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By R. S. Rickard, M. C. Fuerstenau

Anodic polarization curves for iron dissolution and cathodic polarization curves for copper deposition and ferric and hydrogen ion reduction were studied. These results were used to predict the relative rates of the reactions: The rates of the first two reactions were found to be first order with respect to the reacting ion, and the rale-controlling step was diffusion of the ions to the callzode surface. The rate of hydrogen ion reduction in an oxygen-free solution is dependent on the reciprocal of the square root of the hydrogen ion activity. In solutions containing oxygen, the rate of hydrogen reduction becomes dependent on the square root of the partial pressure of oxygen. At equal concentrations copper precipitation occurs about twice as fast as ferric ion reduction. In an air-saturated solution containing 0.01 M cupric ion at pH 2, the rate of hydrogen ion reduction zs about 10 times slower than that of copper precipitation. At pH values below 3, the rate of hydrogen reduction in oxygen-free solutions is very slozu. COPPER cementation has been utilized industrially for many years as a means of recovering copper from aqueous solutions. There are many different types of cementation plants, but all simply provide a means of contacting iron with relatively dilute copper solutions. In the past little or no attention has been paid to rates or mechanisms of the reactions involved. As a result, this and other studies'-3 have been undertaken recently to establish the important parameters in this system. The reactions involved in copper cementation by iron are: Since transfer of charge is involved in every case, these reactions should be considered from an electrochemical point of view. In any electrochemical system involving electrolytic conduction, passage of electrons necessitates ion transfer to the respective electrodes according to Faraday's law. The current in the system will be proportional to the rate of ion transfer, and, therefore, when the current in the galvanic cell is known, the rates of the reactions involved can be determined. Galvanostatic electrode measurements5" are applicable for these electrochemical studies, in that with this technique polarization curves (current density vs electrode potential) are established by impressing a constant current through an electrode and measuring the electrode potential. Once the current density, electrode potential, and reacting area are known for each reaction in this cementation system, the rates of the iron-consuming reactions can be determined. EXPERIMENTAL MATERIALS Several metal electrodes were used in this investigation; they are shown in Table I. Solutions were made with reagent-grade salts and conductivity water. Air, nitrogen, and oxygen were employed. All of these gases were saturated with water and degreased prior to use. EXPERIMENTAL PROCEDURE The experimental work was divided into two general areas. The first area involved galvanostatic measurements, which were used to determine the rates of reactions as a function of various parameters. The second area comprised actual cementation experiments to check the rates predicted from the electrode measurements. Galvanostatic Electrode Experiments. Polarization curves were obtained using a standard galvanostatic technique5'= with the apparatus shown in Fig. 1. The various electrode polarization experiments were run the same way except for changes in solution composition, polarity, and type of measured electrode. The general procedure involved the following steps: 1) a solution was made 0.5 M in sulfate ion and to the desired cation concentrations; this solution was placed in a constant-temperature bath and saturated with the desired gas; 2) the electrodes were cleaned and placed in the electrode holder; 3) the previously cleaned apparatus was assembled and immersed in a constant-temperature water bath (temperature controlled to ± 0.05"C); 4) the electrode was then positioned; the solutions were introduced, and the polarization meas-

Jan 1, 1969

By Michael J. Bailey, Peter M. Douglass

INTRODUCTION Spoil pile slope failures can have costly consequences. In- stability in the form of a single major event or as a recurring problem can 'mean lost production, lost resources and damaged mining equipment. In extreme but not uncomnon cases, a major spoils slide can force the closure and abandonment of a pit. Slope stability is affected by mine operating practices as we1 l as geologic conditions and material parameters. Mine operators can enhance spoil pile stability through constructive changes in their operations. Attention to the causes of in- stability can lead to development of operating practices tailored to site specific problems. Action aimed at limiting future instability is frequently more cost effective than continually "coping" with unstable spoils. The effect of mine operations on material properties is often overlooked because the "data" are not easily quantified nor input directly into stability analysis equations. We have found, however, that miners' experience with their own operation, as well as data pooled from similar operations, yields relation- ships which can be utilized to solve stability problems. The repetitive nature of area type surface coal mines with successive spoil pile rows further enables the development of useful site specific relationships. Stability problems can be mitigated by applying these relationships.

Jan 1, 1983

Fred. T. Greene, Rossland, B. C. (communication to the Secretary): At the beginning of his gaper, Mr. Herzig refers to an article of mine in the Engineering and Mining Journal of January 27, 1900. I would like to add that the method de-

Jan 1, 1901

By W. A. STERLING

IN the opencut iron mines of the Mesabi Range in Minnesota, the trend in mining is in the development of mining equipment and mining methods which will move surface overburden and ore-bearing materials with less labor and at a cheaper cost. This is a must for most of the independent operators. Their reserves of direct-shipping ore are extremely small and their operations are being conducted in small, or intermediate pits, with a high stripping ratio in the outer fringes, or shore lines of older pits. and in ore bodies passing from direct shipping to the washing and the intermediate, or retreat ore state. The trend is toward deeper stripping, longer and steeper hauls, and the necessity of moving a total of from three to five or six tons of overburden and ore material for each ton of shipping-grade ore produced. This naturally calls for greater production, with larger shovels, or draglines. cheaper drilling and blasting costs through the drilling of larger-diameter blastholes, and cheaper haulage through the use of trucks of larger capacity and more extensive use of belt-conveyor systems. This trend is notable both in stripping and mining.

Jan 1, 1948

Rep. William S. Hill (R.- Colo.) will preside over a Congressional hearing investigating the problems of the mining industry to be conducted in Phoenix, Ariz., late in April. Rep. Hill has expressed the desire to hear from the industry itself all possible testimony on the needs of domestic mining and how Congress can help. Rep. John J. Rhodes of Arizona is also expected to attend the hearing. Two new features are incorporated into an SO2 process for treatment of low grade manganese ores disclosed by Chemical Construction Corp. The new approach includes a high temperature autoclaving step and a sintering operation. Data was given for work performed on Cuyuna Range ores.

Jan 4, 1953

By Lewis V. Wade

U.S. Bureau of Mines efforts under longwall research programs to develop the capability to predict support requirements for longwall/ shortwall support systems are discussed. Ground control studies are being conducted in conjunction with several longwall/shortwall demonstration projects. Geologic, support performance, and strata behavior are being documented on these projects. A hypothesis is presented for the prediction of support requirements.

Jan 1, 1978

By William Braden

In view of the current discussion of a proposed change in the United States mining law, abolishing the feature known as the extralateral right of a lode-location, it is an interesting circumstance that in the neighboring Province of British Columbia this feature was tried for eight years and then abandoned. The results of that abandonment have been such as to disprove the proposition, so confidently advanced by many

Jan 1, 1899

By W. F. Stowasser

A downdraft traveling grate process to agglomerate pelletized iron ore concentrates has been successfully demonstrated in a pilot plant at Carrollville, Wis. Work there followed several years of development in the Allis-Chalmers Mfg. Co. laboratories, and the pilot plant phase was carried out in co-operation with Arthur G. McKee & Co., consultants and engineers to the iron and steel industry. End result of the process is conversion of iron ore concentrates into a form which can easily be transported and smelted in the blast furnace.

Jan 5, 1955

By Frank Firmstone

IT is often desirable to obtain one or more accurate horizontal sections of a blast furnace after blowing out. Wishing to do this, last April, in the case of No. 4 furnace at Glendon, which had worn in a very remarkable manner, the method described below was employed, with very good results. A scaffold was fixed in the furnace, and on it was placed a drawing- board, covered with paper, the top of which was made level at exactly the height at which the section was to he taken. (Fig. 8.) The centre of the furnace (which had previously been found, and marked on a plank across the top) was laid off on it by dropping a plumb-bob from above, and a strong needle was driven into the board in the centre. By means of a straight-edge and two plumb- bobs, the line passing through the centres of the front and back arches was also drawn on the board. A pencil was fastened to a light wooden straight-edge at a known

Jan 1, 1875

By Frank Firmstone

It is often desirable to obtain one or more accurate horizontal sections of a blast furnace after blowing out. Wishing to do this, last April, in the case of No. 4 furnace at Glendon, which had worn in a very remarkable manner, the method described below was employed, with very good results. A scaffold was fixed in the furnace, and on it was placed a drawingboard, covered with paper, the top of which was made level at exactly the height at which the section was to he taken. (Fig. 8.) The centre of the furnace (which had previously been found, and marked on a plank across the top) was laid off on it by dropping a plumb-bob from above, and a strong needle was driven into the board in the centre. By means of a straight-edge and two plumbbobs, the line passing through the centres of the front and back arches was also drawn on the board. A pencil was fastened to a light wooden straight-edge at a known

By Barry S. Epstein

Financing the acquisition of a going coal mine operation has not had the exposure other finance-oriented projects have had. Therefore, C.I.T. feels that coal mining people and financial people should improve their understanding of the factors involved in this important type of acquisition. The discussion consists of two major subjects: analysis of the acquisition of the property, and sources and terms of funding the acquisition. Source and Terms of Funding There is a need to keep the competent medium-sized independent operator in the coal business, especially in these times of energy shortage. The creation of a resale market for coal mines encourages new investment in the coal mining business by medium-sized operators and their financial backers. Who provides debt and equity financing to acquire going coal mine operations and on what terms?

Jan 9, 1975

By A. Stumpf, Y. Berube

An experimental apparatus for studying the aqueous oxidation of sulfide minerals is presented. The oxidation kinetics for molybdenite in solutions of caustic soda and dissolved oxygen are discussed; results of leaching experiments on chalcopyrite concentrates are given. Preliminary results on the transfer of oxygen into water are also discussed.

Jan 1, 1974

By D. E. Mikkola, G. E. Poquette

X-ray diffraction was used to study the growth of antiphase domains in quenched (or "disordered&apos;? Cu3Au annealed in the range 300" to 385°C. Measurements of the long-range order parameter indicate that a high degree of order is established rapidly at these annealing temperatures. Average domain sizes obtained by Fourier analysis of the superlattice peak profiles show that antiphase domain growth is analogous to classical metallurgical grain growth (i.e.,fol-lows a D2 US kt relation). The activation energy for the growth process, 44 kcal per mole, indicates diffusion control. The anisotropy in the observed effective domain sizes from seven different superlattice peaks can be best accounted for by a configuration involving antiphase domain boundaries on {100 } and (111 ) planes, where the (100) boundary is the low-energy type, {lOO} Type I. The disappearance of the (111) antiphase domain boundary during domain growth is dif-fusion-controlled with an activation energy of 48.5 kcal per mole. On the other hand, the behavior of the parameter representing the amount of (100) Type I boundary indicates that there may be a conversion of the higher-energy boundary types to (100) Type I boundary during the growth process. THE order-disorder transformation in the alloy Cu3Au has been the subject of numerous experimental investigations over the past 40 years, most of which have involved measurements of convenient physical properties such as resistivity and hardness as a function of heat treatment. The interpretation of these data is difficult because measurements of this type have the disadvantage that they yield total changes resulting from several different atomic processes which may be occurring simultaneously. The present study was undertaken to establish by means of X-ray diffraction the kinetic behavior of one of these atomic processes, namely antiphase domain growth. In the completely ordered state Cu3Au has an L12 structure which can be described as an fcc type arrangement of atoms in which the gold atoms occupy the corner sites and copper atoms the face-centered sites. Three other equivalent unit cells can be formed by allowing two gold atoms to occupy opposite face-centered sites and copper atoms to occupy the remaining corner and face-centered sites. These four different unit cells are crystallographically related by a shift of 1/2<110>. Quenching from above the critical temperature (392°C) to room temperature retains the "disordered" structure-a "random" arrangement of copper and gold atoms having the fcc structure. Annealing the disordered alloy below the critical temperature causes ordering to occur through the nucleation and growth of ordered regions at different points throughout the crystal. These small ordered regions, each based on one of the four types of unit cell, grow by consuming the disordered material until they impinge to form a domain structure in which the domains are antiphase by a shift of 4(110). The boundaries between domains are called antiphase domain boundaries (APDB) and they have been found to lie primarily on &apos; {100} planes in highly ordered Cu3Au. Two types of APDB can occur on ( 100) planes. An example of an (001)1/2[110] shear type APDB is shown in Fig. I. Because of the layer of copper atoms separating the domains in this case, there are no near-neighbor violations across the boundary and it has a low surface ener This type of APDB will be referred to as {lOO} Type I. Fig. 2 shows an (001): [011] climb type APDB, (100) Type 11. This type of APDB can be described as resulting from removal of a (200) plane followed by a shift of 1/2<110> to bring the separated regions together. Near-neighbor violations across (100) Type I1 APDB make it a high-energy boundary. There are numerous other possible APDB configurations; however, it is only worth noting that shear type APDB can be produced on the (111) plane by motion of a normal fcc dislocation with Burgers vector 1/2<110> through the ordered structure. A (111); [110] shear type APDB is shown in Fig. 3. Again, because of the near-neighbor violations this type of APDB has a higher energy than the (100) Type I APDB.

Jan 1, 1970

By Oscar Kuchs

IN January and February of the current year, at the Tooele plant of the International Smelting Co., Tooele, Utah, a modification of the usual method of converting, for the treatment of copper-lead matte from lead blast- furnaces, was developed and put into successful operation. In brief, the method consists in blowing molten matte direct from the blast furnaces in basic-lined converters, without the addition of siliceous fluxing ores, to the almost complete elimination of the lead contained, and to the production of copper bullion, the resulting lead fume being recovered by the filtration of the converter gases through woolen fume bags. The process is carried out in conjunction with the converting of reverberatory copper matte, the heavy iron slag, together with the copper precipitated, being transferred to converters blowing copper matte. The purpose of this transfer is to reduce the copper oxide formed, due to the necessary overblowing of the lead-matte charge, and to utilize, as far as possible, the value of iron from the lead matte, for the fluxing of siliceous dry ores. The final slag from the copper converters is then skimmed off and transferred molten to a reverberatory smelting furnace treating copper ores. This variation from general converting practice was the outgrowth of results obtained during 1913 when it was endeavored to convert copper-lead matte in the usual manner, with the direct addition of siliceous fluxing ores. To make clear the reasons lying back of the process it is necessary to recount at some length the results of operations during that year. In the design of the lead plant it was planned to treat the copper-lead matte from the furnaces by direct converting without reconcentration and thereby to recover the copper, silver, and gold as quickly as possible. A converter plant of ample capacity, treating copper matte, already being in operation, it was only necessary: to install a bag house, a fan, and the necessary flues to complete the equipment.

Jan 7, 1914

By H. Foster Bain

In the preparation of this series of books it was considered particularly appropriate to include this work. Gunther was one of the younger men who was associated with Colonel Mudd in the finding and development of ore deposits. Supported by Mudd, Gunther undertook a systematic survey of the sources of copper of ancient Europe. This survey resulted in the rediscovery of the deposits now worked by the Cyprus Mines Corporation for which Gunther was, until shortly before his death, the resident manager. In finding and developing these mines, Gunther applied the methods and data embodied in this book and proved their usefulness. It is believed that other young engineers may profit similarly. In presenting a new edition, the form and substance of this work have been preserved and no changes have been made in any direct statement of the original author. Individual illustrations, paragraphs and mine descriptions appearing in the first edition have been omitted in order to permit introduction of new material. The latter has been chosen so as to present a somewhat more balanced picture of the mining industry as it now exists. The new material relates largely to the so-called porphyry coppers, to mines in Canada, Rhodesia, Alaska, and a number in the United States that have become important since the book was first written. The new material was prepared by Mr. Russell C. Fleming, using the best that had been published and items of which he had personal knowledge or had obtained by correspondence with men familiar with the deposit described. Whenever possible the description used has been submitted to the original author for correction. In a number of instances

Jan 1, 1932

AT THE beginning of December, the Lausanne Con-ference was in session. The representatives of the United States declared the American position. The representatives of Russia were received and were heard. The Turks appeared at this conference in the attitude of victors, dictating terms. The British refused to surrender Mosul, and December thus ended with this question unsettled. Early in the month the premiers of the principal powers met in London for the discussion of the German reparations question, the temporary agreement expiring on. Jan. 15, 1923. On Dec. 11 the Conference adjourned without getting anywhere, and at the end of December prospects looked more hopeless than ever. The premiers are to meet again on Jan. 2, 1923. The interruption of the London conference was followed by the intimation of early participation of the United States in European affairs in the practical way of a large loan to Germany. These intimations, ema-nating from Washington, appear to have been in the nature of trial balloons. They showed that the wind was unfavorable, the bankers not considering conditions suitable for the flotation of such a loan. British statisticians are puzzled by the fact that the trade returns of Great Britain show a greater turnover in the volume of goods during the first 11 months of 1922 than in 1920, although the rate of labor employ-ment in 1920 was nearly 100 per cent. and in 1922 only about 86 per cent., with an economic situation admit-tedly so bad as to be alarming. The British Parliament was convened under the premiership of Bonar Law. One of its first acts was confirmation of the constitution of the Irish Free State. Civil war in Ireland continued. Poland, like most of the other countries of Europe, is torn between socialism and conservatism, with the former party at present predominant. Early in December, Gabriel Narutowicz, an engineer but a radical, was elected president. On Dec: 14 he entered office and-on Dec. 16 he was assassinated.

Jan 1, 1923

By J. Buchwald, R. W. Heckel

THE DeHoff method&apos; of analysis of ellipsoids of constant shape provides a quantitative metallo-graphic technique whereby the actual size distribution of the ellipsoids may be determined from polished and etched random planar sections. This method provides a useful metallographic tool since it appears to be the only method available for determining the size distribution of nonequiaxed second-phase particles. This method, however, assumes that the type of particle being studied is known to be either oblate or prolate of a fixed minor to major axis ratio, q. This, in general, means that one assumes either oblate or prolate ellipsoids of a given q and checks the total volume and surface area of the second phase as determined from the particle size distribution to values of these quantities determined by other techniques. Suitable check methods may be point counting, lineal fraction, and areal fraction methods for obtaining the total volume and the Smith and Guttman2 method of intercepts for obtaining the total surface area. If the initial guess at particle shape and q were incorrect, i.c., the volume and surface information obtained from the particle size distribution data does not agree with those values obtained by other techniques, another assumption must be made and the particle size dist distribution must be recalculated. A current study in this laboratory has involved a large number of these calculations. To facilitate the handling of the calculations, the DeHoff method was programmed in the FORTRAN language for an IBM 1620 computer. The purpose of this note is to briefly describe this program. The complete program along with a list of variable names, a sample input, and a sample output may be obtained from the senior author. Basically, the program provides for the calculation of particle size distributions for a series of q values for both oblate and prolate ellipsoids for each set of input data. The total volume of second-phase particles per unit volume are calculated for each calculated particle size distribution. The output of the program is arranged to allow a rapid comparison of the calculated volume and surface values to data obtained by independent check measurements. A condensed flow chart of the program in the notation of DeHoff1 is given in Fig. 1 The calculation of the number of particles per unit volume in the jth size class, Ni, according to the DeHoff method&apos; is: where k(q) is the shape-correction factor given by DeHoff as a function of q for both oblate and prolate ellipsoids, A is the size-class increment, k is the number of size classes, ni is the number of particles in the ith class on the planar measurement surface, and B(j,i) are the saltykov3 coefficients which correct for measurement surfaces which do not pass through the major and minor axes of the particles. The values of /3(j,i) are included as a two-dimensional array in the program. Particular values of k(q) are included in the program in increments of q of 0.05. The first calculation is carried out for q = 1 (spheres), the second for q = 0.95 oblate, the third for q = 0.95 prolate, and so forth. The number of q values chosen for the calculation is determined by a control card in the input for each set of data.

Jan 1, 1965

By Randolph C. Specht

A two year study was made of the waste disposal of the pebble rock phosphate industry. Solid slimes are impounded in large settling areas and the process water is re-used. Clear effluent was not found to be toxic to fish, or animal life in field tests or in controlled experiments.

Jan 1, 1950

By D. H. Forbes, I. B. Cadoff, H. M. Manasevit

Single-crystal silicon films have been obtained on several natural crystal faces of BeO using the thermal decomposition of silane and the hydrogen reduction of silicon tetrachloride. From an analysis of X-ray diffraction data it was determined that the following film-substrate orientation relationships exist: (111) Si 11(0001) BeO, (111) Si 11(1011) BeO, (100) Si 11f1010) BeO. and (110) Si 11(1010) BeO. An analysis of the crystallographic relationships between the film and substrate indicates that a match occurs between the silicon atoms in the film and the berylliuni ion sites in the substrate. This correspondence is in agreement with previous work on the deposition of silicon on sapphire.1-3 silicon on spinel: and tungsten on sapphire. The high resistivity, thermal conductivity, and radiation resistance of beryllium oxide make it an important substrate material for the deposition of thin films of silicon or other semiconductors. The importance of semiconductor-insulator composites to the field of integrated microelectronics has been well-documented in the case of silicon on sapphire.&apos;-&apos; The successful growth of large-area single-crystal silicon on an insulator, sapphire, was first reported in 1963.1,2 Since that time studies have been made of the crystallographic relationships between the deposited film and the sapphire substrate. On the basis of the observed relationships, a model has been proposed relative to the crystallographic requirements for epitaxy between the semiconductor film and the metal oxide substrate.3 It is proposed in this model that epitaxy is the result of a match between atoms of the deposited film and the metal ion sites of the substrate plane. This match is not limited to a 1 to 1 correspondence between sites in the two lattices. Sub- sequent studies of the deposition of silicon on spinel4 and tungsten on sapphire5 have yielded data which support this model. On the basis of this previous work it was felt that silicon on BeO should also fit this model. In the present study, the choice of substrate orientation was limited to the natural faces of synthetic BeO crystals. Of the faces available, the (0001) plane seemed the most favorable for epitaxial growth. EXPERIMENTAL PROCEDURE Silicon films were deposited from silane and silicon tetrachloride in the apparatus shown in Fig. 1. The hydrogen ambient gas was purified by passage either through a DEOXO unit, molecular sieves, and a liquid nitrogen cold trap, or through a heated Pd-Ag thimble. The gas was then mixed with the silicon source materiai and passed over the substrate which lies on a spacer above an inductively heated silicon pedestal. The following deposition conditions were used: a hydrogen flow rate of 3 liters per min with silane and silicon tetrachloride concentrations of 0.2 mole pct and a pedestal temperature of 1175" * 5°C as observed with an optical pyrometer assuming an emissivity of 1.0. Deposition was preceded by a 15- to 30-min hydrogen-etch period conducted at a temperature of 1275°C (obs). Adherent silicon films from 2 to 10 u were grown on the various BeO faces. The substrates were synthetically grown beryllium oxide single crystals ranging from 5 to 10 mm in

Jan 1, 1967

By P. G. Shewmon, H. E. Collins

A study has been made to determine the sites at which sulfur adsorption occurs on copper surfaces. measurements were made of the relative torques, Ys, at the intersection of twin boundaries with surfaces near the three low-index orientations, i.e., (100), @lo), and 011), over a range of H2S/H2 ratios. HZS concerztvations j&apos;ro~n 3 to 1500pp)n between 830" and 1050°C were used. It is concluded that sulfur adsorption occurved preferentially though not exclusively at edge sites near the (100) and (110) surfaces in the HzS range — 700 Ppm giving rise to negative torques near these orientations. Beyond this HzS range, adsorption occurred at all sites. Near the (111) surface, 7/y little with HzS concentration up to approxiwzately 75pptn. Above this range, the results indicate adsorption is occurring OH both terrace and edge sites. SCIENTIFIC interest in surfaces and their interactions with a gaseous environment dates back to the beginning of the 19th century. The scientific luminaries of that period—Faraday, Maxwell, Rayleigh, Dewar, and Gibbs—were already concerned about such processes. However, it has only been within the past several decades that adsorption on metal surfaces has been actively studied. This increased interest in adsorption has been brought about by the advent of new and improved experimental techniques and apparatus, e.g., ultrahigh vacuum, and field-emission and ion microscopes. However, most of the work done using these techniques has been carried out at low temperatures. When adsorption studies have been made at either low or high temperatures, they usually gave no indication of the particular surface orientations or type of sites on which adsorption was occurring. In the last few years, there have been a series of studies in which the surface tension, y,, and/or its derivative with respect to orientation, 7, have been studied as a function of orientation and atmosphere.&apos;-7 Nearly all of the work on the relative torque,* ~/y, silver annealed in hydrogen and air.6 Recently Winterbottom and Gjostein" have used a modified and more accurate Mykurian method to determine the y plot of gold in hydrogen The only work in which T/~, has been measured over a range of chemical potentials for a given solute, p2, is that of Robertson and shewmon7 on the Cu-0 system. They measured T/Y, vs Po, (10"" to 10- l3 atm) at 1000°C in various mixtures of Hz0 and HZ. From this work they estimated the value of p2 at which one half of the surface sites are occupied with oxygen, pg, as being in the range 10- l6 to 10- l5 atm of oxygen. They also found that increasing Pa increased the magnitude of ~/y, near the (111) and (100) orientations. This indicates that oxygen is not adsorbed preferentially at step edges, but uniformly over all surface sites. In addition, they did one experiment on sulfur adsorption on copper surfaces, which indicated that sulfur adsorption decreases ~/y, near the (100) orientation, while not affecting ~/y, near the (111). This could be interpreted as indicating that sulfur adsorbs preferentially at step edges near the (100). In this paper the primary objective of the work has been to carry out a study of sulfur adsorption on copper surfaces over a range of temperatures and p,. In conjunction with this work, thermal grooving at grain boundaries has been examined as a method of determining the effect of sulfur adsorption on y,. METHODS Ideally, one would like to have information on the quantity of solute adsorbed on a surface and the types of sites at which it is absorbed as a function of p2. The total quantity adsorbed or the surface excess is given by the thermodynamic equation Thus data on the variation of y, with pz indicates the value of p2 at which adsorption becomes appreciable and the quantity adsorbed. The type of adsorption site is more difficult to deduce but information on this can be obtained from the variation of rz with 8, the angular deviation of the surface orientation. This is obtained from the thermodynamic equationlg Data on t and ys as functions of p2 have been obtained by the following methods. 1) Twin Boundary Grooving—By determining the effect of adsorption on the torque, 7, where T is the variation of surface energy, y,, with orientation, it is possible to obtain some indication as to the preferred sites of adsorption. Experimentally, the torque value measured is the relative torque, 7/ys The twin boundary grooving technique suggested by Mykura&apos;&apos; was used in this study to determine near the three low-index orientations— (loo), (110), and (111). Mykura&apos;s equation relates 7 /yS to measurements of the di-

Jan 1, 1967