from 1600°F. Plates were then tempered 2 hr at 1240°, 1170°, 1080°, or 860°F to obtain Rockwell C hardness of 25, 30, 35, and 40, respectively. Tempering was followed by quenching to room temperature to avoid temper embrittlement. Slack-quenched plates were isothermally transformed for 26 min at 800°F, quenched, and tempered 2 hr at 1170°F. Pearlitic microstructures were obtained by holding 168 hr at 1200° F, followed by quenching. Charpy V-notch specimens were taken both transverse and longitudinal to the main rolling direction, notched perpendicular to the plate surface, and tested. Slabs and plates which were to be homogenized

Jan 1, 1960

By Robert A. Rapp, Ronald L. Pastorek

Solid-state electrochemical measurements by three alternative experimental procedures were made with the cell FeO, Fe3O4 |Zro.85Cao.15O1.85 |Cu| Zr0.85CaO.15O1.85 | FeO, Fe304 to establish the solubility and diffusivity of oxygen in solid copper in the temperature range 800" to 1030°C. The solubility of oxygen in solid copper and the diflusivity of oxygen in solid copper Dgu = 1.7 X 10-2 exp(-16,000/RT) Cm2/sec were determined and confirmed in alternative experiments. The enthalpy of solution of oxygen in solid copper equals —10,000 cal per mole; the partial excess entropy of the oxygen atoms in the Cu-O dilute solution is approximately the same as that found for interstitial atoms in other metals. The diffusivity of oxygen in solid copper is consistent with that expected for an interstitial atom. RELIABLE values for the saturation solubility N(s) and diffusivity DO of oxygen in solid copper have not been unambiguously established in the literature. Following three early determinations by others,1"3 Rhines and Mathewson4 reported that the solubility of oxygen in solid copper increased from 0.007 at. pct 0 at 600°C to about 0.015 pct at 1050°C. Phillips and skinner,, using essentiially the same analytical procedure, reported that the solid solubility increases from 0.0018 at. pct 0 at 550°C to about 0.0075 pct at 1050OC. The only previous value for the diffusivity of oxygen in solid copper was reported by Ransley.6 Ransley deoxidized Cu-Cu2O alloys in an atmosphere of carbon monoxide gas to yield a solubility-diffusivity product. He used the solubility data of Rhines and Mathewson to calculate the diffusivity values. Another method for obtaining the solubility-diffusivity product (N(s) DO) is by measuring the widths of internal-oxidation zones in copper alloys as reported by Verfurth and Rapp.7 However, the calculated N(S)Do products depend upon the alloy content of the specimen, so that the internal oxidation of copper alloys does not follow ideal internal oxidation kinetics. As a result, unequivocal values for the N(s) DO product were not obtained by this procedure. A solid-state coulometric titration technique similar to that employed in this work was introduced by C. Wagner8 to study the dependence on silver activity of the Ag/S ratio in silver sulfide in the temperature range of 160" to 300°C. Similar experiments have been carried out by C. Wagner and co-workers9-11 to study the stoichiometry range of silver and copper tellurides, cuprous sulfide, and cuprous selenide. Numerous authors have carried out electrochemical measurements with a solid oxygen-ion-conducting electrolyte to determine the solubility and/or diffusivity of dissolved oxygen in several liquid metals.12-l6 Rickert and Steiner17,18 have used solid-state electrochemical measurements to determine the diffusivity of oxygen in solid silver from 760" to 900°C. Two different cell geometries were used. In the cell of linear geometry Fe, FeO | ZrO2 + (CaO) | Ag + [0 (dissolved)] [1] oxygen diffused from the interior of the silver electrode to the silver/electrolyte interface where the oxygen activity had been lowered from a fixed initial value to practically zero by the application of voltage to the cell. The diffusivity of oxygen in solid silver was determined from the solution of the diffusion equation and the time dependence of the cell current. However, this determination of the diffusion coefficient depended upon a knowledge of the solubility of oxygen in solid silver. A cylindrical geometry was used for the cell Pt, O2(Po2 = 0.21 atm) | ZrO2 + (CaO) | Ag + [0 (dissolved)] [II] which also allowed the diffusivity of oxygen in solid silver to be determined. These values were in agreement with other available data.l9 Recently, Raleigh20,21 used a method involving the measurement of diffusion-limited currents in a cell involving the AgBr solid electrolyte to determine the diffusion coefficient of silver in Ag-Au alloys at 400°C. Diffusivity values on the order of l0-14 sq cm per sec were measured in the alloy composition range 10 to 60 at. pct Ag in a single experiment. From numerous electrical conductivity and galvanic cell measurements,9&apos;22"26 the solid solution Zr0.85 Ca0.15 O1.85 has been established as an electrolyte with predominant oxygen ion conduction over a wide range of intermediate and high oxygen activities. For interrelating the thermodynamics and the kinetics of the dissolution of oxygen in solid copper in this investigation, a galvanic cell was constructed with FeO-Fe3O4 as the reversible reference electrode, the Zr0.85Ca0.15 O1.85 electrolyte, and a pure copper specimen under-saturated in oxygen as the other electrode. THEORETICAL ANALYSIS Three variations of a high-temperature electrochemical technique were used in this study to provide two determinations each of the solubility and diffusivity

Jan 1, 1970

By John S. Crandall

THE mineral garnet, while ordinarily considered a semiprecious gem stone or a second-grade industrial gem, has also proved itself in the field of industrial abrasives. Its use is well known as a sandpaper grain, and as a sandblasting sand its qualities are rapidly becoming recognized in more and more industries. Production of garnet as an abrasive is confined chiefly to two areas in the United States, North Creek, N. Y., where the Barton Mines Corp. operates, and Emerald Creek, Benewah County, Idaho, where Occurrence: Garnets in the Emerald Creek area occur as disseminated crystals in beds of micaceous schists of the Belt Series, which in this section are estimated to be close to 4000 ft thick. The schists are high in alumina and silica with iron, manganese, and magnesium. Subjection of the original sediments to high temperatures and pressures caused metamorphism to take place with the resultant re-crystallization of high alumina-silica minerals such as garnet, mainly spessartite and almandite varieties, cyanite, sillimanite, chlorite, actinolite, tourmaline, biotite, and muscovite, with minor amounts of ilmenite and magnetite. Quartz is also present in considerable amounts. Fast erosion of the soft mica schists on exposure to weathering has created extensive alluvial deposits containing up to 10 pct garnet having a maximum grain size of 3/16 in. These alluvial sands and gravels are now being treated for the recovery of garnet sands. Treatment: Overburden of 1 to 4 ft must be stripped to expose the garnetiferous gravels. This operation and the subsequent feeding of the gravels to a trommel-screen washing plant are performed by a % yd dragline. The trommel-screen openings are 3/16 in., thus allowing a separation and concentration based on grain size, since over 95 pct of total free garnets are minus 3/16 in. All plus 3/16-in. material is wasted at this point. The minus 3/16-in. material is further concentrated in a sand-drag classifier, where the slimes and silts are washed out and wasted. The sand product from the classifier varies in garnet content from 20 to 60 pct according to the particular section of ground being worked. This sand product is trucked to a jig plant where two sized fractions are made in a trommel-screen. The minus 3/16-in. plus 10-mesh portion is fed to a Pan-American two cell 42-in. jig. The minus 10-mesh portion is treated in a Bendelari three cell 42-in. jig. The jig concentrates are combined to form a 98 pct garnet sand. The jig tailings contain 3 to 5 pct garnet which is mainly flat crystals and chips which will not settle into the jig hutch. Subsequent treatment of these tailings in a scavenger jig followed by drying and electromagnetic separation will, according to tests, reduce the garnet losses in the tailings to something around 1 pct. Jig treatment of this feed approaches ideal as the major portion of the garnet crystals are the natural dodecahedrons and so are, in general, close to spherical. The specific gravity of pure garnet is 4.2, while the next heaviest mineral in the feed is cyanite with a specific gravity of 3.6, then quartz with specific gravity of 2.6. The garnet concentrate is practically free of quartz. The predominant impurity is cyanite which amounts to about 1.5 pct. The rod-like crystals of cyanite appear to up-end in the jig and go into the hutch with the garnets. Some ilmenite and magnetite appear in the concentrate but in very minor amounts. Subsequent washing in a sand-drag classifier removes fine silts and iron oxides. The gravel feed to the washing plant will average 8 pct recoverable garnet content. Concentration ratio in this plant runs about 2.5 to 1. Washing-plant concentrate as fed to the jigs will average 45 pct garnet by weight. Concentration ratio of jigging runs about 2.2 to 1. The garnet concentrate is dried in a rotary oil-fired drier and then fed to vibrating screens in closed circuit with crushing rolls. Practically any grit from 10-mesh down to 150-mesh grain size may be graded to specifications in two 3-deck vibrating screens. The present production, however, is approximately 75 pct No. 36, 15 pct No. 60. and the balance No. 80 and No. 100. Metal-screen cloth is used for sizes down to 36 mesh. From 36 mesh and finer, silk-screen cloth is used since it has less tendency to blind. All garnet sand is bagged in 100 lb self-sealing, sleeve-type paper bags. Practically all shipments are made in carload lots. Car loading is convenient since the plant is in Fernwood on the tracks of a branch line of the Milwaukee railroad. Truck shipments can and are made occasionally.

Jan 1, 1951

By John S. Crandall

THE mineral garnet, while ordinarily considered a semiprecious gem stone or a second-grade industrial gem, has also proved itself in the field of industrial abrasives. Its use is well known as a sandpaper grain, and as a sandblasting sand its qualities are rapidly becoming recognized in more and more industries. Production of garnet as an abrasive is confined chiefly to two areas in the United States, North Creek, N. Y., where the Barton Mines Corp. operates, and Emerald Creek, Benewah County, Idaho, where Occurrence: Garnets in the Emerald Creek area occur as disseminated crystals in beds of micaceous schists of the Belt Series, which in this section are estimated to be close to 4000 ft thick. The schists are high in alumina and silica with iron, manganese, and magnesium. Subjection of the original sediments to high temperatures and pressures caused metamorphism to take place with the resultant re-crystallization of high alumina-silica minerals such as garnet, mainly spessartite and almandite varieties, cyanite, sillimanite, chlorite, actinolite, tourmaline, biotite, and muscovite, with minor amounts of ilmenite and magnetite. Quartz is also present in considerable amounts. Fast erosion of the soft mica schists on exposure to weathering has created extensive alluvial deposits containing up to 10 pct garnet having a maximum grain size of 3/16 in. These alluvial sands and gravels are now being treated for the recovery of garnet sands. Treatment: Overburden of 1 to 4 ft must be stripped to expose the garnetiferous gravels. This operation and the subsequent feeding of the gravels to a trommel-screen washing plant are performed by a % yd dragline. The trommel-screen openings are 3/16 in., thus allowing a separation and concentration based on grain size, since over 95 pct of total free garnets are minus 3/16 in. All plus 3/16-in. material is wasted at this point. The minus 3/16-in. material is further concentrated in a sand-drag classifier, where the slimes and silts are washed out and wasted. The sand product from the classifier varies in garnet content from 20 to 60 pct according to the particular section of ground being worked. This sand product is trucked to a jig plant where two sized fractions are made in a trommel-screen. The minus 3/16-in. plus 10-mesh portion is fed to a Pan-American two cell 42-in. jig. The minus 10-mesh portion is treated in a Bendelari three cell 42-in. jig. The jig concentrates are combined to form a 98 pct garnet sand. The jig tailings contain 3 to 5 pct garnet which is mainly flat crystals and chips which will not settle into the jig hutch. Subsequent treatment of these tailings in a scavenger jig followed by drying and electromagnetic separation will, according to tests, reduce the garnet losses in the tailings to something around 1 pct. Jig treatment of this feed approaches ideal as the major portion of the garnet crystals are the natural dodecahedrons and so are, in general, close to spherical. The specific gravity of pure garnet is 4.2, while the next heaviest mineral in the feed is cyanite with a specific gravity of 3.6, then quartz with specific gravity of 2.6. The garnet concentrate is practically free of quartz. The predominant impurity is cyanite which amounts to about 1.5 pct. The rod-like crystals of cyanite appear to up-end in the jig and go into the hutch with the garnets. Some ilmenite and magnetite appear in the concentrate but in very minor amounts. Subsequent washing in a sand-drag classifier removes fine silts and iron oxides. The gravel feed to the washing plant will average 8 pct recoverable garnet content. Concentration ratio in this plant runs about 2.5 to 1. Washing-plant concentrate as fed to the jigs will average 45 pct garnet by weight. Concentration ratio of jigging runs about 2.2 to 1. The garnet concentrate is dried in a rotary oil-fired drier and then fed to vibrating screens in closed circuit with crushing rolls. Practically any grit from 10-mesh down to 150-mesh grain size may be graded to specifications in two 3-deck vibrating screens. The present production, however, is approximately 75 pct No. 36, 15 pct No. 60. and the balance No. 80 and No. 100. Metal-screen cloth is used for sizes down to 36 mesh. From 36 mesh and finer, silk-screen cloth is used since it has less tendency to blind. All garnet sand is bagged in 100 lb self-sealing, sleeve-type paper bags. Practically all shipments are made in carload lots. Car loading is convenient since the plant is in Fernwood on the tracks of a branch line of the Milwaukee railroad. Truck shipments can and are made occasionally.

Jan 1, 1951

By J. A. Rowland, C. W. Funk

THIS investigation is a part of the United States Bureau of Mines work in conserving the Nation&apos;s resources. The isothermal sections presented were developed as a guide to a comprehensive investigation of the properties and fabricating characteristics of copper-base alloys containing manganese and tin. These alloys are being investigated as possible replacements for the commercial bronzes containing substantial quantities of tin. Development of the isothermal sections has, therefore, been limited to the area between 0 to 20 pct Mn and 0 to 25 pct Sn. Since Heusler1 reported the ferromagnetic properties of the Cu-Mn-Sn alloys in 1903, the system has been the subject of several investigations. These studies were largely concerned with correlation of magnetic properties and crystal structure.2-6 Vero,&apos; however, established the solidus surface of the system, between 20 pct Mn and 40 pct Sn, by thermal and microscopic methods. The a, ß, and y solid solutions were also observed by Vero and reported to extend into the interior of the ternary system. For the present study, the annotated diagram of the Cu-Sn system prepared by Raynor&apos; and the Cu-Mn diagram by Dean and coworkers9 were used as the binary borders of the ternary system. Procedure The metals used in this investigation were electrolytic manganese, washed cathode copper, and three-star tin. The manganese, produced at the Boulder City pilot plant of the Bureau of Mines, had a purity of 99.9 pct; the copper contained less than 0.004 pct Bi and 0.001 pct S; the tin contained 0.070 pct Pb, 0.070 pct Sb, 0.050 pct Fe, and 0.065 pct Si. Heats of 1 lb were melted in alundum crucibles with a 3-kw induction furnace. The heats were chill-cast in iron or copper molds to form 6-in. ingots 3/4 in. in diameter. Molds were washed with graphite or zirconia, depending on the manganese content, and preheated to 150°C. The maximum impurity content of any alloy was 0.03 pct Fe, 0.02 pct Si, and 0.02 pct Al; in most cases, they contained less than half this quantity of any of these impurities. Composition of the alloys and their treatment prior to homogenizing are shown in Fig. 1. Designations adjacent to each composition refer to the heat numbers. With a few exceptions, ingots containing 20 pct Sn or less were hot-swaged. These ingots were swaged, after a 24-hr preheat at 650°C, to obtain a total reduction of 70 pct in cross section. Intermittent reheating was necessary, and reductions were limited to either 0.025 or 0.050 in. in diameter per pass. Selection of a 200-hr homogenizing treatment was based on extensive experiments which indicated that virtual equilibrium was reached after 150 hr. Structures were retained by quenching in water. Grain sizes in the specimens homogenized at 350" and 450°C were generally small. These homogenizing treatments were preceded by a 50-hr anneal at 650°C to facilitate phase identification by increasing the grain size in these specimens. The specimens were furnace-cooled from this temperature to the homogenizing temperature, and the heat treatment was continued for the standard 200-hr period. The homogenized samples were bisected to provide an internal section for metallographic examination. Optimum definition of the microstructure was obtained by successive polishing and etching. Quarter-strength ASTM copper reagent No. 13 gave the most satisfactory results.10 Filings from interior sections of the samples were used for diffraction studies. These filings were annealed in evacuated glass tubes at homogenizing temperatures for periods exceeding 50 hr and quenched in water. During this treatment the manganese content was reduced by significant amounts, probably by vaporization. This change in composition was considered in applying the diffraction data, which were used only as a means of identifying phases where the data were consistent with the metallographic evidence. Phase Identification The a solid solution is readily distinguished by the copper-colored, twinned, polyhedral grains, as shown in Fig. 2, and a face-centered cubic X-ray pattern. Tukon indentations, using a 25-g load, indicate a Knoop hardness of 155 for a quenched from 650°C. Using white light developed by a Wratten 78 A filter, the ß grains in etched specimens have a dark brown tint in contrast to the lighter copper-colored grains of the a phase. Knoop hardness values of 284 were obtained for the ß structure in specimens quenched from 650°C. The ß structure was also distinguished from the a phase by its body-centered cubic lattice. The acicular structure appearing in Fig. 3 was evident in several alloys of higher tin content after quenching from either 750&apos; or 650°C. Since a trans-

Jan 1, 1954

By Wm. C. Madge, H. P. Allen

The chloridizing mill of the Standard Reduction Co. is located about 75 miles south of Salt Lake City on the Tintic branch of the Denver & Rio Grande Western R. R. and 12 miles from the Tintic Standard mine. The daily capacity is 200 toss of a siliceous, low-grade, silver-lead ore from this property. It has operated continuously since it was started in January, 1921. The process consists essentially of a chloridizing roast followed by a percolating leach with a nearly saturated solution of common salt, acidified with sulfuric acid, the precipitation of silver on sponge copper and of copper and lead on tin-plate cuttings. The precipitates are shipped to a smelter. Some of the general ideas involved are said to have been used by Augustin in England, in 1840. A number of textbooks treat of the subject, especially the chloridizing roast followed by a leach with sodium hyposulfite or amalgamation. The process was revived in this district by Theo. P. Holt, N. C. Christensen, the Bureau of Mines, and others. Nature of Ore Treated The average assay of the ore treated during 1924 is as follows: Gold, ounces per ton...................................... 0.025 Silver, ounces per ton..................................... 18.26 Copper, per cent......................................... 0.30 Lead, per cent........................................... 5.00 Silica, per cent........................................... 65.00 Iron, per cent............................................ 10.00 Lime, per cent........................................... 0.70 Sulfur, per cent.......................................... 3.00 Arsenic, per cent......................................... 0.70 The silver is finely disseminated and occurs as native, combined as a sulfide and, to a very small extent, as the chloride. The lead may be present as carbonate, sulfide, or sulfate.

Jan 1, 1926

By H. R. Peiffer

Recently artin has indicated that the recovery of resistivity at 145°C following elongation of molybdenum at room temperature was the result of the annihilation of vacancies. The activation energy for this process was, according to Martin, 1.26 ev. This energy seems to be a reasonable one for the activation energy for the diffusion of vacancies in molybdenum. However, impurity atoms such as carbon, nitrogen, and oxygen4 have an activation energy for diffusion in molybdenum of the same order of magnitude (i.e., 1.45, 1.15, and 2.09 ev, respectively). Cottrell and Churchman have already correlated the return of impurity atoms to dislocations in cold-worked iron with the return of the upper and lower yield point. According to cottrel16 the diffusion of carbon atoms to dislocations results in the return of the yield point. As the carbon atoms become trapped by dislocations, Bhatia has shown that a decrease in the electrical resistivity is to be expected. Cottrell and Churchman were able to correlate experimentally the decrease in electrical resistivity with the return of the yield point. Since one would expect strain aging to occur in molybdenum, an experiment was performed to determine whether the resistivity recovery at 150°C for molybdenum cold-worked at room temperature can be correlated with the return of an upper and lower yield point. For this experiment 3/16-in. tensile bars of Climax molybdenum, 99.961 pct pure, were used. The specimens were annealed at 1000° C for 1 hr in an argon atmosphere and then were elongated up to 10 pct on a Baldwin-Lima-Hamilton FGT

Jan 1, 1959

THE LIFE and works of Alexander Agassiz, first president of the Calumet & Hecla Mining Co., were recalled to memory when a monument bearing his statue was unveiled in Agassiz Park, at Calumet, Mich., on Sept. 26, The statue is the work of Paul W. Bartlett, of New York, and was erected by George R. Agassiz, eldest son of Alexander Agassiz. We are indebted to Rodolphe L. Agassiz, now president of the Calumet & Hecla Consolidated, for the accompanying photograph of the statue. The principal address at the unveiling ceremony was delivered by Allen F. Rees, of Houghton, who said, in part: To the world at large Alexander Agassiz was preeminently the man of science. With all his devotion to the industrial life of this district, he found the time to devote to the con-tinuation of his work of scientific research which had been the life work of his fa-ther, Louis Agassiz. Not only did he acquire eminence for his scientific at-tainments and learn-ing, but he was recognized and hon-ored throughout the civilized world for his achievements and accomplishments in the realm of original research. His work in the fields of nat-ural science, in oceanography, in marine zoology, and in other similar lines of research, has added much to our knowledge of the world&apos;s mysteries. His life was one of accomplishment also in the industrial world. The union in one life of acknowledged achievement as a scientist and the accomplishment of great results in the prac-tical industrial world is a rare thing, and its possibility has never been exemplified in greater measure than in his life and its results.

Jan 11, 1923

By H. F. Seifert

THE classification and preparation of non-ferrous scrap metals is a subject of interest to every individual and corporation that employs in its processes of manufacture non-ferrous metals and alloys and accumulates in such manufacture scrap from these materials for disposition in the form of turnings, borings, short ends, punchings, clippings, grindings, washings, etc. All too frequently the disposition of such scrap is left to individuals who have no knowledge of the subject either from a metallurgical or a commercial standpoint, or both. Much money is thus lost which with a little more intelligent effort might be saved, and in this day of fierce competition and small profits such an opportunity cannot be ignored. The Mineral Resources of the United States for the year 1925, the latest issue available (Part 1, page 221), gives the secondary non-ferrous TABLE 1.-Some Secondary Non-ferrous Metals Recovered in the United States for the Year 1924-25 Material Short Tons Value Copper, including that in alloys other than brass.... 250,600 $ 71,170,400 Brass, scrap remelted 242,300 56,270,800 Lead as metal 112,4201 39,477,100 Lead as alloys 112,460 Zinc as metal 61,430 11,359,000 Zinc -in alloys other than brass 13,300 Tin as metal 1 7,950 35,165,400 Tin in alloys 23,000 Antimony as metal 1 } 3;794,000 Antimony in alloys 10,839 Aluminum as metal 17,700 24 Aluminum in alloys 26,300 ,816,000 Nickel as metal 19 1 1,518,000 Nickel in non-ferrous alloys 2,109 Total 882,600 $243,570,700

Jan 1, 1928

By H. F. Seifert

THE classification and preparation of non-ferrous scrap metals is a subject of interest to every individual and corporation that employs in its processes of manufacture non-ferrous metals and alloys and accumulates in such manufacture scrap from these materials for disposition in the form .of turnings, borings, short ends, punchings, clippings, grindings, washings, etc. All too frequently the disposition-of such scrap is left to individuals who have no knowledge of the subject either from a metallurgical or a commercial standpoint, or both. Much money is thus lost which with a little more intelligent effort might be saved, and in this day of fierce competition and small profits such an opportunity cannot be ignored. The Mineral Resources of the United States for the year 1925, the latest issue available (Part 1, page 221), gives the secondary non-ferrous TABLE 1.-Some. Secondary Non-ferrous Metals Recovered in the United States for the -Year 1924-25 Material Short Tons Value Copper, including that in alloys other than brass.... 250,600 8 71,170,400 Brass, scrap remelted : 242,300 56,270,800 Lead as metal : 112,420 39,477,100 Lead as alloys 112,460 Zinc as metal 61,430 11,359,000 Zinc in alloys other than brass 13,300 Tin as metal 7,950 Tin in alloys 23,000, 35,165,400 Antimony as metal 1 3,794,000 Antimony in alloys : 10,839 Aluminum as metal 17,700 24,816,000 Aluminum in alloys 26,300 Nickel as metal 191 1,518,000 Nickel in non-ferrous alloys 2,109 Total l 882,600 $243,570,700

Jan 1, 1928

By K. P. Gupta, A. K. Pal, L. Chandrasekaran, U. P. Singh

The Mn-Sn binary system, investigated at the high-manganese end and between 500° and 1000° C, shows four phases at temperatures below 727"C, namely the u Mn, the p Mn, the Mn3 Sn, and the Mn, Sn phases, while at higher temperatures only the last three phases remain stable. The solubility of tin in a Mn is very small and the maximum solubility of tin in P Mn phase appears to be abollt 10 at. pct Sn. The solubility range of the Mn,Sn and the Mn, Sn phases is 23.0 to 26.0 and 37.0 to 40.0 at. pct Sn, respectively. The lattice parameter of the 13 Mn phase increases with increasing tin content. The Mn, Sn thase is hexagonal with and appears to be basically of the Ni3 Sn type structure except that for quite a few X-ray diffraction lines the calculated and observed relative intensities do not agree well. The Mn-Sn binary system has been studied by several investigators.&apos;&apos;~ Their results indicate that three intermediate phases, namely, the Mn3Sn, Mn,Sn, and MnSn, phases, exist at high concentrations of tin. However, so far the proper phase equilibrium has not been established at the manganese-rich end and very little data is available for the composition range between pure manganese and Mn3Sn. Moreover, earlier investigators differ in their opinion about the exact composition range at which the Mn3Sn and Mn,Sn phases appear and some doubt has been cast by some investigators3 regarding the structure of Mn3Sn phase which has been reported to be isotypic with Ni3Sn (Mgscd type) structure. In this investigation an attempt has been made to establish the proper phase equilibrium between pure manganese and Mn + 50 at. pct Sn composition in the temperature range of 500" to 1000°C. PROCEDURE The raw materials used were from three different sources. For exploratory work five alloys containing 5, 10, 15, 20, and 25 at. pct Sn were prepared using 99.9 pct pure manganese and tin supplied by E. Merck & Co., Germany. The rest of the alloys and one more 25 at. pct Sn alloy were prepared using 99.9 pct Mn supplied by Gallard Schlesinger Chemical Mfg. Corp., U.S.A., and 99.999 pct Sn supplied by Semi Elements Inc., U.S.A. Weighed amounts of manganese and tin were melted in recrystallized alumina crucibles in an inert gas (argon) high-frequency induction melting furnace. By careful control of temperature and time of melting the losses were reduced to below 0.2 pct in all cases. Since the losses were very small, no attempt was made here to analyze the samples chemically. Alloys were wrapped in molybdenum foil and sealed in small evacuated fused silica capsules. The alloys were annealed at different temperatures, controlled within + l°C, for sufficiently long periods to attain proper phase equilibrium, and subsequently quenched in cold tap water. The annealing periods used at different temperatures were 15 days at 500°C, 7 days at 600°C, 5 days at 700" and 750°C, 3 days at 800°, 850°, and 900°C, 2 days at 968"C, and two alloys annealed at 968°C were reannealed for 10 hr at 1000° C. From each annealed specimen, a part was utilized for metallographic study while another piece was used for X-ray diffraction study. 1.0 pct HNO, solution and oxalic acid solutions of concentrations 0.05 to 1.0 pct were used for etching Mn-Sn alloys above and below the MnsSn composition, respectively. Since all alloys were brittle, X-ray specimens were prepared using the as-crushed -325 mesh alloy powders. Only one 25 at. pct Sn alloy powder was reannealed in an evacuated silica capsule at 800°C for 5 min and water-quenched. X-ray diffraction patterns . for the Mn3Sn phase with the as-crushed and the reannealed powders did not show appreciable change. Un-filtered iron radiation at 25 kv, 15 ma was used with either Norelco 114.6-mm-diam Debye Scherrer Camera (for phase identification) or Norelco 12-cm-diam symmetrical focusing camera (for lattice parameter determination of the 6 Mn phase). The estimated accuracy of lattice parameter determination for the focusing camera was * 0.001A. RESULTS AND DISCUSSIONS The results of metallographic and X-ray diffraction study made with different alloys are shown in Fig. 1. The variations in lattice parameter with composition for the p Mn and the Mn3Sn phases are given in Tables I and 11, respectively, and the lattice parameter as a function of composition for the p Mn phase is shown in Fig. 2. The lattice parameter of the p Mn phase increases with increasing tin content while for the Mn,Sn phase the data obtained from two two-phase alloys and one single-phase alloy indicate increase in a,, and decrease in c, parameters with increasing tin content. The results, Fig. 1, indicate that the solubility of

Jan 1, 1969

By William T. Folwell

The Lucky Friday mine east of Mullan, Idaho, is an outstanding example of a property in the Coeur d’Alene district where a small and insignificant- appearing silver-lead-zinc vein at the surface has changed at depth into a large vein of great importance. The Lucky Friday vein has little if any surface expression and above the 1200 level the ore shoots are small and discontinuous. Between the 1200 level and 2450 level, the lowest developed level, the main ore shoot has shown remarkable improvement on each succeeding lower level, and today the mine is one of the major lead-silver producers in the Coeur d&apos;Alene district. History: The Lucky Friday property is on the north side of the South Fork of the Coeur d&apos;Alene River in sections 25, 26 and 35, T. 48 N., R. 5 E., Hunter mining district, Shoshone County, Idaho. This is about one mile east of the town of Mullan, which serves the eastern portion of the Coeur d&apos;Alene district. The southern part of the property is crossed by a branch line of the Northern Pacific Ry. and by U. S. Highway 10. This highway is the principal road crossing the panhandle of Idaho and connects the district with Spokane, Wash., on the west and Missoula, Mont., on the east. The main portal and surface plant of the Lucky Friday mine is at an elevation of 3365 ft, only a short distance above the valley floor and a few hundred feet from U. S. Highway 10, so the mine is readily accessible for year-round operation.

Jan 12, 1958

IN speaking, on the subject, "Engineer-Citizens," at the Lehigh Valley Mineral Industries Conference dinner, on April 26, at Easton, Pa., George Otis Smith, Director of the United States Geological Survey and President of the American Institute of Mining and Metallurgical Engineers, said in part: "It would be carrying coke to Connellsville to bring to the Lehigh Valley the idea that mineral resources are the foundation of national prosperity. Unfortu-nately, however, this obvious, fact is not everywhere recognized. Too many of our economists, journalists, statesmen and other dopesters of present business con-ditions stress the human factor so strongly that they overlook the material with which men work out their destiny. To them the financial psychology of Wall Street and the political logic of Capitol Hill and the business commonplaces of Main Street all loom far larger than the geology of the Lehigh Valley or the engineering triumphs of Bethlehem, or, the creative thinking at Lehigh and Lafayette. "The present situation in the industrial and .business world is a complex of interacting causes and reacting effects not easily itemized and entered on our trial balance sheet. But, chief among the liabilities of today is the excess of production capacity in most branches of industry. The farmer has no. monopoly in his desire for relief. Whether your professional connections are with steel or cement, coal or oil, copper, or zinc, you; know too well that for, the moment America is over-engined, and you keenly realize the ever-present hazard of industry speeding up regardless of the curves or grades just around the corner.

Jan 5, 1928