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By Charles Y. Clayton

Cast-steel runners, while not interesting from a commercial standpoint, furnish valuable material for microscopic study. Folcyl found not only the usual ingot structure, but zones of Widmannstättian structure, which he explains as due to differential crystallization. The writer, in examining nickel-steel runners, found a type of pro-eutectoid ferrite that is unusual and most probably new. The runner in question was 8.75 cm. (3.5 in.) in diameter and analyzed at its center 2.69 per cent. nickel and 0.350 per cent. carbe a and at its edge 2.62 per cent. nickel and 0.359 per cent. carbon. Th macrostruc-ture, which is the usual type, is shown in Figs. 1 and 2, which are a cross-section and the longitudinal surface, respectively. Slight segregat'ion of ferrite can be seen near the center of the segment and at other points near the edges of polyhedral grains. Stead's reagent brings out the dendritic structure within the grains as shown in Figs. 3 and 4. This texture is what would be expected of such a steel. Figs. 5 to 10 show the peculiar swirls of pro-eutectoid ferrite, the finding of which prompted this paper. These swirls, or eddies, if such a term can be applied, occur in all parts of the runner and in all parts of the individual grains. The upper left-hand figure shows this ferrite at a grain boundary; the middle left-hand figure shows the inner portion of a grain; and the lower left-hand figure shows these swirls at the edge of a grain which is also the outer edge of the runner. Straight-lined ferrite associated with swirls is found in the areas of Figs. 11 and 12. The texture of the carbon-bearing constituent of the runner is shown to some extent in Fig. 12, the pearlite being very fine or sorbitic. Higher magnification does not bring out any new features either in the peculiar ferrite or in the pearlite. Figs. 13 and 14, at 240 diameters, show the curved and straight-lined ferrite.

Jan 1, 1922

By J. E. JR. Johnson

AT the Cleveland meeting of the Institute in October, 1912, I had the honor to present a paper outlining the conditions surrounding the charcoal iron industry, and giving some of the results of an investigation started about three years ago for the purpose of determining the reason for the poor reputation of the Lake Superior charcoal irons as compared with the Southern and Eastern irons. In that paper I explained the effect of high carbon on quality, and tried to make clear that that paper was a preliminary one, as we felt convinced that we should eventually discover other factors affecting quality. The progress of the investigation has brought out facts that seem to us of the utmost importance practically and theoretically, and the purpose of the present paper is to present these facts with the proofs which seem to us to establish them. The closing year of the nineteenth century saw the publication of the first definite and connected statement of the relationship between the cast irons and the steels.' The metallurgical world was ready to accept the fundamental unity of these two series, acceptance being greatly hastened by Professor Howe's classic paper, The Constitution of Cast Iron, presented at the Richmond meeting of the Institute, February, 1901.

Jan 1, 1914

By W. S. Cavender

The Round Mountain mining district, Nye County, Ne- vada, was discovered in 1906 on claims owned by Lewis D. Gordon. Initial mining operations uncovered gold veins of spectacular richness, and within a few days of discovery, Gordon sold his controlling interest for some $87,000. From this sale emerged the Round Mountain Mining Co., predecessor of Nevada Porphyry Gold Mines, Inc., the latter destined to become the major property owner in the area. Vein mining in the district continued sporadically into the early 1930s, yielding 9.3 Mg (330,000 oz) of gold plus substantial silver credits from approximately 626 kt (690,000 st) of ore. In addition to the lode deposits, the early miners recognized the placer potential in the alluvial fan material accumulated around the west and north sides of Round Mountain itself. Intermittent placer operations were carried out for a number of years, and in the 1940s and 1950s, Round Mountain Gold Dredging Co. worked the placers under a lease from Nevada Porphyry Gold Mines. The last placer operation terminated in 1959 when it, like some of its predecessors, proved uneconomic. Total placer production for the district is estimated at 3657 km (4 million yd) of gravel containing 59 Mg (210,000 oz) of gold and possibly 2.0 to 2.3 Mg (70,000 to 80,000 oz) of silver. Round Mountain is a small hill situated on the east flank of the Toquima Range in central Nevada. The hill is com- posed of relatively flat-lying Tertiary rhyolitic ash flow tuffs, which overlie Paleozoic metasediments and Cretaceous granites. Throughout the surrounding Round Mountain mining district, most of the known gold ores occur in the tuffs, although the metasediments and granites are also mineralized. Mineralization is structurally controlled, principally by a series of northwest-trending shears and shattered zones. Vein, stockwork, and disseminated ores occur, usually containing simple quartz-pyrite-gold mineral assemblages. The gold itself is electrum, having a silver content of 30% to 40%. In September, 1967, Elwood Dietrich, a prospector and mine promoter, obtained a purchase option on the 4452 ha (1 1,000 acres) of mineral rights held at Round Mountain by Nevada Porphyry Gold Mines. The original option had a buy-out price of $1 million and was established through Dietrich's friendship with officers of Nevada Porphyry. In April, 1968, Dietrich conveyed his option to Ordrich Gold Reserves Co., a partnership created by a group of west coast investors, mostly employees of the airline industry. There- after, Ordrich invested considerable funds in trying to test and develop the property, but soon recognized the need to seek financial and technical support from the mining industry. In December, 1968, Dietrich contacted Wayne Cavender, then Regional Geologist, Southwest, for Copper Range Exploration Company (CRX) in Tucson, Arizona, and made a data presentation. Shortly thereafter, Cavender was appointed Manager of Exploration and Chief Geologist for Copper Range Co. (parent company of CRX), New York City, and he asked C. Phillips Purdy, CRX Regional Geologist, Northwest, to make an initial property examination. Purdy's one-week field study took place in March, 1969, and resulted in a recommendation that CRX pursue its investigation of the property. The presence of low-grade gold mineralization in both the alluvial gravels and in the bedrock was verifiable, but the placer was deemed to have the greater immediate economic mining potential. At that time, gold was in the $1.41/g ($40 per oz) price range. Working from Purdy's information, Cavender decided to attempt acquisition of the property, and the first in a long series of negotiations was initiated with Ordrich. Basically, CRX felt that the placer had a promising potential for several reasons, including (I) past operators had recovered free gold but not the gold contained in the pebble fraction of the gravels; (2) past operations appeared to have been ineffectively designed or managed and not costefficient; and (3) the price of gold appeared to be poised for an upward move. Negotiations with Ordrich were prolonged and difficult, with CRX competing against several ma* mining companies, but finally an agreement was reached, effective June I, 1970. Gold was then back to $35. It is believed that, in

Jan 1, 1985

By R. R. French

Investigations were conducted by the lndiana Geological Survey for some dry methods of bene-ficiating low-grade gypsum ore. Seventy-two batch and continuous flow tests were performed with a roller mill, rod mill, pebble mill, electronic color sorter, electrostatic separator, and an air separator. Approximately 650 size analyses and 550 chemical analyses were performed during the investigation. Batch samples were tested by the Survey, and most of the continuous flow tests were handled by com-mercial laboratories. INTRODUCTION Although many companies producing gypsum have been interested in dry beneficiation, very little information has been published in the past. One of the most comprehensive investigations was reported by the Canadian Department of Mines.5 Other reports of interest have been published by the Canadian Department of Mines,' the South Australian Department of Mines,2 and the U.S. Bureau of Mines.3 Some beneficiating practices, such as hand picking, selective mining, crushing and screening, milling, and air classifying, were already in use in the Canadian industry prior to MacPherson's investigations.5 MacPherson examined the effect of tabling, air separation, screening, flotation, electrostatic separation, calcining, washing, and various types of milling, in his efforts to eliminate dolomite, limestone, and small amounts of silica and clay from the gypsum ore. RAW MATERIAL Gypsum and anhydrite occur within the lower part of the St. Louis Limestone (Mississippian) in southwestern Indiana. Gypsum in single beds 10 or more ft thick occur at Shoals, Martin County; near Freedom, Owen County; near Bloomfield, Greene County; and in the Devonian strata of LaPorte County. Only the Shoals deposit has been exploited commercially. The western edge of the Shoals deposit is contaminated by a continuous bed of shale, about 1 1/2 to 2 ft thick, near the top of the evaporite and by thin continuous strata or irregular masses of carbonate rock. The low-grade material used in these investigations was obtained from the waste pile of the National Gypsum Co.'s plant at Shoals. The waste ore averaged about 67.4% gypsum and was contaminated by various amounts of shale, dolomite, and limestone. All the material had been previously crushed and screened to minus 1 1/4 to plus 3/8 in. X-ray analyses of powdered, sedimentated, gly-colated, and heat-treated samples of the shale showed that it was composed of slightly structurally disordered illite, Fe-rich chlorite, and very finegrained disseminated silt. The clays and silt were partly cemented with carbonate material. Light-gray argillaceous limestone and gray or brown porous dolomite made up most of the carbonate rock contamination. Crushing Characteristics: The rate unweathered gypsum, carbonate rock, and shale reduce in size was determined by crushing handpicked samples in a rod mill and screening at minus 100 mesh (.0059 in.). Fig. 1 graphically represents the data. These data indicate that carbonate rock should be relatively easy to separate from gypsum, but that shale should be difficult to separate from gypsum by differential crushing. Controlled Samples: Eight rod mill tests of hand-picked samples of mixed gypsum and shale and mixed gypsum and carbonate rock were made. Sample weight and crushing weight were standardized, but the scalping screen size was varied from 3 to 10 mesh (.265 to .0787 in.) in order to obtain the optimum purity and recovery. The data obtained from the tests (see Table I) illustrate that the relatively hard carbonate rock allows appreciable beneficiation (13.6 to 18%), but the low strength gypsum and shale allows only minimal separation (3.1 to 7.5%).* Semi control led Samples: During the investigation considerable slaking of the shale was noted when the ore was subjected to alternate wetting and drying. As demonstrated in laboratory tests, as much as 76% shale can be removed by two cycles of wetting and drying in a 48-hour period with subsequent screening at .265 in. Five ore samples, stockpiled and weathered, were screened, rod-mill crushed and rescreened at .157 or .187 in. with excellent results (Table 11).

Jan 1, 1967

By H. Sigurdson, C. H. Moore

Extensive studies have been carried out on electric furnace and blast furnace slags obtained in the winning of iron from its ores. These slags normally consist of elements of the gangue minerals present in the ores, as well as the added flux materials. In consequence, melts of CaO, MgO, Al2O3 and SiO2 can be considered as representing typical slag compositions. When a slag of this composition cools, it usually crystallizes according to predictions possible from an equilibrium diagram of these constituents, providing the melt is not undercooled to form glass. The melt is either viscous or fluid, depending upon the ratio of binary cations to silica, and crystallizes easily or forms a glass for the same reasons. If the melt is not overheated so that carbides of the metal components of the slag are formed and if the composition of the slag is so adjusted that it has a high fluidity, liquid equilibrium is attained and the slag can be held in a liquid state for extended periods of time. Upon tapping, the slag crystallizes into minerals, the type and proportion of which are determined by the melt composition. Since equilibrium is attained, the holding period is not critical. In melts containing a large increment of titanium, however, the normal slag procedures are not applicable. Titanium, as one of the atomic transition elements, is, at elevated temperatures, capable of being reduced to form metalloid compounds much more readily than the refractory oxides present in normal slags. In consequence, an oxide melt containing titanium never reaches equilibrium in a reducing environment, but continues to shift its composition until cooled. If melts of this nature are cooled and samples submitted to metal-lographic and X ray analysis the course of reaction and crystallization in this type of slag can be determined. Preparation of Slag The slags investigated fell into the system CaO-MgO-TiO2-Al2O3-SiO2 and were produced from ilmenite ores reduced by carbon in an electric furnace. Since the equilibrium series1 and the laboratory smelting of ilmenite2 are described in two of the accompanying papers, detailed description of the smelting procedure is not required here. However, certain essentials must be mentioned. Two types of melts were used to produce slags studied in this investigation. The first series of smelts made to determine proper flux addition were produced in a 4 lb Ajax induction furnace. The charge, consisting of ore with the proper flux addition, was heated in a graphite crucible until fluid, held fluid for a sufficient time period to obtain 1-5 pct FeO content, and poured. Because of the small size of the charge only the final sample of these melts could be examined. In the melts made in the 50 lb arc furnace, however, grab samples taken at 10 min. intervals between time of initial melting and final pouring were available for examination. These samples allowed a much clearer picture of the course of reaction and crystallization. amounts of ferrous oxide and reduced titanium compounds is opaque to transmitted light. Therefore, all petro-graphic studies had to be made on polished slag sections. A representative sample of slag was cut or broken, mounted in a thermosetting plastic, ground flat using 400 grit silicon carbide, the coarse scratches removed with 600 grit silicon carbide and polished on billiard cloth using levigated alumina. Rouge was avoided because of the entrainment of the red particles in pores in the slag, causing a possible confusion with some of the mineral phases. In order to prevent sample projection above the plastic surface red bakelite was used to hold the sample, and backed up with clear lucite. In this manner sample labels could be permanently retained in the mounting. The polished samples were examined on a Bausch and Lomb metallograph at magnifications of 250 X, 500 X, 1000 X and 1800 X. The instrument was equipped for examination of specimens under bright field illumination and with crossed nicols. A magenta tint plate to aid in color tone differentiation was also used. Petrology of Slags In order to determine the composition and mineral relatinos of a previously unreported system petrologically, it is essential that the starting composition, reaction temperature and final composition be known. The chemical composition of the ilmenite ore used in these smelts is given in Table 1, and the complete analysis of a typical high titanium, low iron slag is given in Table 2. In the winning of TiO2 from ilmenite by a smelting process it is necessary to produce a slag which will melt at an economically feasible temperature, remain molten as the iron is removed by reduction, be fluid enough to be readily removed from the furnace, contain a high percentage of TiO2 and a low percentage of reduced titanium com-

Jan 1, 1950

By T. H. Weldon, L. V. Whiton, R. R. McNaughton, J. H. Hargrave

Oxygen enriched air is being used quite extensively in the metallurgical plants of The Consolidated Mining and Smelting Co. of Canada, Limited, at Trail, B.C. The oxygen used for this purpose is a by-product from the Company's chemical plants located in the area. Most of the ore treated in the Trail metallurgical plants comes from Com-inco's Sullivan Mine at Kimberley, B.C. At Kimberley the ore is milled to produce lead and zinc concentrates which are shipped to Trail for further treatment to metal. One section of this paper deals with the use of oxygen enriched air in the suspension roasting of the zinc concentrates. In this process the concentrate is calcined for leaching preparatory to electrolytic recovery of the zinc. A second section of the paper describes the use of oxygen enriched air in operations at the lead smelter. There oxygen enriched air is used in the blast to the lead blast furnaces and in the slag fuming furnace which recovers the lead and zinc contained in lead blast furnace slag. The final section of the paper outlines the precautions necessary for the safe use of oxygen enriched air in any plant operation. The Use of Oxygen Enriched Air in the Suspension Zinc Roasters The suspension roasting of zinc concentrate developed at Trail, B.C., has been described in AIME Vol. 121, "The Electrolytic Zinc Plant of The Consolidated Mining and Smelting Company of Canada, Limited" by B. A. Stimmel, W. 11. Hannay and K. D. McBean. Since the publication of that paper, the use of oxygen enriched air in suspension roasting has been introduced as regular practice with marked advantage. The relative importance of a specific advantage may vary with changing conditions, but, in general, it may be stated that improved operation has been achieved at increased capacities. Suspension roasting is carried out at Trail in converted standard 25 ft diam Wedge roasters. The 2nd, 3rd, 4th and 5th roasting hearths have been removed and the drying hearth covered over. Drying of the concentrate is done on the drying hearth and the 1st roasting hearth. The dried concentrate, after any lump's have been broken up in a ball mill, is fed to a single burner located in the upper part of the combustion chamber. Oxygen is introduced at the burner fan along with the gases from drying, returned combustion gases from the waste heat boiler outlet and the required amount of new air. Up to 60 pct of the concentrate settles out on the 6th roasting hearth, the rest passilig out of the roaster. The product collected in the waste heat boiler is finished calcine, but the dust collected in the cyclones after the boilers is returned to the base of the combustion chamber where the sulphate is decomposed. Gases from the c'yclones go to a Cottrell precipitator. The discharges from the 7th roasting hearth and the waste heat boiler are combined with the Cottrell dust to give the finished calcine. Following small scale tests started in 1933, oxygen enriched air has been used continuously in the suspension roasting of zinc concentrate in Trail, beginning in 1937. A significant factor in promoting its use in this operation was the availability of by-product oxygen from the Company's near-by Chemical and Fertilizer Division. To-day it is standard practice at Trail to use oxygen enriched air for zinc concentrate roasting. The most important requirement in roasting a zinc concentrate for an electrolytic plant is that the zinc in the calcine should have maximum solubility. It is also desirable at Trail that the gas produced for the manufacture of suhhuric acid should have a ~naximum concentration of SO2 and that a substantial recovery of waste heat from the gas be achieved. High solubility of zinc requires that the sulphide sulphur and zinc ferrite in the calcine be kept low. These are both functions of temperature and time, with formation of zinc ferrite also dependent on contact between the iron and zinc particles. One of the inherent advantages of suspension roasting is that minimum time and contact are achieved. The limit on temperature is imposed by the fusion point of the concentrate and not by the need to control zinc ferrite formation. Operating temperatures are normally maintained within the limits of 1725" and 1850°F. A relatively low zinc sulphate in the calcine is required at Trail, and this results from discharging the calcine from the high sulphur dioxide atmosphere at a temperature above 1600°F.

Jan 1, 1950

By F. N. Rhines, A. H. Grobe

At elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible1 and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscaleiormation) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detai1.5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the 1-6 and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 40 alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. Experimental Procedure Silver.—The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942

By J. J. Gilvarry, B. H. Bergstorm

The first part of this paper describes a new approach to the problem of energy relationships in fracture and comminution. The basic theoretical method used (as contrasted to previous empirical or semi-empirical approaches) is an attempt to verify or disprove the hypothesis of von Rittinger, In the second part of the paper, theoretical conclusions for the three headings of single fracture, plural fracture, and comminution are tested. Agreement between theory and experimental results is demonstrated. The classical hypotheses on the energy relationship in brittle fracture are those of von Rittinger-that the energy required is proportional to the new surface formed— and the alternative one of Kick.' Over the years, repeated attempts have been made to discriminate experimentally between the two assumptions, or to replace both of them, as has been done by Bond? However, no semblance of agreement seems to exist among different investigators. This paper is the first in a series essaying a new approach to the entire problem of energy relationships in fracture and comminution. The purpose of this program of research is to verify (or disprove) the hypothesis of von Rittinger. In contrast to previous empirical or semi-empirical approaches to the problem, the basic method adopted is theoretical. The prime aim is to determine the distribution function for fragment size theoretically and to verify the predicted distribution experimentally. This approach should make possible determination of the total surface of the particles by integration over the corresponding distribution function; one may hope that this direct procedure will yield more definitive results than use of gas adsorption or other methods. The surface area so obtained can then be compared with experimental energies, as obtained by Bergstrom, Sollenberger, and Mitchell,4 for example. It is convenient to distinguish between single fratture, plural fracture, and comminution. Single fracture of a brittle solid is defined as fracture by an external stress system which is removed instantly and permanently when fracture is initiated. Plural fracture consists of single fracture of the original specimen, followed by a sequence of only a few secondary fractures; comminution differs in that the sequence of secondary fractures consists of a large number of repetitive steps. For single fracture, Gilvarrys has given a rigorous derivation of the proper distribution function for fragment size, based on a closely defined physical model and deduced strictly by the laws of probability. Gilvarry and Bergstrome have compared the predictions of the theory with experiment, and have found excellent agreement. The prior work of Gilvarry and of Gilvarry and Bergstrom considers only single and plural fracture. The purpose of the present paper is to extend the discussion to the case of comminution. For prefatory purposes, the theory of Gilvarry for single fracture will be outlined. The considerations will then be applied to the cases of plural fracture and comminution. SINGLE FRACTURE The derivation is based on the Poisson law.7 For Points distributed with mean density y over a domain, this law states that the probability p(t)dt of one point lying in the range t to t + dt with none in the interval 0 to Ms p(t)dt = ye-yt dt. For this distribution to be valid, it is necessary and sufficient that the points be distributed at random, individually and collectively in the sense of ~~~.7 The former qualification requires that the position of One Point be independent of another, and the latter implies that the probability of a region containing a

Jan 1, 1961

By L. Cichowicz, K. K. Millheim

The constant-rate drawdown test performance for a low-permeability, verticany fractured gas well was investigated. A series of gar wells were tested by flowing each well at constant rate until the data could be analyzed using con-ventional radial flow theory. Each well was then shut in to build up. After a sufficient buildup was obtained, another flow Iest commenced but at a higher flow rate than Ihe first test. Again, the well was shut in when radial fiow was obtained. his procedure was repeated for three to four different flow rates. Two wells in the San Juan basin were tested using this procedure. Both wellere fractured after completion, cleaned up and then shut in until flow testing commenced. Test designs of both wells permitted investigation of the most realistic values of egective permeability, wellbore radius and turbulence factor. Also, being able to determine the eflective fracture flow area and vertical fraclure efficiency was inherent with this testing approach. It was observed that fractures in both wells influenced the Pressure behavior for approximately Is to 40 hours (depending on the flow rate) before radial flow was evident. After this time, drawdown data were analyzed using radial pow theory. When a low-permeability gas well has vertitally oriented, induced fractures, the early flow geometry ic. essentially linear. It will be shown how to determine when a flow test has been conducted long enough so lha' the most representative values of effective permeahiiity. wellbore radius and turbulence factw can be calculated. From the linear pressure data, valuable information about The fracture treatment, such as the effective flow area and vertical fracture efficiency, can be determined for vertically froctured wells. Introduction During tests on gas wells in the Sari Juan basin7 initial transient behavior lasted for many days because of the low permeability of some porous media. As a result, stabilized flow performance could not be obtained. If these wells received some type of stimulation treatment, early pressure behavior deviated from conventional theoretical radial Row. When conventional radial flow theory was used to analyze these low-permeability fractured gas wells, larger values of flow capacity and absolute open flow potentials (AOF) sometimes resulted. Wells were assigned open flow poten- tials that proved to be 3 to 10 times higher than the well would sustain over a longer period of production. In some cases where the wells had flowed for longer periods of time during a constant-rate drawdown test, it was noticed that the effective flow capacity appeared to be decreasing with time until a certain value was reached. The early nonradial pressure behavior can be explained If linear flow is assumed. Rusell and Truitt mathematic. ally investigated the vertically fractured well in a bounded area. They showed that early flow behavior was essentially linear and, for x,/x. approximately less than 0.10 radial flow was obtained after short periods of time. Then realistic values of effective permeability and skin could be determined. Scotta experimentaliy studied the vertically fractured well with a heat flow analog. He showed that earb flow was linear, Both studies indicate that, for small values of x,/x,, linear flow approaches radial flow if the well is tested long enough, To help prove this concept of early linear flow caused by induced vertical fractures, two low-permeability gas wells were tested. Both wells received large fracture treatments prior to testing. A vertical fracture was indicated from the analysis of fracture treatments, As anticipated, tests of both wells indicated early linear flow that was later followed by a period of radial flow, Data collected from each well were analyzed. From the well tests, plus other information on each well, the effective permeability, wellbore radius and turbulence factor were calculated. Effective fracture flow areas calculated from test analyses for each well proved to be approximately one-fourth the created area calculated from classic hydraulic fracturing theory: other fractured wells that were tested but not presented in this paper also indicated that the effective fracture flow area was one-fourth to one-third the created area predicted from hydraulic fracturing theory. The vertical fracturing efficiency was estimated from the calculated values of effective wellbore radius and fracture flow area. For the two wells tested, calculated fracture lengths x, were 112 and 105 ft, and the vertical fracturing efficiencies E, were 122 and 183 percent. Development of Flow Model Agnew' showed that most induced fractures below 1,500 ft are vertical. Anderson and Stah15 indicated that most of the fractures they studied were vertical. Thc model proposed for early flow in most vertically fractured gas wells is shown by Fig. 1. This model should approximate early flow behavior until radial flow is reached, at which time a radial model with an effective wellbore radius of 0.5 they will

Jan 1, 1969

By A. H. Grobe, F. N. Rhines

At elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible1 and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscaleiormation) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detai1.5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the 1-6 and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 40 alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. Experimental Procedure Silver.—The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942

By F. E. Pawlek, J. K. Gerlach

The chloridizing roasting of ores is applied when metal sulfides and oxides are to be converted into soluble or volatile compounds. The chlorine required is either obtained from the admixed chlorides of sodium or calcium or added in the gaseous state. In the first part of the investigations the reaction rate of the chlorides of sodium or calcium with gas mixtures of SO,-0, or SO ,-O2 ,-SO , was measured. The rate for reactions with gas mixtures SO2-O2 is ThE chloridizing roasting of ores is applied when metal sulfides and oxides are to be converted into soluble or volatile compounds. At present the process is mainly applied to produce nonferrous metals which occur in pyrite cinders in small concentrations. Thereby the nonferrous metals are converted into water-soluble, acid-soluble, or volatile compounds whereas all the iron remains as insoluble oxide. The chlorine required is either obtained from the admixed chlorides of sodium or calcium or added in the gaseous state. The reactions occurring during the roasting process can be divided into two groups: solid-solid reaction and gas-solid reaction. The reactions between solids proceed by means of solid-state diffusion and are therefore of low velocity. The heterogeneous reactions between solids and gases of the roasting atmosphere5 are high-velocity processes and determine the velocity of the chloridizing roasting. These gas-solid reactions shall be the subject of the paper presented. In order to investigate the still little-known processes which occur during the chloridizing roasting 6-' the complex reaction is split into several partial steps. First the reactions of NaCl and CaCl, with gas mixtures of SO2 and 0, have been investigated at temperatures between 500" and 600°C by measuring the weight increase of the samples. The gas mixtures used in this series of experiments had first variable compositions, then the amount of SO 2 had been increased. Furthermore the influence of Fe 2 O3 admixtures upon these reactions, the behavior of pure Fe 2 O3 with the gaseous reactants, and the chlorination of the sulfides of lead, copper, nickel, and zinc have been investigated. FORMATION OF GASEOUS CHLORINE Pyrite cinders are never completely roasted and therefore contain still a small amount of sulfide sulfur. When heated again in air, this sulfur is converted into SO,. Accordingly the formation of chlorine can first be described by the reactions: dependent on the composition of the gas phase. If more than 1 pct SO 3 is added to the roasting gas, the reaction rate is determined only by the concentrations of the SO,. In the second part the reactions between chlorine and metal sulfides are discussed. The rate of formation of gaseous chlorine is higher by me order of magnitude than is the reaction rate between ZnS and chlorine. The reaction rate of NiS and PbS lies considerably below that of ZnS. The conversion rate of both pure Fe 2 O 3 and Fe 2 O 3 containing NaCl or CaCl2 when reacting with SO2-O2, mixtures with and without SO3 portions was measured at temperatures of 500", 550°, and 600°C. The weight increase of pressings was determined by means of a spiral balanceg and the reaction rate calculated therefrom according to Eqs. [ll to [31 and [5] to [7]. The prepared samples were suspended on a platinum filament in a vertically mounted tube of mullite (ID 4 cm, length 110 cm) which could be heated by a resistance tube furnace. The platinum filament was tied to the lower end of the spiral balance. A supremax glass tube (length 70 cm) was mounted gas-tight on top of the reaction tube. The unit was sealed up at its top by a ground-in stopper which was holding the spiral balance with the sample. The spiral balance therefore hung outside the high-temperature region of the furnace. Fig. 2 shows the experimental arrangement schematically. While lowering the sample into the reaction tube pure nitrogen was flowing through the reaction zone providing a protective atmosphere. After the sample had reached the reaction temperature within approximately 1 min, the protective gas was replaced by the sulfur dioxide-oxygen reaction mixture. It took about 30 sec until the mixture filled the tube homogeneously. A Ni/NiCr thermocouple placed in the center of the furnace where the sample hung during the measure-

Jan 1, 1968

By P. E. Baker

An experimental study of heat flow in steam flooding was carried out with steam displacing water in a plane-radial fluid-flow model. Temperature distributions in the model reservoir, overburden, and substratum were measured at frequent intervals during flooding by means of a fixed array of thermocouples. Heat losses to overburden and substratum and the division of heat between the steam and hot-water zones in the reservoir were calculated from the temperature data by performing numerical integrations over the appropriate volumes. Temperature profiles and heat distribution results are presented. Some results were (1) the fraction of injected heat that is lost to overburden and substratum, when expressed as a function of time, did not depend on injection rate; (2) a significant portion of the injected heat was contained in the hot-water zone ahead of and underlying the steam front in the reservoir. The division of heat between the steam and hot-water zones did depend on injection rate; and (3) considerable gravity override was observed. The experimental results are compared with those of several published theoretical studies of heat transfer in hot-fluid injection; approximate agreement on heat losses is found with some of the most idealized theories. A valid comparison cannot be made in regard to steam us hot-water zone; basic interpretation of the hot-water zone, in terms of a vertical steam front, is clouded by gravity override in the experiments. INTRODUCTION The experimental study reported here primarily concerns two problems of heat transfer in steam flooding that have economic and engineering importance. These are (1) the fraction of injected heat lost to the overburden and substratum, and (2) the division of the remaining heat between a zone containing steam and a zone of hot water at lower-than-boiling temperature. The volume of the steamed region, which has a direct effect on oil recovery, can be calculated readily from these results. Several valuable theoretical studies have been published on this problem, but no experimental tests of the theories have previously appeared. Tests were needed because the effects of the necessary simplifications in the theories could not be determined otherwise. The basic, untested theoretical problem is the effect of "decoupling" heat and mass transfer, and the resulting inability to include the effects of heat transfer and condensation on fluid flow. The theoretical problem solved so far has been a heat transfer problem in which fluid is present as a heat carrier and flows in a stipulated manner, either linear or plane-radial. The simplifications that have sometimes been made in regard to thermal conductivity by, for example, Marx and Langenheim,l Lauwerier2 and Thomas3 apparently do not have an important effect on heat loss calculations, although the results of the different methods disagree to a certain extent, as shown by Spillette4 and by Ramey.5 A recent paper by the author6 compared the results of experiments in hot-water flooding with several theoretical results and showed a rather poor agreement. It will be seen that the experimental heat loss results for steam flooding, however, show acceptable agreement. These comparisons are discussed in a later section. EXPERIMENTAL APPARATUS AND PROCEDURE The system studied was one in which a sand pack, initially water saturated and at a uniform temperature, was flooded with steam at a constant rate and temperature. The temperature distribution in the "reservoir" and adjacent "strata" was measured with an array of thermocouples, and heat losses were determined from these measurements. The sand pack contained no oil because the only concern of the experiments was heat flow, and it was important to have the flow pattern as simple

Jan 1, 1970

By L. Valentik

Many attempts have been made during the last 40 years to evaluate the performance of gravity separation equipement, that is, the effectiveness with which light and heavy particles are separated. The most comprehensive treatment of the subject was made by Cerchar at the 1st International Conference on Coal Preparation held in Paris in 1950. The methods suggested by the Conference were accepted and very widely used in the last two decades. This paper discusses an improved method of evaluation in the light of the now-accepted standard presentation. The float-and-sink analysis of the product is presented on a Gaussian distribution curve, resulting in an easier visualization of the inherent difficulties of separation. The ogives of the distribution curve me then plotted, giving a quantitative measure of the deviation from perfect separation as an error distance instead of an error area. Illustrations of the new method are given both for gravel and for coal preparation, but the content is valid and applicable to other types of minerals which are separated by gravity methods. Many attempts had been made during the last forty years to evaluate the performance of heavy-media separation (HMS) equipment, that is, the effectiveness with which floats and sinks are separated.'-' The most comprehensive treatment of the subject was made by Cerchar at the 1st International Conference on Coal Preparation held in Paris. 6 The primary aim was the thorough understanding of the mechanism of separation and the unified presentation of data on gravity separation so that the evaluation and comparison of washery performance could be made from all over the world. No strict overall standardization has been achieved, but after the conference a more or less uniform presentation of performance was accepted, which, during the last two decades, has been very widely used. In this paper, illustration of the old methods and an improved method of evaluation will be given. HEAVY-MEDIA SEPARATION (HMS) PERFORMANCE CRITERIA In the ideal HMS process, all material lower in density than the specific gravity of separation (SGS) would be recovered as floats and all material of higher density would appear as sinks. In order to evaluate the misplaced material, the washery products are tested at the density at which the washing unit is operated. The original type of plot1,7, 8 is shown in Fig 1; this was developed primarily for coal cleaning units. The curve for raw coal represents the cumulative percentages of sink material. The refuse curve is also plotted as a cumulative sink, the percentages being expressed in terms of raw coal. This diagrammatic representation of the results of washing units has the merit of easy visual observance of the degree of separation obtained. The error areas (cross-hatched) are a measure of the amount of misplaced material and therefore they can be used to characterize the quality of separation. The ideal and actual separating performance between floats and sinks can be best seen from the partition curve developed by Tromp,2 where the ordinate is the percentage recovery of the sinks, and the abscissa is the specific gravity (Fig. 2). It can be seen from the shape of the curve that as the SGS is approached, the proportion of material reporting to the improper product increases rapidly. In fact, the SGS can be defined as the density of the material in the feed that is distributed equally between float-and-sink products. When the upper half of the curve is inverted, a shape similar to that of a Gaussian error distribution curve is obtained and therefore the analysis of gravity separation may be carried out by using the law of probability. The shape of the curve in Fig. 2 is determined partly by the density composition of the feed, and partly by the sharpness with which the unit separates floats from the sinks.9, l0

Jan 1, 1970

By W. E. Ruder

IT has been pointed out by Stead 1 that grains of considerable coarseness may be developed in steels containing from 3 to 5 per cent. of silicon, and in a previous paper 2 the present author has shown that under the proper conditions of annealing single grains having an area of 50 sq. cm. may be obtained. It is the purpose of this paper to discuss in more detail the conditions, promoting the growth of these grains, in the hope that the experiments described may throw some additional light upon the general problem of grain growth in metals. These silicon steels lend themselves particularly well to such experiments because of the ease with which the change in structure may be followed and because of the fact that the effect of the carbon present is largely obliterated by the high percentage of silicon. This forms a solid solution with the iron, which acts very much like a pure metal. This alloy has been found to have but one critical point, viz., Are. This point, determined by Roberts-Austen for Hadfield's 4 per cent. Si alloy, was found to lie at 703° C. Vigouroux3, in working with pure Fe-Si alloys, finds this point to rise from 750° C. for 0.5 per cent. Si to 860° for 6 per cent alloy, with a flat region in the curve from 3 to 4 per cent. Si. No accurate determination of this point has been undertaken by the present author, but it has been roughly determined to lie between 730° and 750°.

Jan 12, 1913

By J. E. Berry

AII evaluation is made of the acoustic velocity log for measurement of formation porosity. Plots of field-observer1 velocities vs core-measured porosities of sandstones and limestotnes with inter intergranular porosity show that the velocity log gives a useful measure of porotity, in agreement with published data. A new method of plotting electrical and velocity log data makes it easier to recognize hydrocarbon-water coritnct~ from log darn and to make serni-quantitative estinlates of hydrocarbon saturation. Two examples of this interpretation technique are given. This paper also discusses the various factors that affect acoustic velocity and shows how corrections can be made for some of these factors. INTRODUCTION Although the continuous velocity log was developed primarily as an aid to seismic interpretation, it is finding widespread use for measurement of porosity. The purpose of this paper is to evaluate this use of the log. Results are presented for the velocity-porosity relationship in many sandstones and one limestone. Practical applications of porosity values derived from the velocity log to improve interpretation of electrical surveys are presented. Various parameters which affect velocity in porous media are considered. Porosity, composition, cementa-tion, pressure difference (overburden pressure minus fluid pressure), fluid saturation, and wellability are discussed. Some of the ideas are opinions based on general considerations of well logging problems while others are supported by published data and our own observations. Major conclusions from these studies arc given in the body of the paper and detailed discussions of some of the various factors affecting porosity are given in the Appendix. POROSITY Sandstones The primary factor affecting the velocity of sound in porous media is porosity. Wyllie, et al,1 have reported a time average equation for the relationship between velocity and porosity.* This has found considerable acceptance in the industry. Other relationships between velocity and porosity have been proposed, none of which are entirely satisfactory. It is doubtful that any one relationship will completely describe all situations. We have tried an empirical relationship based on correlating log velocities with core-measured porosities. Measured porosities were averaged over a depth interval equal to the spacing used in recording the velocity logs. The depth range for the information used was from 2,000 to 12,000 ft. Velocity measurements were normalized for the effects of depth and overburden pressure. A detailed discussion of the basis for this normalization is given in the Appendix. The change is usually insignificant and when working with individual formations it can be neglected. All velocity measurements were normalized to a depth of 10,000 ft. The velocity-porosity data for sandstones in Fig. 1 came from 20 wells scattered throughout the Mid-Continent and Gulf Coast areas. The scatter of the data points is attributed to three causes: 1. There is no theoretical basis for expecting an exact velocity vs porosity relationship and it is not possible to correct precisely for the effects of such factors as impurities, grain shape, manner of cementation, etc. Some of these factors are discussed in the Appendix. 2. Porosities measured by core analysis are not necessarily representative of what the velocity log "sees". 3. Inaccuracies appear in the velocity log reading. This is particularly true of velocities from one-receiver logging tools.*" A linear-time curve (time-average equation) is plotted in Fig. 1 along with the best straight line through the points. Velocities used for the linear-time curves were 19,500 ft/sec for the matrix velocity (zero porosity) and 5,500 ft/sec for fluid velocity. For clean sandstones with velocities greater than 10,000 ft/sec, there is little difference between the velocity-porosity and the time-porosity curves. Both curves are well within the scatter of data points. The data points in Fig. 1 were restricted primarily to clean sandstones, using the SP and/or gamma-ray logs as clues to the lithology. Where a lithologic de-

By P. Gobin, J. Perez, P. Peguin

The strain-amplitude- dependent part of the internal friction of alluminum after several ther momechanical treatments has been measured in the I-cycle range and at the ambient temperature. The internal friction in the outer layer of the torsional specimen us stress is computed from the experimental data. The curues obtained are analyzed in tevnzs of u coirzbinntion of AH and p, which aye, respectively, due to the vecersible unpinning from weak pills and to the plastic strain. Considerirlg the notion of thermally activated unpinning and repinning, it is shown that in our experimental conditions tlze dislocation lines acl as in the H model of Granato and Liiclze. It is also seen that the internal friction p which appears at higher- strains call be described by a simple expression which is in good agreement with our results. A qualitative interpretatiorz is proposed by combining these new types of intelpnal fviction. We define the internal friction 6 as half the ratio of the dissipated energy aW during one cycle to the maximum supplied strain energy W of a material submitted to a periodic stress. Experiment and theory show that internal friction varies with stress above a critical value.' Below this value the internal friction is strain-amplitude-independent and is often masked by an experimental background; so we shall call it AB. ~bove this critical value, the internal friction is strain-amplitude-dependent. This quantity is usually called aH:' and it can be explained as a thermal unpinning of dislocations.3-6 Furthermore, at higher stresses, a rapid increase of internal friction appears. This phenomenon could be caused by the plastic strain,' so we shall call it Ap. It seems interesting to us to study the influence of several t her momechanical treatments on the curve internal friction 6 vs strain E, in order to study the variation of AH and p with the concentration and the repartition of linear and point defects. In order to try to explain the results obtained, we shall propose and discuss models for H and hp and shall show that we obtain a combination of these two types of internal friction. 1) EXPERIMENTAL PROCEDURE 1) Preparation and Treatment of Specimens. We

Jan 1, 1968

By R. T. Keyes, R. B. Clay, L. L. Udy, V. O. Cook, M. A. Cook

Based on compressibility and stress wave velocity in rock, initial explosive loading conditions, the thermochemistry of the explosive and reasonable description of the pressure-distance relations behind the shock front, the distribution of energy between the products of detonation and the burden are estimated as a function of time for various loading conditions. These include 'powder factor', loading density A (fraction of borehole occupied by explosive), and the explosive itself. Factors responsible for rock fragmentation are discussed in terms of: 1) 'release wave fracturing', 2) 'shear wave fracturing', and 3) 'release of loading fracturing' or 'rock bursting'. Release wave fracturing appears to occur only in the immediate vicinity of free faces, and shear wave fracturing only adjacent to the borehole under normal blasting conditions. Rock bursting is thus considered to be the most important means of rock fracturing in blasting. Means for maximizing it are considered. The most important factors to consider include maximum available energy A, explosive density p1, loading density A and 'powder factor'. Maximum efficiency is attained in general by maximizing the A . p1 product. This is achieved by using high density explosives at a loading density of unity (A = 1.0). Ways for achieving this condition are discussed. The bulk-handled aluminized slurry blasting agents have the desired properties for achieving optimum conditions for high blasting efficiency based on the theory outlined herein. Factors considered most important in the blasting of rock are: 1) The maximum available energy A, determined by the heat of explosion Q and the mechanical efficiency ?, a factor intimately associated with the mode of application (A = Q at highest gas concentrations). 2) The 'borehole pressure', pb, or the maximum pressure developed in the borehole after passage of the detonation wave and before the burden has had time to move or become compressed appreciably. (Owing to the short duration of the detonation wave at any particular point in the borehole, the fact that the explosive may not always fill the borehole completely and the further fact that the burden may not actually see the detonation pressure, the borehole pressure is considered more significant than the detonation pressure p2 as a performance factor in borehole blasting.) The borehole pressure is determined by the explosion or adiabatic pressure, p3 , and the loading density, A, or the fraction of the borehole filled by explosive. 3) The physical conditions important in the application of the explosive are: a) The 'powder factor,' (We/Wr), or the ratio of the wt of the explosive to that of the rock being blasted expressed as lb per ton or more generally in lb/cu yd. b) The bulk density, p1 ?. c) The 'burden' or 'line of least resistance,' the spacing between boreholes, the geometry of the borehole pattern and sequence of firing. d) The physical and chemical properties of the rock, most significant of which are possible heterogeneties, such as faulting, prefracture, and greater than micro-scale chemical heterogeneities. (This factor is not considered here but deserves a great deal of careful consideration.) All of these factors need to be carefully considered in the most economical engineering of a blast. Here is considered firstly an outline of the present status of dynamic rock mechanics, particularly as it pertains to blasting. The factors pertaining to the most efficient application of blasting agents are also considered, followed by a discussion of methods of application to achieve optimum explosives performance. ROCK MECHANICS Dynamic rock mechanics is currently a rapidly developing science contributing greatly to a better understanding and consequently the more effective application of explosives in blasting of rock.1-22 Basic to the development of the science of dynamic rock mechanics were the advances of Goransen23 and the Los Alamos and NOL groups24-28 concerning rock and stress wave phenomena and the transmission and reflection characteristics of stress waves at interfaces between different media. Basing considerations on this new knowledge as well as new experimental methods of study (ultra-high speed streak and framing cameras and electronic timers) the theory of fracture and failure of solids under impulsive loading by stress waves developed rapidly.14,16,27-29 Also the

Jan 1, 1967

By B. F. Oliver, F. Garofalo

Gas-metal heterogeneous reactions and zone-lrelting were sinultarneously employed to produce several high-purity irons with low interstitial contents in a levitating- zone melter. Successive zone-tneltitzg pusses were made in carious sequences of atmospheves which included prepuvified tank hy-drogeta, water vapor hydrogen, palladiuril-purified hydrogen, and vacuunm of 2 x 10-6 Torr. Different irons ranging in purity from 99.89 to 99.996 pct with residual curbon contents of 17, 8 to 10, and 3 to 5 ppm have been Drepared. No measuvable gradient in the residual carbon content was observed along the entire zone-melted length (6-10 in.) in I-ilz.-diameter bars. The absence of a carbon-concentration gradient in the solid indicates an apparent distvihution coefficient of 1, an unusual condition. Internal friction, solid-state extraction, and hot-hardness results indicate that the level of mobile carbon in a iron depends on the gas-metal heterogeneous reactions employed. Purification under an oxidizing atmosphere resulted in the immobilization of nearly all of the carbon present at leuels of 10 ppm or less. Continuation of purification in a reducing atmosphere veturued the carbon to a state of mobility which was aguin reversed by further purification in all oxidizing atmosphere. The immobilization of curbon at "vesidual levels " is believed to be associated with a strong interaction between carbon and oxygen atoms. frons with low carbon and nitrogen contetzts which did not exhibit a hot-hardness peak were produced after zone ynelting in vacuum. CARBON, nitrogen, and oxygen have strong and well-known effects on many properties of iron. These effects persist even at concentrations of 5 to 20 ppm. The intent of the present investigation was to establish procedures for the preparation of high-purity iron with concentrations of these elements in the range of 5 to 20 ppm and lower. The results reported here deal with the procedures employed to prepare high-purity iron, and with observations on the behavior of certain elements at "residual levels": particularly carbon. The details of the (levitating) zone melter in which the final purification steps are performed and the necessary control of the pertinent solidification variables have been described previously.1,2 MATERIALS AND PROCEDURES Commercial electrolytic iron was induction vacuum-melted and cast into 30-lb ingots. Melt additions and ingot analyses for carbon, oxygen, and nitrogen are noted in Table I. All ingots were melted in stabilized zirconia crucibles conditioned with one iron wash heat. Middle sections of the ingots were forged to 1-1/4-in. rounds, machined to 1-in.-diameter bars, then cut to 36-in. lengths. The zone-melting operations were performed on six iron bars (A to F) at a freezing velocity of 2 in. per hr with the freezing interface rotating2 at 200, 300, or 400 rpm. Liquid zones were passed through the bars in various sequences of atmospheres, Table 11, including prepurified tank H2, palladium-purified Hz, wet H2, and system vacuum of 2 x 1018 Torr. Wet-Hz atmospheres were obtained by bubbling palladium-purified Hz through water exhibiting a resistance of 3 megohms. This water was heated with a platinum-immersion heater and was degassed prior to use. Zone melting in a wet-HZ atmosphere resulted in oxidation of the elements which are oxi-dizable with respect to iron. Fine oxide particles were observed on the surface of the liquid zone, and were encased in the bar surface with the passage of the molten zone. Between each zone pass, the surface of the bar was removed by filing and deep etching; this was continued until the oxide formation ceased. The filings were magnetically separated and the residues analyzed by optical spectroscopy. These were especially high in silicon and manganese. Samples were removed from the iron bars, with few exceptions, following each zone-melting operation. A 0.08-in.-thick disc was cut with an Al2O3 cut-off wheel at a point 1/2 in. above the beginning of freezing. Material from each disc was used for hot-hardness measurements, resistivity-ratio measurements, and carbon, nitrogen, and oxygen analyses. Analyses for most other elements were

Jan 1, 1965

By M. N. Short, I. A. Ettlinger

M. N. Short,? Washington, D. C., and I. A. Ettlinger, New York', N. Y. (New York Meeting. February, 1926) The Pioneer mining district, better known as the Superior district, from its principal town, is located in Pinal County in south-central Arizona about 80 miles east of Phoenix and 22 miles west of Miami. The region embraces a, confused series of mountain ranges of moderate height but precipitous slopes, between which lie irregular valleys filled with alluvial detritus. The average elevation is about 2800 ft. in the valleys and the summits of the ranges reach 2000 ft. above this. Superior is situated on the north bank of Queen Creek where it emerges from one of those ranges into a more or less basin-shaped valley. The drainage of Queen Creek is to the southwest and the flood waters spread out and lose themselves in the desert northeast of Florence, the county seat of Pinal County. The Magma copper mine (Fig. 1) is the only producer in the district. Although discovered in 1875, its production has been important only

Jan 1, 1927

By C. S. Giggins, F. S. Pettit

The oxidation of Ni-Cr alloys in 0.1 atm of oxygen has been studied at temperatures between 800" and 1200°C. For alloys with 30 wt pct or more Cr, continuous layers of Cr2O3 are formed during oxidation. In the case of alloys with chromium concentrations between approximately 5 to 30 wt pct, external scales of Cr203 are formed over grain boundaries whereas internal precipitates of Cr2O3 and external layers of NiO are formed at other areas on the alloy surface. When such conditions are present on the alloy surface, chromium diffuses laterally from those areas covered with a continuous layer of Cr2O3 to areas where a Cr2O3 sub scale exists and it is possible for the sub-scale zone to become separated from the alloy by a continuous layer of Cr2O3. Whether such a state will be attained depends upon the initial grain size of the alloy and the oxidation time. When the concentration of chromium in the alloy is less than 5 pct, Cr2O3 is formed internally both at grain boundaries and within the interior of grains and the alloy is covered with an external layer of NiO. MECHANISMS which describe the growth of oxide scales on nickel-base superalloys are complex and the effects produced by the various elements in these alloys on the oxidation behavior of superalloys are not clearly understood. In order to determine the influence of the different elements on the oxidation behavior of superalloys, it is first necessary to examine the oxidation properties of binary nickel-base systems which contain the principal elements present in the superalloys and then progressively more complex systems until compositions typical of the superalloys are attained. Chromium is present in virtually all nickel-base superalloys and the purpose of the present studies was to examine the selective oxidation of chromium in Ni-Cr alloys. The oxidation characteristics of Ni-Cr alloys have been extensively studied1-" to date principally as a result of the high oxidation resistance exhibited by some of these alloys. Ni-20Cr* has long been known *All compositions are given as wcight percent unless specified otherwise. to be oxidation resistant and is commonly used as resistance heating elements for service temperatures up to 1100°C. This alloy cannot be used for extended periods of time at higher temperatures because of the apparent reaction of the external scale with oxygen to form gaseous CrO3. In spite of the considerable work cited above some important aspects of Ni-Cr oxidation still remain unresolved. Virtually all of the previous studies agree that small additions of chromium to nickel, e.g., <10 wt pct Cr, result in increased oxidation rates as compared to that of pure nickel, whereas larger additions, e.g., 20 to 30 wt pct Cr, form alloys with substantially lower oxidation rates. The controversial aspects of the oxidation mechanisms for these alloys that still remain unresolved are as follows: 1) A description of the oxidation mechanism for the low chromium alloys. 2) A description of the oxidation mechanism for the high chromium alloys, particularly with respect to the composition of the external scale which results in the lower oxidation rates. 3) The specific alloy compositions at which the oxidation mechanism changes from that obtained for low chromium contents to that of the high chromium alloys and the reason for this transition. EXPERIMENTAL The Ni-Cr alloys listed in Table I were prepared from high purity metals by nonconsumably arc melting and casting as buttons. These alloys were then given a preliminary annealing treatment in argon at 815°C for 100 hr to promote homogeneity. Each button was cut into 0.250 in. thick sections that were subsequently cold-rolled to 0.050 in. thicknesses and annealed in argon at 815°C for 48 hr to provide a twinned, equi-axed grain structure. The grain size for these alloys was not uniform and the limits, within which the average grain size lies, are given in Table I for the single-phase alloys. All the alloys were single phase with the exception of the Ni4OCr alloy in agreement with the Ni-Cr phase diagram.&apos;&apos; Rectangular specimens were cut from the sheet to provide surface areas of approximately 2.5 sq cm. Exact areas were determined with a micrometer after surface preparation was completed. All of the specimens except the Ni-40Cr alloy and pure chromium were polished through 600-grit Sic abrasive paper, ultrasonically agitated in ethylene trichloride, rinsed with ethyl alcohol, and electro-polished. The specimens were electropolished in a 10 vol pct H2SO4 (conc), 6 vol pct lactic acid, methyl alcohol solution at 70" to 80°C for 2 min at a current density of 0.8 to 1.2 amp per sq cm. This electro-polishing procedure did not produce acceptable surfaces on the Ni-40Cr alloy nor on pure chromium and the oxidation properties of these materials were obtained for specimens polished through 600-grit Sic

Jan 1, 1970