Search Documents

By Thomas T., Read

IT will be recalled that the first professor of metallurgy in the United States, appointed in 1855, never really gave any instruction in metallurgy and gradually turned into a professor of mineralogy. Metallurgy was included with. mining in the early curricula, two students who took the B.S. in mining engineering from the Polytechnic College of Pennsylvania in 1862 wrote their graduation theses on the metallurgy of copper and zinc, respectively. Even after Columbia School of Mines established, in 1868, a separate curriculum leading to the Ph.B. degree in metallurgy, very few students elected it,* preferring to take the mining degree, since they received in its curriculum nearly all the metallurgical instruction they would have in the metallurgical curriculum. For many years a large proportion of the men who attained prominence in metallurgical enterprises had taken mining rather than metallurgical degrees. METALLURGY Clifton Sorby's study of thin sections of rocks under the micro¬scope, beginning in 1850, and its subsequent development by Zirkel and others, had made microscopic petrography a recog¬nized department of geological research as early as 1873. . It was inevitable that the idea of studying polished metal surfaces-¬under the microscope by reflected instead of transmitted light would occur to investigators. Sorby himself did it in 1864, and Adolph Martens and Floris Osmond may -be especially named among the many European workers who, by the late eighties, had so developed the, necessary techniques that they were able to photograph polished metal surfaces at magnifications as high

Jan 1, 1941

By Lewis T. Wright

(Pittsburg Meeting, March, 1910.) I HAVE long been aware that ferruginous copper furnace slags if fused in the electric arc will yield metallic iron containing copper, and in order to confirm this knowledge, and to obtain further information of the behavior of such slags in the high temperature and reducing conditions of the electric furnace, a number of samples of slag were fused in an experimental electric furnace. The results obtained, given in Table I., show that a very large amount of metallic iron was produced, and that this iron carried with it practically all the copper, gold, and silver, and more than 50 per cent. of the sulphur, of the original slag. The metallic buttons formed in the electric furnace were clean, hard, but not brittle.

Mar 1, 1910

By Samuel S. M. Chan

The magnetic susceptibilities of some ores and the major rock formations of the Precambrian Belt Supergroup in the Coeur d'Alene mining district were determined both in the laboratory by the use of the Gouy method and in the field with a Bison susceptibility unit. Trace element analysis of the same group of rock samples was also made using the atomic adsorption technique. Results of this preliminary study indicate that some correlation exists between the magnetic susceptibilities and the various rock formations. This may be useful for regional mapping and mineral exploration.

Jan 1, 1974

By Henry G. Morris

The use of compressed air for the transmission of power has reached so great a development that we find numerous large establishments devoted to the manufacture of machinery for its production and application, and special periodicals published for the dissemination of information on the subject. Moreover, its employment is so general in mining operations that no apology is needed for the presentation to the Institute of such a paper as the present. The admirable articles of Mr. E. A. Rix, published in Conzpressed Air, show a wide range in the mechanical efficiency of air-compressors, varying, under different conditions, from 15 to 60 per cent.; and it is evident that any

Jan 1, 1902

Freeport's Floating Mine Begins Sulphur Operation Eight years of research were culminated when Freeport Sulphur Co.'s floating mine plant went into operation on Bay Ste. Elaine in the remote Louisiana bayou country 60 miles southwest of New Orleans.

Jan 1, 1953

By John F. Lundeberg

CLAUSS1 observed that if isothermal creep data could be approximated as straight lines on a log stress-log time plot, a relationship existed that could be expressed as log t = m log s + b [ l] where t = time,

Jan 1, 1965

By M. E. Nicholson

IN order to understand how alloying elements influence hardenability through their effect on the rate of pearlite nucleation, it is advantageous to use a model to describe the mechanism of pearlite nucleation. The model which currently is most widely accepted has been described, among others, by Mehl et a1.1-3 and by Hultgren.4 Pearlite nucleation involves both the nucleation of ferrite and cementite.4,5 Cementite nucleates first, followed rapidly by the formation of ferrite at the cementite-austenite interface. The conclusion that cementite is the first phase to form during the process of pearlite nucleation is based, in part, on the observation that proeutectoid cementite is continuous with pearlitic cementite and that the orientation relationship between proeutectoid ferrite and austenite is not the same as that between pearlitic: ferrite and austenite.6,7 Recently, Smith" has suggested that the dissimilarity in orientation relations, instead of indicating the pearlite nucleation sequence, may be evidence that pearlite is nucleated in a grain adjacent to the one in which it is growing. Also, Modin9 as shown that ferrite in pearlite may be continuous with proeutectoid ferrite, and he has also shown that proeutectoid cementite is not always continuous with pearlitic cementite. Thus, it appears that the conclusion that cementite always initiates the pearlite nucleation process is open to serious question. The author believes that important evidence on the question of how pearlite is nucleated exists in the rates of pearlite nucleation of different steels. The following is a review and analysis of this evidence. If the nucleation of pearlite is considered as requiring the nucleation of both cementite and ferrite, then the time to nucleate pearlite consists of the time to nucleate the first phase to form, plus the time to nucleate the second phase at the advancing interface of the first. In the absence of a visible proeutectoid constituent, the second phase must be nucleated very soon after the first. If cementite is the first phase to form, the time to nucleate pearlite will be approximately equal to the time to nucleate cementite. Since the nucleation rate of a phase precipitating from solid solution increases with the degree of supersaturation, it would be expected that the rate of pearlite nucleation should increase with increasing carbon content. Digges10 has shown that the reverse is true. He determined the quenching velocity necessary to suppress pearlite formation in plain carbon steels as a function of carbon content. His results showed that pearlite formation could be suppressed with lower quenching velocities as the carbon content of the steel increased, at least up to 1.25 pct C, the highest carbon content he studied. Thus, it would appear that in plain carbon steels, in which pearlite is formed at the nose of the C-curve, the hypothesis that cementite nucleates first does not predict the observed change in nucleation rate. The validity of the current model of pearlite nucleation may be tested also by determining whether or not it predicts the relative influence of alloying elements on the nucleation of ferrite and pearlite. This can be done best by a consideration of the changes in a TTT diagram produced by a change in alloy content. Hultgren4 suggests that the general shape of a TTT diagram, as well as what constituents will form from austenite, can be predicted from the relative nucleation rates of ferrite and cementite. This is illustrated in the schematic diagram for a hypoeutectoid low alloy or plain carbon steel shown in Fig. 1. The C-curves for ferrite nucleation and for cementite nucleation are represented by AA' and CC', respectively, and the start of ferrite formation and pearlite formation are represented by AX and BC respectively. Adopting the current theory, Hultgren suggests that between X and C pearlite forms directly from austenite, since cementite nucleates more rapidly than ferrite in this temperature range. Conversely, at temperatures above Tx, ferrite is the first to nucleate and proeutectoid ferrite is formed. As proeutectoid ferrite grows, austenite becomes enriched in carbon, so that the cementite nucleation rate is increased. As a result, pearlite nucleation above temperature Tx is accelerated, beginning along BX and not along C'X. Temperature T, represents the temperature at which the nucleation rate of ferrite equals that of cementite. By extending this type of reasoning, using the principle that the nucleation rates of ferrite and cementite increase with increasing supersaturation of austenite with respect to these phases, it should be possible to predict the influence of carbon content on the shape of the isothermal transformation diagram. For a slightly higher carbon content than that of Fig. 1, the curve A A' representing the beginning of ferrite formation should be moved to the right, whereas the curve CC' representing the beginning of cementite formation should be moved to the left. For hypoeutectoid plain carbon and low alloy steels, this prediction does not agree with existing data. Instead, as the carbon content is increased, the pearlite curve moves to the right along with the ferrite curve and always appears to join it tangen-tially. This behavior is demonstrated by the TTT-curves of a series of manganese steels" shown in Fig. 2. In this figure, TTT-curves for four alloys containing 0.20, 0.40, 0.60, and 1.20 pct C are superimposed. The curves are identified in the figure legend. The letters F, P, and C are used to indicate the start of ferrite, pearlite, and cementite formation, respectively. In these steels, it appears that the nucleation of ferrite and of pearlite are related processes. As a result of the foregoing evidence, it is proposed that the formation of pearlite be considered as follows: Either ferrite or cementite may nucleate from austenite, then grow until the remaining phase is nucleated at the interface between the growing phase and austenite. (The growth of the first phase to form is assumed to be accompanied by a composition change in the adjoining austenite.) According to this model there are two modes of nucleating pearlite: 1—where cementite initiates the succession

Jan 1, 1955

By H. H. Reamer, B. H. Sage

The formation volume and the relative volume of the liquid Phase of mixtures of Condensate and gas from five different parts of a field in the Louisiana area have been established experimentally. These studies included gas-condensate ratios as high as 25.000 cu ft/bbl at pressures up to 5,000 psi. The gravities of the tank condensates were between 53.9° and 63.9° API. The compositions of the condensate and gas samples inves-ligated are presented in tabular form. The formation volume. the relative volume of the liquid phase. and the specific volume of the mixtures are available. A rough correlation of the formation volume as a function of pressure. temperature, and gas-condensate ratio has been presented. This correlation i-considered applicable only to the range of conditions covered in this investigation for systems of similar nature and com-position. INTRODUCTION Often a knowledge of the influence of temperature. Pres sure, and relative quantities of condensate and gas upon the volumetric behavior of fluid*. from a given field has been employed in estimating the Conditions existing in the reservoir. The early work of Beecher and Parkhurst' and the more rrcent Studies of the Dominguez' and San Joaqnin Valley Field;: are examples of experimental studies of this character. Correlation of the volumetric behavior of naturally occurring hydrocarbon mixtures has Proved To be feasible' . at low gas-conden-sate ratios-; for fluids*. from a single geographic area. Progres 5 is being made in the Prediction of the volumetric behavior of distillate systems at high gas-condensate ratios and pressure.. However. the estimation of the retrograde". ' dew-point pressure still remains uncertain and probably can best be established by experiment. For this reason it appears of interest to make available experimental information about the volumetric behavior of mixtures of condensate and gas from five different part.; of a single field. This material shows a rough similarity to data for mixtures of condensate and gas from San Joaqnin ' Valley Fields. In the present paper. 110 attempt has been made to coordinate the available information on tbe volumetric behavior of fluids from condensate fields. It appears hopeful that progress can be realized by the utilization of recently developed equa-tions of state.!' However. the primary problem in any such correlation is the proper identification of the components and constituents of naturally occuring systems. Additional experimental information may be required to permit the determination of the values of the constants of the equation of state for References given at end of paper. Manuscriptt received in the office of the Petroleum Branch June 11. 1951. *For present purposes low gas- condensate ratios will he considered as those below 3,000 cu ft/bbl, and the region of high gas-condensate ratio will be limited to compositions containing more than 5,000 cu ft of pas per bbl of condensate. Mixtures Containing between 3,000 and 5.000 CII ft OF gas per bbl will be considered of intermediate gas-condensate ratio.

Jan 1, 1952

By William H. Spice

The area on which oil and gas development is reported covers 30 counties, which are included in the Texas Railroad Commission's District No. I. This area not only includes the old established Balcones fault-line group of producing fields but also includes the southwest extension of this trend and some of the deeper Wilcox (Eocene) exploratory development. (Fig. J.) In the old Balcones fault-line zone, three new fields were discovered during 1941. These fields are comparatively small, producing from Dale limestone or Austin chalk. No new fields were discovered during the year in the Edwards (Lower Cretaceous) limestone horizon. One new shallow field was discovered in the Reklaw (Eocene) sand horizon and, in the southwestern part of the district, one oil field and one gas field were discovered in the Navarro (Upper Cretaceous) sand horizon. An extremely important extension was made to the one producing Wilcox (Eocene) field of the district in the Washburn Ranch field of La Salle County. The district produced 6,650,357 bbl. during 1941, which was a 12 per cent decrease under production for 1940. Approximately 4,954,000 bbl. of this total production was produced by the three Edwards limestone fields, Luling, Salt Flat and Darst Creek, the remaining production coming from the other 43 active fields in the district. In all, 3694 wells were producing at the end of 1941, compared with 3559 wells at the end of the previous year. During the year, 139 new producing wells were completed and 29 wells were abandoned in the producing fields. The increase in producing wells represents an increase in new wells over abandonments in these fields, together with a decrease in wells temporarily shut down as of the end of 1941. The majority of production drilling was carried on in the following fields; Bee Creek, Chicon Lake, Elm Creek, Gas Ridge, Pearsall and Tenney Creek. Approximately 250 wells were drilled during 1941, of which 110 were exploratory wells completed as failures throughout the district. Considerable exploratory work was continued during 1941 along the Wilcox trend. Geophysical work employing various types of geophysical methods and leasing activity was continued along this trend, particularly by the major companies. The significance of this activity is apparent from the successful extension and development in the Washburn field of La Salle County, where several well-developed gas-and-oil producing horizons have been developed in the lower Wilcox section between 5100 and 5600 ft. as noted in the following paragraphs. Continued exploratory activity along this general trend as far as present conditions will permit is predicted for 1942. New Fields Elgin Field, Bastrop County.—No. I-A Hiram Walker, Marts and Beaven, Inc., discovery well of the Elgin field, was com pleted on Apr. 22, 1941, in broken Austin chalk from 2820 to 2840 ft., pumping 105 bbl. per day, 36.8°A.P.I. gravity. The well apparently is producing from a crevice in

Jan 1, 1942

By William H. Spice

The area on which oil and gas development is reported covers 30 counties, which are included in the Texas Railroad Commission's District No. I. This area not only includes the old established Balcones fault-line group of producing fields but also includes the southwest extension of this trend and some of the deeper Wilcox (Eocene) exploratory development. (Fig. J.) In the old Balcones fault-line zone, three new fields were discovered during 1941. These fields are comparatively small, producing from Dale limestone or Austin chalk. No new fields were discovered during the year in the Edwards (Lower Cretaceous) limestone horizon. One new shallow field was discovered in the Reklaw (Eocene) sand horizon and, in the southwestern part of the district, one oil field and one gas field were discovered in the Navarro (Upper Cretaceous) sand horizon. An extremely important extension was made to the one producing Wilcox (Eocene) field of the district in the Washburn Ranch field of La Salle County. The district produced 6,650,357 bbl. during 1941, which was a 12 per cent decrease under production for 1940. Approximately 4,954,000 bbl. of this total production was produced by the three Edwards limestone fields, Luling, Salt Flat and Darst Creek, the remaining production coming from the other 43 active fields in the district. In all, 3694 wells were producing at the end of 1941, compared with 3559 wells at the end of the previous year. During the year, 139 new producing wells were completed and 29 wells were abandoned in the producing fields. The increase in producing wells represents an increase in new wells over abandonments in these fields, together with a decrease in wells temporarily shut down as of the end of 1941. The majority of production drilling was carried on in the following fields; Bee Creek, Chicon Lake, Elm Creek, Gas Ridge, Pearsall and Tenney Creek. Approximately 250 wells were drilled during 1941, of which 110 were exploratory wells completed as failures throughout the district. Considerable exploratory work was continued during 1941 along the Wilcox trend. Geophysical work employing various types of geophysical methods and leasing activity was continued along this trend, particularly by the major companies. The significance of this activity is apparent from the successful extension and development in the Washburn field of La Salle County, where several well-developed gas-and-oil producing horizons have been developed in the lower Wilcox section between 5100 and 5600 ft. as noted in the following paragraphs. Continued exploratory activity along this general trend as far as present conditions will permit is predicted for 1942. New Fields Elgin Field, Bastrop County.—No. I-A Hiram Walker, Marts and Beaven, Inc., discovery well of the Elgin field, was com pleted on Apr. 22, 1941, in broken Austin chalk from 2820 to 2840 ft., pumping 105 bbl. per day, 36.8°A.P.I. gravity. The well apparently is producing from a crevice in

Jan 1, 1942

By Heinrich Ries

Fullers' earth is a clay-like substance, which has the property of decolorizing or clarifying oils. An ultimate chemical analysis shows it to differ from most ordinary clays in having usually a high percentage of combined water and a low amount of alumina. There is probably a large amount of hydrous silica present. Fullers' earth possesses little or no plasticity, and in order to work properly has to be ground very fine. A chemical analysis is of little value at present in determining its quality; only a practical test suffices. Up to about two years ago all of the fullers' earth used in this country was imported from England; but about that time deposits were discovered in Florida, "† and since then rumors of its occurrence have been coming from all parts of the country. Next to the Florida deposits of fullers' earth, those of South Dakota are the most extensive thus far discovered in this country. The earth was first discovered near Fairburn, Custer county, and other deposits have since been prospected at Argyle, Minnekahta and other localities. Fairburn.—One of the first deposits located and opened up is five miles southeast of Fairburn, Custer county. The mine is a mile from the Fremont, Elkhorn and Missouri Valley Railroad, and the section exposed shows, beginning at the top: Feet. Micaceous sandy clay,......... 6 Fullers' earth,..........9 Micaceous sandstone,......... The fullers' earth passes upwards into the sandy clay, but in its purer portions it is a yellowish, gritty clay, with a somewhat

Jan 1, 1898

By A. C. Butterworth

M OST operators of open-pit mines in the Lake Superior iron ore district are quite familiar with the use of fuel oil in the heavy-duty Diesel engines commonly used in truck-haulage service but some operators, including my own company, Pickands Mather, have had butane-engine trucks in service for several years, and less is known of their operation. One of the first installations of trucks for iron-ore haulage was in 1939 at a deep open-pit mine on the Cuyuna Range. These superseded standard-gauge steam haulage. Trucks then obtainable were equipped with 150-hp Diesel engines, and the speed of these units on an 8 % grade would have been so slow, considering the depth of the pit, that plans for an all-truck haul out of the pit were rejected. About this time one of the engine manufacturers brought out an auto-

Jan 1, 1948

By J. J. Jonas, J. L. Uvira

Equipment was constructed which permitted the hot compression of 99.8 pct Armco iron and 2.8 pct Si steel at constant true strain rates of 0.05 to 1 per sec over the temperature range 600" to 1000°C. A maximum true strain of 1.9 could be attained, followed by immediate quenching or by isothermal annealing. True stress-true strain curves were obtained, and the steady-state flout stress, a, strain rate, i, and temperature, T, were found to fit the following expression: The constants A, a, n', and AH were determined for the two ,materials. The activation energies obtained for Arrnco iron and silicon steel are 66 and 80 kcal per mole, respectively, and approximate those for seu- diffusion and for creep. This indicates that hot compression is a diffusion-controlled thermally activated process. THE hot compression of iron and steel is usually carried out in the austenite temperature range,1"7 as this is the one of greatest interest with respect to industrial hot working. However, a disadvantage of testing in the austenite range is that the hot-worked structure is destroyed by the phase transformations taking place during cooling. The present study was therefore carried out in the ferritic temperature range, and the hot-worked substructures were preserved by rapid quenching after deformation. The substructural results will be described in a separate paper, and the present communication is restricted to the strain rate/stress/temperature relationship observed during hot working. The results of hot-compression testing are usually given in the form of true stress/true strain curves, with a different curve for each temperature/strain rate ~ornbination.',~,~ Sometimes simple algebraic equations are fitted to the curves, so that certain extrapolations or interpolations can be performed.1'2'5 These equations are, however, devoid of mechanistic interpretations. The present study was undertaken to show that hot compression can be described by an equation of the type used in creep studies. That is, it will be shown that the temperature dependence of the strain rate in hot working is well-represented by an Arrhenius term, with an activation energy similar to that for creep. Also it will be seen that the stress dependence of the strain rate is similar to that for creep EXPERIMENTAL METHOD AND MATERIALS The investigation was carried out with the following three ferrous materials: 1) Armco iron; 2) Armco iron with 0.26 pct Mn; 3) 2.8 pct Si steel. The first two materials were utilized for investigations performed in the temperature range 600" to 800°C; the last one was used for tests at temperatures from 600" to 1000°C. The materials were of commercial purity,* as shown in Table I. Cylinders of five different sizes were prepared by strain annealing. The resulting mean grain diameter was 3 mm in the 1-in. Armco iron and 2 mm in the other sizes and grades. Different ratios of diameter/height were used to enable the determination of the coefficient of friction. The specimen faces were provided with concentric grooves, which acted as lubricant holders during compression, as recommended by English and ~ackofen' and others.2'9 Powdered glass lubricants were applied to the samples before hot compression to decrease friction and barreling, following the practice of previous investigator~.~~~~~~~~ Different mixtures of glass powder were used for each temperature, after the determination of suitable compositions by experiment.'' Equipment for Hot Compression. Hot-compression tests were carried out on an adapted 150-ton vertical hydraulic extrusion press and also on a modified high-temperature creep machine. The modified extrusion press was used for temperatures up to 800°C. The following items were added to the press: a) a high-temperature furnace with built-in upper and lower platens; and b) a transmission assembly, which permitted the attainment of logarithmically decreasing crosshead speeds. These accessories are described in detail in Ref. 11.

Jan 1, 1969

By D. R. Walker, M. C. Shaw

Dimitri Kececioglu (Allis-Chalmers Manufacturing Co., Milwaukee)—The idea of applying metal cutting theory to comminution and vice versa is very impressive. Among others, the demarcation of wheel-grinding data into two regions, namely Kick's and Rittinger's, draws attention here. A study of Figs. 6 to 9 shows the following: In Fig. 6, 1 point out of 8; in Fig. 7, 4 points out of 26; in Fig. 8 only 1 point out of 13; and in Fig. 9 practically none out of 13 points fall out of curve No. 2. Also when grinding particles smaller than 5x10." in. it is difficult to measure very accurately the grinding forces, chip geometry, and particle size. In view of the above it would be difficult to make a positive and distinct demarcation of the Wheel-grinding data into two regions, namely, Kick's and Rittinger's. The idea of using machine grinding to determine the comminution properties of materials is indeed unique. The following cautions come to mind, however, regarding applicability of machine grinding data to comminution: 1—Grinding gives uniform particle size, whereas comminution gives a variety of particle sizes in the same process. The fact that grinding gives uniform particle size is not necessarily an advantage because in comminution the overall energy under actual comminution is desired and comminution invariably results in the production of a variety of particle sizes. 2—In grinding, a small particle is ground off a comparatively large surface. In comminution small bodies are broken down to smaller bodies. This makes it difficult to establish a concept of reduction ratio in machine grinding. 3—The mechanics of machine grinding involve direct shearing action under very high strain and comparatively high compression at the shear zone, whereas: comminution involves direct dynamic compression and surface friction with comparatively little strain and shear. Consequently the mechanics of machine grinding appear to be different from those involved in comminution. Hence one might arrive at erroneous con- clusions when comminution characteristics are eval-uated from machine grinding results. It is noticed also that functions other 'than Eq. 16 which do not involve the concept of direct proportionality of useful energy input to new surface area created (Eq. 2 and particularly Eq. 12) may be derived to fit the, data of curve No. 2. One such relationship may be u = ct-", where c is a positive constant and n is a positive constant less than unity. This, of course, is made possible because data of a very small range. of particle size are being fitted by the curves of No. 2 and the hereby suggested relationship. A sound comminution theory should be applicable to a relatively large range of particle size. George B. Clark (Department of Mining Engineering, University of Illinois)—While the experimental work of Walker and Shawin this article is of intrinsic value in revealing certain fundamental aspects of machine grinding, milling, and related processes and in adding to the store of information concerning the comminution of solid materials by this particular process, it appears doubtful that the results of their research can be employed to verify either Kick's or Rittinger's theories. Both these laws were originally developed and proposed on the basis of very simple, idealized hypotheses. The creation of parallel idealized physical laboratory conditions which would be required for either their proof or disproof appear to be well beyond the scope of human ingenuity, at least at present. One great weakness of the imputed verification is that the spread of the points plotted on the graphs is not sufficient to permit accurate 'curve fitting. The range of particle sizes included in the belt and wheel grinding is not extensive enough to show any general trends, particularly for the horizontal portion of the curves, said to represent Kick's laws. That the milling; grinding, and turning data obtained by Walker and Shaw for both metals and minerals happen to comply with. certain interpretations of these two theories under certain specialized conditions

Jan 1, 1955

By George B. Clark

COMMERCIAL strip mining of coal was first begun in the state of Illinois in 1911.1 The annual tonnage of coal produced from coal strip mines in the state was very small until 1924, when the strip mines shipped 1.68 pet of the total state shipping mine tonnage. Since then, strip mines have gradually come into their own by producing a sizable percentage of the coal produced in the state. Table 1 shows the coal tonnage shipped from both underground and strip coal mines in the state of Illinois for selected years. The table illustrates the major role that strip mines play in the state's coal industry. Today, strip mining is generally conducted in areas where the coal seams lie so close to the surface of earth that a stripping method of mining the coal seam is cheaper than an underground method. Strip mining not only recovers 100 pct of the coal deposit, but may also be used as a method of mining large acreages of coal abandoned by the closing of underground mines.

Jan 1, 1949

By EDWARD B. DURHAH

The illustration Fig. 12, of the paper of Edward B. Durham, "Electrolytic Refining at the U. S. Mint, San Francisco, Cal.," printed in Bulletin No. 58, October, 1911, p. 830, contained an error. The corrected diagram is printed below.

Nov 1, 1911

By W. F. Domis, F. von Gemmingen, F. Garofalo

The effect of rain size on the creep behavior of an austenitic iron-base alloy has been studied at 1300° F under conditions of constant stress. The average grain diameter varied between 9 and 190 p (ASTM 10.7-2). The subgrain size and apparent activation energy for creep were not found to depend in any systematic manner on gain size. Grain hozmdary serrations were observed in all specimens tested. The variation of the secondary-creep rate, 2,, with the pain diameter, 1, is given by: es = K(213m + 1 )/l.]; 1, is the grain diameter zohere is reaches a minimum. Results in the literature shoujthat 1,increases as the temperature increases. At low creep temperatures is is therefore proportional to 12, at intermediate temperatures <, exhibits a minimum, and at high creep temperatures is is proportional to 1/1. The dependence ofis on the stress, u, is given by: t, = A" (sinh acrln, a and n show little variation with 1. The dependence of A" on 1 is given by: A" = KA[(21k + 13)/1]. For 1 » >>lmn = 4, and at constant values 01- isat lozu stress levels, the steady-state stress is given by the Hall-Petch relation. The variation of c, with grain size is believed to he associated particularly with grain boundary generation of dislocations which becomes more important with increasing temperatures. SEEMINGLY inconsistent experimental findings have led to a certain amount of confusion concerning the effect of grain size on creep behavior. The confusion is attributed to a lack of test results obtained over sufficiently wide ranges in grain size, stress, and temperature. Experimental results presented in this paper and results available in the literature1-5 show a consistent behavior and lead to a unified concept for the dependence of secondary-or steady-state creep rate on grain size. In accordance with this concept, which is substantiated experimentally, secondary-creep rate should increase with increasing grain diameter at low creep temperatures, leading to greater creep strengths for fine-grained materials. At intermediate temperatures the secondary-creep rate should decrease to a minimum and then increase as the grain size is increased. At high creep temperatures the secondary-creep rate should decrease with increasing grain size, leading to greater creep strengths for coarse-grained materials. Whether a temperature is high or low for creep in a metal or alloy depends primarily on its melting temperature. MATERIAL AND TEST PROCEDURES The material tested was an austenitic iron-base alloy of the following composition (wt pct): C, 0.005; N, 0.017; Mn, 1.26; Ni, 14.21; and Cr, 17.18. Two 15 -lb ingots were forged and hot-rolled to 5/8-in.-diam bars which were then cold-rolled and cold-swaged to a diameter of 0.49 in. These were sectioned into 3-in.-long blanks and heat-treated at various temperatures to obtain different grain sizes. The procedures employed and the results obtained are summarized in Table I. The secondary treatment at 1400° F followed the primary treatment without intermediate cooling to room temperature. This final treatment was employed to minimize various effects arising from heating to different temperatures during the primary treatment, particularly differences in intragranular dislocation structure, segregation of interstitial atoms at grain boundaries, and density of grain boundary ledges. The intragranular dislocation structure was examined by electron transmission metallography after each of the treatments described in Table I. Isolated dislocations and a few tangles were observed but no evidence of subgrains was found after any of the treatments. No grain-size effect was evident on the density and distribution of dislocations. Stabilization of grain boundary structure is particularly important because, as will be discussed later, grain boundaries influence high-temperature creep behavior. Magnetic-permeability measurements after each treatment and

Jan 1, 1964

By E. R. Macgregor, J. Halpern

The kinetics of the reduction of cupric salts in aqueous solution by molecular hydrogen to metallic copper are described. The rate of reduction appears to be homogeneously determined and shows a marked inverse dependence on the hydrogen-ion concentration. Precipitation of copper is more rapid and complete in sulfate than in per-chlorate solution. A mechanism is proposed which accounts for this behavior. IN recent years a number of important hydro-metallurgical processes have been developed in which metallic salts in aqueous solution are reduced by gaseous hydrogen, usually at elevated temperatures and pressures, and thereby precipitated either in metallic form (e.g. Ni, Co, Cu) or as an oxide or salt of lower valence (e.g. VO, and VA).1 ; In connection with applications such as these, most of which involve heterogeneously catalyzed reactions, recent demonstrations"-" that salts of certain metals, e.g., Cu", Ag&apos; , Hg" , and Hg,+ can activate molecular hydrogen homogeneously and thus catalyze hydrogenation reactions in aqueous solution, are of considerable interest. For example, cupric salts catalyze the otherwise slow homogeneous reduction of dichromate and ceric salts by hydrogen, i.e. Cr,O; + 3HL. + 8H1 ? 2Cr&apos;- -- 7H,O [1] 2Ce &apos; ! H.. ? 2Ce" | 2H . [2] In perchloric-acid solution, where Cu" is not appreciably complexed, the kinetics have been found" " to be of the form -d [H,] _- k,[HJ [CU"]&apos; dt -LCu+&apos; l+ (k ,/k,) [H] [3] where, K = 1x10"&apos; exp [—26,600/RT] 1, mole-&apos; min-&apos; ... [4] and (k ,/k,) - 0.25 at 110°C. This kinetic behavior suggests that the reaction proceeds by a mechanism involving the following sequence of steps kt Cu" +H1CuH&apos; 4-HA [51 k., CUH + CU" ? + 2Cu f H&apos; [GI 6Cu&apos;+ Cr,07 + 14H&apos;+ 2Cr- (¦ 7H,O + 6Cu" [&apos;i] fast The catalytic activities of the undissociated cupric-sulphate and cupric-acetate complexes are somewhat greater (by factors of 6.5 and 120, respectively) than that of the simple hydrated Cu" ion.&apos;" These considerations suggest that, in contrast to the other hydrometallurgical hydrogenation reactions, referred to previously, reduction of cupric salts in aqueous solutions by molecular hydrogen, should proceed homogeneously, and in the absence of an extraneous catalyst. This has already been demonstrated" for acetate-buffered solutions where the product of the reaction is a precipitate of cuprous oxide (Cu,O). In the present paper, an investigation of the reduction of cupric salts in perchloric-acid and sulphuric-acid solutions, leading to the precipitation of metallic copper, is described. Some results for the sulphate system, which is of considerable hydrometallurgical interest, have been reported previously by Ipatieff",&apos; " and by Schaufel-berger&apos; but these do not give a quantitative account, of the kinetics and mechanism of the reaction. Experimental The reduction experiments were conducted in the 1-gal, titanium-lined autoclave described in connection with earlier related investigations," " and using a similar procedure. The solutions were made up by dissolving known amounts of CP grade Cu(ClO,), and HC10, (or CuSO, and HISO,) in dis-tilled water. While in the autoclave, the solution was stirred and maintained at a constant temperature (±loc) and under a constant partial pressure of hydrogen gas. It was ascertained that the agitation (provided by two 3-in., four-bladed stirrers, rotating at 900 rpm) was adequate so that at no time was the rate of reaction limited by solution of hydrogen. During each experiment, samples of the solution were withdrawn periodically, allowed to cool, and the concentration of copper remaining in solution was then determined electrolytically. Some Cu&apos; is formed during the reaction, but undergoes disproportionation when the solution is cooled to room temperature. For purposes of kinetic calcula-

Jan 1, 1959

By M. A. Grossman

The harden ability of most steels can be predicted within 10 to I5 per cent provided the complete chemical composition is known, including "incidental" elements; and provided the as-quenched grain size is known; and provided, finally, that the composition and heating temperatures for hardening are such as to result in austenite free from carbide particles. In the method proposed herein, the steel is considered as having a base hardenability due to its carbon content alone (the hardenability of a "pure steel" of the given carbon content, without any other elements), and this base hardenability is multiplied by a multiplying factor for each chemical element present. After multiplying all these together, the final product is the hardenability. Grain size may be taken into account either in the base hardenability or after the multiplication. Hardenability is stated in terms of "ideal critical diameter", namely, the diameter of bar, in inches, that will just harden all the way through (absence of un-hardened core) in an "ideal" quench, and the calculation may also be related to the Jominy test The data bring out certain features rather clearly. For example: i. It is quite useless to attempt to predict hardenability unless all elements, including "incidentals,,) are known; thus an "incidental,, chromium content of 0.20 per cent increases the hardenability by about 50 per cent. 2. The relative effectiveness of different alloys is sometimes unexpected; thus molybdenum when calculated in this way appears to be of the same order of effectiveness as manganese, rather than much more powerful, as would appear to be common experience; observe that an increase from no manaanese to 0.20 per cent Mn provides a multiplying factor of 1.67, and an increase from no molybdenum to 0.20 per cent Mo provides a factor of 1.63, an increase of over 60 per cent in each case. However, if to a steel containing 0.50 per cent Mn there is added "20 points of manganese," the factor is raised from 2.65 (for 0.50 per cent Mn) to 3.35 (for 0.70 per cent Mn), or an increase of only 26 per cent. Thus the fist small addition of an element has a much more powerful percentage effect than an equal further addition when some is already present, and in most cases the effect of molybdenum is considered in relation to a steel in which molybdenum is absent. 3. If two elements are equally effective, a greater hardenability will be obtained by using, for example, 0.5 per cent of each than by using I.o per cent of either of them alone. 4. A knowledge of the as-quenched grain size is essential for precise work, since a difference of only one grain size number (say No. 7 instead of No. 6) makes a difference of almost 10 per cent in hardenability (in these units); this, however, does not apply to certain It should be emphasized that in chromium steels (over 0.30 per cent Cr) and chrome-molybdenum and chrome-vanadium steels, un-dissolved carbides are likely to be present in the steel as quenched, and that in such cases the charts can indicate only a maximum Passible hardenability, whereas the extent of hardening actually obtained may be much less. Thus tests on a number of chrome-molybdenum steels have indicated a degree of hardening amounting to only 50 to 65 per cent of the maximum possible, and in chromium steels from full hardening (100 per cent) down to as low as 70 per cent. On the other hand, when the amount of such elements is small (Cr under 0.30 per cent, Mo up to 0.25 per cent in the

Jan 1, 1942

By M. A. Grossman

The harden ability of most steels can be predicted within 10 to I5 per cent provided the complete chemical composition is known, including "incidental" elements; and provided the as-quenched grain size is known; and provided, finally, that the composition and heating temperatures for hardening are such as to result in austenite free from carbide particles. In the method proposed herein, the steel is considered as having a base hardenability due to its carbon content alone (the hardenability of a "pure steel" of the given carbon content, without any other elements), and this base hardenability is multiplied by a multiplying factor for each chemical element present. After multiplying all these together, the final product is the hardenability. Grain size may be taken into account either in the base hardenability or after the multiplication. Hardenability is stated in terms of "ideal critical diameter", namely, the diameter of bar, in inches, that will just harden all the way through (absence of un-hardened core) in an "ideal" quench, and the calculation may also be related to the Jominy test The data bring out certain features rather clearly. For example: i. It is quite useless to attempt to predict hardenability unless all elements, including "incidentals,,) are known; thus an "incidental,, chromium content of 0.20 per cent increases the hardenability by about 50 per cent. 2. The relative effectiveness of different alloys is sometimes unexpected; thus molybdenum when calculated in this way appears to be of the same order of effectiveness as manganese, rather than much more powerful, as would appear to be common experience; observe that an increase from no manaanese to 0.20 per cent Mn provides a multiplying factor of 1.67, and an increase from no molybdenum to 0.20 per cent Mo provides a factor of 1.63, an increase of over 60 per cent in each case. However, if to a steel containing 0.50 per cent Mn there is added "20 points of manganese," the factor is raised from 2.65 (for 0.50 per cent Mn) to 3.35 (for 0.70 per cent Mn), or an increase of only 26 per cent. Thus the fist small addition of an element has a much more powerful percentage effect than an equal further addition when some is already present, and in most cases the effect of molybdenum is considered in relation to a steel in which molybdenum is absent. 3. If two elements are equally effective, a greater hardenability will be obtained by using, for example, 0.5 per cent of each than by using I.o per cent of either of them alone. 4. A knowledge of the as-quenched grain size is essential for precise work, since a difference of only one grain size number (say No. 7 instead of No. 6) makes a difference of almost 10 per cent in hardenability (in these units); this, however, does not apply to certain It should be emphasized that in chromium steels (over 0.30 per cent Cr) and chrome-molybdenum and chrome-vanadium steels, un-dissolved carbides are likely to be present in the steel as quenched, and that in such cases the charts can indicate only a maximum Passible hardenability, whereas the extent of hardening actually obtained may be much less. Thus tests on a number of chrome-molybdenum steels have indicated a degree of hardening amounting to only 50 to 65 per cent of the maximum possible, and in chromium steels from full hardening (100 per cent) down to as low as 70 per cent. On the other hand, when the amount of such elements is small (Cr under 0.30 per cent, Mo up to 0.25 per cent in the

Jan 1, 1942