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The Sub-committee on Coal Mining, since its appointment, has been collecting data about subsidences in coal mines in this country, and thinks that almost all of the available data about occurrences of this sort in bituminous mines has been collected. Similar data is being compiled for the anthracite regions, which it is hoped will be ready for the 1927 meeting. As most of the bituminous seams are nearly level, the records obtained give the problem in its simplest form, without complications due to the pitch of the seam. Copies of the questionnaire, Appendix A, were mailed to all of the coal operators' associations, to most of the large operating companies and to many engineers, with the request that any data on the subject be returned to the committee, or that advice of any subsidences known be given: the replies to most of the questionnaires were general, although some specific cases were given. Many of the companies were unable to reply to all questions, as they lacked the necessary data, but in nearly every case where accuratc data was available, it was cheerfully furnished, and any additional information requested was secured. All specific cases of subsidence were followed up by correspondence, and in several cases by personal inspection. Figs. 1 to 31 were made from the information furnished. Table 1 gives measurements of elevations taken in one case at intervals from October, 1913, to May, 1918. With one exception, where the evidence cannot be released on account of a lawsuit, it is believed that the cases submitted with this report include practically all that have happened in bituminous coal mining in this country of which actual measurements were secured. Some of these have been published by Young and Stoek,l and some have been secured from other publications. In collecting these data, the subcommittee had the Engineering Societies Library extend its bibliography to date; this list is given in Appendix B. To assist in the study of the problem, all of the subsidence literature in English was examined for cases in which spccific measurements were given, and the essential data for each case are shown in Appendix C.

Jan 1, 1927

By F. N. Koepel, L. A. Callaway

The property of the Andes Copper Mining Co. is in the central part of the Republic of Chile, Province of Atacama, about 75 miles to the eastward from the port of Chafñaral. At this point the Andean system is made up of two principal ranges, and the mine and metallurgical plant are both on the westerly slope of the outer or western range. Mean elevation of the mine is 10,500 ft., while at the plant the elevation ranges from 9445 to 9700 ft. A meter gage railroad extends from the company's port at Barquito, near Chañaral, to the reduction plant at Potrerillos. This road has a total length of 94 miles, of which 57.79 miles are owned by the Andes Copper Mining Co. and the remainder of the road is controlled by the State. Development of the Potrerillos mine and installation of the metallurgical equipment presented unusual difficulties due to the arid nature of the country, high altitude and remoteness of the location from any considerable center of population. As a primary step it was necessary that railroad transportation be provided in order that mine development and plant construction could go forward on an economical basis. Provision of an adequate supply of water for domestic and metallurgical uses involved the construction of approximately 178 miles of pipe lines, all of which have their sources at altitudes ranging from 12,000 to 14,000 ft. above sea level and traverse rough and difficult terrane. Water for metallurgical use is brought to Potrerillos from the Ola River, a stream originating in the high cordillera to the eastward from the property. It is delivered by means of a steel pipe line, 32 miles long, having diameters ranging from 22 to 36 in. Domestic water is supplied to the various camps through a system of pipe lines aggregating 146 miles in length, the Ola water being unfit for this purpose. These conductors gather water from numerous springs in the high mountains to the eastward from Potrerillos and deliver it to the mine, the reduction works and the port at Barquito. Extensive permanent housing facilities had to be provided as it was necessary to care for more than 3000 workmen and employees at the

Jan 1, 1934

By Henry Rawdon

ANY laboratory corrosion test, as judged from the practical point of view, is valuable only to the extent that it foretells what will, in all probability, occur in service. Such a test is most properly to be considered as a "pilot test, " that is, a test which indicates the direction along which action may be expected to occur rather than as a truly quantitative test which would be expected to tell just how and to what extent the action would proceed. It is generally recognized that laboratory corrosion tests should be chosen with particular reference to the character of service expected for any particular type of metal, so far as it can be foreseen. Even when this requirement has been fulfilled, however, the question whether the actual service behavior of the material is in accordance and general agreement with predictions based upon such laboratory tests is always a pertinent one. The information available in the technical literature bearing on the correlation between the service behavior of metals from the corrosion standpoint, and the results obtained with the same metals in laboratory corrosion tests is very meager, indeed. The results which have been obtained in weather-exposure tests of sheet duralumin which form the body of this discussion are presented here for their bearing on this particular phase of the problem of the corrosion resistance of duralumin. Although the exposure tests described have not been completed, in the sense that all of the tests, in the series initially laid down, have been accomplished, still the general trend shown by the results is so clear that a number of definite conclusions at this stage (subject, of course, to possible modification in the light of later results) are believed to be warranted. The tests reported upon here form one phase of the much broader study of this subject which has been under way for several years in which the National Advisory Committee for Aeronautics, the Bureau of Aeronautics of the Navy Department, the Army Air Corps and the Bureau of Standards have cooperated. Without the very helpful cooperation of the manufacturers in furnishing the

Jan 1, 1929

By R. M. Brick

THE Institute of Metals Division Lecture in 1936, given by R. F. Mehl, on diffusion in solid metals1, was introduced with the statement that "the phenomena of diffusion are intimately related to many basic prob-lems of the metallic state, but in addition to this the process of diffusion is of first importance practically." In view of the scope of that lecture, it does not seem necessary to review the importance, history or present status of diffusion problems. One aspect of the subject of diffusion that has received little attention became of some immediate importance in the course of a study on segrega-tion. When a solid solution alloy freezes, the familiar mechanism of solidification requires that the first nuclei formed be low in solute con-centration, with a resultant normal segregation or coring effect during freezing. Theoretically, diffusion of solute atoms during solidification should result in a homogeneous solid solution. Actually, of course, it is impossible in most binary alloys to obtain a cooling rate that will permit diffusion to eliminate coring in the freezing dendrites. For a given alloy, the extent of diffusion attained up to the point of final solidification will determine the degree of enrichment in solute atoms of the final liquid phase. The flow of this liquid into dendritic contraction channels and the solute concentration of the liquid seem to be the determining factors as to whether the final gross segregation is normal, inverse or absent. The purpose of the present study of diffusion was to determine to some extent the separate diffusion rates of copper and magnesium into pure aluminum with a view to clarifying previous results on segregation in these alloys; i.e., the fact that under similar freezing conditions alumimum-copper alloys segregate inversely and aluminum-magnesium alloys segre-gate normally. Of concomitant interest were the questions of the homogenization times required for segregated ingots or partially melted, i.e., "burnt," structures, and the solution heat-treatment times required for cast, hardenable aluminum-copper and aluminum-magnesium alloys, for worked and annealed structures, and so forth.

Jan 1, 1937

By C. G. Fink, G. L. Putnam

The dissolution of gold by cyanide solutions was studied by determining the time required for the solvents to dissolve gold leaf. Minute traces, even 0.5 ppm, of sulphide ion retard the dissolution of gold, and this behavior cannot be accounted for by the presently accepted hypotheses involving oxygen-depletion or thiocyanate formation. On the other hand, traces of the salts of lead, bismuth, mercury, and thallium considerably accelerate the dissolution. The beneficial effect of lead is dependent upon the pH and cyanide ion concentration of the solution. ALTHOUGH cyanide solvents are used very ex-x*. tensively for the recovery of gold from ores and concentrates, the normal rate of solution of the precious metal as determined by Barsky, Swainson, and Hedley,1 and others2 is less than about 3 mg per sq cm of exposed gold surface per hour, corresponding to a corrosion depth of approximately 1.5 microns (0.00006 in.) per hr. Although the slow rate may be increased to some extent in certain cases, as, for example, when the the gold is partially imbedded in iron pyrites,3 the leaching operation is generally the most time-consuming step of the cyanide process. Frequently it is necessary for the leaching solvents to remain in contact with the ores for 50 to 200 hr in order to dissolve all of the gold particles.' Not only does the slow solution rate cause some increase in the capital costs, but the cyanide consumption also may be increased because of vaporization of hydrocyanic acid and secondary reactions with minerals such as malachite (CuCO3 • Cu(OH)2), and pyrrhotite, which often are associated with gold. It is not surprising that numerous attempts have been made to accelerate the dissolution of gold in cyanide solutions. Experimental Gold Leaf Test: The gold leaf test was apparently originated by M. Faraday, who, by means of it, discovered that dilute cyanide solutions would dissolve gold readily in the presence of oxygen. The usefulness and reliability of the test have been discussed elsewhere.5,6 Essentially, the method consists of determining the time required for 5-ml portions of cyanide solvents to dissolve squares of 23 carat gold leaf, 0.5 cm on edge, when shaken in 10-ml test tubes with the solvents. The weight of gold leaf per test was 0.051 mg as determined by the direct weighing of a leaf 8.6x8.6 cm (weight = 15 mg) and measuring the area of the test sample (0.25 sq cm). Gold leaf is of remarkably uniform thickness.6 Since gold leaf, like native gold, contains small amounts of copper and silver, the results are comparable with those one might expect in cyaniding gold ores. As six or more tests can be made simul- taneously, the relative efficiencies of the solvents can be evaluated readily. All dilute solutions of lead, bismuth, thallium and mercury salts were prepared by the ordinary dilution method used by chemists. Our C.P. sodium cyanide and buffering reagents had no detectable amounts of either sulphide ion or heavy metals. Soluble Sulphides in the Cyanide Process: The action of soluble sulphides is of interest in the study of the dissolution of gold in cyanide solutions. That gold ores which contain compounds of arsenic and antimony often are not amenable to direct cyanide treatment is well known, and it said that arsenic and antimony are "cyanicides."7 It is commonly believed that part of the sulphur content of such ores is soluble in alkaline solutions to give sulphide ion, which reacts with the free cyanide content of the leaching solutions to form inert thio-cyanates or reacts with the dissolved oxygen to form sulphites or sulphates.8 A purpose of this paper is to demonstrate that sulphide ion may behave in a manner that cannot be explained by either the oxygen-depletion or thiocyanate formation theories and to prove directly that concentrations of sulphide ion which cannot be detected even by colorimetric methods may retard the dissolution of gold.

Jan 1, 1951

By C. G. Fink, G. L. Putnam

The dissolution of gold by cyanide solutions was studied by determining the time required for the solvents to dissolve gold leaf. Minute traces, even 0.5 ppm, of sulphide ion retard the dissolution of gold, and this behavior cannot be accounted for by the presently accepted hypotheses involving oxygen-depletion or thiocyanate formation. On the other hand, traces of the salts of lead, bismuth, mercury, and thallium considerably accelerate the dissolution. The beneficial effect of lead is dependent upon the pH and cyanide ion concentration of the solution. ALTHOUGH cyanide solvents are used very ex-x*. tensively for the recovery of gold from ores and concentrates, the normal rate of solution of the precious metal as determined by Barsky, Swainson, and Hedley,1 and others2 is less than about 3 mg per sq cm of exposed gold surface per hour, corresponding to a corrosion depth of approximately 1.5 microns (0.00006 in.) per hr. Although the slow rate may be increased to some extent in certain cases, as, for example, when the the gold is partially imbedded in iron pyrites,3 the leaching operation is generally the most time-consuming step of the cyanide process. Frequently it is necessary for the leaching solvents to remain in contact with the ores for 50 to 200 hr in order to dissolve all of the gold particles.' Not only does the slow solution rate cause some increase in the capital costs, but the cyanide consumption also may be increased because of vaporization of hydrocyanic acid and secondary reactions with minerals such as malachite (CuCO3 • Cu(OH)2), and pyrrhotite, which often are associated with gold. It is not surprising that numerous attempts have been made to accelerate the dissolution of gold in cyanide solutions. Experimental Gold Leaf Test: The gold leaf test was apparently originated by M. Faraday, who, by means of it, discovered that dilute cyanide solutions would dissolve gold readily in the presence of oxygen. The usefulness and reliability of the test have been discussed elsewhere.5,6 Essentially, the method consists of determining the time required for 5-ml portions of cyanide solvents to dissolve squares of 23 carat gold leaf, 0.5 cm on edge, when shaken in 10-ml test tubes with the solvents. The weight of gold leaf per test was 0.051 mg as determined by the direct weighing of a leaf 8.6x8.6 cm (weight = 15 mg) and measuring the area of the test sample (0.25 sq cm). Gold leaf is of remarkably uniform thickness.6 Since gold leaf, like native gold, contains small amounts of copper and silver, the results are comparable with those one might expect in cyaniding gold ores. As six or more tests can be made simul- taneously, the relative efficiencies of the solvents can be evaluated readily. All dilute solutions of lead, bismuth, thallium and mercury salts were prepared by the ordinary dilution method used by chemists. Our C.P. sodium cyanide and buffering reagents had no detectable amounts of either sulphide ion or heavy metals. Soluble Sulphides in the Cyanide Process: The action of soluble sulphides is of interest in the study of the dissolution of gold in cyanide solutions. That gold ores which contain compounds of arsenic and antimony often are not amenable to direct cyanide treatment is well known, and it said that arsenic and antimony are "cyanicides."7 It is commonly believed that part of the sulphur content of such ores is soluble in alkaline solutions to give sulphide ion, which reacts with the free cyanide content of the leaching solutions to form inert thio-cyanates or reacts with the dissolved oxygen to form sulphites or sulphates.8 A purpose of this paper is to demonstrate that sulphide ion may behave in a manner that cannot be explained by either the oxygen-depletion or thiocyanate formation theories and to prove directly that concentrations of sulphide ion which cannot be detected even by colorimetric methods may retard the dissolution of gold.

Jan 1, 1951

By Rudolph G. Wuerker

THE scarcity of values of tensile strength of rocks has been explained by the lack of successful testing procedures. In the case of mine rock a description is given' of the difficulties encountered in testing a cylindrical specimen, such as a core, by conventional methods. Over a period of years the following method has given definite and reproducible results with the weakest as well as with the strongest rocks. It does not completely supersede the use of cores with special fixtures but is a supplement in all cases where cores cannot be obtained, as from soft rocks, or in cases where it is less expensive to prepare test specimens by cutting them out of the rock instead of drilling cores. Principle and equipment are the same as for the test for tensile strength of hydraulic-cement mortar.' The test specimen, Fig. 1, has the shape of a briquet. While in the original cement mortar test the briquet is cast in a special mold, it is prepared from rocks in different ways, depending on how easily they can be cut and shaped. Soft rocks, which cannot be core-drilled with a carboloy or diamond bit, are simply hand-cut. Only two dimensions need be watched. The first is the 1-in. diam at the narrowest cross-section of the briquet. The other critical measure is the radius of curvature of the waistline, as the roller supports in the grips have a fixed distance. This radius is ground out of the solid by means of a carborundum grinding wheel having a 3/4-in. radius. Medium hard rocks can be core-drilled with a carboloy bit. The resulting core can be used for nondestructive sonic testing first, and after that for any destructive test. By using an EX-bit and by carefully placing the coreholes, preferably by using a tenplate such as shown in Fig. 1, it is possible to obtain from the rock a punched sample from which numerous tensile briquets can be made. The outside radius of the EX-bit differs from the radius of curvature of the briquet by 1/8 in., but this still permits placing and aligning the specimen in the grips. In the case of bedded rocks the core might have bedding planes normal to the plane of the briquets, and rocks can be tested in any arrangement of the bedding planes desired. Hard rocks, limestones, igneous, and metamor-whic rocks can only be diamond-drilled or diamond-cut. Here the method of getting the tension briquets by accurate placing of EX-drill holes is especially economical. The tops of the briquets made from hard rocks cannot be rounded; they are straight cuts made with a diamond cut-off saw and rounded off on a polishing wheel. Results: As long as specimens broke over the waistline the results were considered acceptable. Further statistical treatment of the tests' showed a satisfactory percentage of standard deviation. The tensile strength values obtained by this method do not represent true values because of the stress concentration caused by the curvature of the side of the piece and because of the closeness of the grips. The ratio of maximum to average stress at the plane of failure has been determined to be about 1.75." All tensile strength values listed in Table I are corrected accordingly. To avoid this stress-concentration, if there are a sufficient number of cores, tensile strength can be measured by imbedding the cores in mortar in the two outer briquets in the gangmold.4 Strain-Measurements: The applicability of the briquet specimens for strain observations was tested in the case of sandstone and shale. Two element Rosette SR-4 strain gages were used. Young's modulus and Poisson's ratio, both in tension, were computed and found to be different from those in compression, determined during the same test series and from the same rock, see Table I. References 1 L. Obert, S. L. Windes. and W. I. Duvall: Standardized Tests for Determining the Physical Properties of Mine Rock. U. S. Bur. Mines R.I. 3891 (1946). 2 Test for Tensile Strength of Hydraulic-Cement Mortar, ASTM Standard C 190-44. S F. O. Auderegg, R. Weller, and B. Fried: Tension Specimen Shape and Apparent Strength. Proc. ASTM 11939) 39, pp. 1261-1269. 4 API Code 32.

Jan 1, 1956

By R. D. Stover, F. O. Shuck

The variation of binary-diffusion coefficients with composition in the liquid Bi-Sn system at 300°C was measured using the capillary-reservoir technique. The experimental coefficients did not exhibit a simple composition dependence. A number of tests were also made to determine the effect of variation of density with composition on convection within the capillaries. These tests indicate that the density changes arising from composition duferences may give rise to high diffusion coefficients unless care is taken to maintain a stable configuration. In recent years there has been considerable interest in diffusion in liquid metals. However, the bulk of the work done to date has involved measurements of self-diffusion or diffusion of dilute concentrations of "solute" metals. Because there are possible applications to liquid phase processing of metal alloys and since additional data may help to clarify the nature of diffusion in liquid metals, investigations of the concentration variation of diffusion coefficients in binary alloys have been undertaken. Of past studies only two have covered large ranges of binary composition. Niwa et al.' investigated the Pb-Sn, Bi-Pb, and Bi-Sn systems and Grace and Derge2 investigated the Bi-Pb system. Because of the discrepancy between the data of these investigators, it was deemed desirable to check the possibility of convection arising from the variation of density with composition. The capillary-reservoir technique of Anderson and saddington3 was chosen for the present investigation since it has been widely used for measurements involving dilute solute concentrations and it was the technique used by Grace and Derge.2 It was necessary, however, to modify the normal procedure of using a pure metal bath to avoid measurement of integral diffusion coefficients over large concentration ranges. The alloy system chosen for study was the Bi-Sn system for which there are some data available.' EXPERIMENTAL PROCEDURE In order to utilize the capillary-reservoir technique for measurements of diffusion coefficients as a function of composition, it was necessary to modify the normal procedure slightly. This modification consisted of using a reservoir composition which was only slightly different from that in the set of capillaries, in order that the integral coefficients measured might be taken over a small composition range and might thereby be assumed to approximate the differential coefficient at some average composition between that of the capillary and that of the bath. It was found that a composition difference of approximately 0.10 mass fraction provided a satisfactory compromise between a small increment in composition and reasonable accuracy in measuring changes of composition. The alloys were prepared from tin and bismuth of 99.999 pct purity. The materials were first cleaned of surface oxides, then weighed and melted to form a homogeneous alloy in a Pyrex filling apparatus. The capillaries used were of precision bore Pyrex tubing 1.000 *0.005 mm bore. Capillaries of various lengths (from 2.85 to 5.85 cm) were cut and sealed at one end by fusing a 3-mm Pyrex rod to the end. The capillaries were filled by inserting them into the filling chamber, evacuating the chamber, submerging the capillaries, and pressurizing the chamber with argon. Two sets of capillaries were prepared for each run. One set contained an alloy more dense than the bath alloy and one set a less dense alloy. This procedure was followed so that the effect of density difference on the measurement could be determined. After filling one set of capillaries, these were placed open end up in a capillary holder and transferred to the diffusion chamber which consisted of a Pyrex tube inserted into a graphite block. The second set of capillaries was then filled and placed into the diffusion chamber. The reservoir alloy, which had been melted in a separate crucible, then was poured carefully into the diffusion chamber. Sufficient reservoir alloy was used to cover all capillaries to a depth of several centimeters. All of these operations: capillary filling, melting of alloys, and diffusion anneal, were carried out in a fused-salt bath which maintained a temperature of 300"*1°C. All capillaries were permitted to diffuse for approximately 48 hr. At the end of the diffusion period the capillary holder was removed from the bath and

Jan 1, 1969

By T. W. Watson, D. R. Flynn

Measurements have been made of the thermal conductivity and electrical resistivity of two specimens of 0.005-cm (2-mil) Be-Cufoil over the temperature range -140° to +200°C. The thermal cmductivity of Be-Cu Alloy 125 was found to be significantly higher than that of Alloy 25, which had a higher impurity content. The thermal conductivity and electrical resistivity values obtained were in concordance with the Smith and Palmer relation for copper alloys which states that ? = 0.0239 (T/p) + 0.075 where A is thermal conductivity (W cm-' deg-'), p is electrical resistivity (microhm-cm), and T is absolute temperature (OK) , indicating that the Smith and Palmer relation can be used to predict the thermal conductivity of this type of Be-Cu alloy over the temperature range -140" to + 200°C to within an accuracy suitable for most engineering applications. THE National Aeronautics and Space Administration, Goddard Space Flight Center, Greenbelt, Md., requested the National Bureau of Standards to measure the thermal conductivity of 0.005-cm Be-Cu foil which was to be used to fabricate antennae for use in Radio Astronomy Explorer space craft. It was felt that measurements had to be made on the actual antenna material, rather than on a thick bar of similar material, since the cold-working and age-hardening properties of the alloy would make it very difficult, if not impossible, to place a thick bar in the same metallurgical state as the 0.005-cm material. As discussed in Section 111 of this paper, the thermal conductivity of many copper alloys can be computed rather accurately from electrical resistivity data using an empirical relation developed by Smith and palmer' and further confirmed by owell.' However, there has been very little work done on correlating thermal and electrical conductivities on Be-Cu alloys. We were reluctant to assume the validity of the Smith-Palmer relation on Be-Cu alloys because of the very large mass difference between beryllium and copper. As will be seen, however, our experimental results indicate that the Smith-Palmer relation is valid for the two alloys on which we made measurements. I) DESCRIPTION OF SAMPLES Samples of Be-Cu Alloy 25 and Be-Cu Alloy 125 were furnished to NBS in the form of rolled strip material, 0.005 cm thick by 5.08 cm wide. The Be-Cu Alloy 25 was purchased by NBS in the form of a continuous length of flat strip. The Be-Cu Alloy 125 was furnished to NBS by Goddard Space Flight Center in the form of two lengths of strip that had been formed into "tubing" of about 1.2 cm diam, with one side of the strip overlapping (but not connected to) the other side by about 90 deg. This "tubing" had been opened up to be flat and then rolled onto spools of about 3 cm diam. When unrolled, the strip would spring back into tubular form. Samples of both of the Be-Cu alloys were chemically analyzed by the NBS Analytical Chemistry Division. The beryllium content was determined quantitatively by the phosphate-gravimetric method to be 1.83 wt pct for Alloy 25 and 1.80 wt pct for Alloy 125. The two alloys were also examined by a general qualitative spectrochemical method for metallic elements. The Alloy 25 specimen contained between 0.1 and 1.0 wt pct Al, Co, Fe, and Si and between 0.01 and 0.1 pct Ni. The Alloy 125 specimen contained between 0.1 and 1.0 pct Co and between 0.01 and 0.1 pct Al, Fe, and Si. Other metallic elements present were in amounts less than 0.01 pct. The NBS Engineering Metallurgy Section measured the tensile strength, elongation, and Knoop hardness of both the Be-Cu Alloy 25 and the Be-Cu Alloy 125. These are given in Table I. The NBS Engineering Metallurgy Section also prepared photomicrographs of the two alloys; these are shown in Figs. 1 and 2.

Jan 1, 1969

By P. R. Hines

Diphenyl guanidine is used as an accelerator in vulcanizing rubber. Other rubber accelerators are also flotation collectors, e.g., dithiocarbamate, thiazole, and the xanthates. Urea and its derivatives are good flotation collectors,' and guanidine is the nitrogen analog of urea. These two characteristics suggested testing diphenyl guanidine as a flotation collector. Diphenyl guanidine has been tried in flotation work previously, but references give no details.'.' Bunker Hill Co. of Kellogg, Idaho, supplied the ore sample used in these tests. The sample was typical of the ore milled in 1949 and contained 4.52 pct Pb and 1.08 pct Zn. A flotation test made by the author with potassium ethyl xanthate as a collector, the same flotation reagents, and the same grind employed in regular Bunker Hill mill practice was the standard for comparing results with the compounds and derivatives of guanidine. The compounds and derivatives of guanidine are only fair collectors of galena. However, if potassium ethyl xanthate were used in the galena float, its presence later in the sphalerite float would make it impossible to introduce another type of collector and be certain which collector contributed the result, so the compound or derivative of guanidine under test was used in both the galena and sphalerite floats in Table I. On both the galena and the sphalerite in the Bunker Hill ore, the depressing action of sodium cyanide and zinc sulfate is much greater with collectors of the guanidine type than with the xanthates. If the depressing agents are left out when a guanidine type of collector is used, but a pH of 8.6 is maintained with either lime or sodium carbonate, the depressing action is approximately the same as in the standard xanthate test. Consequently the depressing agents, sodium cyanide and zinc, were not used in the galena floats of tests 1226, 1228, and 1286, Table I, so the galena floats would be on a comparable basis with the standard xanthate test. As shown by the tests in Table I, the loss in the tail when diphenyl guanidine is used is 8.3 to 9.3 pct, as compared to 17.6 pct with potassium ethyl xanthate, or a recovery of 2.3 to 2.0 lb more zinc. Concentrate grade is 13.7 pct with potassium ethyl xanthate and increases to 22.9 and 31.8 pct with diphenyl guanidine, showing a much higher selectivity. Unless the Barrett's No. 4 coal tar creosote is considered to be a collector, no collector other than diphenyl guanidine is present in the tests, Nos. 1226, 1228, and 1286. Tests 1218, 1253, and 1263 in Table I1 were run to check the effect of the depressing agents used in flotation of the galena (sodium cyanide and zinc sulfate) upon subsequent flotation of sphalerite by diphenyl guanidine. Urea was substituted for potassium ethyl xanthate in tests 1253 and 1263 because it is a good collector for galena and a poor one for sphalerite, and the effect of the depressing agents is more marked with urea than with potassium ethyl xanthate. Test 1205 checks the effect of urea alone without any depressing agents when used for the flotation of galena. Table I1 shows that diphenyl guanidine as a collector for sphalerite is compatible with other flotation reagents used in floating galena. When the depressing agents sodium cyanide and zinc sulfate are used in the galena flotation step, the amount of lime in the sphalerite flotation must be increased (compare 1253 and 1263). Table I11 gives some of the compounds of guanidine which were tested and compared. Some of the compounds and derivatives of guanidine* are solu- * Diphenyl guanidine is in commercial production and is available on the market. ble in water and others are not. Those tested were fed dry. When an organic collector is promising, its compounds and derivatives should be tested and their comparative collecting power recorded. Eventually, in this way, it may be possible to discover some of the essential chemical characteristics of a good collector. For example, it is interesting to compare the diphenyl and dibutyl derivatives in Table IV with those of urea in Table 111, Example 3, U. S. Patent 2,664,198. All are good collectors. Table I shows some of the effects of lime on recovery of sphalerite by diphenyl guanidine. Table V

Jan 1, 1960

By F. Garofalo

It has been shown by various investigators that during constant stress creep the dependence of minimum creep rate, 6,, on stress, o, is given by em = A onat low stress levels, md by 6, = A' exp [ß s] at high stress levels. In these relations A, n, A', and ß are constant at constant temperature. A single relation has been found which satisfies conditions for both high and low stresses and agrees well with experimental results. This relation is 2, = AN (sinh a s)n, where A" is a constant at constunt temperature and a = p/n. This relation also satisfies the linear relation, 6, = k s, found at temperatures near the melting point at low stresses. EXPERIMENTAL creep results have led to a number of empirical relationships between minimum creep rate, 6,, and the applied stress, s. Under conditions of constant stress it is generally found that at low-stress levels,'-' the dependence of minimum creep rate is given by 6, = Asn. At high-stress levels'74 the experimental results fit the relation, 6, = A' exp [po l. In these relations A, n, A' and ß are constant at constant temperature. A model based on climb-of-edge dislocations from a pile-up array leads to a relation similar to that found experimentally at low stresses.' On the other hand. theories based on chemical-reaction rate,5 nonconservatively moving dislocation jogs, and jog migration and climb-of-edge dislocations4 lead to a relation similar to that found experimentally at high stresses. No difference in mechanism between low and high stress levels has been clearly defined; it is questionable whether such a difference really exists. In any event, the major argument usually given in substantiation of a change in mechanism from low to high stresses is that no single relation exists for defining the stress dependence of the creep rate over wide ranges in stress. However, such a relation has been found and is of the form, dm = A" (sinh a s)n, where A" is a constant at con- stant temperature and a = ß/n. This relation agrees well with experimental results over wide ranges in stress and temperature for copper, aluminum, an A1-3.1 pct Mg alloy, and an austenitic stainless steel. STRESS DEPENDENCE OF MINIMUM CREEP RATE At low stress levels the minimum creep rate, gm, depends on the stress, 0, under conditions of constant stress creep through the relation em=Aon [1] The quantities A and n have been defined previously. In the range in which this relation applies, a linear dependence is found in a log em,-log o plot. Above the stress range of application of relation [I], the minimum creep rate increases much mar; rapidly than predicted by relation [I]. This behavior is shown in Fig. 1 for a series of creep tests on copper4 at various temperatures ranging from 673 o to 973°K. Relation [I] is satisfied at the lower stresses, although the results at 973°K are quite limited. In all cases the transition beyond the applicable range of relation [I] is a gradual one indicating no abrupt change in mechanism. For all test temperatures, values of n have been determined from the results in Fig. 1. These are reported in Table I under Alog tm/hlog o. At high stress levels the stress dependence of minimum creep rate under conditions of constant stress is given by im = A' exp [ß a] 2] All factors have been defined previously. In a log em-0 plot, relation [2] predicts a linear function. Experimentally, a pronounced deviation from the prediction of relation [2] is found at lower stresses. As the stress is lowered, the minimum creep rate decreases more rapidly than predicted by relation [2]. This shown for copper in Fig. 2. Again it is found that the transition from high to low stresses is gradual and no really sharp change is found. Values of p determined from the high stress results are given in Table I. The dependence of minimum creep rate on stress at constant temperature for all ranges in stress

Jan 1, 1963

By J. T. Norton, J. G. McMullin

The ternary system of gold-silver-copper is characterized by a solid solubility gap and a two phase region in which copper-poor and silver-poor phases coexist. At about 30 pct gold, the two phases become mutually soluble at temperatures below the melting temperature. As the gold content is increased, the solubility temperature of the alloys decreases until at about 80 pct gold, the two phases are soluble down to the lowest temperature at which the alloys will recrystallize. Although the general form of the two phase region is known, its boundaries do not seem to have been investigated extensively. In an X ray diffraction study, Masing and Kloiberl have outlined the boundaries of this two phase field at 400 and 750°C. Using only microscopic techniques, Pickus and Pickus2 determined a vertical section of the ternary diagram showing the 14 kt alloys (58.3 pct gold). These two reports are riot in complete agreement. It has been shown3 that some of the ternary alloys are susceptible to age hardening and that the hardening is caused by the separation of a homogeneous alloy into two phases at the aging temperature. While the gold-copper binary system is an outstanding example of super lattice formation, Hultgren4 has shown that a few per cent of silver added to gold-copper destroys the tendency for ordering. Because of the age hardening possibilities of these alloys, it seemed advisable to investigate the boundaries of the two phase field more in detail using an X ray diffraction method, so as to permit a better understanding of the aging phenomena and enable predictions as to the behavior of other alloys to be made. This is especially true for the 18 kt alloys (75.0 pct Au) at the lower temperatures since they are known to exhibit age hardening. Twelve ternary alloys were prepared having the compositions shown in Table 1 and graphically in Fig 1. The gold used was fine gold bars supplied by Handy and Harmon. The silver was a bar of high purity silver from the U. S. Bureau of Standards. The copper was a bar of vacuum-treated, high conductivity copper from the National Research Corporation. The pure metals in the form of powder were weighed out in proper proportions and melted in graphite in a high frequency induction vacuum furnace. They were heated to 1100°C and slowly cooled. The ingots were then removed from the crucible, inverted, returned to the crucible and remelted. This remelting procedure was intended to reduce segregation in the ingots. After remelting, the ingots were checked for weight loss. The weight loss in each ten gram ingot was held to less than 25 mg. The remelted ingots were cold rolled and then given a homogenizing heat treatment of 16 hr at 760°C to remove any remaining segregation. Powder specimens were prepared by cutting the ingots with a fine file, one half the required amount of powder being taken from each end of the ingots. When the X ray diffraction pattern showed any difference in lattice constant between the ends of the ingot, the ingot was remelted and given an additional homogenization treatment. All powder samples were sealed in evacuated pyrex tubes for heat treatment. Ordinary pyrex proved satisfactory for temperatures up to 650°C but above that temperature it was necessary to use a special high temperature pyrex glass. Annealing at temperatures below 500°C was done in a salt bath whereas for temperatures of 500°C and above an electric muffle furnace was used. In both furnaces the temperature control was ± 5°C. In all annealing treatments samples of cold worked powder were placed in a furnace which was already at temperature. In this manner the specimens recrystallized directly to the equilibrium structure for that temperature. Time at temperature was selected so as to allow complete recrystallization, but very little grain growth. Specimens were quenched from the annealing temperatures by breaking the pyrex tubes in cold water. X ray diffraction photograms were made of all the heat treated powders using copper radiation and a Phragmen

Jan 1, 1950

By P. G. Winchell, A. J. Heckler

An experimentally simple method for determining the effect of alloying elements on the activity of carbon is validated in Fe-Ni-C austenite. The technique consists of the equilibration of carbon between specimens of different nickel contents within a sealed silica capsule. The attainment of carbon equilibrium within each capsule is evidenced by: 1) in each capsule specimens of the same nickel content attained the same final carbon content regardless of their initial carbon contents, 2) in every capsule the final carbon content was reached for most nickel contents by carburizing and by decarburizing. The activity of carbon attained within each capsule was calculated from the carbon content of a binary Fe-C alloy placed within the capsule, and from the activity coefficient of carbon in the Fe-C system as found by Smith for CO/CO2/C equilibrium. The activity of carbon in Fe-Ni-C austenite determined by this method at 1000°C agrees with prior work by Smith, who used mother method. The measurements are extended to 800°and 1200°C. The activity coefficient of carbon 7c, in Fe-Ni-C austenite is given by: where xC is the ratio of carbon to metal atoms and XNi is the ratio of nickel to metal atoms and where the standard state is chosen such that yC = 1 as xc approaches zero in Fe-C alloys. This equation appears to be valid for xni < 0.3, and 1073° < T<1473°K. ThE activity of carbon in Fe-C austenite has been measured by smithL at 800°, 1000°, and 1200°C. Smith has also studied the effect of nickel on the activity A. J, HECKLER and P. G. WINCHELL are Graduate Student and Associate Professor of Metallurgical Engineering, respectively, School of Metallurgical Engineering, Purdue University, Lafayette, Ind. This paper is based on a thesis submitted ty,to Purdue University, in partial fulfillment of the requirements for the degree of M.S. in Metallurgical Engineering which A. J. HECKLER received from Purdue in January 1962. Manuscript submitted August 13, 1962. IMD of carbon in austenite at 1000°C. In both these studies the activity of carbon was fixed by a flowing CO-C02* *Gas mixtures of hydrogen and methane were also used in Ref. 1 but these results are not incorporated in Ref. 2 or in the present study. gas mixture. In the present work, Smith&apos;s results for Fe-Ni-C austenite are confirmed and extended to 800" and 1200°C by a different experimental technique. EXPERIMENTAL PROCEDURE In essence the experimental technique consisted of enclosing specimens of various nickel contents in an initially evacuated silica capsule and annealing the capsule until carbon equilibrium was attained among the enclosed specimens. The carbon activity obtained within the capsule was determined from the final carbon content of the binary Fe-C alloy included in each capsule and the results of smith.&apos; In order to evaluate this method the absence of nickel transfer between specimens must be established and the attainment of carbon equilibrium between samples must be assured. The absence of nickel transfer was demonstrated in the case of an originally pure iron sample which was annealed at 1200°C in a capsule with a 27.3 at. pct Ni alloy. The final nickel content of the iron specimen was less than 0.1 at. pct, a change which has a negligible effect on carbon activity. The attainment of carbon equilibrium was demonstrated within every capsule and in over half the results by achieving the same final carbon content in a sample which carburized during equilibration and in a sample of the same nickel content which decarburized during equilibration. The base Fe-Ni alloys were vacuum melted from Ferrovac E or electrolytic iron and Mond or electrolytic nickel. The samples were rolled and/or swaged and their carbon content adjusted to the desired pre-equilibration level either by methane-hydrogen carburization or by direct carbon transfer from a graphite source in a sealed silica capsule. As mentioned previously, high-carbon and low-carbon samples were prepared for most nickel levels in each capsule. The specimens were cleaned and

Jan 1, 1963

By James L. Poole

INTRODUCTION Companies in the mining industry are subjected at times to currency exchange rate risks and interest rate risks. The former occurs any time a firm deals in more than one currency. The latter occurs anytime a firm is financing itself with borrowings that have a floating interest rate (although a fixed rate can be a problem at times). FOREIGN EXCHANGE RISKS There are two general reasons why exchange rate risks (FX risk) can occur: First, a firm may be building a mine or plant in another country where financing for the plan is denominated in funds other than the country hosting the plant. For example, if a Canadian firm is building a smelter in another country which is being financed with Canadian dollars, the C$100 million for labor, which must be paid in the local currency, has subjected the firm to a C$100 million FX exposure risk. If after the cost estimates were made the local currency appreciates 30% against the Canadian dollar, the cost of labor has increased to C$130 million. (Of course, the local currency could also devalue during this period making the labor cost component less than estimated.) The other reason exchange rate risk arises is due to the fact that the costs of production in one country producing minerals may be incurred in one currency while the production is sold in another currency, such as coal being exported from Canada to Japan under contracts denominated in Yen. In this example, the Canadian firm is exporting coal to Japan and being paid in yen in 30 days at a contract price of 100 Y per ton. Furthermore, assume that the mining firm anticipates a depreciation of the yen against the Canadian dollar of 5% in the next 30 days. Therefore, the mining firm stands to lose 5% of the value of its shipment in a month&apos;s time not including carrying costs. In both cases, the mining company risks an adverse change in the exchange rate, that is, the currency the company holds may decrease in value relative to the other currency. There are a number of ways to mitigate the exposure to foreign exchange which can be utilized by the mining company. Optimally, a company should try to match all their inflows and all their outflows in the same currency. For example, if a Canadian firm has mining costs and debt service costs both denominated in Canadian dollars then 100% of their receipts would need to be in Canadian dollars. If a Canadian firm has 70% of its cash outflows in Canadian dollars and 30% of its cash outflow in American dollars in the form of a loan amortization then their receipts would need to be 70% in Canadian dollars and 30% in U.S. dollars. This general principle of matching cash receipts and cash costs in the same currency works fine in a perfect world but what of the real world when these cannot be matched? In actual practice, however, the financial markets have developed a number of ways in which foreign exchange risks can he managed or reduced. FORWARD MARKETS One method is to use the forward markets which are made on a world-wide basis by the commerical banks for foreign exchange. If a firm wanted to lock in the current exchange rate for the receipt of a foreign currency at some point in the future, they could do so by contracting on the forward market with a bank selling that foreign currency at the current rate at the future date. For example, assume that a Canadian firm is exporting coal to Japan which would pay yen in 90 days. If a firm wanted to lock in today&apos;s exchange rate they could contract with a bank to sell on the forward market yen in 90 days. When the yen was received the contract would be executed by selling the yen to the bank and receiving the previously agreed upon number of Canadian dollars. Generally speaking, the forward market can be used to sell forward about 12 months. The costs of selling (or buying) forward

Jan 1, 1985

By J. B. Cheatham, J. G. Yarbrough

Although adequate removal of cuttings from beneath a drill bit is important for efficient drilling operations, very little basic data are available relative to the fundamentals of chip removal by hydraulic jets. A discussion is presented in this paper of an experimental investigation of the jetting action of hydraulic jets in removing loose particles from the bottom of a cylindrical hole. Conditions for which the jet is no longer capable of removing chips from the bottom of the hole are determined. This situation represents equilibrium between the chip removal force and chip Bolddown forces such as gravity and pressure. In most of the tests loose particles were jetted with water or a water-glycerine mixture to determine the dependence of chip removal on hole size, jet size, height of jet off bottom of hole, flow rate, particle density and fluid viscosity. ,A test with a pressurized mud system indicated that relatively low pressures can completely overcome the removal action of a hydraulic jet. Although the system studied herein is not directly applicable to a rotary drill bit, the work with such simplified systems can provide a better understanding of the chip removal action of jets, and with logical extensions it may provide a reasonable basis for the best use of fluid jets in drilling. INTRODUCTION The primary deterrent to maximum drilling rates is the inability of the drilling system to remove rock cuttings efficiently enough to prevent interference with the drilling action.1-2 The objective of chip removal studies is to permit predicting and controlling removal forces under downhole drilling conditions. Conditions at the bottom of a hole during rotary drilling are exceedingly complex and are not likely to be described in a quantitative way by investigations in terms of the total drilling action until a better understanding is developed of the simplified components of the problem.3 The present study is concerned with the elementary condition of removal of chips by a single central jet. Even this relatively simple model provides mathematical difficulties because of the turbulent nature of the flow from the jet and because of the shape of the bottom of the hole beneath the jet. Theoretical and experimental studies have been made of turbulent jets impinging normally on an infinite body and deductions based on analytical solutions to simplified problems can give some insight into the problem of cutting removal by a jet. However, because of the present lack of understanding of the behavior of the interaction between the fluid jet and the chips being removed, an experimental approach was chosen for the present study. Methods have been developed for maximizing hydraulic horsepower, impact force and jet velocity; but whether maximizing these parameters maximizes chip removal with present drilling bits has not been demonstrated. Simplifying the problem of chip removal may make it possible to develop some understanding of the manner in which the jet velocity is dissipated. Better understanding of a simple case should materially assist in extending analysis to more complicated cases. Thus, we are not concerned in the present study with the rock fracturing process itself but only with the removal of the debris from the bottom of the hole. A problem which is quite similar to the chip removal problem is the suspension of solids in stirred vessels. This problem has been studied by the chemical industry and correlations have been obtained by dimensional analysis which permit the design of mixing vats7 An approach similar to that used in the mixing vat problem is used in the analysis of the jetting data in the present paper. EXPERIMENTAL PROCEDURE The test equipment arrangement shown sche-matically in Fig. 1 allows the jetting action to remove particles until an equilibrium height is attained for each combination of hole size, jet size and flow rate.*** Equilibrium conditions require that the removal force is unable to remove additional particles. This balance between holddown and removal forces implies a relationship between the two forces which is constant for the particular system. When the holddown forces are constant,

Jan 1, 1965

By R. A. Thomas, R. L. Solbod

The importance of transverse diffusion on the finger development in a miscible-phase displacement at an adverse mobility ratio of tbree was studied in a porous plate 1/4-in. thick, 3-in. wide and 18-in. long. Fast displacement rates (29 ft/D) and slow rates (1.6 ft/D) were used to determine the effect of residence time on the geometry of the fingers. The shape of the fingers was observed directly by use of the X-ray technique. At fast rates numerous narrow fingers were observed, but at slow rates a single somewhat bulging finger was produced. The amount of material moved transversely by diffusion across the plate was sufficient to modify the finger geometry in the slow-rate run because of the long residence time. These results are in contradiction to some of the postulates in the literature. The composition of the effluent stream, however, was not affected by the flow rate. This result is not inconsistent with the observed change in the shape of the finger in a short model, but it seems likely that a short model does not offer adequate and proper scaling of the reservoir. The model used was probably a valid one for studying the effect of transverse diffusion on the finger geometry, but a longer model would be needed for proper scaling of the effect of the change in the finger shape on the efficiency of displacement as measured by the composition of the effluent stream. INTRODUCTION Fingering can be defined as the uneven advance of the injected phase as it moves into a porous medium displacing the resident phase from the pore spaces of the rock. The use of this term is usually restticted to the situation in which the displacing phase is less viscous or more mobile than the fluid being displaced. Under these conditions, not only are fingers formed, but the length and width of the fingers grow with distance traveled in the porous medium. This subject has become one of great interest to the oil industry because of the present trend toward the use of various forms of miscible-phase displacement to increase oil recovery. Since in nearly all of the known modifications of the miscible-phase displacements an unfavorable mobility ratio exists (the displacing phase has a lower viscosity than that of the crude oil), the conditions are proper for fingering to develop. An appreciable amount of fingering appears to be a severe handicap to these processes for it increases the volume of agent required for the process to be a success, and such an increase puts a severe strain on the economics of the proposed processes. In some cases, such as for a mobility ratio of 200 unfavorable, it has already been demonstrated that the proposed process would not be economic if the fingering in the field were to be of the same magnitude as that observed in the laboratory. A number of aspects of fingering have been studied and reported in the literature. While the phenomenon of fingering cannot be regarded as a completely understood subject, considerable information exists on the effect of the path length and the mobility ratio on the growth of fingers. Less-complete data are available on the effect of the diameter of the flow path on the character and amount of the fingering, and even less agreement in results exists on the effect of rate of flow on the nature of fingering. This paper deals with one aspect of this latter subject. OBJECTIVE The objective of this study was narrowed down to one rather specific feature of the behavior of fingers in miscible-phase displacement in porous media. The variable studied was the effect of rate of flow on the nature and the development of fingers. It should be made clear at this point that, while rate was the apparent variable, the real variable was residence time; that is, at low rates the fluids are present at a given spot in the porous medium for a longer time interval than at fast rates. The purpose of the study, therefore, was to determine the changes which occur in the fingering and the possible benefits which might accrue from a longer residence time during that period when fingers are

By J. B. Cheatham, R. B. Paslay

Rock stresses and steady-state flow rates induced by the pressure gradient associated with the flow of formation fluid into a borehole have been analytically determined for a permeable, elastic material saturated with an incompressible fluid. In this analysis, the material properties and loading are considered to be symmetric about the axis of the borehole and independent of axial position. For Case I the material is assumed to have uniform permeability in the radial direction, whereas for Case 11 the permeability is assumed to have been reduced in a localized region adjacent to the hole by either normal well completion and production operations or deliberate plugging during air drilling. Results of a numerical example indicate that, in the absence of plugging, the rock shear strength must be approximately two-thirds the formation fluid pressure in order to prevent rock failure. The required rock strength is high for small radial zones of plugging and decreases as the region of reduced permeability becomes larger; however, a depth of plugging can be reached beyond which there is no real gain in strength, although the flow rate can be further reduced. INTRODUCTION During normal production of oil from a well, it is often desirable to increase the production rate of the formation fluid by increasing the pressure gradient through the formation adjacent to the borehole. Depending upon the magnitude of this pressure gradient and strength of the rock material, this production-rate increase can cause sloughing of the hole wall. In many cases, the production - rate increase can result in excessive sand production, increased wear of production equipment, lost production time and expensive workover jobs. In addition, the phenomenon of increased rock bit penetration rate with the use of a gaseous instead of a liquid drilling fluid has been observed in oilfield drilling operations and experimentally demonstrated by various investigators for several years. The improvement obtained by employing this technique can be quite significant and offers apromising method for reducing drilling costs. However, air drilling is currently limited to geographical locations where high-capacity water-bearing formations are not encountered. This limitation has prevented widespread adoption of air-drilling techniques, because the water influx into the borehole interferes with efficient removal of the drilling cuttings and usually results in a condition such that the bit becomes "balled-up" or stuck in the hole. In an attempt to remove the water - intrusion limitation from air drilling, various chemical and mechanical water shut-off methods have been proposed. Goodwin and Teplitzl suggested one such proposal whereby the permeability of the water-bearing rock structure was reduced in the vicinity of the borehole. Although the development of a shut-off method based upon this approach would certainly be welcomed by the oil industry, it is conceivable that, under certain conditions of the pressure gradient, strength of the rock material and depth of the modified permeability zone, a stress field can be created that will result in an unstable hole. As part of their study, an analytical solution is given for stresses in an idealized model of a hole and the surrounding rock material. The purpose of the present study is to extend the analysis of Goodwin and Teplitz to gain more insight into the details and consequences of excessive production rates and formation water shut-off. In particular, simplified models of these problems have been analytically examined, which makes possible the evaluation of the type of stress fields that can be anticipated as a result of these production and drilling practices. Both problems solved concern the determination of the steady-state volume flow rate of the formation fluid and the resulting steady-state stress and displacement distribution in a hollow, cylindrical configuration. The cylinder of Case I, corresponding to the production-rate problem, consists of a material with a constant permeability from the inside surface to the outside surface; the cylinder of Case 11, corresponding to the water shut-off problem, consists of a material with a constant permeability from the inside surface to an intermediate concentric cylindrical surface and a second constant permeability from the intermediate surface to the outside surface-

By T. Yamasaki, S. Usu

Adsorption of potassium dodecyl xanthate from aqueous solutions on artificial and natural zinc sul-fides was studied by means of infrared absorption spectroscopy. The adsorption species and their stabilities varied depending upon the conditions of the surfaces of the zinc sulfides. Adsorption products were analyzed after they had been removed from the surface with pyridine. Zinc dodecyl xanthate was confirmed for surfaces covered with oxidized products while dodecyl alcohol and carbon disulfide were detected on purified or weakly oxidized surfaces. It is of great significance to study the adsorbed species of collectors on the surface of sulfide minerals with a view of increasing our understanding of the mechanism of flotation. Compared with other methods, infrared spectroscopy promises to be of particular value in determining the nature of the species adsorbed at the mineral/solution interface since it gives direct identification of the adsorption products; and, furthermore, it has an advantage over the electron diffraction technique which has been employed in similar problems in that infrared spectroscopy utilizes radiation of very low energy so that the probability of changing the unstable surface films during examination should be correspondingly decreased. Infrared spectroscopic studies concerned with sulfide mineral flotation have already been reported by several investigators on zinc sulfide-hexanthi01&apos; and lead sulfide-xanthate2,3 systems. The purpose of the present study was to investigate the adsorption of potassium dodecyl xanthate (KDX) at the zinc sulfide-aqueous solution interface by means of infrared spectroscopy. Rarely is the pure zinc sulfide-xanthate system encountered in practical flotation since zinc sulfide is usually activated with small amounts of certain metallic ions, such as copper ion. However, investigation of the pure zinc sulfide-xanthate system appeared promising for studying the fundamental mechanism of the adsorption of xanthate on the sulfide minerals. Although there are few cases where xanthates having an alkyl radical higher than hexyl are employed in practical operations, KDX was used in this study since it was reported that the adsorbability of xanthate on zinc sulfide was increased with an increasing number of carbon atoms of the alkyl radicals.4 EXPERIMENTAL Samples: Experiments were made on artificial zinc sulfide and natural sphalerite. The artificial zinc sulfide was obtained commercially from Dainihon Toryo Co. as a fluorescent pigment of the purest grade A. Considering the fact that there are often cases where the surface of sulfide minerals are apt to be oxidized so that the adsorption of xanthate at sulfide mineral/solution interfaces may be substantially affected, two different procedures were employed in preparing the samples of the artificial zinc sulfide. 1) The zinc sulfide was washed with hot concentrated ammonium chloride solution (300 g per liter) to remove surface oxidation products and followed by washing with deoxygenated hot distilled water by centrifugation until the constant electric conductivity of the solution was reached (Sample I) (specific conductivity of the solution = 8.6 x l0-5 ohm-&apos; cm-&apos;). 2) Sample I in a suspension of 5% by weight was oxidized with a 1.5% aqueous hydrogen peroxide solution for about one hour, and then was washed with distilled water as mentioned in the preparation of Sample I (Sample 11) (specific conductivity of the solution = 1.0 x 10"4 ohm-&apos; cm-&apos;). Both Samples I and II were dried under vacuum and stored in a vacuum desiccator. The specific surface areas of the samples determined by the BET method using carbon dioxide gas were 19 x l04 cm2 per g for Sample I and 35 x l04 cm2 per g for Sample 11. In addition, a sample which was derived from Sample I was also prepared. In 40 ml of 3 x 10-2 M zinc sulfate solution was placed 2 g of Sample I for 2 hours, washed with distilled water by successive centrifugation until no sulfate ion could be detected and dried under vacuum (Sample 111). The purpose of this treatment will be described later. Natural sphalerite was carefully selected by hand, ground in a mechanical agate mortar for about 40

Jan 1, 1965

By J. F. Smith, J. E. Davison

A value for the enthalpy of formation of z2 of -3.14 i 0.21 kcal per g-atom has been measured by the technique of acid solution calorimetry. This result is in quite good agreement with two earlier determinations by tin solution calorimetry and by direct reaction caloriinetry, and averaging of values determined from the three independent calorimetric techniques gives enhanced precision and accuracy with AHh8 (CaMgZ) = - 3.15 i 0.05 kcal per g-atom. For comparison with experimental data, values for the enthalpies of formation of CaMgz, SrMgz, and BaMgz of -9.8, -7.9, and -2.8 kcal per g-atom were estimated from a calculation based on the LVigizer-Seitz approximation as modified by Raimes for polyvalent elements. While complete quantitative accord between these calculated talues and available experimental data is lacking, nonetheless numerical accord is better than might be expected and, more importantly, parallel numerical trends are observed between experimental and calculated vnlues. WITHIN the past decade the enthalpy of formation of CaMg, has been determined a) from measurement of magnesium vapor pressures over binary Ca-Mg alloys,&apos; b) by solution calorimetry with liquid tin as the solvent,&apos; c) from measurement of hydrogen vapor pressures over ternary alloys of calcium, magnesium, and hydrogen,3 and d) by direct reaction alorimetr. The value from tin solution calorimetry is the most precise and is probably the most reliable, and this value is within the quoted uncertainties of the other three experimental results. The overall agreement among the four independent investigations is quite good, particularly so when the diversity of techniques is noted. On the basis of this agreement, CaMgz was chosen as a test material to evaluate the operation of a newly constructed apparatus for the determination of enthalpies of formation of intermetallic phases by acid solution calorimetry. This was believed to be a severe test because of the high chemical reactivity of both calcium and magnesium which reactivity presumably accounts for the fact that an early determination5 of the enthalpies of formation of Ca-Mg alloys by acid solution calorimetry yielded values significantly more negative than the four recent determinations. EXPERIMENTAL APPARATUS AND MATERIALS Experimental Apparatus. The enthalpy of formation of CaMg, was determined by measuring the difference between the heat evolved when dissolving the metallic compound and the heat evolved when dissolving equivalent amounts of unreacted metallic elements in hydro- chloric acid. This was done differentially with an apparatus consisting of twin calorimeters which were constructed to be as nearly identical as possible. The advantage of differential calorimetry is that systematic errors arising from the individual calorimeter design tend to cancel. A schematic representation of the apparatus is shown in Fig. 1. A dead air space around both calorimeters was provided by a large, thermally insulated jacket. Each calorimeter consisted of a 2-liter Dewar flask which was completely enclosed in a copper container. Each Dewar contained 1600 g of 2.5hr HCl to act as the solvent, and thermal effects resulting from solvent evaporation were minimized by covering the acid with 50 g of mineral oil. There was no detectable reaction between the acid and the mineral oil. Equivalent amounts of mechanical energy were added to the calorimeters through twin stirring rods which were driven at the same rpm by a single motor with the intent of the stirring being to maintain thermal equilibrium throughout the solvent. To calibrate the heat capacities of the calorimeters, known amounts of electrical energy could be added by passing measured voltages and currents for known times through submerged heaters, approximately 20 ohms, which were wound noninductively from Manganin wire. A 6-v storage battery was used as a power source, and a dummy heater was used as an exercise circuit to allow the battery to stabilize at a constant electromotive force before energizing one or the other of the calorimetric heaters. A type K-2 potentiometer was used to measure the potential drop across an energized heater while the current was determined from the potential drop across an external standard resistor. Times of energization were measured with an electric timer, and the electrical energy supplied to a heater

Jan 1, 1969

By J. C. Sarace, S. M. Sze, C. R. Crowell

Thin films of tungsten 077 n-type germanium, silicon, and gallium arsenide were obtained by reacting tungsten hexafluoride with the semiconductor surface in an argom atmosplrere at temperatures between 325° and 400° C. Capacity-voltage, current-iloltage, and photoelectric measurements were used to investigate the characteristics of the tungsten -semiconductor diodes thus Produced. The junctions are shown to he very close to ideal Schottky barlp/ers with barrier heights measured with respect to the Fermi energy of 0.18, 0.65, and 0.78 1.1 jar W-Ge, W-Si, and W-GaAs, respectively. The electrical properties of the W-Si interface show no deterioration when heated to 1000°C in dry forming gas for 5 min. A theoretical value of the Richardson constant, A, appropriate to the semiconductor-hand structure has been used in evaluating the current-voltage characteristics. ThE W-Si surface-barrier diode was initially proposed for investigation because the eutectic temperature with silicon (1400°C) is much higher than that in the Si-Au system 1370°C).1 This would permit more flexibility in heat treatment and possibly provide greater reliability at elevated temperatures. The lower work function of tungsten (4.54 ev)2 compared with that of gold (4.78 ev)3 also suggested that a lower barrier height would be obtained with tungsten and hence a lower forward bias and lower minority carrier injection ratio for a given current density. The investigation was extended to include the characterization of W-Ge md W-GaAs surface-barrier diodes. The tungsten films have been produced by reacting WF6 with germanium, silicon, and GaAs surfaces in an argon atmosphere at temperatures from 300° to 500°C.4 This process is a very satisfactory alternative to the relatively difficult process of evaporating tungsten films in vacuo. To ensure an adequate electrical characterization of the tungsten-semiconductor interface, three types of barrier-height measurements have been performed. The mutually consistent results obtained lead to the conclusion that the tungsten-semiconductor junctions are indeed of the Schottky type. EXPERIMENTAL PROCEDURE The apparatus used for producing tungsten films is shown schematically in Fig. 1. It consists of an argon carrier gas line to which metered amounts of tungsten hexafluoride can be rapidly added. The mixture passes through a heated reaction tube containing the semiconductor slices and is exhausted to a hood. The argon is purified by passage through a 6-in. column of titanium turnings maintained at 800°C. The tungsten hexafluoride dispensing arrangement was designed by V. C. Garbarini and W. R. Bracht.4 A measured amount of liquid tungsten hexafluoride is injected into the argon stream and vaporizes. The mixture passes through a sodium fluoride absorption cell to remove traces of hydrogen fluoride, then into the nickel reaction tube. The tube is 12 in. long with an inside diameter of 1/2 in. The center section is heated by a furnace of the self-supporting wire-filament type. It was chosen for its rapid heatup and cooling. The wall thickness is 10 mils except for a 3-in. hot zone which is 30 mils thick to reduce thermal gradients along the length. The samples to be coated are placed on a sapphire plate and centered in this section. The tungsten is deposited with the following sequential steps: the loaded reaction tube is flushed with argon at a rate of 500 cu cm per min and heated to 370°C. Then 0.45 g of liquid tungsten hexafluoride is injected into the argon stream. The samples are held at this temperature for 2 min. The tube and samples are then cooled to room temperature and the samples removed. Tungsten films were grown on (111) faces of silicon and germanium polished with Linde A abrasive and lightly etched with HF-HNO3. The GaAs surfaces were (100) faces chemically polished with a H2SO4-H2O2 solution. The films have typical sheet resistances of 0.2, 8, and 15 52/0 when grown on germanium, silicon, and GaAs, respectively. After the tungsten deposition, ohmic contacts were alloyed on the back surfaces of the wafers. Ohmic contacts to the germanium and silicon were obtained by alloying Au-Sb at 370°C, ohmic con-

Jan 1, 1965