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By Heihachi Kamura

In this research, the proper temperature for the reduction of iron ores by carbon monoxide was determined. Also, the difference of the rate of reduction on the sizes of ore under four mesh per linear inch was estimated, but no evidence could be found. Rates of reduction on the seven kinds of ore were compared with the results of the experiment, showing a close relation between reducibility and density of ore. Finally, the maximum size of ore that can be reduced in applicable length of time was determined. The author thinks that the process of production of steel may be replaced by low-temperature reduction of iron ores some time in the future. THE reduction of iron oxide, such as Fe203, to iron in the blast furnace is performed principally by carbon monoxide, but partly by solid carbon by the two following reactions: Fe203 + 3CO = 2Fe + 3CO2 2Fe203 + 3C = 4Fe + 3CO2 It is known that reduction by carbon monoxide takes place at a much lower temperature than reduction by carbon and that the reducing action of carbon monoxide progresses to the inside of the ore in lump form by gaseous diffusion. In the reduction by carbon, however, the reducing action takes place only at the contact surface of the ore and carbon, so that the more complete the reduction by carbon monoxide, the more efficient is the operation. However, the reduction does not progress as shown in the foregoing formula, because carbon dioxide acts oxidizingly on the metallic iron to such a degree that when the gaseous composition reaches a certain proportion of carbon dioxide to carbon monoxide, the reduction practically stops, even though the gases are moving slowly through the heated ore. The proportions of carbon monoxide and carbon dioxide in the gas depend on the kind of iron oxide and the temperature of reduction, also the duration of time in the reaction. The longer the time of the reaction, the higher the proportion of carbon dioxide obtained in the gas, but finally it will attain to a condition of equilibrium.

Jan 1, 1925

By C. O. Burgess, A. B. Kinzel

Although vanadium is an important constituent of almost every brand of high-speed steel manufactured today, little is known as to its role in this series of alloys. The now standard 18 per cent tungsten and 4 per cent chromium constituents were the result of developments and improvements before 1903. In that year, vanadium was added to the steel by Dr. J. A. Mathews. This proved to be an outstanding contribution, so that the standard high-speed steel of today is generally referred to as the 18-4-1 type—18 per cent W, 4 per cent Cr and 1 per cent V. Various modifications have been attempted since then, but with the exception of the introduction of cobalt, no striking improvements have occurred. Vanadium has been increased to 2 per cent in many of the common brands, and at least one brand contains 5 per cent V in addition to the usual tungsten and chromium. The carbon has been gradually increased so that it is not uncommon to find 0.80 per cent in the standard grade, although the carbon in the 5 per cent vanadium steel mentioned above is approximately 1 per cent, and even 1.2 per cent has been made experimentally. The role of vanadium has never been well understood, and although vanadium has been increased to 2.5 and even 5 per cent in certain high speed steels, it has not been generally established that the higher vanadium contents result in superior cutting properties. However, in all of the investigations, of which the writers are aware, the interrelation of the vanadium and carbon contents was not considered as a prime factor. The carbon content was held at 1.2 per cent or less—generally at the usual 0.65 to 0.75 per cent. Theoretical Aspects Although the role of vanadium is not understood, there are theoretical considerations which indicate definite reasons for the improved cutting effciency due to vanadium. Refinement of the secondary grain is one distinct possibility. The well-known action of vanadium in limiting grain size might well be expected to operate in high-speed steels, and even though its action were not evident in the parent austenite grain.

Jan 1, 1932

By Leonard Waldo

The recent and rapid development of the physics of engineering materials at temperatures as low as that of liquid air and as high as that of the electric are, has drawn renewed attention to the absence of tables, properly printed and spaced, for the convenient and accurate translation of temperature from centigrade to Fahrenheit scales and vice versa. It is to be noted that the Fahrenheit scale is the almost universal usage in foundries and shops in the United States, though the laboratories of the same works employ the centigrade notation. The growing use of the electric furnace in Germany and France calls for much American citation all in centigrade high temperatures, and while the arithmetical calculation is simple, it becomes burdensome when often repeated. I have been surprised at the numerous reprints of Table I. from centigrade to Fahrenheit degrees, first privately printed for personal use, which have been made by works, blue-prints, text-books, and technical journals, and I hope that Table II., from Fahrenheit to centigrade degrees, will be equally useful. For mental calculation the easiest rule to convert centigrade into Fahrenheit is to add 32° to twice the centigrade reading less one-tenth of this product: Thus 1000' C. = 2000" — 200" + 32" = 1832" F., and to convert Fahrenheit to centigrade, subtract 32" from the Fahrenheit reading, multiply by 10 and divide by 2 and 9 successively : Thus 1000° F. = 1000° — 32° = 968° X 10 = 9680° - 2 = 4840° - 9 = 537.77° C. Another and often very convenient method is by 'use of a graphic construction as follows :

Jan 1, 1913

By Charles Y. Clayton

A study of the literature shows that the greater part of research work on annealing of cold-worked iron has been for the purpose of studying the effect on grain-size and properties other than hardness. No reference has been found of experimental work of the same nature as that explained in this short paper. The material used throughout was Vismera iron, an iron containing 0.03 carbon and made several years ago by the Inland Steel Co. One-half inch stock was cut into cylinders % in. long. The cylinders were then compressed for 60 sec. in a Reihle testing machine under loads as indicated below: CoMPressiON, Average Length, Series Pounds Inches 1 10,000 0.693 2 15,000 .599 3 20,000 .501 4 25,000 .426 5 30,000 .378 6 35,000 .351 7 40,000 .311 Fig. 1 shows these cylinders after compression. Each series consisted of 17 specimens lettered 0, B, C, D, E, F, G, H, I, J, K, L, M, N, P, Q and R. One specimen of each series was reserved for study of the properties in the cold-worked condition. The other specimens were annealed in a Hump furnace for 1/2 hr. at the following temperatures: TEmpeRa- TempeRa- Letters tuRe,° C. LettERs tuRe °C. B............................... 250 J.............................. 650 C............................... 300 K............................. 700 D............................... 350 L.............................. 750 E............................... 400 M............................. 800 F................................ 450 N............................. 851 G............................... 500 0. . :........................... 900 H............................... 550 P.............................. 950 I................................ 600 Q............................. L000

Jan 1, 1926

By H. A. Davies

DURING a current program of research on the structure and properties of liquid sodium alloys, the need arose for information on the solubilities as a function of temperature of several B subgroup metals in liquid sodium. In the absence of reliable information in the literature for several of these systems, par- ticularly at temperatures in the range 100° to 300°C, an apparatus was constructed to determine solubilities by a direct melt-sampling technique, followed by wet-chemical analysis for both sodium and the solute metal. The details of the technique have been described previously.' The solubility of indium in liquid sodium was determined at eight temperatures in the range 100° to 270°C. The solubility as a function of temperature is shown on Fig. 1; this represents the liquidus line over this composition range. A cooling curve was plotted after the completion of the sampling and an arrest was observed at 94.9°C which must be interpreted as being the result of a eutectic reaction. By extrapolation of the liquidus to this temperature, the eutectic composition was estimated to be about 0.25 at. pct In. The present estimate of the eutectic temperature and composition are in good agreement with the values of 96.0° to 96.2°C and between 0.28 and 0.45 at. pct In, respectively, which were reported by Heycock and Neville.2 However, no further information on the liquidus of this system at the sodium-rich end could be found in the literature for comparison. One compound: NaIn, has been reported in this sys-

Jan 1, 1968

By S. E. Bretherton

THIS title introduces the subject I wish to describe to my fellow members, very few of whom, I hope, have ever had as much trouble with the smelting of ore containing much zinc, either in the lead blast furnace or the matting furnace, its circumstances have forced upon me: First, for several years in Leadville, Colo., after the sulphide ores containing zinc had been developed with greater depth and were sold to the interests with which I was connected for smelting in the blast furnace for the recovery of the lead, silver, and gold; then, in New Mexico and Arizona, where the principal source of ore supply for our custom smelter was from miners who sent most of their product in the form of concentrates, which we briquetted and smelted in the blast. furnace, producing a matte containing copper, silver, and gold, for which we were paid; together with some zinc and lead, which was penalized if in excess of a maximum base set by the refinery to which we sold our copper matte; last, but not least, my experience in Shasta county, Cal., where for the sake of recovering $13 per ton value in copper, silver, and gold, I have smelted ore containing as high as 40 per cent. zinc (the last. 18,951 tons smelted averaged 15 3/10, per cent. zinc) which we not only lost, but which it cost us money to lose.

Jan 8, 1913

By Reed W. Hyde

Some information has been published on the sulphur dioxide concentration of gases from D wight-Lloyd machines sintering lead ores but most of this relates to the customary practice in which the charge is relatively high in lead and is sintered in two passes Over the machine. It is thought, therefore, that the following observations on sintering in one pass a low-lead, low-sulphur charge may be of interest. The data were obtained in sintering lead sulphide notation concentrates mixed with minus 20.mesh oxide ore, the mixture carrying 16,8 per cent Pb and 5.3 per cent S. No returns were used because of the limited amount of sulphur available as fuel, but the mixture pelletized readily. to make a satisfactorily permeable bed on the sintering machine. As there was a possibility that the SO z might be utilized, a series of runs was made to determine the concentration ofSO2 in the gases at different points along the wind box, and the effect on this concentration of changes in the wind-box vacuum. Several runs each were made with vacuums (as measured in inches of water at the wind box) of (1 2 to 1 in., ('1 4 to 3% in. and (3) 6 to 5% in. The averages of the determinations from each series are platted On the graph (Fig, 1). The vertical scale shows the percentage by volume of SOz (as determined by the Reich method), and the horizontal scale shows the time e~pressed as percentage of the total sintering time. Sintering was considered to be complete when no SOz could be detected in the gases. In all cases the depth of bed was 4 1/2 in. and the weight of dry charge per square foot of hearth area was 45.2 lb. Other data are given in the table. The volume of gases corresponding to the several points along the wind box at which SO2 determinations were made could not be measured, but has been calculated from the SO2 Content and sulphur elimination on the assumption that the volume is uniform throughout the sintering period. This is not strictly true, as with a given vacuum the volume usually will drop slightly toward the middle of the period and increase toward the end. However, this made is a reasonable approximation. several interesting features are brought out by these data. In general, the published data on SO 2 concentration in sintering under ordinary conditions show a high SO2 concentration in the early stages followed by a rapid decrease in concentration and with relatively little SOz in the gases from the last half or third of the operation. In other words, the greater part of the sulphur elimination is obtained in the first third or half of the period. In these runs, the 6-in. vacuum, which approximates the usual operating condition, gives a curve that follows this customary pattern. Maximum SO2 concentration is obtained 234 min. after

Jan 1, 1944

By R. J. Sherman, M. R. Achter

Creep rates have been measured for nickel at 1200°F in air and in vacuum, and related to the depth of surface cracks in the specimens tested in the two environments. The surface cracks were observed to grow faster in air than in vacuum in both short-time and long-time tests. Crack depths, however, could be correlated with creep rates only in the short-time tests. Although no cracks were observed in a relatively brittle Ni-Cr-A1 alloy creep tested at 1300°F, the appearance of alloy specimens fractured after interruption in creep indicated that there was a decrease of intergranular cohesion resulting from the diffusion of atmospheric gases into grain boundaries. PREVIOUS investigations1-3 have demonstrated that the effect of atmosphere on the high-temperature strength of nickel and nickel-base alloys may be reversed by changes in the stress or temperature of the test. At high stress and low temperature the creep-rupture life is longer in vacuum than in air, while at high temperature and low stress the relative strengths are reversed. A mechanism to explain this behavior was proposed based on two competing processes. Oxidation hardens and strengthens a metal, but adsorption of gas, by lowering surface energy, reduces the work required to propagate an intergranular crack. The controlling process is determined by temperature and stress. Basic to this mechanism is the concept that environment determines the ease of propagation of intergranular cracks and thus affects creep rate and rupture life. To explore the mechanism in greater detail, this investigation was undertaken to determine the effect of atmosphere on crack initiation and propagation rates in nickel1 and a relatively brittle Ni-Cr-A1 alloy.3 EXPERIMENTAL PROCEDURE The materials were the same as used previously. Nickel of 99.8 pct purity had the following impurity content: 0.02 pct Co, 0.03 pct Fe, 0.02 pct Mg, 0.03 pct Si, and 0.008 pct C. Rods were cold swaged from 1/2 in. to 3/8 in. in diam and machined into speci- mens with gage sections 1/4 in. in diam by 1-1/4 in. long. They were annealed in vacuum at 1600" F for 1 hr to achieve a grain size of 0.07 mm. The alloy was composed of 19.1 pct Cr, 3.6 pct Al, 1.7 pct Si, 0.57 pct Fe, 0.10 pct Mg, 0.027 pct C, 0.004 pct S, and the balance Ni. Sheet specimens of 0.500-in. width and 1.25-in. gage length were machined from 0.033-in.-thick strip and annealed in vacuum at 2000° F for 2 hr, resulting in a grain size of 0.036 mm. Large amounts of an intergranular phase were introduced as a result of the anneal. Creep tests on both materials, using equipment previously described by Shahinian; were conducted in air and in a vacuum of 1 x 10-5 mm Hg. They were continued to rupture and interrupted at various stages of the test. Although extensions were measured from dial gage readings of movement of the lever arm, it is considered that valid comparisons of creep rate may be made in this manner.l Two parameters were measured metallograph-ically* on longitudinal sections of nickel specimens interrupted during creep—the mean depth of surface cracks 2, and the density n as the number of cracks per unit length of surface. They were combined into one parameter by the relation p = n-d [1] As used here, p is equal to the total of crack depths per unit length of surface. RESULTS Nickel. It is well known that the incidence of intergranular cracking is increased with increasing rupture life. Indeed, it is evident in Tables I and I1

Jan 1, 1962

By J. A. Jaekel, W. C. Aitkenhead

Uranium deposits in the Spokane Indian Reservation, as well as those around Mt. Spokane, are essentially low grade, much of the ore containing less than 0.2 pct U3O8. The Mining Experiment Station of the Division of Industrial Research, State College of Washington, has been engaged in intensive research on the amenability of these low grade ores to froth flotation. The results: successful flotation of autinite, chief mineral constituent. At the outset of this work the goal was a concentrate of 1 pct U3O8 with a 90 pct recovery from ores containing less than 0.2 pct U3O8. Most of the work has been done on argillite ore from the Midnight mine on the Spokane Indian Reservation. The goal has not been attained using this ore, but samples of the granite ore from Mt. Spokane yielded successful results. For example, a concentrate containing 11.2 pcl U3O8 was produced from a Mt. Spokane high grade ore containing 1.27 pct U3O8 with a recovery of 97.8 pct. Another Mt. Spokane ore yielded a concentrate of 5.0 pct U3O8 from an ore containing 0.13 pct U3O8. with a recovery of 85 pct. This same ore gave a recovery of 93.5 pct when the grade of concentrate was reduced to 2.0 pct. It has been concluded that a successful method for floating autunite has been developed and that the mediocre results from the Midnight argillite ore are probably caused by the presence of some other uranium mineral or minerals less amenable to these reagents. The experimenters tested a third type of Washington ore, found on the Northwest Uranium Mines Inc. property on the Spokane Indian Reservation. This is a conglomerate of pebbles and small boulders of partially decomposed granite and is shot through with autunite. Its characteristics lie between those of the Midnight ore and the granite ore from the Spokane district. It responds better than the ore from Midnight but not as well as that from Mt. Spokane. As the fatty acids are the only type of collectors showing promise, investigation has been concerned with these acids and the optimum conditions for their use. The first method for treating the argillite ore from the Spokane Indian Reservation made use of Cyanamid's R-708 as a collector, a tall oil product described as a substitute for oleic acid. Although the investigators proved that R-708 is a collector for autunite when mixtures of autunite and silica sand are used, results on the ore were mediocre. Tests of other fatty acids revealed that the solid fatty acids of the saturated series are collectors for autunite and that their collecting power increases with the length of the carbon chain. The even carbon members of the whole series were tested from the 10 carbon acid (capric) to the 22 carbon acid (be-henic). The least expensive collector, stearic acid (18 carbon), proved to be a good one, so this was used in most of the tests. In first attempts with stearic acid, the collector was dissolved in various hydrocarbons and the solutions were added to the flotation cell. Cyclohexane, gasoline, fuel oil, kerosene, and other solvents were tried. Small amounts of high grade concentrates could be brought up, but recoveries were low. Finally emulsions of stearic acid were tried. It was discovered that stearic acid alone has little collecting power except when conditioning is carried out at high temperature. When hydrocarbon solvents were also present, it proved to be an excellent collector. An example of one emulsion that proved satisfactory for some ores is given as follows: 1 part stearic acid by weight, 1 part sodium oleate by weight, 1.2 parts kerosene by weight, 100 parts water. In some successful tests part of the stearic acid was replaced by oleic acid. The emulsions were made by agitating the stearic acid and sodium oleate together with hot water, then adding the kerosene and agitating while cooling. In the five tests reported in Table 1, 650 g of ore were ground with 650 cc water in a laboratory rod mill. The pulp was filtered to eliminate excess water and the ground ore transferred to a stainless steel beaker for conditioning at high pulp density. In most of the tests sodium hydroxide was added to the conditioner during agitation, then the collector emulsion, and finally the sodium silicate. The amount of alkali was adjusted to give a pH of 8.5 to 9.0 in the flotation cell. After conditioning the pulp was transferred to a laboratory flotation cell and the test completed in a normal manner. It is interesting to note that a deposit of high grade concentrate forms on the conditioning agitator and in the conditioning vessel, and at times on the agitator of the flotation cell itself. A few grams of concentrate running as high as 4 pct U3O8 were recovered from the conditioner when Midnight ore containing less than 0.2 pct U3O8 was treated. In the examples given in Table I this conditioner concentrate is calculated as part of the total concentrate. The authors have not yet fully explored the possi-

Jan 1, 1960

By M. L. Hammond, G. M. Bowers

Silicon dioxide films have been prepared on silicon wafers by the oxidation of SiH, near 400°C. Results previously reported by Goldsmith and Kern7 have been qualitatively corrobovated using a system of different geometry, and significantly greater deposition rates have been achieved. The deposition rate is independent of thickness and nearly independent of the O2/SiH, ratio over a wide range; however, the rate is strongly temperature-dependent. The structure of the deposit depends upon the cleanliness of the substrate, and the electrical field strength of the deposited oxide depends upon the nature of the electrodes. MULTILEVEL interconnects in integrated circuits using aluminum metallization require an insulator that can be deposited at low temperature. Because the A1-Si eutectic is only 577°C, the maximum deposition temperature must be below about 500°C to prevent reaction of the aluminum with the silicon and with other materials in the integrated circuit. Many methods of depositing insulating films of SiO, and other dielectrics have been reported'-6 but the technique described by Goldsmith and Kern7 offers the simplest method of preparing SiO, films. The technique involves the reaction of SiH, and 0, to form SiO, films in the 300" to 500°C temperature range. Previous work using this gas system has been reported8 and the initial development work at Philco Microelectronics was done at the East Coast R&D Laboratories. 9 This paper corroborates some of the results of Goldsmith and Kern,7 shows that much higher deposition rates can be obtained than previously reported, and presents some observations on the structure of deposited SiO, films. EXPERIMENTAL CONDITIONS Fig. 1 is a schematic drawing of the apparatus used in this study. It differs from that of Goldsmith and Kern in that 1) the gases are mixed before they enter the reaction chamber, 2) there is no fritted glass diffuser, and 3) the wafers are stationary during deposition. The control thermocouple was in a well located 0.06-in. from the substrate, and three gas supplies were used: 1 pct SiH4 in N 2, O 2, and N 2. Water vapor must be excluded from the plumbing to prevent the formation of colloidal SiO, and the SiH4 must be diluted with an inert gas because SiH4-0, mixtures are extremely flammable above about 4 pct SiH The wafer temperature was determined by attaching a thermocouple to a test wafer and the temperature was maintained to +5 C. The conditions used in this investigation are listed in Table I. The temperature range was chosen for compatibility with the A1-Si system. The volume ratio of 0, to SiH4 is the actual volume of 0, delivered to that of SiH4, taking into account the initial dilution of the SiH4. This ratio, which was used by Goldsmith and Kern,7 is a useful indicator of the experimental conditions. The active/inactive ratio is the ratio of the volume of active gases, SiH4 and O2, delivered to the volume of dilution gas. The active/inactive ratio is an important parameter to specify for deposition rate determinations since it determines the amounts of reactants that arrive at the sample per unit time. Fairly high dilution ratios were necessary to achieve uniform deposits of SiO,. Most of the process characterizations were performed on the polished (111) face of 3 to 5 ohm-cm, n-type silicon wafers which were 0.009 in. thick; but the data approximately apply to deposition of SiO, on thin films of aluminum. It is difficult to obtain accurate deposition rate data over aluminum films because of coarsening the aluminum surface during exposure to 300" to 400°C. The deposited SiO, film fol-

Jan 1, 1969

By J. Chipman, J. C. Fulton

Reduction of Si from slag to carbon-saturated iron is a very slow reaction. The rate is nearly independent of stirring but is accelerated markedly by increased temperature. In a slag containing 45 pct SiO2, 38 pct CaO, 17 pct Al2O3, the energy of activation is approximately 130 kcal. AT temperatures of 1450" to 1600°C occurring in the hearth of the iron blast furnace, chemical reactions are normally expected to proceed with great rapidity. Many of the reactions of iron making are indeed quite rapid and attain a condition corresponding roughly to a state of equilibrium before metal and slag are tapped from the furnace. The one conspicuous exception is the reaction by which carbon in the coke or metal reacts with silica in the slag to deliver silicon to the metal. From the practical viewpoint the slowness of this reaction is indeed fortunate, for if it were fast enough to reach equilibrium during the time of contact, it would be difficult to produce pig iron of the desired low silicon content. The one other reaction which under certain circumstances can also be very slow is the transfer of sulfur from blast-furnace metal to slag. In their laboratory exeriments on this reaction, Hatch and Chipman found that at least 5 hr were required for the attainment of equilibrium in a small crucible and that the reaction was not accelerated by increasing the rate of stirring. Subsequently it was shown2 that the presence of a reducible oxide MnO greatly inhibited sulfur removal, and finally that SiO2 itself3 under some conditions has sufficient oxidizing Dower to interfere with sulfur transfer. The kinetics of sulfur removal are now rather well understood,4 and it has been shown3,5 that when the silicon content of the metal is high enough to prevent reduction of SiO,, the desulfurizing process is rapid. Thus the observations of slow removal of sulfur are associated with the coincident slow reduction of SiO2, a process which transfers both silicon and oxygen to the metal phase. It is, of course, the oxygen which interferes with sulfur removal. An explanation of the slowness of the silica reduction reaction has not been obtained. The sulfur transfer process has been shown by the authors5 to be at least partially transport-controlled in the absence of interference by silica. Under the experimental conditions. 99 pct of the total transfer at 1600" was accomplished within an hour. Under similar conditions the reduction of silica may not proceed half-way to equilibrium6 in 8 hr. It is scarcely imaginable that silica reduction could be transport-controlled when the slag contains 44 pct SiO2 and the metal about 1.4 pct C. The experiments reported here show definitely that it is controlled by a slow step or steps in the chemical reaction. One might expect to find such a slow step in the breaking of SiO bonds or in the slow removal of oxygen by carbon at the slag-metal or metal-crucible interface or by bubble formation. EXPERIMENTAL PROCEDURE The experimental procedure used in this investigation was similar to that used in the study of the kinetics of desulfurization.5 A sketch of the graphite crucible and stirrer used in the current work is shown in Fig. 1. The quantity of metal and slag used was adjusted so that the slag-metal interface was located between the top and bottom blades on the stirrer; the top of the slag layer was above the top blade. The stirrer shaft was hollow down to the metal level and served as thermocouple well or optical pyrometer target. Stirring speeds of 0 to 500 rpm were used. A carbon monoxide atmosphere was maintained in the furnace by flushing the gas over the slag surface, except in run No. 220 when it was bubbled

Jan 1, 1960

By C. C. Martin, M. C. Fuerstenau, R. B. Bhappu

Experiments revealed that quartz could not be floated in conductivity water at any pH with a long-chained sulfonate as collector. Various cations, Fe+++, Al+++, Pb++, Mn++, Mg++, Ca++, are shown to function as activators when the pH is such that the cation hydrolyzes. As the solubility product of the various cation-sulfonates was exceeded at the concentrations involved, precipitated cation-hydroxy-sulfonates, e.g. Fe (RSO3)2OH must be functioning as the collector in these systems. A number of interesting and important phenomena were revealed during a study of the response of beryl to sulfonate flotation.' Perhaps the most important observation is the effect of various cations on flotation response. Experiments showed that in the vicinity of pH 3.0, about three ppm Fe+++ increased recovery of leached beryl from about 60 pct to 100 pct, whereas about four ppm Ca+ + reduced the recovery from 60 pct to 2 pct. With the exception of ferric iron, all of the other cations investigated reduced flotation recoveries drastically at this pH. As postulated in the paper Sulfonate Flotation of Beryl,' even with low concentrations of polyvalent cations and sulfonate (on the order of one ppm), cation-sulfonates are precipitated immediately in solution. That is, blueish-white clouds were noted to form after given additions of salts to known solutions of sulfonate. Furthermore, it was also shown that one-hundred-fold more ferric iron than necessary to form the precipitated cloud had to be added to effect complete flotation. In other words, some form of solid ferric sulfonate was found to function as the collector in these systems. The form of the compound was suggested to be Fe(RCO3)2OH and that bonding to the surface occurs through the hydrogen of the hy-droxyl. As the form of this compound was shown to be dependent on the extent of hydrolysis of ferric iron, it is to be expected that ferric iron will be unique in some pH region. Further, if the presence of hydroxyl in the neutral precipitated compound is of primary importance, then other cations should function similarly but at different values of pH, since they will hydrolyze at different concentrations of hydroxyl ion. To determine whether the premise of hydrolysis is correct, the study was extended to quartz systems in the presence of various cations at various values of pH. EXPERIMENTAL MATERIALS AND METHOD Sodium alkyl aryl sulfonate was chosen as the collector for the experimental work. The reagent, sup plied as a courtesy sample by the Shell Chemical Co., has the following physical properties: Physical form Solid — Finely ground Sulfonate content, pct wt 95 to 97 Molecular Weight 450 to 470 Number of carbon atoms in hydrocarbon chain 25 to 30 Melting Point, OF 250 to 260 Solubility Soluble in water with gel formation at concentrations higher than 25 pct by weight sulfonate This particular reagent was chosen because of its high active sulfonate content, long-chain length, and solid form. With the exception of the frother and sulfonate, all other chemicals were of reagent grade quality. Conductivity water was used in the experimental work. This water, made by passing distilled water through an ion exchange column, had an average measured conductivity of one micromho. Experiments were conducted at room temperature in a small glass flotation cell with the following procedure: 1) A redetermined amount of water and salt solution (e.g. CaC12 . 2H2O) were combined and the pH adjusted to a given value. 2) A given amount of sulfonate was added so that final solution volume was 130 cc. 3) One drop of Dow 250 frother was added. 4) Five g of quartz were added and the system conditioned for five minutes. 5) The pH of the system was measured (termed flotation pH).

Jan 1, 1963

By Rex B. McLellan, W. A. Oates, William W. Dunn

Vapor transport experiments have been carried out in order to determine the saturation solubility of carbon in cobalt and nickel with respect to graphite over a large temperature range. Some of the uncertainty existing in the thermodynamics of these systems has been removed and accurate estimates of the heat and entropy of solution of carbon in nickel and cobalt have been deduced. The relatitle partial entropies of carbon are considered to be predominantly vibrational in origin. ALTHOUGH the thermodynamic properties of solid solutions of carbon in cobalt and in nickel have been investigated previously, the results of these investigations show a marked lack of agreement amongst themselves. In this investigation simple vapor transport experiments have been undertaken in order to measure the temperature variation of the saturation solubility of carbon in nickel and cobalt with the object of removing to some degree the uncertainties in the thermodynamics of these systems. In the case of the C-Co system, early measurements of the saturation solubility of graphite in Co show results at the same temperature differing by almost an order of magnitude.1-5 Recently Schenck, Frohberg, and Jaspert6 measured the equilibrium between CH4-H2 mixtures and C-Co solid solutions at five temperatures ranging from 850° to 1050°C. Their values of the activity of carbon in the solid solution, deduced from a knowledge of the chemical potential of carbon atoms in the gas, varies linearly with composition at each temperature and the authors concluded that the solutions were Henryan. The saturation solubilities deduced from Schenck, Frohberg, and Jaspert's measurements are in good agreement with the solubility determined at 1000°C by Rao and Nicholson7 and the value at 1000°C deduced from the measurements of smith8 on the equilibrium between CO/CO2 mixtures and C-Co solutions. The object of this investigation was to check the results of Schenck, Frohberg, and Jaspert and also to extend the range of solubility data to higher temperatures. In the case of the C-Ni system, there is fairly good agreement between the values given by schaefer9 for the saturation solubility of carbon C, in nickel, the value given at 1000°C by Rao and Nicholson,7 and that deduced from Smith's8 measurements of the equilibrium between C-Ni solutions and CO/CO2 mixtures at 1000°C. The values of C, deduced from Schenck, Frohberg, and Jaspert's6 measurements of the carbon activity in nickel are also in fairly good agreement. However, there is a large discrepancy between the above set of measurements and those of Lander, Kern, and Beach," who measured the carbon solubility of nickel in equilibrium with graphite by depositing an excess of graphite on the surface of Ni-foils from a gaseous mixture and subsequently diffusing in the carbon. These results are considerably higher than those mentioned above. The determinations6 of carbon activity a, in nickel from the CH4-H2 equilibrium showed that at all the temperatures investigated, the ac-values varied linearly with concentration up to about a, = 0.6 and then began to increase with concentration much more rapidly. On the basis of auxiliary experiments in which C-Ni solutions were equilibrated with graphite, Schenck, Frohberg, and Jaspert concluded that their CH4-H2 solid equilibrations at high values of a, were spurious and a, behaved linearly with composition up to the saturation limit (a, = 1). The short linear extrapolations of Schenck, Frohberg, and Jaspert's a, data yield values of C, in good agreement with those of Lander, Kern, and Beach." The solubility data for nickel discussed here is presented in Fig. 1 in the form of plots of ln[Cc/(l - 2cc)] vs 1/T. The discrepancies mentioned are clearly seen. In this investigation a vapor transport method is used to measure C, over as wide a temperature range

Jan 1, 1969

By I. Zaplatynskyj, G. C. Kuczynski

SINCE the excellent studies of metal powder compaction executed by Kamm, Steinberg, and Wulff, no work on the subject has appeared in the technical literature. Kamm et al. were the first to investigate quantitatively the distribution of density in a powder compact, as a function of pressure, height and diameter of the die, powder particle size, etc. For this purpose they devised a very ingenious method. They inserted a thin lead grid into a die and then filled the die with powder. During cold pressing, the lead grid -moved downward. Due to its deformability it followed closely the downward descent of the adjacent powder. The die was then radiographed and, from the deformations of the grid openings measured on the radiographs, the density in the vicinity of each opening was evaluated. Their findings led them to the conclusion that the friction on the side walls of the die is a major controlling factor of the density distribution inside the cold pressed powder compacts. However, it is difficult to conduct tests similar to those of Kamm, Steinberg, and Wulff in a processing plant laboratory, which usually lacks the necessary expensive radiographic equipment. The purpose of this note is to describe a method which makes it possible to determine the density distribution in green powder compacts with the same accuracy as the lead-grid method but which is far simpler and faster and requires only standard laboratory equipment. Instead of using a lead grid, the hardness at selected points of the sectioned compact is determined. If the relationship between hardness and density is known the density distribution is readily obtained. This relationship is easily found from measuring hardness and densities of thin compacts. In such compacts the density, for all practical purposes, is constant throughout. The method was tested on a Plast nickel powder, grade FlA-A20, kindly supplied by Plast Metals Co. Thin compacts (height to diameter ratio 0.2) were pressed in a single action cylindrica1 die at various pressures. The density of the compacts was determined by weighing and by measuring the height and diameter with a micrometer. Subsequently the Rh hardness was determined. Up to ten readings were taken on each specimen. The difference in hardness readings on each compact was never greater than three corresponding to about 0.1 g per cu cm uncertainty in density. By varying the compaction pressure of the samples, a whole scale of densities was obtained allowing construction of a set of density-hardness calibration curves. To test the method several compacts of different height were pressed under varying pressures. Die walls were always well lubricated. After pressing, the compacts were mounted in bakelite and halved by grinding, and hardness readings taken along the diameters of the specimens. The distance between adjacent indentations was about 2.5 mm. After hardness readings were translated into densities, contour maps of densities of the compacts were prepared. One of them is reproduced in Fig. 1. The areas encompassed by the curves are labeled with numbers representing the density in g per cu cm of those regions. In Fig. 2 the same results are re-plotted to emphasize the radial density changes at various depths. The results thus obtained confirm the findings of Kamm, Steinberg, and Wulff kentioned previously. They are recapitulated here briefly. 1—The densest part of a compact pressed from one side is at the outer circumference at the top and the least dense part at the bottom, at the outer circumference. Figs. 1 and 2 show this clearly. 2—The density near the cylindrical surfaces of the compact decreases uniformly with height from top to bottom. 3—The density variation increases with the height to diameter ratio. References R. Kamm, M. A. Steinberg, and J. Wulff: Trans. AIME (1941) 171,'R. p. 439 ;MetaLs Technology (February 1941). R.p. Kamm, M. A. Steinberg, and J. Wulff: Trans. AlME (1949) 180, 2R.P. 694; MetalS Technology (December 1948).

Jan 1, 1957

By Robert J. Willard

The scanning electron microscope (SEM), became commercially available in 1966. Embodying some unique features not provided by conventional electron microscopes, this new electron-optical instrument offers the scientific community a new way of observing the surfaces of materials. In rock mechanics research, the SEM should prove a useful basic tool in characterizing rock fracture on a very small scale and thus contribute to a better understanding of rock behavior at larger scales. This article presents one example of how the SEM is being applied to such research at the Twin Cities Mining Research Center operated by the U.S. Bureau of Mines in Minneapolis. This research center conducts theoretical and experimental studies on a broad range of mechanisms that induce disintegration by the application of energy to rock.1 Some of these studies are concerned with the relation of microstructure to rock behavior and are carried out mainly with the petrographic microscope. At the same time, however, the center recognizes that this relation must be studied through several orders of magnitude, from lattice-size units of rock-forming minerals to field-size rock units. The SEM fits this scheme by extending the capability of the petrographic microscope into smaller orders of magnitude. However, because its resolution is limited to about 200 A at 10,000x, the SEM is not capable of resolving lattice-size units, and hence a conventional electron microscope with a much greater resolution capability is necessary at this order of magnitude.

Jan 6, 1969

By U. N. Bhrany, J. H. Brown

The specifications of particle size and the size analyses of fine particulate materials are commonly presented without reference to the method of analysis. A review of the various sizing methods showed that not only numerous sources of error but also different definitions of size are inherent in the different methods of analysis. To demonstrate the magnitude of the differences, the size distribution of finely crushed quartz was determined by several methods and a critical comparison of the data was made. The experimental results show that appreciably different sizes may be indicated for one material depending on the method of analysis used. However, because the shape of the size-distribution curves determined by almost all methods was constant, a simple method of correlating the data can be adopted. Conversion factors, by which size measurements obtained by the various methods can be expressed in terms of screen sizes, are presented as one method of correlating the results. The size analysis and size specification for lump rock and particulate materials are commonly determined with sieves. With this technique, a readily reproducible measure of size can be obtained merely by duplicating the sieve and the method of sizing. For coarse materials, such as lumps of rock, this technique is simple and effective; and the effects of properties of the material such as shape can be readily understood. When very small particles are measured, however, problems arise. Small sieves are difficult to construct and maintain, and size separations become sensitive to the analytical procedure. For these difficult sieve sizes and for still smaller particles, other sizing techniques employing, for example, sedimentation, light extinction, and microscopy are available. Because these various techniques employ different size-dependent responses to establish size, it is appropriate to examine them and the results they yield to determine their relationships and their limitations. The 'size' of a lump of rock is not an absolute quantity, but rather a defined one. With sieves, for example, the size is defined by the screen aperture and no reference is made to the actual shape of the particle, yet only in the case of a regular body, such as a sphere, can the sieve size be related to the shape. With sieves only two dimensions of a particle can be suggested, for the sieve makes no allowance for the length of the particle passing through an aperture. Similarly, the size of a particle as measured by a microscopic technique need bear no relationship to the size as measured by sieves, although the two measurements may be related statistically. In fact, all size measurements are not only defined quantities, but the measurement actually used is an average that is controlled by the technique employed and, hopefully, reflects the property in question of the material of interest. Many papers have been presented that illustrate the accuracy of the various sizing methods, present the advantages of certain methods for certain applications, and describe the principles and technical backgrounds of the various methods. No attempt will be made in the present paper to review this work in detail. The purpose of the present paper is to examine the limitations of the various sizing methods, and to demonstrate experimentally the relationships between the sizes as determined by the various methods of analysis. It is hoped that by recognition of these limitations and relationships, errors in size specification and size interpretation will be avoided. REVIEW OF SIZING METHODS In specifying the size of a material, not only the data but also the method of measurement must be stated. For example, the size of the lump might be specified as its total volume, as its weight, as its maximum dimension, or as its minimum cross section; any one definition might be completely satisfactory for one problem, but not for another. In practice, size analyses follow four basic approaches and fortunately, the conditions that restrict each approach are known. These major methods include: 1) screen analysis, 2) direct measurement of particle dimensions, 3) determination of equivalent spherical size in response to fluid flow, and 4) specific surface determination. Each of these techniques has several variations and some new techniques are also available, but the limitations of the basic techniques are sufficient to permit at least a preliminary

Jan 1, 1962

By J. M. Karpinski

The need for standard test methods in the minerals beneficiation industry is growing with the increasing complexity of our processes and the more stringent requirements imposed on the quality and uniformity of our products. Although solutions of our problems have never been easy, they will become increasingly difficult to achieve unless we can develop a reliable and reproducible set of test methods. Historically speaking, our need was greatest for methods of chemical analysis. As these methods developed, they improved our ability to determine the grade of ore and measure the effect of our beneficiation attempts. The entire concept of grade and recovery is only as old as chemical analysis. Then came physical measurements. Each new concept in minerals beneficiation was related to certain properties and required corresponding test methods: specific density for jigging, magnetic susceptibility for magnetic separation, and tumbler strength for pellets. And associated with each process was the need for size determination. Size measurement is probably the first physical test ever conceived, and yet we are still improving on it. Dry sieving was quite acceptable for direct-shipping ores, but we had to go to wet sieving to control pelletizing and flotation. Subsieve analyzers have extended our routine measurements to the subsieve sizes, hut not below a few microns. As we all know, the solution of slimes- beneficiation and pollution-abatement problems is hampered by the lack of reliable and reproducible test methods in the fine-particle size range.

Jan 1, 1971

Background The annual awards, which have been given by the US National Committee for Rock Mechanics since its inception in 1969, recognize out- standing research in rock mechanics. Such recognition has always been accompanied by a plaque or certificate for the winners and a presentation at the symposium awards banquet. Starting this year, the US National Committee will give the winners even more recognition and allow the rock mechanics community to benefit from the papers by publishing abstracts of the work in the proceedings of the 25th US Symposium on Rock Mechanics and in various society journals and news letters. "We hope this will stimulate the production of more research papers," said William R. Judd, former chairman on the subpanel of awards. "It's beneficial for researchers to have their work published as an award paper." There are four categories of awards: Basic Research, Applied Research, Case History, and Student Masters' Thesis. Approximately ten papers are nominated annually for each category; however, in some years awards are not made in all four categories. For instance, there were not enough case history nominations in 1983 for an award, but there were two equally outstanding recipients of the award for applied research. The winners of the 1983 research awards reflect the wide variety of professions involved with rock mechanics. They are introduced on the following pages by category, and accompanied by an abstract of the paper

Jan 1, 1984

By E. C. W. Perryman

IN spite of the large amount of work which has been carried out on the recrystallization of aluminum and its alloys, there has been no complete investigation of the recrystallization characteristics of A1-Mg alloys. The most complete investigation is that reported by Bungardt and Osswald' who, working with commercial-purity materials, found that the temperature both of beginning and of complete recrystallization increased with magnesium content up to about 2 pct Mg, then decreased with a further increase in magnesium up to 5.0 pct, and thereafter increased again. Michaud and Segolz working with 99.93 pct A1 also found the temperature of beginning of recrystallization to decrease as the magnesium content increased from 2.13 pct to about 4.5 pct. Chossat3 using aluminum of 99.99 pct purity found that 0.12 pct Mg had no effect but that 0.4 pct Mg increased the recrystallization temperature by about 30°C. That no effect was found for 0.12 pct Mg does not agree with the later results reported by Demer and Beck4 who found that 0.025 pct Mg in 99.99 pct A1 increased the time for complete recrystallization and furthermore increased the activation energy for the recrystallization process. Kratz" using 99.997 pct A1 found that 0.5 pct Mg increased both the temperature of beginning and of complete recrystallization by 100°C. Chadwick and Hooper" working with commercial-purity material found that 1 pct Mg increased the temperature of complete recrystallization by about 40 °C for cold reductions in the range 17 to 72 pct. With smaller amounts of cold work produced by stretching (10 pct strain), they found no significant effect of magnesium. The latter result agrees with that obtained by Williams and Eborall' who found no effect of 2 pct Mg on the recrystallization temperature of commercial-purity aluminum strained 10 pct or less by stretching. Experimental Procedure Material Used: The chemical analyses of the materials used throughout this investigation are given in Table I. Fabrication: The alloys were cast in iron molds which had been washed thoroughly with alumina. After scalping, the ingots were annealed for 16 hr at 450°C, pressed, annealed at 450°C for 16 hr and hot rolled to 0.25 in. After hot rolling, the slabs were alternately annealed and cold rolled to 0.036 in. Cold-rolling reductions between intermediate anneals were kept at about 30 pct and a high intermediate annealing temperature of 450°C was used so as to obtain, as nearly as possible, similar starting grain sizes for the different materials. All intermediate anneals were done in a salt bath and were followed by cold-water quenching so as to retain all the magnesium in solid solution. The final cold reductions investigated were 20, 30, 40, 50, 60, and 80 pct. The initial grain sizes, that is, the grain size before the final cold reduction, were all very similar. Annealing Procedure: Specimens, 1 in. sq, were cut from the 0.036 in. sheet and annealed in a salt bath, the temperature of which was controlled to k2"C. Separate specimens were annealed for different times at 350°, 375", 400°, and in one or two cases at 415°C and after annealing were quenched in cold water. The time taken for a specimen to reach temperature was approximately 5 sec. Metal-lographic examination after annealing showed that no precipitation of Mg+413 occurred during cooling. Procedures Used for Determining Recrystallization Characteristics: All specimens were electrolyti-cally polished and etched by the method described previously1° and polishing was continued until about 0.002 in. had been removed from each side of the specimen. Using this technique, the smallest recrys-tallized grain which could be observed with cer-

Jan 1, 1956

By L. A. Weitzenkamp, N. M. Bashara

A study of the electrical conductivity of gold films less than 200 in thickness indicates a negative temperature coefficient of resistance and a thermal actiuatlon energy of less than 0.25 ev. The films consist of discrete metal islands of linear dimensions from a few angstroms to 1000A. Films were able to withstand applied fields up to 60,000 v per cm before breakdown occurred. A model for the conduction mechanism is proposed which involtes a Potential barrier due to work junction, irriage forces , and an electrostatic potential arising from separating an electron from a neutral island leaving behind a positively charged metal island. Activation energies of less than 0.25 ev ave consistent with this model, which includes a tunneling andor Thermal mechanism for conduction between the separate metal islands. An apparent satuvation effect in conductivity at high fields is observed experimentally. The saturation effect may be explained by the influence of the electrostatic contribution to the potential barriers for the transition through several islands adjacent to the original island which was activated to give up an electron. The proposed model gives Poor quantitative agyeement for the intermal electrical field between islands. ThIS paper will relate the structure of discontinuous metal films to the electrical properties and will emphasize the following topics: 1) the relation of the conduction mechanism to particle size and a comparison of particle size from electrical measurements with electron-microscope studies; 2) the saturation of the conductivity at high electric fields; and finally, 3) a comparison between the external field applied and the apparent field between particles. che- latter comparison points to a need for a modification in the model for the conduction mechanism first proposed by orter' and expanded by Neugebauer and webb2 which will be dealt with in the discussion. The paper is based on results on gold films on glass microscope slides. The clms were vacuum-evaporated and were about lOOA thick, thickness being measured by interferometry. It has been observed that metal films of this thickness do not exhibit bulk metallic conduction. Films thinner than some critical thiclmess, depending upon substrate temperature and other factors, have conductivities which increase with increasing temperature with thermal activation energies of less than 0.25 ev. Electron-microscope studies3 have shown that these films consist of discrete metal islands having linear dimnsions from a few angstroms to approximately 1000A. When the metal is being vacuum-deposited on the substrate, islands on the order of a few angstroms appear first. As the deposition continues the islands may tend to agglomerate into larger particles and may eventually grow together into a continuous film,3''' In our tests the conductivity of the gold films was found to be about ten orders of magnitude less than the bulk conductivity of gold. When oxygen was introduced into the test chamber the conductivity decreased by a factor of about one-third. This can be related to an increase in work function for gold caused by adsorption of oxygen, as reported by Oullet and Rideal.s Exposure to an atmosphere of water vapor caused an increase in conductivity by a factor of 2 or 3 when a low field was applied. When the films were exposed to water vapor under a high field the conductivity increased by as much as two orders of magnitude. The activation energies measured were much less than the work function for gold, 0.25 ev or less, with the smaller activation energies observed for thicker films. It will be shown that the activation energy is a function of particle size and spacing. In general the model for the potential between metal islands would include the effective work function, the image force, the applied field, and an electrostatic term. The electrostatic contribution arises from the potential required to separate an electron from a conducting sphere. According to Neugebauer and webb2 the maximum potential due to the field and the electrostatic term only is

Jan 1, 1967