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By T. N. Williamson

6.3-1. Historical Development. Rotary drilling has been used in surface mining for many years. Its principal use is for primary blasthole drilling. In this use, holes in the range from 4 to 15 in. in diameter are drilled in overburden and massive ore bodies for large initial blasting operation. With properly designed shot patterns and loading, secondary blasting is seldom required. The use of rotary drilling with diamond bits for exploration is discussed in Chapter 3.1. Small rotary drillholes of approximately 2-in. diameter are employed as blastholes to shatter uncovered coal seams, but this is a minor part of surface mining drilling operations. Another minor use of rotary drills in surface mining is for placing wire saw poles in dimension stone quarries, usually accomplished with large-diameter calyx or steel shot drills. Primary blasthole drilling by the rotary method was performed with drag bits until 1949 (19). Its use in mining was only in soft formations, so that rotary drills prior to that time were found principally in overburden drilling for the surface mining of coal. In 1949 it was found that air circulation to remove cuttings resulted in increased penetration rate and prolonged life for the rolling-cutter type of bits. Prior to that time, and since their introduction in oil well drilling in 1907, water had been used for circulation with these bits. The dependence on water to clean the hole had delayed the acceptance of bits with rolling cutters in mines because of water haulage and freezing problems as well as the loss of water through cracks in the formation. After rolling cutters were introduced, subsequent improvements in tools made rotary drilling adaptable to harder formations (18). This system is now used in the hardest formations encountered in mining. 6.3-2. Principles of Operation. ENERGY. Rotary drills attack rock with energy supplied to the bit by a rotating drill stem, and infrequently by

Jan 1, 1968

By B. M. Larsen, T. E. Brower

IN two previous papersl,2 dealing with the carbon-oxygen reaction, and the simultaneous content of each, in liquid steel in the furnace, we have made use of the quantity 0[O], defined as the excess oxygen beyond what would be in equilibrium with carbon then present if the pressure of carbon monoxide were I atm,; that is, if [C] X [O] is taken as 0.00222, 0[O] = [O] - 0,00222/[C] where [O] is the percentage of oxygen by weight as measured by the method described earlier.' This quantity 0[O] proves to be substantially independent of carbon content over the range 0.08 to 1.2 per cent, as well as of the basicity of the slag, and is nearly always within the limits 0.015 to 0.025 per cent when the bath is boiling normally and is in what we have termed a steady state. Apparently it must be at least about 0.014 per cent before boiling occurs; but this threshold value seems to depend upon the ease of bubble formation at the metal-hearth interface, hence upon the condition of the surface of the hearth. In any case, 0[O], on the average, changes considerably following any disturbance of the bath, as by addition of ore. The present paper deals with the average changes in ?[O] level following addition of Spiegel or crop ends, or after procedures to promote stirring, or by tapping of the steel from the furnace. The observations were made on a large number of commercial heats, and consequently are subject to the influence of various disturbing factors; the results have the compensating merit of showing the consistency obtainable under the limitations imposed by practical operation. VARIABILITY OF EXCESS OXYGEN IN NORMAL OPEN-HEARTH OPERATION The preceding general statements refer to the average value of ?[O] particularly in heats that are boiling actively; on individual heats, which are less active, there may be a variable time lag between the disturbance and its effect, which complicates the interpretation of what is going on. For instance, if in the normal refining process boiling is sluggish, the slag usually is gaining oxygen from the gas phase above it, or from added ore, faster than it is losing oxygen to the metal; yet when the bath starts to boil vigorously, the opposite condition may prevail for some time. The consequence of this lag is a variation of ?[O], the interpretation of which in a single heat may not be immediately obvious, This condition is illustrated in Figs. I and 2. In Fig, I, ?[O] at the beginning of the test period was near the lower limit of its usual range (dashed lines) in the steady state as a consequence of the lime boil, which had ended about as indicated. The bath is now cold, carbon drop is slow, and the first small ore feed causes only a small rise in 0[O]; as the temperature rises and as lime dissolves in the slag, and the bath becomes more active, the

Jan 1, 1946

By E. W. McAllister

The decision of the California Oil Umpire's' office to accept well potentials established from subsurface-pressure data has brought to the attention of many operators for the first time the application of such data to production problems. This paper reviews the development and application of subsurface-pressure data in kettleman Hills, where these data have been used in production work since 1932. The Kettleman Hills field was discovered in October 1928. The first subsurface-pressure surveys were made early in 1932 and by the middle of 1933 the two major operators in the field were making routine pressure runs in thcir respective wells. Shortly therefter, these companies agreed to exchange pressure data, and later a third company entered into the agreement. This made it possible to analyze the effects upon the reservoir pressure of past production practices, which are discussed in the latter part of the report. It is interesting that many of the applications of subsurface-pressure data discussed herein were anticipated by C. L. Clark and C. B. Kimberlint in a report2 dated March 1933. PRODUCTIVITY Index In the majority of individual well problems involving the use of subsurface- pressure data, it is necessary to use a factor known as the "productivity index," which indicates the ability of a well to produce and represents the number of barrels of oil or oil and water per day that will enter the well bore for each pound per square inch pressure drop made opposite the producing interval of the well. The productivity index may be determined from pressure and production data for one or more rates of flow and a static or shut-in pressure survey or from production and pressure data for two or more rates of flow. Productivity indices may be based upon either net oil or total fluid production. All indices referred to in this report are based upon net oil. The value of the productivity index for Kettlcman Hills wells decreases generally with time and it is not uncommon for the index to vary in value at any specific time fur various rates of flow. The decline of the productivity index may be attributed partly to the loss of reservoir pressure. As the reservoir pressure decreases, gas originally in solution is released from the oil, congesting the flow of fluids through the formation and increasing the viscosity and surface tension of the oil; thus the flow resistance of the fluids through the formation is increased, resulting in a decrease of the productivity index. For convenient reference, the productivity indices for each well are plotted against time and a curve is drawn through the points showing the trend of the average index value. Plotted on Fig. I are index values for five

Jan 1, 1941

By Wm. R. Webster

THIS is a contribution for the proposed new discussion on the physics of steel. The former discussion on the subject started with the consideration of five papers presented at the Chicago meeting in 1893, and continued for several years. The Suggested Lines of Discussion, prepared by Doctor Howe, covered a wide field and added greatly to the success of the work. Naturally, the first step in a new discussion will be to remodel and bring up to date the old Suggested Lines of Discussion so as to embody all the important advances in the metallurgy of steel that have a bearing on the physics of steel and keep the papers and discussions within the field of work undertaken. This paper will be devoted to the practical application, in rolling steel, of the effects of carbon, phosphorus, and manganese on its tensile strength, with some suggestions on further research work. Dr. J. E. Stead, in his paper Influence of Some Elements on the Mechanical Properties of Steel,1 gave a complete review of all that had been done during the past thirty years. He gave full credit to all investigators who worked on these lines, also their results, with his views on same, and in many cases his own results. All of this data and much new valuable information were put in convenient shape for reference and study. To do this required a great deal of work, which is fully appreciated by the steel manufacturers and investigators. The variations in the values given by the different investigators for the increase of the tensile strength of steel for each 0.01 per cent. of carbon, phosphorus, and manganese were largely due to the steels they worked on, the large or small variations in the amount of the elements present, and the omission to take into consideration all the factors, from the blast furnace through to finished rolled material, that affect the character of the steel. For instance, a poorly made dirty steel requires considerably more carbon to give the same ultimate strength than a well-made clean steel with the same phosphorus and manganese content.

Jan 3, 1921

By D. V. Carter, C. Williams

During 1943 five oil fields and two gas-condensate fields were discovered in the East and East Central Texas district. The New Hope field, discovered by Tide Water-Seaboard in Franklin County, is the most important oil discovery since the Hawkins field in 1940. At the close of the year two oil sands were producing and two additional oil sands were being tested. The gas-condensate fields of Appleby in Nacog-doches County and the Stewards Mill field in Freestone County had only one producing well each. The Carthage field was extended 3 miles north and 4 miles west. Another well that was testing at the year end indicated a probable eastward extension of several miles. The Quitman field, in Wood County, was the most active from the standpoint of drilling operations. Approximately 48 wells were complcted during the year. The second and third most active fields were Hawkins field, Wood County, and Kildare field, Cass County, respectively. Wartime restrictions of material, together with manpower shortage and Federal spacing regulations, reduced the number of oil and gas-well completions from 265 in I942 to 171 in 1943. This represents a drop of 35 percent, or approximately 1/3, enough to replace the 531 producing wells abandoned in the district during the year. No changes were made in the price of crude oil in the district in 1943. The district produced 177,652,940 bbl. of condensate and oil during 1943. This represents an increase of approximately 11 per cent compared with the previous year. The East Texas field, which is the largest and most important field in the district, had an annual production of 128,568,647 bbl. of oil, which is approximately 6.5 per cent more than the previous year, and represents 72 per cent of the district's production of condensate and oil for the year. The district had an estimated basic daily allowable of approximately 509,000 bbl. of oil on Dec. 31, 1943. The entire district produced approximately 30 pcr cent of the state's production for the year 1943. The Hawkins field, Wood County, was operated 271 days during the year and with an average daily production of approximately 52,488 bbl. for the year. This field, which is the second largest in the district, produced 14,224,164 bbl, of oil during the year. Changes in annual production in certain fields in the district can be attributed to their ability to produce at higher rates, the demand, and transportation facilities in the war effort. The East Texas field showed an over-all decrease in reservoir pressure of 8.30 lb. during the year. Indications were that through the first quarter of 1944 the return of salt water to the reservoir was having a beneficial effect. It is hoped that, as more and more water is returned to the reser-

Jan 1, 1944

By Burnham E. Field

The chemical industry is constantly looking for new materials which either are more resistant to corrosion than those now available or have improved physical properties to meet the requirements of higher temperatures and greater pressures. Attack by acids is one of the more important forms of corrosion and in the last few years the development of acid-resistant alloys has been quite rapid. Perhaps the most notable example is that of nitric acid, the problem of which has largely been solved by the chromium-iron and chromium-iron-nickel alloys. Sulfuric acid may be handled in lead, iron, or the iron-silicon alloys, depending on conditions. As to hydrochloric acid, no metal or alloy can be called entirely satisfactory for handling this acid under plant conditions.' The results of our investigations on the resistance of the nickel-molybdenum alloys to hydrochloric acid have been confirmed by those of Guertler, Rohn, Schulz, Jenge, and others12 but thus far only one such alloy has approached commercial production in Germany; this contains approximately 15 per cent. chromium and 7 per cent. molybdenum with the remainder chiefly nickel. Dr. S. W. Parr, as far back as 1914, developed a complex alloy known as "illium," with a nickel base and containing some molybdenum. 3 Dr. Parr was primarily interested in an alloy for lining bomb calorimeters, and while illium does show good resistance to acid it is too expensive for general use. Two United States

Jan 1, 1929

By A. A. Jr. Smith, J. S. Smart

The controlled amounts of phosphorus, arsenic, sulphur or selenium found in commercial coppers perform a variety of highly useful functions. Indeed, a large segment of modern copper technology is essentially dependent upon the presence of one or more of these elements. Consequently, the literature contains many references to their effects but the scope is broad and has been only partly covered. New data are presented herewith directed toward a better understanding of the basic behavior of these elements in copper, with particular emphasis on the composition range o to 0.05 per cent. These data are a part of a general program of research on the effects of impurities on the properties of oxygen-bearing and oxygen-free copper, other portions of which have been reported previously. Schematically, the behavior of individual elements is determined from measurements of conductivity and softening temperature,'v2 and the binary alloys employed are synthesized from high-purity copper in order to eliminate interference from the effects of extraneous impurities. Alloys of selected composition were first prepared in the oxygen-free form by continuously casting the melts in the form of %-in. diameter rod. Oxygen was added subsequently to portions of the alloys, either by remelting or by diffusion at 8jo°C. from a surface scale. Test wires wcre drawn one B. and S. number per pass, using four 30-min. 600°C. anneals at 0.3125, 0.257, 0.204 and 0.162 in., and a final cold reduction of 75 per cent to 0.081 in. Oxygen-bearing slugs made by remelting nere hot-rolled to 4ia in.. drawn to 0.162 in., annealed for 30 min. at 6o0°C. and cold-drawn 75 per cent to 0.081 inch. The alloys containing phosphorus, having been compounded very early in the program, were prepared in the form of 3i6-in. rod, and processed to wire with only the last three intermediate anneals listed above, all of these having been conducted in commercial nitrogen. In addition, the conductivity anneals on these alloys were also performed in the same atmosphere, and the small amount of oxygen present as an impurity in the gas resulted in some loss of accuracy at temperatures of 700' to 8o0°C., as will be shown later. Subsequently, the anneals for all oxygen-free alloys were conducted in hydrogen to prevent oxidation, and purified nitrogen was employed only for oxygen-bearing samples. All conductivity anneals wcre of one hour duration followed by a rapid quench in 10 per cent HZSO*. Effect of Phosphorus The widespread use of phosphorus as a deoxidant has resulted in universal appreci-

Jan 1, 1946

By J. S. Kennedy, A. A. Lerew, C. M. Judson, G. L. Simard

DITHIOPHOSPHATE collectors are commonly used in the flotation of sulphide minerals. Studies of the interaction of a typical dithiophosphate collector with galena surfaces have been previously reported from. these laboratories." These fundamental studies were carried out by employing phosphorus labeled radioactive dithiophosphate. Radioactivity determinations then could be used to measure readily and accurately the small concentrations of dithiophosphate that, are present under conditions of flotation processes. Measurements were made on ground mineral, determining the amount sorbed indirectly from the concentrations in solution; and studies were also made with single crystals, determining the amount sorbed directly by counting the crystal surface. The rates, isotherms and reversibility characteristics of dithiophosphate sorption, the competition between phosphate and dithiophosphate for the mineral surface, and the exchange of sorbed dithiophosphate with dissolved dithiophosphate were studied. These studies have now been extended by sorption measurements in flotations with a Fagergren, machine. For this work, the selective flotation of galena and sphalerite from quartz was chosen, using ammonium di-(sec-butyl) dithiophosphate as. the collector, sodium cyanide as depressant for sphalerite, and copper sulphate as an activator for sphalerite. While the selective flotation of galena and sphalerite using a single dithiophosphate collector is not typical of flotation practice (two different collectors are generally used), it was found that a reasonably good separation could be obtained by using zinc sulphate with the sodium cyanide in the galena flotation and by cleaning the sphalerite concentrate or by carrying out the sphalerite. flotation in an alkaline medium. Data of practical importance on the distribution of collector between the concentrates, tailings, and solutions were obtained, particularly with regard to the effect of copper sulphate and sodium cyanide. In addition to the. selective flotation of galena and sphalerite from quartz, single flotations of galena-quartz and sphalerite-quartz mixtures were carried out, along with blank flotations on quartz alone. The present paper describes the results of these experiments. As in previous papers, the term sorption is used to designate uptake of collector by the mineral, without implication as to the nature of the processes involved. Experimental Materials: The mineral system was a ground synthetic mixture of galena, sphalerite, and quartz. The galena was from Galena, Kans., and contained 75 pct lead (theoretical 85.6 pct Pb for PbS); the sphalerite, from Ottowa County, Okla., contained 63 pct zinc (theoretical 67.2 pet Zn for ZnS) ; and the quartz from Klondike, Mo., analyzed as 99.97 pet SiO2. Sulphur labeled radioactive di-(sec-butyl) dithiophosphate was prepared from S82 supplied by the Oak Ridge National Laboratory on allocation from the U. S. Atomic Energy Commission. The synthesis consisted of precipitating barium sulphate, reducing the barium sulphate to barium sulphide, acidifying to form hydrogen sulphide, and oxidizing the hydrogen sulphide with iodine to elemental sulphur.

Jan 1, 1952

By M. Muskat, H. H. Evinger

A methoD of calculating productivity factors for oil, gas, and water systems in the steady state is presented as an illustration of the quantitative application of the fundamental data on the flow properties of heterogeneous fluid systems. While the numerical results of the calculations cannot be applied directly to field conditions, because they are based on permea-bility data for unconsolidated sands and involve specific assumptions regarding the nature of the reservoir fluids, the methods of analysis and interpretation should havc significance in considering certain specific field situations when the necessary field and laboratory data become available. Moreover, it is felt that even under the idealized conditions to which the numerical calculations refer they should serve to give at least the orders of magnitude of the effects of gas-oil ratio and connate water on observed productivity factors. Within the indicated limitations, the computations imply that the foregoing factors can explain only a part of the apparent discrepancy between the homogeneous fluid productivity factors and those obtained recently in field measurements on the West Coast. IntroductioN Sufficient laboratory research has been carried out in the last several years on the fundamental features of the flow of heterogeneous fluids through porous media to call for consideration of what can be done with this type of information. It has, of course, already led to a, much clearer general understanding of the mechanics of oil production. However, examples of the quantitative application of the results of such laboratory studies are few in the literature. part of the explanation for this fact lies undoubtedly in the lack of sufficient laboratory data relating to practical fluids and sand systems such as would occur ill actual oil reservoirs. However, unless it can be shown that if such data were obtained quantitative applications could be made, serious doubt may be cast upon the desirability of carrying on further extensive experimental research work on fluid flow. The purpose of this paper is to present one approach to the problem of quantitative application of laboratory data to practical field problems. Because the published results on the basic experiments with three-phase fluid systems in porous media are limited entirely to uncon-solidated sands, the numerical applications made here will not pertain directly to any actual field situation. However, they should serve to illustrate what could be done with fundamental laboratory data if they were extended to cover the field of consolidated sands. From this point of view, it is hoped it will serve to encourage further laboratory research on this problem. The particular application to be treated here relates to the calculation of the productivity factors for oil-gas-water systems in the steady state. This specific problem seems especially appropriate for discussion in view of the recent publication by Johnston1 of the results of produc-

Jan 1, 1942

By Nelson Severinghaus

Crushed stone leads all industrial mineral, except cement in annual value of production in the United States. It is also interesting to note that crushed stone value is exceeded only by that of fuels, cement, and iron ore among all mineral products of this country. An industry which started with hand-sledging to produce smaller sizes of broken stone for hard surfaced improvement of roadways as designed by McAdam in England about 1815 has grown into a complex industrial giant. Most of this growth started with the invention of a mechanical rock crusher just under one hundred years age (1858) by Eli Whitney Blake. This invention made possible the production of greater tonnages of smaller sizes of broken stone and greatly accelerated its use for Macadam road pavements and for railroad ballast. Stones Used for Crushing All three of the major geologic classifications of stone, sedimentary, igneous, and metamorphic, are widely used in the production of crushed stone. Satisfactory physical and chemical properties can be found in each type so that economic availability becomes the prime determinant for development. Table 1 lists more common rocks of the three main groups with average values of specific gravity and toughness as measured by Deval test. This widely used classification was suggested by C. E. Lord, of U. S. Bureau of Public Roads. The physical properties were compiled by D. O. Woolf in "The Results of Physical Tests of Road Building Rock," U. S. Department of Agriculture, Bulletin 76. It should be noted that the figures given in Table 1 are averages. Very substantial variations in the physical properties of rocks within any one classification will occur. The solid surface of the earth was first made up of igneous rocks resulting from the solidification or crystallization of molten material upon cooling. These igneous rocks were disintegrated into sand, clay, and gravel by the weathering action of wind, water, chemicals, [ ] and temperature changes. The products of weathering were transported by wind and streams until they reached less turbulent areas such as oceans or lakes and were deposited. Chemical deposition between grains of sand or clay or the physical action of pressure and heat then solidified them into sedimentary rocks

Jan 1, 1960

By A. W. Schlechten, R. P. Abendroth

Equilibrium H2S/4 ratios were determined as functions of temperatunz and composition in a hydrogen recirculation apparatus. A high-temperature solid solution exists in the range two-phase regionfrom TiS 1.96, to TiS1.30, Various thermodynamic quantities were calculated from the data. COMPOUNDS in the titanium -sulfur system have not receiyed much attention in the past, probably because they do not occur naturally in the earth's crust. However, titanium-sulfur compounds have been used in various metallurgical processes. The U.S. Bureau of klines' studied the formation of ti- tanium-sulfide mattes from charges composed of rutile, pyrite, and carbon, with the resulting sulfide matte being chlorinated to form titanium tetrachlo-ride. Fishel, Roe, and Ellis' investigated the de-sulfurizing action of titanium in steels, and Schwarz and Koster studied the preparation of metallic titanium from the sulfide using aluminum and magnesium reduction. The thermodynamic properties of some of the compounds present in the titanium-sulfur system may prove to be of some use in the consideration of future processes using these sulfides, and would

Jan 1, 1960

By D. L. Albright, R. W. Kraft

Solidification experiments were conducted with the objective of testing the theory of eutectic colony formation. Appropriate control of variables in tests on a series of high-purity aluminum-copper specimens of eutectic composition resulted in the observation of three types of eutectic microstructures, these being a unique structure consisting of lamellae essentially parallel to one another, a banded structure, and the colony structure. Lamellar faults, which are morphologically similar in many respects to edge dislocation models in crystals, produced a complex substructure in these specimens. SOLUTE rejection at the advancing solid-liquid interface of a unidirectionally solidified single-phase metal can cause the liquid immediately in front of the interface to become constitutionally super-cooled below the equilibrium liquidus temperature. Constitutional super-cooling occurs if the solidification rate, R, is too rapid, or if the thermal gradient in the liquid at the interface, G, is too low. 1 This constitutionally supercooled layer in turn stabilizes a cellular rather than a planar interface.&apos; A similar cellular interface has been observed when lamellar and other types of eutectics were unidirectionally solidified, and it has been shown that the cellular interface led to the formation of eutectic colonies.&apos; The lamellar structure is fan-shaped at the edges of colonies (which correspond to valleys or grooves in the cellular interface) because the lamellae grow normal to the local interface. One of the possible mechanisms which might cause the formation of the cellular interface, in the case of solidifying eutectic alloys, is constitutional supercooling of the liquid with respect to a third component rejected by both phases of the eutectic.3,4 On the basis of the analogy between the solidification of single-phase metals and binary eutectics, a eutectic alloy should solidify with a planar interface if the ratio of G/R is sufficiently high to compensate for any impurity which might be present and causing constitutional supercooling. The fan-like microstruc-ture of eutectic colonies should not occur under these conditions and the lamellae should be parallel to one another and to the solidification direction for extended distances. The experiments conducted in this investigation were designed to test these ideas. Following a resume of the experimental procedure, the various microstructures observed during the study are described, and their relationship to the growth conditions which produced them is discussed. EXPERIMENTAL PROCEDURE The eutectic between an aluminum solid solution and 0 phase (approximate composition CuA12) was chosen for this work for the following reasons: it was known that a lamellar structure forms, the eutectic temperature is low enough to facilitate experimental work, and the components can be procured commercially in a very pure form. High-purity copper (est. 99.999 pct Cu, obtained from National Research Corp.) and spectrographic aluminum rods, having impurities other than copper estimated to be Zn-15 ppm, Mg-10 ppm, Fe-3 ppm, Na-2 ppm, Cd-1 ppm, and Mn < 1 ppm, were melted in a stabilized zirconia crucible in a vacuum induction furnace at a pressure of 10 pof Hg. The melt was superheated to about 1000°C to assure mixing, cooled to 780°C and cast into an investment mold which yielded sixteen cylindrical specimen blanks 1/2 in. in diam and 5 1/2 in. long. The casting was allowed to solidify under vacuum. This master heat had an analysis of 32.6 wt pct Cu and 67.4 wt pct A1 by difference. The cylindrical specimen blanks were remelted and solidified unidirectionally in an apparatus illustrated schematically in Fig. 1. An RF induction coil heated

Jan 1, 1962

By Saluja, Sunder S.

Man had to learn to break rocks as early as the Stone Age, when they formed his main source of raw material. He started with chipping and over the years has reached a stage where he can employ atomic blasts and break, with one blast, millions of tons of rock. In between these two extremes there have been several stages of development including fire setting, use of the expansion of water on freezing in chipped cracks in cold climates, the use of low or deflagrating explosive black powder in about the 17th century, the use of high explosives with the discovery of nitroglycerine in 1846 by Sobrero, followed by the monumental discoveries of the great Swedish scientist Alfred Nobel in the latter half of the nineteenth century.

Jan 1, 1968

By R. E. Pray, M. C. Fuerstenau, J. D. Miller, B. F. Perinne

Quartz cannot be floated with potassium amyl xanthate as collector at any pH. Complete flotation is achieved with certain minimal additions of amyl xanthate and Pb from pH 5.8 to 8.5 and with amyl xanthate and Zn from pH 7.5 to 8.1. The active species of these metal ions responsible for activation are shown to be PbOH and ZnOH No flotation was effected when Cu and Mg were added as activators. Previous work1,2,3,4,5,6,7 has shown that quartz may be floated in the presence of sulfonate or soap when the following two criteria are met: 1) some portion of the added metal ion has hydro-lyzed to its first hydroxy complex, and 2) a precipitate of the metal-collector has formed. Since sulfonate and soap, two substantially different anionic collectors, conform to these criteria, this phenomenon may well be expected to be of a general nature. In this view then, it would appear that any anionic collector, including xanthates, should also float quartz when these two criteria are met. The object of this paper is to demonstrate the conditions under which quartz will respond to flotation in the presence of potassium amyl xanthate. EXPERIMENTAL MATERIALS AND TECHNIQUES Quartz was prepared by leaching the sized sample (48 x 150 mesh) with HC1 until no iron could be detected in the leach liquor. Conductivity water, made by passing distilled water through an ion exchange column, was used in the investigation. Potassium amyl xanthate was selected as collector. Purification of this reagent was effected with the following method: 1) a laboratory sample of potassium amyl xanthate was dissolved to saturation in hot ethyl alcohol and filtered several times while still hot, 2) the filtrate was cooled, during which time potassium amyl xanthate crystallized out of solution; the xanthate was then separated from the solution by filtration, 3) the amyl xanthate was dissolved in fresh hot ethyl alcohol and filtered, 4) step (2) was repeated, 5) the crystalline potassium amyl xanthate was washed with ethyl ether five times, and 6) the xanthate was dried for 24 hours under continuous vacuum. Inorganic impurities are insoluble in hot ethyl alcohol whereas dixanthogen is soluble in ethyl ether. Five-gram charges of 48x150 mesh quartz were conditioned for 3 min in 125 cc of solution containing the reagents and were floated with the small-scale cell and procedure described in previous papers.478 Reagent grade HCl and NaOH were used for pH adjustment, while reagent n-amyl alcohol was added as frother. Frother addition is necessary with this technique, but it should be mentioned that data, similar to those shown in Fig. 2 for 1 x10-4 mole per liter Pb++ and 1 X 10-4 mole per liter AX-, were also obtained with a Hallimond cell in the absence of frother. EXPERIMENTAL RESULTS Clean quartz could not be floated with amyl xanthate at any pH. Flotation was achieved under certain conditions, however, when various metal ions were added to the system. The activating ions used were lead, zinc, copper and magnesium, added as reagent grade chloride salts. Lead as Activator: The effect of Pb++ as activator was examined at five different additions of amyl xanthate (Fig. 1, 2 and 3). When 1x 10-5 mole per liter xanthate was added in the presence of 1 x 10"4 mole per liter Pb ++, no flotation was obtained at pH 6.5 or below, while a recovery of about 60% was effected at pH 7. When the pH was increased to 7.8, no flotation was again obtained, Complete depression was noted from pH 7.8 to about 10, at which point a recovery of about 30% was achieved. At about pH 11, the precipitate of lead amyl xanthate which was present below this pH dissolved and complete depression occurred. When 2.5x 10-5 mole per liter xanthate was added with the same lead addition, no flotation was obtained at pH 5.8 and below, whereas a recovery of

Jan 1, 1965

By G. Sachs, G. Espey

It is well known that high residual stresses are created in tubing by the sinking process, in which no internal tool or mandrel is used.l-4 In this process, the wall thickness is usually slightly increased.4,5 In tube drawing with a plug, the residual stresses are gradually reduced with increasing reduction of wall, and, by the conventional approximation methods of stress measurement, no stress is detected in tubing in which the wall reduction is over 50 per cent of the total reduction in cross-sectional area.l,6 It has also been observed that higher stresses are set up by the use of wide-angle dies than by acute dies.? &apos;he actual stress distribution in drawn tubing has been investigated by a few workers,7"9 but has not been related to the conditions of the drawing process. Some attempts have been made to correlate accelerated cracking tests for stresses in brass products with the magnitude of the circumferential stresses and the condition of the metal. l-10 Materials and Preparation The material used in this experiment was commercial cartridge-brass (70 per cent Cu, 30 per cent Zn) tubing in the straightened and annealed condition.† This tubing was of various outside diameters and had a wall thickness of 0.032 in. It was sunk to 1/2-in. outside diameter by means of an experimental 10,000-lb. hydraulic draw-bench, with a maximum drawing speed of 8 ft. per minute. All dies were of 1/2-in. diameter. Various die materials and contours were used in order to study the effect of die design on residual stresses in the tubing; the specifications for the dies are given in Fig. I. Castor oil was used throughout as lubricant. Chattering occurred in sinking some of the tubing, particularly when dies having the more acute angles were used, but the tubes showing chatter marks did not differ markedly from those with a smooth surface regarding the magnitude of residual stress. The source of the chattering has not yet been revealed. The wall of the tubing becomes thicker during s nking, as previously observed.4,5 The increases in wall thickness were 3, 7 and 9.5 per cent on the average for 6, 20 and 33 per cent reductions in diameter, no effect of the contour being noticeable. The reductions mentioned throughout this investigation do not consider this fact, but are reductions of the outside diameter. For the evaluation of the residual stress two fundamentally different methods were used. The approximation methodl,ll of splitting a certain length of tubing was employed to obtain a bird&apos;s-eye view of the effect of various drawing conditions on the circumferential stress measured by the diameter change occurring On splitting. For

Jan 1, 1942

By H. T. Bowman

For more than 80 years the Bessemer process has depended upon the ability, skill, and judgment of the blower, although as early as the I860&apos;s it was recognized that the process would benefit by some type of instrumental contro1.l IIowever, instruments with sufficient recording speeds did not exist, so the end-point determination was always dependent upon the blower&apos;s eye. This placed an obstacle in the way of precise experimental work, because of the absence of the necessary records and reference points as reported by Work.2 The use of the photocell provided the instantaneous record of the blow that made this experimental work possible and provided more scientific control for the process as discussed by Graham,3 A brief description of the progress of the blow will illustrate the recording function of the instrument. The silicon in the iron is being oxidized during the first minutes of the blow, as pointed out by Henning4 in a table showing the order of metalloid elimination. The product of this oxidation is a solid that remains in the converter, so there is virtually no flame during this part of the blow. This low flame luminosity is illustrated by the flame recording shown in Fig. I, where the silicon blow is plainly marked. The dull flame of the silicon blow gradually gives way to the brilliant carbon flame as the increasing quantities of carbon monoxide formed inside the converter burn to dioxide upon contact with the atmosphere above the vessel. When the carbon reaches some low value under 0.20 per cent, there is insufficient menoxide formed to maintain the dioxide flame, so its intensity drops. Throughout the flame drop carbon continues to burn, until at some value around 0.05 per cent an arrest occurs in the recorded drop. This point has been designated as the end point. The period of time from this end point until the vessel is turned upon its side and blowing has stopped has been called the afterblow. This afterblow is used as a measure of the degree of metal oxidation, and uniformity demands that it be controlled within narrow limits. Iron and blowing conditions are likely to change several times during a turn, necessitating corresponding changes in end-point control. It is the purpose of this paper to discuss these changes, the factors that make them necessary, and their bearing upon the quality of steel. Carbon-FeO Relationship In the Bessemer process oxidation relationships are precise. Fig. 2 shows a graph of the carbon-FeO relationship. The familiar "bomb-test" method, described by Mccutcheon and Rautio,5 was used for obtaining these and all other dissolved FeO values herein reported, all tests being taken from the converter before deoxidation unless otherwise noted. All tests of 0.10 per. cent carbon and above were obtained from metal blown for duplexing. McGinley and Woodworth6 reported iron oxide values for blown metal, but their tests were obtained by a . different method than were those

Jan 1, 1942

By R. W. Gurry

When a steel in the austenitic state, with all its carbon in solution, is maintained, at constant temperature, in contact with a gas that removes the carbon from the surface, yet without otherwise altering the composition of the steel, the change in weight of the specimen, after any period of exposure, is a direct measure of the amount of carbon it has then lost. The purpose of the present paper is to show how, by application of established mathematical reasoning based on the fundamental diffusion law and on certain postulates, this loss of weight yields a complete picture of the distribution of carbon throughout a specimen of regular shape after any period of exposure, with all the accuracy required in any practical occurrence of decarburization. Precisely the same is true for the gain in weight during the reverse process of carburization, or for the gradual gain or loss of any element, so long as the steel comprises only a single phase at temperature, provided always that the experimental conditions conform to the postulates. The change in carbon content from surface to center of the specimen is always continuous, when everything is in solution, even though under the microscope the decarburized zone (or carburized rim) may appear to be sharply defined. The experimental procedure is described and some typical results are presented, which are then interpreted by application of the diffusion law. Experimental Procedure Initially an endeavor was made to follow the gain of weight during the process of carburization in a hydrogen-toluene atmosphere, but it was soon found that the specimen became coated with graphite, which could not be removed without some loss of metal; therefore it was decided to continue carburization until the steel was saturated throughout, to remove all graphite from the surface of the specimen, and then to follow the loss of weight during decarburization in a moist hydrogen atmosphere at the same temperature as that used for carburizing. The carburizing procedure has been described in an earlier paper;&apos; it suffices to state here that the carburization lasted about I40 hr. at 760°C. (1760°F.) and 44 hr. at iiio°C. (2030°F.), these periods being long enough-—on the basis of the calculations presented later—to ensure that the specimen was about 99.9 per cent saturated at each temperature. The specimen was a cylinder about 3.8 cm. long and 0.475 cm. in diameter; the materials were carbonyl iron, a commercial low-metalloid iron, and a steel with 3.6 per cent nickel and the usual proportion of other elements. The fully carburized specimen, after cooling at the top of the furnace tube, was placed in a lathe and sandpapered to remove all graphite; then the diameter was measured with a micrometer caliper, and the initial weighing (corresponding to complete saturation) was made. By means of a

Jan 1, 1942

By R. W. Gurry

When a steel in the austenitic state, with all its carbon in solution, is maintained, at constant temperature, in contact with a gas that removes the carbon from the surface, yet without otherwise altering the composition of the steel, the change in weight of the specimen, after any period of exposure, is a direct measure of the amount of carbon it has then lost. The purpose of the present paper is to show how, by application of established mathematical reasoning based on the fundamental diffusion law and on certain postulates, this loss of weight yields a complete picture of the distribution of carbon throughout a specimen of regular shape after any period of exposure, with all the accuracy required in any practical occurrence of decarburization. Precisely the same is true for the gain in weight during the reverse process of carburization, or for the gradual gain or loss of any element, so long as the steel comprises only a single phase at temperature, provided always that the experimental conditions conform to the postulates. The change in carbon content from surface to center of the specimen is always continuous, when everything is in solution, even though under the microscope the decarburized zone (or carburized rim) may appear to be sharply defined. The experimental procedure is described and some typical results are presented, which are then interpreted by application of the diffusion law. Experimental Procedure Initially an endeavor was made to follow the gain of weight during the process of carburization in a hydrogen-toluene atmosphere, but it was soon found that the specimen became coated with graphite, which could not be removed without some loss of metal; therefore it was decided to continue carburization until the steel was saturated throughout, to remove all graphite from the surface of the specimen, and then to follow the loss of weight during decarburization in a moist hydrogen atmosphere at the same temperature as that used for carburizing. The carburizing procedure has been described in an earlier paper;&apos; it suffices to state here that the carburization lasted about I40 hr. at 760°C. (1760°F.) and 44 hr. at iiio°C. (2030°F.), these periods being long enough-—on the basis of the calculations presented later—to ensure that the specimen was about 99.9 per cent saturated at each temperature. The specimen was a cylinder about 3.8 cm. long and 0.475 cm. in diameter; the materials were carbonyl iron, a commercial low-metalloid iron, and a steel with 3.6 per cent nickel and the usual proportion of other elements. The fully carburized specimen, after cooling at the top of the furnace tube, was placed in a lathe and sandpapered to remove all graphite; then the diameter was measured with a micrometer caliper, and the initial weighing (corresponding to complete saturation) was made. By means of a

Jan 1, 1942

By R. W. Smith, T. J. Smolik

Recent work indicates that fluosilicate ions and or fluosilicate amine complex ions play important roles in fluoride activation of bery and feldspars in cationic flotation systems. In an attempt to further confirm conclusions reached in this earlier work, an infrared and X-ray diffraction study of the action of fluorides in cationic flotation of silicates was undertaken. It should be noted that in recent years considerable use has been made of infrared spectroscopy in studies of surface phenomena,2-4 and these studies have established the excellence of the technique. In the present study infrared spectra were obtained for various products of the reaction of HF and dode-cyclamine hydrochloride with quartz, microcline and beryl. These spectra were compared with one another and spectra of several inorganic and organic substances. In addition to infrared spectra, X-ray diffraction patterns were run on many of the reaction products obtained. A model 137 B Perkin Elmer Infracord double beam spectrophotometer containing sodium chloride optics was used to obtain the spectra. Infrared samples, except for the dodecylamine sample, were prepared by thoroughly mixing the substance to be analyzed with purified KBr in steel vessels on a Wig-L-Bug amalgamator. One-half in. pellets weighing 100 mg were than pressed under vacuum. Details concerning percentage of the substance to be analyzed in the pellets are indicated on the spectra. In all cases except for dodecylamine a KBr pellet was placed in the reference beam of the spectrophotometer to cancel bands due to possible impurities in the KBr. The dodecylamine sample on which an infrared spectrum was obtained was prepared by placing pure dodecylamine between two salt plates. X-ray diffraction patterns were obtained with a Norelco instrument, using a copper target tube, nickel filter and Geiger tube detector. The samples were ground into powders and either placed on glass slides with glue or placed into regular powder sample holders for diffraction studies. Goniometer scanning speed varied from 1°/min to 1/8°/min. EXPERIMENTAL RESULTS AND DISCUSSION Infrared spectra of microcline, beryl and quartz were obtained first and are shown in Fig. 1. These spectra agree reasonably well with previously reported spectra.5,6 The microcline (Fig. 1 a) and beryl (Fig. 1 b) were from good Black Hills crystals. The quartz (Fig. 1 c) was from a large, clear Brazilian crystal. It is not clear whether absorption bands of minerals are due to molecular vibrations, lattice vibrations or both. Fig. 2 shows infrared spectra of dodecylamine (Fig. 2 a) and dodecylamine hydrochloride (Fig. 2 b). The dodecylamine spectrum checks quite closely with that reported in Sadtler.8 Little is known of the spectra of hydrochloride salts of amines,9 and a spectrum of dodecylamine hydrochloride could not be

Jan 1, 1965

By H. T. Bowman

For more than 80 years the Bessemer process has depended upon the ability, skill, and judgment of the blower, although as early as the I860&apos;s it was recognized that the process would benefit by some type of instrumental contro1.l IIowever, instruments with sufficient recording speeds did not exist, so the end-point determination was always dependent upon the blower&apos;s eye. This placed an obstacle in the way of precise experimental work, because of the absence of the necessary records and reference points as reported by Work.2 The use of the photocell provided the instantaneous record of the blow that made this experimental work possible and provided more scientific control for the process as discussed by Graham,3 A brief description of the progress of the blow will illustrate the recording function of the instrument. The silicon in the iron is being oxidized during the first minutes of the blow, as pointed out by Henning4 in a table showing the order of metalloid elimination. The product of this oxidation is a solid that remains in the converter, so there is virtually no flame during this part of the blow. This low flame luminosity is illustrated by the flame recording shown in Fig. I, where the silicon blow is plainly marked. The dull flame of the silicon blow gradually gives way to the brilliant carbon flame as the increasing quantities of carbon monoxide formed inside the converter burn to dioxide upon contact with the atmosphere above the vessel. When the carbon reaches some low value under 0.20 per cent, there is insufficient menoxide formed to maintain the dioxide flame, so its intensity drops. Throughout the flame drop carbon continues to burn, until at some value around 0.05 per cent an arrest occurs in the recorded drop. This point has been designated as the end point. The period of time from this end point until the vessel is turned upon its side and blowing has stopped has been called the afterblow. This afterblow is used as a measure of the degree of metal oxidation, and uniformity demands that it be controlled within narrow limits. Iron and blowing conditions are likely to change several times during a turn, necessitating corresponding changes in end-point control. It is the purpose of this paper to discuss these changes, the factors that make them necessary, and their bearing upon the quality of steel. Carbon-FeO Relationship In the Bessemer process oxidation relationships are precise. Fig. 2 shows a graph of the carbon-FeO relationship. The familiar "bomb-test" method, described by Mccutcheon and Rautio,5 was used for obtaining these and all other dissolved FeO values herein reported, all tests being taken from the converter before deoxidation unless otherwise noted. All tests of 0.10 per. cent carbon and above were obtained from metal blown for duplexing. McGinley and Woodworth6 reported iron oxide values for blown metal, but their tests were obtained by a . different method than were those

Jan 1, 1942