Search Documents

By R. F. Stahl, W. A. Martin

A marked gravitational segregation of liquid has been observed to take place in a number of volumetric fields toward the later stages of their oil-producing periods. This phenomenon has been pronounced in thick, highly permeable sand formations such as those of the wilcox zone in Oklahoma City. This observation has prompted considerable research directed toward the semiquantitative determination of the equilibrium saturation distribution of oil vertically throughout a formation at final depletion. In this paper, data are also presented showing the transient distribution of liquid at different stages of the depletion period. Other experimental results show the effect of temperature on the drainage rates of water, Wilcox crude oil, and a close-cut heptane fraction. Intermittent drainage of liquid produced saturation gradients that might well be expected from the flow theories involved, Yields of the various liquids varied from 50 to 75 per cent of the original fluid content of the sand-packed (4 in. by 8 ft.) vertical tube. Introduction In certain volumetric Oil fields the performance of the reservoir during the latter part Of its producing life is governed to a large extent by the downward movement of liquid due to the force of gravity. This is especially true of formations having thick or tilting beds of uniformly high permeability, free of shale breaks. Laverett4 and Katz3 have presented original data and discussed the theory relating to the capillary and gravitational forces acting On liquids contained in a sand body. These investigators have pointed out the importance of such studies in the estimation of future reserves as well as the original fluid content of a reservoir. In this previous work, no data have been reported showing the history of saturation distributions during the drainage period. Since a knowledge Of these transients is helpful in obtaining crude Oil from such a reservoir, the authors have obtained these data during this investigation. Experimental Apparatus The drainage tests were carried out in two vertical tubes, 8 ft. high and consisting of 2-in. and 4-in. standard wrought-iron pipe, respectively. Each tube was equipped with a water jacket, which could be kept virtually isothermal ( ± 1.0ºF.). A diagrammatic sketch of the 4-in. tube and its auxiliaries is shown in Fig. 1. At 6 in. above the base of the tube, and at every foot above this point, core nipples were inserted through the water jacket. These nipples were closely fitted with steel-plug inserts during each drainage run. At the end of the run, these inserts were removed so that cores could be obtained from the sand-packed tube.

Jan 1, 1943

By A. K. Jena, M. O. Bever

The thermodynamic behavior of dilute solutions of copper, silver, and gold in liquid tin is not explained by current solution theories.1-3 The relative partial gram-atomic enthalpies, or heats of solution, of silver, gold, and platinum in liquid lead at 623°K have been measured in the investigation reported here. Their interpretation requires a modification of the regular-solution theory although lead-rich solutions may be expected to be simpler than tin-rich solutions. The liquid metal solution calorimeter used has been described.4 At the start of a run the bath consisted of 621 g of reagent-grade lead. Several calibrating additions of lead were made during a run; a value of 3.48 kcal per g-atom5 was taken for H623°K - H273°K Two runs were made with each of the solutes silver, gold, and platinum. Annealed wire samples of 99.999+ pct purity were used. Four to six samples each weighing 0.5 to 1,0 g were added from 273°K to the bath at 623°K and the associated heat effects were measured. The samples dissolved in approximately 3 min. No serious experimental difficulties were encountered. The heat effects of the additions in a run plotted against the average atom fraction of solute before and after each addition314 were linear functions of the concentration in lead of silver, gold, and platinum, respectively. By subtracting the difference between the heat contents of a solute element at 623° and. 273°K5 from the measuredheat effects, the partial gram-atomic enthalpy relative to the solid solute was obtained. The relativ: partial gram-atomic enthalpy at infinite dilution and the concentration dependence of the partial gram-atomic enthalpies obtained from the plots of vs atomic fraction x are listed in Table I. The relative partial gram-atomic enthalpy at infinite dilution of silver in lead of 5.46 kcal per g-atom at 623°K compares with values at 723°K of 5.74' and 5.765 kcal per g-atom. These data yield a temperature coefficient of 3.0 cal per g-atom-OK. The partial gram-atomic enthalpy at infinite dilution of gold in lead at 623°K is 0.89 kcal per g-atom compared with 0.85 kcal per g-atoms (obtained by extrapolation) and 0.95 kcal per g-atom.5 By combining these values for 623°K with those for several other temperatures5" the temperature coefficient of was found to be 3.2 cal per g-atom-OK. No thermodynamic data are

Jan 1, 1968

By H. A. Hancock, L. M. Pidgeon

Equilibrium carbon monoxide pressures were measured over the reaction between chromium oxide and a number of solid ferrochromium alloys in the composition range 0.4 to 4.8 pct C and 0 to 49 pct Fe. Measurements were also made for the carbides Cr23C6 and Cr7C3 which agreed well with previous investigations. Between 1050°and 1400°C the pvessures varied from 0.1 to 56 mm and increased markedly with the iron and carbon contents of the alloys. The data were used to estimate the activity of carbon in the alloys and to calculate the equilibrium conditions for the decarburization of a useful range of ferrochromium alloys. WHEN ferrochromium is produced by the reduction of chromite with carbon in an electric arc furnace it invariably contains up to 10 wt pct C. For many purposes such as the production of stainless steel, it is necessary that the carbon content be as low as from 0.02 to 0.05 pct. Thus an important part of the ferrochromium industry consists of the production of low carbon ferrochromium. The classical Bessemer steelmaking technique cannot be used to oxidize low carbon contents in chromium and ferrochromium alloys without also oxidizing the chromium. Recently a new commercial process2-4 has been introduced for oxidizing carbon from high chromium content alloys which consists of heating the solid alloy with such oxidizing agents as Cr2O3, Fe2O3, or SiO2 in a retort at reduced pressures. By maintaining the carbon monoxide pressure below the equilibrium value for the system, the carbon can be removed as carbon monoxide without oxidizing the chromium. The equilibrium conditions for the decarburization of solid chromium carbon alloys have been determined by Boericke5 who measured the carbon monoxide pressure over the reaction between the various chromium carbides and chromium oxide. A typical reaction is shown below. Cr23C6 + 2Cr2O3 =u 27Cr + 6CO [1] These values are not applicable to the decarburization of commercial ferrochromium alloys which invariably contain major amounts of iron. The present investigation was therefore undertaken to measure the change in the equilibrium carbon monoxide pressure brought about by additions of iron to the Cr-C-0 system, thus extending the work of Boericke into the region of the production of low carbon ferrochromium. MATERIALS AND METHOD Materials. Measurements were made on two carbides of chromium, Cr233C6 and Cr7C3, and fifteen Fe-Cr-C alloys. The chromium carbides were made

Jan 1, 1963

By W. A. Koehler, M. E. Hinkle

THE oxidation of pyrites and marcasite in coal-mine strata to produce discolored acid mine drainage has long been explained by chemical reactions occurring in three stages: 1. The iron sulphide minerals are oxidized by air in the presence of water to produce a nearly colorless solution of ferrous (iron) sulphate and some sulphuric acid. 2, The ferrous sulphate and part of the sulphuric acid combine with additional oxygen to form ferric (iron) sulphate. 3. The ferric sulphate hydrolyzes to form a reddish-brown precipitate and additional sulphuric acid. Nevertheless, chemical data alone are not sufficient to explain all observed facts. The first stage seems to proceed more slowly in the chemical laboratory than in nature. The second and third stages normally occur to a marked extent within a few days with raw mine water. However, the visible discoloration that characterizes these latter stages will not develop for months if the mine water is sterilized. By means of bacteriological techniques, two organisms have been isolated from acid coal-mine drainage. These are believed to have a part in promoting the chemical reactions summarized above. One organism is considered to be Thio-6aciZZus thiooxidans, which is known to be able to convert elementary sulphur or sodium thiosulphate to sulphuric acid. Its relation to the formation of acid mine drainage has not Yet been established. Apparently it does not Promote the oxidation of ferrous iron compounds in mine drainage to the ferric state. The second organism has not been identified by name but is described as " Gram negative, non-spore-forming rods approximately 0.4 micron wide by 0.8 to 1.0 micron long." A pure culture of this when added to sterile mine water will cause the latter to become amber and develop the typical rusty precipitate. However, it has not been found to convert sulphur compounds to sulphuric acid. Further research is planned to determine whether or not these microorganisms play a significant part in the first stage of oxidation whereby pyrites and marcasite minerals go into solution. Some of the conditions found in abandoned sections of coal mines, such as a reduced Percentage of Oxygen and increased percentage of carboll 'dioxide in the air, as well as the existing temperature and acidity ranges, will be tolerated by and may even be favorable to these organisms. Acid Coal Mine Drainage Acid coal mine drainage has been the concern of coal mine operators, industrialists, sportsmen and public officials for many years. The amount of acid flowing into our streams in the coal-producing areas varies considerably from mine to mine and from

Jan 1, 1949

By E. S. Wheeler

The conversion plant of the Clirnax Molybdenum Co. is at Langeloth, Washington . County, Pennsylvania, approximately 30 miles west of Pittsburgh. The molybdenite concentrates converted originate in the company's mine and mill at Climax, Co1orado.l They are delivered to the Langeloth plant by rail packed in 175-lb. bags. War production of concentrates at the mill started in 1918 but it was not until about 1920 that any peacetime uses of the metal began to develop. Early conversion of Climax concentrates was mainly into ferromolybden um, produced for the company by a custom smelter. Chronology of Plant Development In 1924 a small hand-rabbled roaster was built at Langeloth, the roasted concentrates being used principally in the production of calcium molybdate by a conventional wet method. The size of the original plant is indicated by the fact that during 1925 about 400,000 lb. of molybdenum was converted. In 1925-1926, a multiple-hearth roaster was erected (12-ft. 0.d. 8-hearth Nichols-Herreshoff); also the first experimental ferromolybdenum was produced at Langeloth. At this time sa.1cium molybdate was produced in the furnace by a process to be described. With continued interest in and increased use of molybdenum, it was necessary to arrange for enlargement of plant facilities. Although only one 12-hearth 16-ft. 0.d. roaster was erected at this time (1929), plans were prepared for a duplicate unit, which was completed in 193 5, giving a potential roasting capacity of some 16,000 lb. Mo per day under the then prevailing roasting practice. Shortly after this second unit had gone into production, increased demand overtaxed the plant, and as a result two 12-hearth 18-ft. 0.d. roasters were placed in operation in 1936 and 1937. This gave the plant a potential roasting capacity of 40,000 to 50,000 lb. Mo per day, and necessitated major changes in auxiliary handling equipment as well as improved facilities for producing ferromolybdenum. Following the introduction (1938) of a new product—molybdic oxide briquets— and because of the constantly growing demand for molybdenum, plant facilities were again enlarged in 1940 and 1941 by the erection of two 16-hearth 18-ft. 0.d. roasters. These two new units, along with a change in roasting practice, brought the potential roasting capacity to 150,ooo to 190,000 Ib. Mo per day, based on about 15 lb. per sq. ft. of hearth area. Other departments of the plant have necessarily grown, until today the plant is modern throughout and completely mechanized, with equipment geared to produce marketable products as follows:

Jan 1, 1944

By J. R. Kyte, R. L. Dalton, V. O. Naumann, R. L. Ridings, R. W. Greene

This paper presents a one-dimensional numerical method for calculating dissolved-gas-drive behavior for a single well or a linear reservoir. Pressure and saturation distributions can be calculated, including the effects of capillary and gravity forces. The analysis has been programmed for solution on the IBM 7090 digital computer. A comparison of experimental and calculated behavior for two linear models demonstrates that the method is suitable for calculating dissolved-gas-drive behavior under reservoir conditions of flow. Dissolved-gas-drive tests were run, at different production rates and with oils of different viscosities, on short (6.ft) and long (173ft) flow models. For tests approximating reservoir pressure gradients and flow rates, there was excellent agreement between experimental and calculated results. A series of calculations of well behavior for thin, horizontal, homogeneous, dissolved-gas-drive reservoirs shows that ultimate recovery is independent of production rate or well spacing in such cases. These calculations also show that Muskat's method and similar material-balance analyses are not applicable under some conditions particularly for high pressure drawdowns. INTRODUCTION The problem of calculating dissolved-gas-drive reservoir performance has received a great deal of attention throughout the oil-producing indusfry for many years. Really significant advances, however, have been made only in recent years. The rapid evolution of high-speed computing equipment and techniques has opened up new approaches to the problem and led to realistic, quantitative analyses free of many of the assumptions and limitations of earlier methods. The one-dimensional numerical method described in this paper includes the effects of both gravity and capillary forces. A number of test calculations, based on different rates, spacings, and rock and fluid properties, have shown that the method is adequate for systems that can be reasonably represented by a one-dimensional model (linear or radial) and in which fluid segregation perpendicular to the direction of flow is not important. Along with the development of mathematical methods, an experimental program was conducted and the data were used to test the validity of the theoretical basis of the mathematical method. Linear models were used and all experiments were run using 1,000-psig bubble-point oils. The use of long, high-pressure models enabled us to more closely approach reservoir gradients and flow rates. MATHEMATICAL FORMULATION DIFFERENTIAL EQUATIONS The differential equations describing dissolved-gas-drive behavior in one dimension dare summarized here. They include Darcy's law for flow of oil and gas (Eqs. 1 and 2) and the equations for conservation of mass for oil and gas (Eqs. 3 and 4). The oil and gas pressures are related by capillary pressure (Eq. 51.

By M. I. Jacobson, M. L. Hammond

The solid solubilities of high-purity silver, aluminum, chromium, copper, and iron in zone-refined beryllium have been determined. Diffusion couple sandwiches of beryllium with aluminum, copper, and silver foil and diffusion couples of beryllium with two-phase alloys in the Be-Cr. Be-Fe, and Be-Ag systems were analyzed by electron beam micro-probe techniques. This paper describes the material used, the experimental methods for preparing the diffusion couples and the alloys, the analytical techniques, and the results obtained. The results are compared with those of previous investigators who used materials of lower purity. ~NVESTIGATORS of beryllium phase diagrams have often been hampered in their interpretations of certain phase boundaries because of the relatively low purity of the beryllium used. This has sometimes resulted in the appearance of three phases in the regions where only two should exist. Advances in purification methods, specifically zone refining, have made available beryllium that is considerably purer than the material previously used for phase diagram studies. The primary object of this investigation was to reex-amine portions of the beryllium-rich end of the binary systems of beryllium with silver, aluminum, chromium, copper, and iron to determine more accurately the limits of terminal solid solubility. The five elements—silver, aluminum, chromium, copper, and iron—include some which are commonly found as the major impurities in beryllium, some of which are being used as solid-solution alloying elements, and some of which are used in ductile matrix alloys. They are thus of considerable importance to physical metallurgists who must work with beryllium but who must rely on the present inaccurate or incomplete diagrams. The determination of more reliable diagrams would aid researchers concerned with the problems of alloying, heat treatment, and ductility. MATERIAL The beryllium was acquired from the Franklin Institute in the form of a single-crystal, 6 in. long by 1 in. in diam, zone-refined in three passes from Pechiney SR-grade beryllium bar. The principal impurities, as determined by mass spectrography at Battelle Memorial Institute, are shown in Table I. Vacuum-melted copper, silver, and aluminum, and electron-beam zone-refined iron were obtained from the Materials Research Corp. in the form of 1/2-in.- diam bars. Iodide chromium was obtained as flakes from the Chromalloy Corp. Analyses supplied with these metals are shown in Table 11. EXPERIMENTAL PROCEDURE Preparation of Diffusion Couples. Two types of dif-fusion couples were used in this study. For the copper, silver, and aluminum systems, the couples were sand-

Jan 1, 1969

By Paul A. Schafer

BALATOC mine, the principal gold-producing mine in the Philippines, is 10 miles southeast of Baguio, in the Cordillera Central of northern Luzon.1 The region is a deeply dissected plateau, ranging in altitude from 3000 t0 5000 ft. above sea level. The rocks consist chiefly of granodiorite, diorite, and remnants of metamorphosed sediments, cut by dikes of andesite porphyry and quartz-diorite porphyry. All are intruded by a volcanic breccia plug, oval in horizontal section, about 3200 ft. long and 2300 ft. wide, which is the north central part of the mineralized area. Three main vein systems have been developed (Fig. 1): q6, 231 and 364, which strike about N.70°E. and dip 5o to 90°S. Each system is a braided zone consisting of many individual components. They are disturbed by a series of premineral faults or shear zones striking about N.45°E. Twelve of these produce important effects on the persistence, character, and quality of veins. From west to east the faults are named (after claims): Hog, Big Gun, Bull, Pine, Lolita, Bar No. I, Bar No. 2, Curt, Sun, Helen, Itoe, and Frog. They are early breaks formed prior to the N.70°E. vein fractures. Mineralization occurs on them but, with several prominent exceptions, they are too low grade to mine. A number of northwesterly striking faults complete the structural pattern. Although they are relatively abundant, the effect on the veins is so small that they do not present any problems in mining or development. All of these faults that have been observed are later than the N.70°E. veins and offset them to the left. NORTHEAST FAULTS The early northeast faults* are notably continuous in spite of their small displacements, 20 to 100 ft. Frequently they appear so weak that their importance is masked and their identity clouded. The gouge along any of these faults may vary from exceedingly weak at one point to very strong at another point only a short distance away. In other words, the amount of gouge depends on the changes of attitude of the fault plane, and is no indication of the extent of the movement. Places where walls are spread apart are filled with gouge squeezed from tight places. Also, mineralization sometimes obscures fault gouges by replacement. The mineralization of northeast faults has produced several important ore bodies; namely, 231 west on Pine fault and q6 vein on the same fault. To a smaller extent, Lolita, Curt, Bull, Bar No. I, and Sun

Jan 1, 1942

By Earl G. Alexander, W. R. Runyan

The nature of silicon growths which form on amorphous silicon dioxide during epitaxial deposition in unmasked areas was investigated. Octahedral silicon crystals nucleate and grow on the oxide at pinholes, adjacent to foreign matter, and probably at oxygen-deficient sites. Generation of these oxygen-deficient sites on the oxide surface is shown to be thermody-namically favorable under usual deposition conditions. The conditions which affect saturation (SiCl4 concentration, flow rate, temperature) determine the number of sites on which silicon will nucleate and grow. Reaction product HCl is likely responsible for suppressing silicon growths on the oxide near exposed areas of silicon. Evidence is given that the oxide-silicon interaction occurs in hydrogen only and involves water as a transport agent. SINCE shortly after the first epitaxial layers of silicon and germanium were grown over large areas, efforts have been underway to grow selectively on specified portions of the surface. Such selective growth should be particularly applicable to monolithic integrated circuits. Usually the approach has been to use a mask to delineate the desired area,'-7 but the VLS methoda can also be used, and direct programmed atomic beam deposition has been suggested.9 The masking techniques may embody two forms: in one the mask is a material which can later be removed along with any growths attached to it; in the other, attempts are made to prevent growth on the mask, so that over a whole slice the only deposition that will occur is in the unmasked regions. The present work is concerned with only the latter case, and specifically with silicon. Joyce and Baldrey1 suggested the use of thermally grown silicon dioxide as a mask material and showed that for the proper choice of operating conditions (total flow, SiCl4 concentration, total deposition time, and temperature) spurious growth could be minimized and that if the deposition times were not too large, and the criteria not too stringent, a usable process occurred. Later Schnable et al 4 observed that after extended deposition times, during which most of the silicon dioxide became covered with growth, there was always a band of oxide around the exposed silicon area that was quite free of spurious silicon crystallites. This latter observation is particularly intriguing since it extends the hope that with proper precautions masking can be much more versatile than it presently is. EXPERIMENTAL PROCEDURE Silicon substrates oriented to within 1.5 deg of a (111) plane were prepared by etch polishing lapped

Jan 1, 1967

By T. D. Guldem, J. L. Kaae

ALLOYS with nominal composition of 45-Fe 35-Ni 20-Cr, ASTM-B-163, known under the commercial names of Incoloy 800 and Sanicro 31 (Alloy 800), are often employed at elevated temperatures for extended periods. Therefore, knowledge of the aging behavior of these alloys is of considerable importance. Significant decreases in ductility and increases in yield strength have been observed in the 45-Fe 35-Ni 20-Cr alloys containing about 0.4 pct Ti and 0.4 pct A1 after long-term aging at 540" to 700"~."~ However, no direct evidence has been presented for precipitation phenomena that might result in such changes. Strengthening effects have been attributed to the effects of local or-dering.3 Since y' precipitation (Ni3A1, Ti) is known to occur in similar alloys which contain more titanium and aluminum,4-7 it was decided to explore the possibility that y' might precipitate in these alloys and might be responsible for the changes in mechanical properties on aging. This note reports some observations of two distict types of matrix precipitates made by means of transmission electron microscopy, in a 45-Fe 35-Ni 20-Cr alloy containing 0.31 pct Ti and 0.4 pct Al. The steel used in this investigation was obtained from the Sand-vik Steel Works; it is designated Sanicro-31 (Alloy 800). The chemical composition of the alloy is given in Table I. Aging of solution-treated material at 700" and 800°C for 130 and 100 hr, respectively, produced the matrix precipitates shown in Figs. l(a) and l(b). It is apparent from these micrographs that the precipitate particles occurred in the form of thin square plates parallel to the matrix cube planes. Extraction replication and selected-area electron diffraction showed that the precipitates were M23C6. Coherency strains, consistent with the semicoherent nature of small M23C6 precipitates,' were evident for certain imaging conditions. In addition to matrix precipitation, preferential precipitation of M23C6 on dislocations was common, as has been reported previously for austenitic stainless steels.'" Specimens aged for longer times (-300 hr) at 700°C exhibited a different type of coherent matrix precipitate in addition to the M23C6. An example is shown in Figs. 2(a) and 2(b). In addition to the few large M23C6 precipitates, small precipitates exhibiting strain contrastl0,ll are present. The "line of no contrast" of the strain field of a given precipitate lies along differ-

Jan 1, 1970

By A. L. Holley

There is a growing demand for pure and cheap material for fine open-hearth steel; a material not only very free from phosphorus, but from carbon and silicon; so that it may he rapidly converted into steel. Iron and steel scrap are not trustworthy as to quality, and they are often dear. There are three methods of purifying cheap materials for the open hearth. 1. Mechanical puddling, as done at Creusot, which removes 90' per cent. of the phosphorus from the pig iron. 2. Krupp's washing process (the conduct and results of which 1 fully described in a former paper*), which eliminates 70 to 80 per cent. of the phosphorus and most of the sulphur and silicon from pig iron. Neither of these processes would sufficiently purify, for very fine steel, those very impure pigs which are cheapest in many parts of the United States. 3. The process of producing directly from the ore an iron which is practically pure chemically, although mechanically mixed with the impurities of the ore. This is the oldest of iron processes ; one form of it, the CataIan forge, employed to produce charcoal blooms, is still in use, but its great cost is rapidly throwing it out of competition. Among the modern attempts to produce iron direct from the one, on a large scale and at a cheap rate, several have been in various respects successful. Dr. Siemens's process of treating a ton and a half or more of ore and the coal to deoxidize it, in a rotating gas furnace, and bringing out, in some four hours, a ball of chemically pure iron so soft that the fluid and impure slag may be sqneezed out of it, is the most attractive and the most highly developed of all the modern direct processes. I hare watched it, from time to time, since 1874, and have noted a steady improvement. It may now be said to have passed the experimental stage, although, like older processes, it must be adapted by practice to special materials. The cause which has been more potent than all others, including the defects of the best direct processes, to bring these processes into disrepute, is the wasteful treatment of the direct product. With one or two exceptions (when failure mas due to other and obvious causes), the direct product has been made into wrought iron (weld iron). Even Dr. Siemens has, at Towcester, in England, and at Park, Bro. & Co.'s, in Pittsburg, set up his apparatus for this purpose. Is it likely that

Jan 1, 1880

By E. T. Turkdogan, P. Grieveson

Experimental results are given for the rate 0.f solution of nitrogen in y iron in the temperature range 1000° to 1200°C. It is shown that, when purified reacting gas is used, the rate-controlling process is the diffusion of nitrogen into the iron. The difhsiuity of nitrogen in y iron is calculated from the results and the equation logD = —(8800/T) — 0.04 is recommended to represent the temperature dependence of the diffusivity. In some experiments using unpurified nitrogen, solution rates are found to be slower than those attributable to a solely solid-state diffusion process. Indications are that in the presence of impurities in the gas, e.g., H,O, chemisorption of nitrogen at the surface is hindered and becomes a rate-controlling process for the transfer of nitrogen across the gas -metal interface. ALTHOUGH the solubility of nitrogen in y iron at known nitrogen activities has been well-established,'-a the kinetics of the solution of nitrogen in iron are not known. The work of Darken, Smith, and Filer' indicates that at temperatures below about 1300°C the rate of solution of nitrogen in y iron is controlled by a chemical reaction at the metal surface, while at temperatures above about 1300°C the rate-controlling process is the diffusion of nitrogen in the metal. Fast and verrijps studied the denitro-genization of y iron using wet hydrogen at 950°C and their results clearly indicate that the rate of nitrogen removal is controlled by diffusion of nitrogen in the metal. In Part I of this series of papers, the kinetics of the solution of nitrogen in y iron are discussed in the light of the present experimental work. EXPERIMENTAL Apparatus. The reaction chamber consisted of a platinum wire-wound resistance furnace with a re-crystallized alumina reaction tube. The temoerature of the furnace, which was automatically controlled to approximately 1°C, was measured with a Pt/Pt-13 pct Rh thermocouple and a potentiometer. The temperature distribution in the working zone of the furnace was determined using a calibrated Pt/Pt-13 pct Rh thermocouple and the hot zone was found to be approximately 3 in. long with a temperature variation of * 3°C. A series of experiments was also carried out at 1000°C and pressures above atmospheric using a pressure vessel which was similar in construction to that described elsewhere.1° Materials. Ferrovac E grade iron used in all ex-

Jan 1, 1964

By Torgrim Eftestoel, Leif Olsen, Ove Sandberg

IN the vertical contact Soederberg electrode for aluminum furnaces more or less serious cracks are sometimes formed in the electrode, with harmful effect on furnace operation. The problem of crack formation has been studied on a laboratory scale to obtain a better understanding of this phenomenon. The primary cause of crack formation is the shrinkage of the electrode carbon, which is opposed by the normal thermal expansion of the steel contact studs. The forces thus set up are active in the temperature interval from which the electrode obtains a rigid structure (450" to 500°C) to furnace operational temperature (950°C). A visualization of our reasoning is given in Fig. 1, which shows the different behavior of mild steel and electrode carbon during baking. Research work performed to determine relationships between crack formation and shrinkage will be described. A brief description of the method developed for measurement of shrinkage will be given, as well as a critical analysis of this method. Also, raw material quality and paste composition variables will be related to shrinkage phenomena. Laboratory Test of Crack. Formation To test the tendency toward crack formations of Soederberg electrodes from different pastes, experiments were performed to simulate conditions of actual commercial electrodes, and are described as follows. A cylindrical test electrode is prepared by tamping the electrode paste to be examined in a sheet iron casing, 350 mm diam by 700 mm height. The casing is perforated, with the holes (2 mm diam) 50 mm apart, to facilitate the escape of volatile matter during baking. A cylindrical steel stud of actual service size, 100 mm diam, is welded eccentrically to the bottom steel plate, and protrudes up through the paste. During baking, a crack may thus occur in the weaker part of the test electrode. The electrode is baked by lowering the assembly slowly into an electric furnace, the temperature of which is kept constant at 900°C. After baking of the electrode, the sheet iron casing is removed and the electrode inspected for cracks. The pictures in Fig. 2 are of three different pastes baked according to the present method. Electrode 1 has a large crack; electrode 2, a somewhat smaller one; and electrode 3, only a minor crack. As will be seen from the simplified sieve analysis diagram of Fig. 2, the compositions of the pastes in question are very different. This subject will be discussed later in greater detail. Crack Formation and Shrinkage Relationships It is well known that shrinkage occurs in coke in the higher temperature ranges of coal

Jan 1, 1958

By O. Chanute

all of' level atid grade curve excepting Nos. 897, 898, 899, and 900, because of the impossibility of grouping them in the same nlonner, no two Iraving the chemical composition and physical prnprtiw as tho only v:iriubles. Phosphorus ~tnits have been taken to show the relatia h:wdnes. Of these 16 groups, 10 decidedly indicate slower wear firr tile harder rail. Of the remaining 6 groups, three (groups 2, 9, and 15) come well within the limits of error (.25 pound per yard) inherent in the palculation of the data as pointed out by Dr. Dndley; they catrnot, therefore, be considered tls exceptions. Group 2 and 15 arc but little outside of the limita of error. Rail 923 of group 9 is obviously abnornlal. This is probahly due to its being overheated, which the chemical analysis shows might easily be the case, and which the physical tc~ts and its low specific gravity tend to c-nfirm. We inry say, then, thnt 13 of these 16 groups fairly indicate, if they do not definitely point out, th:kt, under the same condition% tbe harder rail gives the slower wear. Of course, these comparisons are too few to enable us to arrive at positive ~?o-nclusions; but indications thus obtained are, I believe, fir more vsluitblc and tresttvc~rthy than those fhzt averages rvottld give us, mnde up from any ~lumhr of rails under intloy difi~rcal, conditions. Finally, it, seems to me, that the conclusions arrived at earlier in my remarks, together with, and confirmed by the last, show strong evidence that, under the same conditions, the harder rail will givc the slower wear. 0. C~~anute, New York CITY: We are very much shlipl, 1 ant sure, to Mr. Sandberg for his paper upn " Rail Ryaifications and Rail Inspertion in Europe." We have in thp United States bithhrto Been inspecting mils sonlewl~at haphazard, and we ore glad to gtbt tfie results of Mr. Sandberg's long experience. We recognize that he was an)ong the first, if not the very firwt, to iipply mare rittional and scientific rules to the designing of irou rails., niora recently, to adapt tlitve rules to the clesigtting of steel I':I~]R, to conform to the oapaljilities and rqniretnento of this new n1:ttcrial. Although we have generally adopted, in this country, sectinns for hteel rails which marly of our railway men think even bottar than those of Mr. Snlldlmrg, he is neverthelees the Ieat3er in foot.iito11~ we have followed ever since it has been est~blished

Jan 1, 1881

By G. Gutzeit

METAL-ORGANIC INNER COMPLEXES AN inner complex is a cyclic chemical structure containing an inorganic cation that is bound simultaneously to several atoms in a single organic molecule; on the one hand by means of ordinary valence bonds (electron exchange), on the other hand through the action of the electric field thus created, which satisfies the so-called secondary valences. The relative positions of the salt-forming and complex-forming groups are such that most frequently a four, five, or six-membered ring results through this double attachment of the cation.1-6 The formation of inner-complex ring systems depends not only upon the nature and suitable position of the salt-forming and complex-forming groups for ring closure, but, to a great extent, also on the nature of the metallic cation entering the reaction. This selective character of chelate-forming organic compounds is one of their most interesting and most valuable properties. As a matter of fact, the largest number of their practical applications is based upon their specificity. 4,1-13 Once a chelate compound is formed, its character is definitely "organic" in nature. In other words, its properties are conditioned to a much larger degree by the carbon chains or rings than by the metallic atom. Many inner complexes are soluble in nonpolar solvents such as benzene, paraffin oil or carbon tetrachloride, while the chelate-forming reagent before closure of the metal-organic ring is water soluble. (Example: copper complex of salicyl-aldoxime.) It is obvious that such particular properties as those indicated above can be utilized whenever specificity and practically complete binding of inorganic ions into an undissociable complex are required. One of the well-known applications of chelate-forming compounds has been the development of specific reagents in analytical chemistry,, creation of the spot-test method,4,14-16 and the application of the same principles to the contact print method for determining minerals.17 CHELATE-FORMING COMPOUNDS AS COLLECTORS In the field of flotation, where selectivity is often a quality of paramount importance for the collector, various workers have lately attempted to apply their knowledge of specific organic analytical reagents to this purpose. A. C. Vivian18 has concentrated cassiterite by using ammonium nitrosophenylhydroxylamine (Cupferron) C6H5NO(=NONH4). Holman19 has tested dimethylglyoxime for the flotation of nickel oxide minerals, while deWitt has shown in a series of systematic experiments that alpha-dioximes were generally selective collectors for nickel ores. Taurin NH2(CH2)2SO3H has been proposed for the concentration of oxidized lead ores.19 Diphenylthiocarbazone

Jan 1, 1946

By C. E. Berry

Natural stone or manufactured porcelain pebbles are used as the grinding elements in pebble mills and the mills are lined with stone or porcelain blocks. Steel balls usually form the grinding medium in ball mills, and the mills may be lined with steel. Pebble mills are used to avoid contamination by metal of the material being ground, to avoid rapid wear due to corrosion, and for other specialized reasons. Belgian silex (silica) blocks formerly were used widely for lining pebble mills, because of their good resistance to wear, light color, and low cost, but the importation of these blocks was suspended early in the war. The stocks of Belgian silex diminished so rapidly that it was found desirable to compare the properties of a number of domestic substitutes for use in critical operations. Accordingly, a study was made to determine the best substitutes for fine grinding of white pigment and for certain heavy-chemical process work such as the disintegration of phosphate rock in weak phosphoric acid solution. A comprehensive survey of substitute lining materials was not contemplated. It was stipulated at the beginning of the investigation that only materials on the market, available in large quantities, would be tested and that these should be reasonable substitutes from a a ance viewpoint as determined from known physical characteristics. Marble and limestone, for example, could be eliminated immediately. Quartzite, granite and porcelain were selected as likely substitutes for Belgian silex and were subjected to quality tests. Materials Tested 1. Belgian Si1ex.—Sample blocks of a standard grade were taken from crates in which they had been imported. The stone was light gray in color and contained inclusions of small clusters of quartz crystals as well as light colored portions that might be calcite. This was a siliceous rock which appeared to be of igneous origin. 2. Quartzite.—Samples of quartzite were obtained from a quarry in Minnesota. The blocks exhibited a crystalline fracture. The stone was pink in color and composed of fine quartz crystals bound together with a siliceous cement. 3. Granite A was a fine-grained granite quarried in South Carolina. 4. Granite B was coarse-grained granite quarried in South Carolina. 5. Granite C was a coarse-grained granite quarried in North Carolina. 6. Porcelain A.—Sample blocks of the pebble-mill lining material were obtained direct from the manufacturer. It was white in color and of lower specific gravity than the natural materials. It did not have a crystalline structure. 7. Porcelain B.—Sample pebble-mill lining blocks of the porcelain were received direct from the manufacturer. It was white

Jan 1, 1948

By William Lodding

Muscovite was the crystalline material used in the experiments discussed in this paper. It was both wet and dry ground for various periods of time. The effects (physical and chemical changes) produced in grinding are analyzed by use of thermal analysis. That grinding may change a crystalline material both in a physical and in a chemical sense has been shown by a number of authors in recent years. Mackenziel and Bartha2 reported the effects of careful grinding on muscovite, quartz, gypsum, dolomite, etc. Increase in specific surface produced by grinding implies increase in total energy of a system. Newly produced surfaces are chemically more reactive; dislocations may be introduced during grinding and, on the other hand, existing strain may be released by the same process, as shown by Holt, et a1.3 All these changes are easily detected by thermal analysis, but it is not easy to separate the multiplicity of effects registered and to arrive at quantitative interpretations. This paper is an attempt to analyze, by the use of thermal analysis, some effects produced in grinding. In differential thermal analysis (DTA) one measures the sum of all thermal changes occurring in a substance during heating or cooling; e.g., chemical changes, such as decompositions, synthesis, oxidation, reduction, etc., and physical changes such as phase transformations, changes in specific surface and thermal conductivity, strain release, etc. By thermogravimetric analysis (TGA), on the other hand, only chemical changes involving weight loss or gain are recorded. Similarly, gas evolution analysis (GEA) will register only reactions involving gas evolution. By performing two or all three of these methods of thermal analysis simultaneously and on the same specimen, one can separate the different effects registered and, by difference, evaluate their magnitude. The results of TGA are usually plotted as percent weight against furnace temp. When one differentiates weight against furnace temp, a rate of weight-change curve is obtained, and the resulting differential thermogravimetric (DTG) plots are similar in appearance to DTA thermograms for the same reaction. While the integrated area under a DTA peak represents enthalpy and can be expressed in calories per gram the area under the corresponding DTG peak represents the weight change which took place during a reaction. The similarity of DTA and DTG thermograms obtained from one material can be seen in Figs. 1 and 2. EXPERIMENTAL A Fisher mortar grinder and a porcelain mill with burundum balls were used for both dry and wet grinding. Muscovite was first carefully hand-filed and screened on 20 and 100 mesh. The middle fraction was considered essentially unaltered muscovite.

Jan 1, 1968

By W. C. Hagel

Previous inuestigators have repovted unusually low H* and Do values for self-dzf@szon in certazn bcc metals, e.g., chromium nnd y -uvanium. It has been postulated that this is nn experimental crl -tetion for the existpnce of a four -atom ring meclzanzsm, mid there could be. zmpovtant theoretrcal Implicatlons. By utilizing a precise sectioning technique with Cr51 as the tracer, self-dzffi-lsion measurements in large grains of 99.99-pct Cr were extended from 1200° fo 1600"C. A least- squares analysis of the data yields that D 0.280 exp (-73,20U/RT) cm2 sec-'. These AH* and Do unlues are not anomalous; there is little reason to believe that n vacancy mechanism is not opevatiue. Apparent differences at lower temperatures may result from preferential diffusion along short-circuititing paths and/or sample contamination. WITH continued technological effort, chromium and chromium-base alloys should ultimately become useful high-temperature structural materials. Accurate measurements of self-diffusion coefficients in the pure metal are necessary for a quantitative understanding of sintering, grain growth, creep, and other related rate processes. However, two conflicting determinations have been reported.* Using an Since careful diffusion studies normally yield Do values ranging from 0.1 to 10 cm2 sec-l, the Paxton-Gondolf results require independent experimental corroboration before an undue amount of speculation arises to explain the apparent anomaly. As discussed by Nowick6 and clearly shown by Hoffman and Turn-bull7 for self-diffusion in silver, a low AH* and Do can arise from preferential diffusion along grain boundaries or other short-circuiting paths. The most reliable data come from high-temperature measurements where volume effects predominate. Following a precise sectioning technique developed for determining silver diffusion in the intermetallic compound AgMg8 and cation diffusion in the corundum oxide Cr2O3,9 the purpose of this study was to measure true volume diffusion in high-purity, large-grain samples at higher temperatures than considered previously. Another point of interest is the frequent proposal10-12 that chromium undergoes an allotropic transformation between 1375" and 1800°C where the diffusion data might then show a discontinuity. I EXPERIMENTAL 1) Sample Preparation. The highest purity (99.997 pet) Cr currently available is produced by reduction of chromium tri-iodide. Three pounds of the resulting crystal bar were shipped in a sealed container with a complete chemical analysis from the vendor.* In conformity with the procedure used for

Jan 1, 1962

By C. E. Berry

Natural stone or manufactured porcelain pebbles are used as the grinding elements in pebble mills and the mills are lined with stone or porcelain blocks. Steel balls usually form the grinding medium in ball mills, and the mills may be lined with steel. Pebble mills are used to avoid contamination by metal of the material being ground, to avoid rapid wear due to corrosion, and for other specialized reasons. Belgian silex (silica) blocks formerly were used widely for lining pebble mills, because of their good resistance to wear, light color, and low cost, but the importation of these blocks was suspended early in the war. The stocks of Belgian silex diminished so rapidly that it was found desirable to compare the properties of a number of domestic substitutes for use in critical operations. Accordingly, a study was made to determine the best substitutes for fine grinding of white pigment and for certain heavy-chemical process work such as the disintegration of phosphate rock in weak phosphoric acid solution. A comprehensive survey of substitute lining materials was not contemplated. It was stipulated at the beginning of the investigation that only materials on the market, available in large quantities, would be tested and that these should be reasonable substitutes from a a ance viewpoint as determined from known physical characteristics. Marble and limestone, for example, could be eliminated immediately. Quartzite, granite and porcelain were selected as likely substitutes for Belgian silex and were subjected to quality tests. Materials Tested 1. Belgian Si1ex.—Sample blocks of a standard grade were taken from crates in which they had been imported. The stone was light gray in color and contained inclusions of small clusters of quartz crystals as well as light colored portions that might be calcite. This was a siliceous rock which appeared to be of igneous origin. 2. Quartzite.—Samples of quartzite were obtained from a quarry in Minnesota. The blocks exhibited a crystalline fracture. The stone was pink in color and composed of fine quartz crystals bound together with a siliceous cement. 3. Granite A was a fine-grained granite quarried in South Carolina. 4. Granite B was coarse-grained granite quarried in South Carolina. 5. Granite C was a coarse-grained granite quarried in North Carolina. 6. Porcelain A.—Sample blocks of the pebble-mill lining material were obtained direct from the manufacturer. It was white in color and of lower specific gravity than the natural materials. It did not have a crystalline structure. 7. Porcelain B.—Sample pebble-mill lining blocks of the porcelain were received direct from the manufacturer. It was white

Jan 1, 1948

By J. E. Hilliard

A procedure is described for determining, from measurements on a section, the moments of any degree n (i.e., the mean value of Dn, where D is a linear dimension) of the size distribution of particles (or grains) in an opaque sarnple. The analysis is applicable to particles of alnzost any shape and to any mixture of shapes. However, if absolute values of the wloments are required, it is necessary to know what shapes are present and the relative frequency of their occurrence. In addition, certain shape-dependent parameters have to be evaluated before the formulas can be used. The measurement required is the distribution of intercept lengths. This can be determined either visually or with an automatic scanning instrument. Corrections me derived for the bias due to instrumental end effects. The proposed analysis has the following advantages over existing ones: 1) Confidence limits are easily estimated for the measured properties or, conversely, the number of counts required to achieve a given accuracy can be determined. 2) The analysis is not restricted to particles of a special shape. 3) The error resulting from any known degree of departure of the actual from the assumed particle shape can be estimated. 4) The computations are simple and, apart from a change in constants, are independent of particle shape. 5) The number of particles per unit volume can be determined by a simple counting procedure. MANY procedures have been described for determining the size distribution of particles from measurements on a section (or plane of polish). They differ from one another in the property measured on the section (radius, intercept length, profile area) and in the method used for the numerical solution of the integral equation relating the property to the particle size distribution. However, all existing analyses share at least two of the following disadvantages. 1) They are limited to a particular shape of particle (usually spherical). 2) It is very difficult to determine how the statistical sampling error is propagated into the computed size distribution. The investigator thus has no means of knowing the reliability of his result and, what is of equal concern, he is unable to estimate how many measurements are required to obtain a result of the required accuracy. 3) It is also difficult to assess the error resulting from any deviation between the actual and assumed particle shape. The foregoing limitations stem from the complex relationship between the particle size distribution and the distribution of the property measured on the section. As will be shown, they can be avoided by defining the size distribution in terms of discrete parameters

Jan 1, 1969