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By Paul L. Horrer

Costly damage by severe wave attack to many engineering structures has illustrated the need for a consideration of the nature of wave action in plans for offshore drilling operations. Using wave data it is possible to answer questions pertaining to engineering problems such as platform elevation, structure orientation, and expected wave forces. For locations where wave records are not available a technique can be used to obtain information about wave characteristics from past meteorological data and near shore submarine topography. Forces exerted on structures by waves may be divided into four parts. A completed study is given in which frequencies of various wave heights and maximum frictional drag forces are computed for a typical offshore drilling site. INTRODUCTION Waves of tremendous proportions accompanying hurricane winds crash against breakwaters and other offshore structures causing untold damages. Wave forces exerted on structures at these times are enormous, as shown by past records of incidents where massive portions of breakwaters have been broken off and moved by waves. On other similar occasions, whole structure; have been unloosed and smashed or floated away. These incidents, which seem almost incredible, serve to illustrate the great amount of energy contained in large waves, and to show that this energy results in powerful forces destructive to offshore installation~ which are not designed sufficiently strong to withstand wave attack. In the past the expected frequencies of waves having various characteristic.% have rarely been considered in the design of structure affected by wave action. As a result, many structures have failed to accomplish the purpose for which they were designed or have collapsed under wave attack. Others have been constructed to withstand greater wave energy than is ever encountered, with resulting waste of material and construction time. In this study an analysis is made of the frequencies of waves having different characteristics which affect the plans for offshore drilling installations. After such an analysis the erection of these structures can proceed with less risk involved and with more efficiency and economy. ENGINEERING ASPECTS In the offshore drilling program wave forces play an extremely important part in design and construction of drilling rigs in shallow water. The design of a platform or other structure from which drilling equipment is operated is critical, becauze any damage to the platform may endanger personnel and result in complete loss of equipment. Since a platform built too close to the water would be battered by breakers, and one built unnecessarily high would involve undue expense, it is necessary to know the most desirable elevation at which the platform should be erected. This is only one of many questions about structural planning which can be answered using existing technique for determining wave characteristics. The purpose of efficient design for the portions of many types of offshore structures which are acted upon by wave forces is the same as that of all designs which deal with frictional forces of a fluid on a solid. For these structures the problem is comparable to that encountered by undersea craft moving through water, except that in the case of a fixed structure the force is produced by the water moving past the model. For off shore sructures which are extremely rigid the frictional forces may be nearly negligible compared with the impact or shock forces imparted by breaking waves. In all case; the better design is that which offers the least resistance to the opposing forces. From a consideration of wave forces, each drilling structure varies in efficiency depending upon the type and amount of superstructure in contact with the waves. For example, round piling and bracing offer less resistance to wave forces than do I-shaped ones. All network superstructure such as cross bracing should be kept to a minimum and at as low an elevation as possible, so that it will not expecience the pressure exerted at the tops of breaking waves. Models of proposed structures can be tested in wave tanks and in the field to ascertain the efficiency of specific designs. Past experience in beach and shoreline engineering has shown that, although changes in the topography of the bottom very near shore do not seem to be occurring, the natural forces involved may be in a delicate balance such that a static state exists. Interruptions of any of these natural forces by erecting offshore structures are likely to cause undesirable effects. Changes in beach profile result partly from sediment being brought into suspension by the orbital motion of waves and partly from the transport of sediment by longshore currents. With the erection of an offshore structure and consequent change in the combined effects of these two forces, unfavorable deposition upon, or erosion of, the bottom at the site may occur. Therefore, combination wave and current studies are essential for the solution of problems involved in the design of most marine structures. TECHNIQUE FOR OBTAINING WAVE INFORMATION In determining the probable effect of wave action on an offshore drilling structure, it is first necessary to know the usual frequencies of certain wave types for the given location. A technique has been developed which provides a means for obtaining information about wave characteristics in the

Jan 1, 1949

By C. O. Burgess, W. D. Forgeng

DESPITE the increasing interest in and the technical importance of iron-chromium-manganese alloys, very little published information is available regarding their constitution. F. M. Becket's paper1 in 1930 represents the first correlated effort in the field of these alloys. The paper served particularly to draw attention to the commercial possibilities of iron-rich alloys containing chromium and manganese in balanced proportions. The duplex structure of alloys within the commercial range was briefly discussed, but exposition of their structural constitution was necessarily limited because the physical properties and corrosion resistance of the alloys were the main subjects of the paper. Both prior to and following the publication of F. M. Becket's paper, and at his instigation, an extensive investigation of the constitution of iron-chromium-manganese alloys of commercial purity was in progress at the Union Carbide and Carbon Research Laboratories, Inc. The present paper is based on the results of that investigation. In the last few years, investigations covering various portions of this alloy system have also been made in Europe. W. Koester briefly mentioned the effect of annealing on chromium-manganese steel2 and later3 constructed approximate sections of the iron-chromium-manganese equilibrium diagram. M. Schmidt and H. Legat14 even more recently studied this system, and their article and conclusions are of interest as representing an entirely independent study of a number of iron-chromium-manganese alloys. Koester's sections are shown in Fig. 1. The figures summarize the effect of manganese additions to iron alloys containing 5, 10, 15 and 20 per cent Cr as well as the effect of increasing chromium content on iron alloys containing 3, 8, 20 and 30 per cent Mn. These diagrams, within their composition limits, substantiated in some measure the results of our investigation. However, in our work some differences as regards the position of the mixed alpha-gamma fields were found as compared to Koester's work, and we were able to detect the presence of

Jan 1, 1938

By G. Sachs, L. J. Ebert, W. F. Brown

INTRODUCTION ISOTHERMAL transformation, or "austempering," of a carbon-containing austenite at elevated temperatures yields so-called "intermediate products." Their structure and properties are, for a given hardness, rather different from those of "tempered martensite" obtained on conventional quenching and tempering.1 Several investigators2,3 have found that for high carbon and slightly alloyed steels the intermediate products formed at temperatures close to that of the martensite reaction possess strength properties superior to those of tempered martensite. The structure of these low temperature, intermediate products is generally acicular (bainite) but clearly different from that of martensite. However, at higher austempering temperatures, between 1000 and 1300°F (540 and 700°C) carbon steels were found to exhibit a rather low ductility.4-5 Thus notch bar tensile tests showed the ratio between notch strength and regular tensile strength to decrease with increasing austempering temperature. For ductilities below a few percent this notch strength ratio is a measure of ductility, according to investigations on low alloy steels.6-7 Furthermore the presence of intermediate products formed unintentionally on quenching was considered as responsible for the low ductility and impact energy of some heat treated steels.8 These intermediate products could result from partial transformation at the so-called "nose-temperature" where the rate of the transformation is a maximum. Tempering improved such mixtures of martensite and intermediate products, their properties approaching those of tempered martensite of equal hardness. The following investigation constitutes an attempt to determine certain strength properties of a partially austempered and subsequently quenched low alloy steel, namely, a chromium steel (SAE 5140). The structures formed by such a treatment should consist of a mixture of intermediate products formed on austempering and a martensite formed on oil quenching from the austempering temperature. It was intended, by varying the austempering time, to vary the quantity of the intermediate products between zero and 100 pct. The austempering temperature of 860°F was selected after extensive preliminary tests close to the nose-temperature. Austempering at this temperature yielded an acicular intermediate product. Additional tests under less exacting conditions were made for an austempering temperature of 950°F where the intermediate product appeared to be very fine pearlite. To determine the effects of tempering on structures containing various amounts of

Jan 1, 1948

By Norman Brown, J. V. Rinnovatore

It was found that a shear stress applied during the recovery had no effect on the amount of recovery if the stress was less than the instantaneous yield point irrespective of the direction of the stress. Large ajplied stresses during recovery had a marked effect, which depended on the direction of stressing. Single strain reversals at -72°C not only produced the Bausch-inger effect but also increased the flow stress. The increase inflow stress was attributed to vacancies, which have appreciable mobility at -72 °C. THEORIES I-' of recovery suggest that the internal stress field of the dislocations plays an essential role. Most investigations of recovery use time and temperature as the independent variables; however, here stress has been introduced as a variable in two ways: 1) by varying the internal stress field according to the amount of strain prior to recovery and 2) by applying an external stress during recovery. Tannen- baum and Kauzrnann studied the effect of applying a stress during recovery by measuring the change in creep rate after recovery; they found that stresses as high as 95 pct of the creep stress had no effect on recovery. Earlier, Wood and scrutton6 showed that an applied stress during creep increased the rate of poly-gonization. The experiment by Wood involved poly-crystalline aluminum whereas Tannenbaum and Kauzmann used a single crystal of zinc. In this investigation, zinc single crystals were used and deformed in a manner to prevent polygonization. Thus, the main difference between this investigation and that of Tannenbaum and Kauzmann is the use of the stress-strain curve instead of creep rate as the index of recovery. In addition, the applied stress during recovery varied

Jan 1, 1961

By Harry L. McNeill

THE Selective Media Process was developed by the author in a laboratory provided by The Steårns-Roger Manufacturing Co. It is the outcome of an [ ] investigation into the possibilities of coarse beneficiation by sink and float without using the conventional heavy media. Commercial work to date has been limited to the treatment of minus 3/8-in. iron ore at the Hill Trumbull washing plant of the Cleveland Cliffs Iron Co., at Calumet, Minnesota. Two cut away prints of the machine are shown (Figs. I and 2). A rotary conical impeller is mounted within a stationary cone (Fig. 2). This impeller is adjustable vertically by a 12-ton screw jack. The speed of the impeller can be varied from 14 to 32 r.p.m. by the Reeves variable-speed motor pulley mounted on the 7 ½ -hp. motor drive. Attached to the bottom of the stationary cone is the automatic control valve for sink product, actuated by a ¼ -hp. gear motor. The sink product is dewatered in a conventional drag driven by a 7 ½ -hp. motor and discharged onto an inclined conveyor containing from 6 to 10 per cent moisture. Two plants are operated at the Hill Trumbull property. All the ore is first treated in a typical washing plant (Fig. 3). When treating "wash ore" a finished concentrate can be produced by the log washers and Akins classifiers, as the separation involves only fine silica (minus 48-mesh) and free iron. However, when "jig ore" is fed to the washing plant the coarse

Jan 1, 1946

By Samuel S. Wyer

The following description of methods for conducting gas-producer tests is probably the first attempt to give the subject an analytical, thorough and comprehensive treatment. In some cases where tests have been made, the methods have been so unsystematic and ambiguous that it has been impossible to secure comparable results. To eliminate this difficulty, the following provisional code of gas-producer tests— which has some resemblance to the code of boiler-trials of the American Society of MechanicalEngineers—has been developed. The primary object in testing a gas-producer is to determine whether the producer is working satisfactorily or, what is the same thing, to see if the efficiency is as high as it should be with the type of producer in question; and also to find out if the composition of the resulting gas is adapted to the work it has to do. In order that the test shall be of any value, it must be thorough and comprehensive, and must be conducted with skill and care. When so conducted, the test will reveal the economy of the'producer; and, by making suitable changes, the efficiency will often be increased very much. As a result of the tests made by Jenkins,' the efficiency was raised from 56.2

Jan 1, 1906

By S. F. Reiter

The paper presents isothermal recrystallization curves for 0.08 and 0.15 pct C steel at subcritical temperatures following small amounts of plastic deformation. The effects of deformation, temperature, and aging on nucleation and growth rates ore described. The free energy of activation for grain boundary migration in steel is given. SEVERAL excellent reviews of the literature have appeared concerning the recrystallization of metals.'-' The present investigation follows the approach advanced by Mehl, Stanley, and Anderson,6-7 in which the rate of recrystallization was analyzed in terms of N, the rate of nucleation, and G, the rate of growth of recrystallization nuclei. Two lots of low carbon, capped steel of the analysis given in Table I were studied. Each lot consisted of a 150 lb coil which had been hot rolled to 0.083 in. and then cold rolled to 0.042 in. at the mill. Strips 0.930 in. wide were sheared perpendicular to the rolling direction. Both steels were normalized before studying their recrystallization characteristics. The strips were cleaned, painted with a magnesia-acetone paste, and made into packs of equal weight, wrapped in 0.002 in. copper foil. The packs were placed in a salt bath at 900°C for 30 min and air cooled. A relief anneal followed in a second salt bath for 15 min at 650°C. The relief anneal was found necessary from early tests in which a longer incubation period and slower rate of recrystallization were observed in relief-annealed lot A steel than in similar material which was strained and recrystallized directly after being normalized. This effect, which indicates the presence of transformation and/or cooling stresses in steel air cooled from above the A, temperature, has also been observed by Samuels8 and Masing.9 Figs. 1 and 2 show the microstructure of lot A and B materials and illustrate the rather uniform No. 8 ASTM grain size produced by this heat treatment. Winlock and Leiter10 observed that strip specimens which had their sharp edges removed elongated more uniformly than those which were not polished. Similarly, when the sheared edges were removed on a belt grinder, it was found in the present investigation that such samples recrystallized more uniformly than did unpolished strips. Therefore, all strips were carefully rounded prior to their extension. The approximate strain limits for the production of large recrystallized grains are from 6 to 12 pct extension." It was found that for the purpose of this investigation, 8 and 9 pct elongation were suitable deformations. The strain rate employed was 0.01 in. per in. per min and produced a yield point elongation of 4 pct. Winlock and Leiter found that mild steel of No. 8 ASTM grain size gave the same yield point elongation when extended at 0.012 in. per in. per min. All of the lot A and B strips extended in tension developed a straight, stretcher strain line at each grip when the upper yield point was reached. The lines were parallel and made an angle of 55" with the edge of the strip. They approached each other with increasing strain and met near the center of the sample at the end of the yield point elongation. Immediately thereafter, a small drop in load was observed and then the load increased in a regular manner with increasing extension. The grips were initially 8 in. apart. After extension, the 6 in. gage length was carefully cut into 1 in. samples. The remainder of the strip was discarded. After a flash pickle in hot 50-50 hydrochloric acid, six samples, each of which had been taken from a different strip, were placed in a basket and submerged in a lead pot for isothermal recrystallization. Although no recovery effect was observed, strain aging did occur after extension. Therefore, samples were always recrystallized within 24 hr after their cold deformation. After recrystallization, the samples were etched with a solution comprised of one part by volume of nitric acid with three parts of water. Bromide printing paper was exposed directly at low magnifications and later used with a mask to measure the desired quantities. First, the average diameter of the largest grain visible in each sample was determined using dividers. Next, the number of recrystallized grains per unit area was counted and recorded as n. Then, for each sample, the combined area of the recrystallized grains was measured by transcribing the grain outlines to standard graph paper. Many determinations of the area of the recrystallized grains were repeated five times and indicated a standard error that was not greater than 25 pct. The average area for six samples was divided by the area of the mask to yield the percentage recrystallized. Recrystallization of 0.08 Pct C Steel The progress of recrystallization at 670°C after 8 pct elongation of lot A steel is shown in Fig. 3, a through f. The shapes of the growing crystals are approximately equiaxed, as is assumed in the

Jan 1, 1953

By James Norman

SEPARATION of minerals by froth flotation is rightly called an art. It can truthfully be said that no two ores separate in the same way. The difference in results obtained when natural and synthetic mixtures of minerals are separated is so great that such tests frequently have been worthless in attempting to select conditions in which a natural mixture will separate. With a few rare exceptions, the natural mixture is much more difficult to treat than a synthetic mixture, and a much poorer separation is obtained. Perhaps several experimenters have wondered why 10 or 20 per cent of a mineral being floated from an ore does not float and is different from the 90 or 80 per cent that is recovered. In experimental tests on pure sphalerite, observers1 have noted that varying amounts of sphalerite may be froth-floated with pine oil alone, the amount recovered in the froth depending apparently upon the source of the sulphide. The only explanation of results such as these, barring insufficiency of frother or time of flotation, is that the surface of the mineral floated is different from that of the mineral depressed. This difference often has been found to be caused by natural contamination of mineral surfaces, apparently brought about by weathering and exposure to natural solu-tions. There is virtually no rock that is absolutely unweathered. One of the writers had an exceedingly instructive experience in 1931 while working with United Verde copper-zinc iron sulphide ore in Arizona. Nonselective flotation of chalcopyrite and sphalerite away from some of the pyrite was all that could be accomplished. All known depressants produced only slight effect. Sodium cyanide showed some effect, but so much had to be used that only a small amount of chalcopyrite could be

Jan 1, 1939

By John S. Crandall

The mineral garnet, while ordinarily considered a semiprecious gem stone or a second-grade industrial gem, has also proved itself in the field of industrial abrasives. Its use is well known as a sand-paper grain, and as a sandblasting sand its qualities are rapidly becoming recognized in more and more industries. Production of garnet as an abrasive is confined chiefly to two areas in the United States, North Creek, N. Y., where the Barton Mines Corp. operates, and Emerald Creek, Benewah County, Idaho, where the Garnet Mines, Inc., and the Idaho Garnet Abrasive Co. with mills at Fernwood, Idaho, operate. This paper is confined to a discussion of production and marketing of garnet sand by Idaho Garnet Abrasive Co.

Jan 5, 1950

By Bunting S. Crocker

Bunting S. Crocker (Executive Vice President, Kilborn Engineering Ltd., Toronto, Ont., Canada)-This is an interesting report on laboratory-scale testing with pebble charges in 12-in.-diam mills, and the author correctly concludes that useful laboratory testing can be done. In the opening paragraphs he states, "laboratory pebble-milling tests have been considered too difficult to perform and not relevant enough to the actual grinding situation"!! This is definitely not so! The writer published detailed tests done in a 12-in.-diam mill comparing pebble and steel balls in 1952 6 and again in 1954 7. We note that our review paper in 1963 was the only one mentioned in the References. The author states that "a smooth lining is more frequently used in commercial-scale pebble grinding." The writer has designed some 22 plants treating 134,000 tpd in North America and Australia. He has also visited pebble installations in Norway, Sweden, Finland, and South Africa. All these plants correctly use heavier lifters than would be considered standard for ball mills of a similar size. Smooth liners are not recommended in wet ore treating plants. In the 1952 paper6 it was clearly demonstrated in the test work that the individual ore pebbles had to be the same weight-not the same diameter or size-as the steel balls if comparable grinding results were to be obtained. In the tests performed in this study most of the pebbles "passed 50-mm round hole screen openings and remained on a 40-mm round hole sieve. Correspondingly most of the ball mill experiments were performed with 50 or 40-mm steel balls". Thus, the balls and pebbles were essentially the same size or diameter. This means we are comparing apples and oranges. When the feed being ground is fine enough the pebbles will be superior. When the feed is coarse the steel balls will be the better. This is similar to grinding tests in which two sizes of steel balls are compared. In the middle of the article, "Crocker5 has reported that equal weights of pebbles and steel balls achieve the same grinding capacities under similar conditions …", then he proceeds to question this postulate. In the eight reports that I have published, I have never made this statement. What I have said is "for comparable grinding, the individual pebbles in the mill charge should be the same weight as the individual steel balls." This is not the first time that I have been misquoted on this point! It is most unfortunate that this test work has been done with a ball and pebble of the same diameter and not the same weight. It is impossible to properly evaluate the results. I also regret the fact that the screen analyses of the tests were not shown. Many of us who have been 40 years or less in the grinding game can easily read screen analyses at a glance. We can tell whether the top meshes are being ground by the ball charge, etc., etc. The graphs are fine for the summary or to illustrate conclusions but are often misleading in the report itself. However, we do agree that useful pebble grinding tests can be done in a 12-in. mill.

Jan 1, 1973

By H. S. Munroe

AN elaborate discussion under this heading formed a chapter in one of the reports made by Professor Raymond as Commissioner of Mining Statistics.* In a subsequent report- was printed a paper, by Mr. William Main, Jr., of Columbia, South Carolina, containing a theoretical investigation into the effect of the velocity of impact on the effective ditty of stamps. A visit to the Lake Superior copper region last summer suggested an inquiry into the relative efficiency and economy of the enormous steam stamps of the copper-mills, as compared with the results obtained with the cant and tappet stamps commonly used in the West. The atmospheric stamp used at the Phoenix Mill promised to add interest to the inquiry, as giving an example of unusually high speed, this stamp making 160 drops per minute. In introducing his subject Dr. Raymond makes the following remarks, which are quite apropos of the present investigation : "In considering the economical application of stamping machinery, we meet, at- the beginning, with serious difficulties in obtaining accurate data for comparison. The weight and fall of stamps vary as the shoes and dies wear out; and this may lead to a change of speed also. Moreover, defects in engines, boilers, or machinery for the transmission of power, may occasion serious losses, which cannot fairly be charged to the arrangements of the stamps proper. Again, the capacity of stamp-mills is directly dependent, in some degree, upon the nature and extent of discharge, fineness of screens, and other peculiarities of the battery. Finally the hardness and tenacity of the rock crushed varies so much that comparisons between different localities cannot be implicitly trusted. The safest experiments are those made in the same mill, by changing first one and then another condition of working; but this is seldom possible for such * Mineral Resources West of the Rocky Mountains, 1871, p. 380. †- Mineral Resources West of the Rocky Mountains,, 1873, p. 345.

Jan 1, 1881

By S. F. Emmons

" The obscurity which still veils from us the true nature of veins will become more and more cleared up when they can be considered in connection with the geological structure of the regions in which they occur."* These words, according to Lossen, the biographer of the late Dr. A. von Groddeck, of Clausthal, were the last received by him from that eminent man, perhaps the most far-sighted and carefully progressive of recent writers on ore-deposits. They seem to me to form a fitting text for what I am about to say; since I find that many of the conclusions at which I have arrived by my own study of the structural relations of ore-deposits, or, in other words, of the structural and dynamic geology of the regions in which they occur in this country, have been similarly determined by him within recent years in Europe, and especially in his home field of work, the Hartz. I shall not enter upon a detailed account of how far other workers may have arrived at similar conclusions with myself, since these questions of priority are of little interest, except to those immediately concerned; but will briefly present the methods by which, in my work in this country, I have arrived at certain generalizations, and will point out the practical bearing which they may have upon the work of mining engineers. In my first thorough and systematic examination of an important group of ore-deposits, viz., that of Leadville, Colorado, I was enabled, through the generous facilities afforded me by the then Director of the Geological Survey, Mr. Clarence King, to make a most elaborate and detailed study of the geology, not only of the immediate vicinity of the mines, but of the adjacent mountain regions, based upon accurate topographical and underground maps, and

Jan 1, 1888

By H. S. Geismer

Campbell,' in 1896 said: "The Birmingham district in Alabama has certain great advantages for there are few places in the world where fuel and ore are so near together, although, unfortunately, both are of inferior quality; the ore being low in iron and high in phosphorus and the coal giving a weak and impure coke." This statement could not have been questioned in 1894, but by 1896 several Robinson-Ramsay washers had been put into operation and weak and impure coke was a thing of the past. The Warrior coal field of Alabama contains six seams that yield coking coal of excellent quality. In descending order, they are Brookwood, Milldale, Pratt, America, Mary Lee, and Black Creek. In each of these, however, bands of rock and bone coal of varying thickness are stratified with the coal; and while some of these impurities can be separated from the coal by the miner, much of it must be loaded out with the coal. Consequently, unless the coal is washed before being coked, it will yield a coke of varying ash and sulfur content quite unsatisfactory for blastfurnace use. At present, the Gulf States Steel Co. is producing run-of-mine coal at its Virginia mine, from the America seam, that is uniformly low enough in ash to permit of coking without washing, but this is the only exception to the above statement. Alabama was the first state to experiment seriously with coal washers, was the first to install washers on a large scale and, up to the present, has maintained the lead. The Alabama State Mine Inspector reports that during 1923 20,919,303 tons of bituminous coal was mined in Alabama; 12,858,499 tons of which was delivered to coal washers for treatment.

Jan 1, 1925

By H. H. Reamer, B. H. Sage

Attempts have been made to predict the volumetric and phase behavior of naturally occurring hydrocarbon mix-turesl-6 but these methods have not been extended to the higher pressures and tem-peratures that are currently encountered in some producing formations. Furthermore, the methods of prediction at present avail-able have not been tested in a sufficient number of cases to ensure their applica-bility to all naturally occurring hydrocar-bon mixtures, even at the lower pressures and temperatures. For these reasons the behavior of a number of hydrocarbon mix-tures from a field in which the subsurface pressures are above 4500 lb. per sq. in.t and the temperatures are in the neighbor-hood of 250°F. was investigated. Method The objective of this program was to determine the volumetric behavior of ma-terial as it existed in the reservoir as a function of pressure, temperature and com-position. Strictly speaking, this cannot be accomplished in any simple fashion. How- ever, the variations in composition that are encountered within a producing reservoir may be approximated roughly by means of mixtures made up of two arbitrarily chosen constituents. Experience indicates that the liquid and gas phases from a high-pressure gas trap afford a simple source of material for this purpose. Throughout this discus-sion the samples of the gas phase and liquid phase from the production trap will be called the "trap-gas sample" and the "trap-liquid sample," respectively. The volumetric behavior of both of the trap samples was determined throughout the temperature interval between 100" and 250°F. at pressures up to 5000 lb. per sq. in. In addition, the behavior of eight different mixtures containing varying proportions of the two trap samples was studied throughout the same temperature and pressure intervals. The experimental results yielded information concerning the specific volume of the material as a function of pressure, temperature and the relative quantity of the trap samples. The relative amount of each of the paraffin hydrocarbons of lower molecular weight than n-hexane was determined for each of the trap samples. In addition, the specific weight, viscosity and average molecular weight of the hexanes-and-heavier fraction of the trap-liquid sample were determined as well as similar information for each of five fractions separated from this material by distillation. From these data the weight fractions of each of the components from methane through pentane were determined for the trap samples and eight systematically chosen mixtures. Materials The gas and liquid samples were obtained from the production trap of a well in the Rio Bravo field in California during the fall of 1939. Information concerning the condi- 70

Jan 1, 1941

By H. H. Reamer, B. H. Sage

Attempts have been made to predict the volumetric and phase behavior of naturally occurring hydrocarbon mix-turesl-6 but these methods have not been extended to the higher pressures and tem-peratures that are currently encountered in some producing formations. Furthermore, the methods of prediction at present avail-able have not been tested in a sufficient number of cases to ensure their applica-bility to all naturally occurring hydrocar-bon mixtures, even at the lower pressures and temperatures. For these reasons the behavior of a number of hydrocarbon mix-tures from a field in which the subsurface pressures are above 4500 lb. per sq. in.t and the temperatures are in the neighbor-hood of 250°F. was investigated. Method The objective of this program was to determine the volumetric behavior of ma-terial as it existed in the reservoir as a function of pressure, temperature and com-position. Strictly speaking, this cannot be accomplished in any simple fashion. How- ever, the variations in composition that are encountered within a producing reservoir may be approximated roughly by means of mixtures made up of two arbitrarily chosen constituents. Experience indicates that the liquid and gas phases from a high-pressure gas trap afford a simple source of material for this purpose. Throughout this discus-sion the samples of the gas phase and liquid phase from the production trap will be called the "trap-gas sample" and the "trap-liquid sample," respectively. The volumetric behavior of both of the trap samples was determined throughout the temperature interval between 100" and 250°F. at pressures up to 5000 lb. per sq. in. In addition, the behavior of eight different mixtures containing varying proportions of the two trap samples was studied throughout the same temperature and pressure intervals. The experimental results yielded information concerning the specific volume of the material as a function of pressure, temperature and the relative quantity of the trap samples. The relative amount of each of the paraffin hydrocarbons of lower molecular weight than n-hexane was determined for each of the trap samples. In addition, the specific weight, viscosity and average molecular weight of the hexanes-and-heavier fraction of the trap-liquid sample were determined as well as similar information for each of five fractions separated from this material by distillation. From these data the weight fractions of each of the components from methane through pentane were determined for the trap samples and eight systematically chosen mixtures. Materials The gas and liquid samples were obtained from the production trap of a well in the Rio Bravo field in California during the fall of 1939. Information concerning the condi- 70

Jan 1, 1941

By Willard S. Morse

In my paper on "The Lixiviation of Silver-Ores by the Russell Process at Aspen, Colorado" (page 137 of the present volume), attention was called to the decrease in "chlorination " during the washing of the roasted ore with water, to remove soluble salts, before leaching with hyposulphite and Russell solutions. This decrease in " chlorination," which is due to conversion of the silver chloride to some other form not soluble in hyposulphite solutions, and which, for the sake of brevity, will be termed the "going-back" of chlorination, has been a serious obstacle to the successful operation of several leaching-works, and was at Aspen the only difficulty encountered. I have never seen any explanation of the cause of this failure to extract, in actual practice in the mill, the amount of silver chloride shown by laboratory-leachings to be present in the roasted ore; and the purpose of this paper is to record the conclusions arrived at concerning the cause of the phenomenon, and the data upon which they are based. The average decrease in chlorination by washing with water in the Aspen ores for a period of fourteen months was as follows:

Jan 1, 1896

By G. S. Brooks

(New York Meeting, February, 1913.) THE tendency of the oxides of such metals as aluminum, zinc, chromium, and calcium to form compounds at high temperatures with iron oxide is well established by past investigation. Data of this reaction, as developed in laboratory research, have been contributed by Burleigh, Hofman, and Wells, in America, and by many others abroad. A partial bibliography of the subject is appended. From these authorities we learn that the ferric oxide here has the function of an acid, giving in the case of ZnO a zinc ferrite, with a normal composition of ZnOFe2O3. This formation of zinc ferrite particularly affects the success of such processes as leaching or magnetic separation, and thus becomes practically important to the metallurgist. But the meager existing data do not entirely agree; and quantitative results from muffle-practice are conspicuously absent. Furthermore, it being of some general importance to the zinc smelter in both roasting and reduction, the following few notes of operations on a commercial scale are contributed

Jan 5, 1913

By Stuart McHugh, Douglas Keough

INTRODUCTION AND BACKGROUND Because of the potential for large reserves from increased production in the eastern Devonian shales, the Department of Energy (DOE), Morgantown Energy Technology Center (METC) selected these materials for the application and evaluation of existing and novel well stimulation techniques. One technique selected for further study was pulse tailoring, or tailored pulse loading, i.e., shaping the input borehole pressure history to produce a specific fracture pattern and to increase communication with the reservoir. The complexity and expense of in-situ mineback experiments prohibits direct evaluation of pulse tailoring in various geologic formations. An alternative approach used by SRI International consisted of evaluating fracture enhancement by computational simulations with supporting laboratory experiments and using data from field tests by other agencies to validate the computational model (McHugh and Keough, 1980). Laboratory experiments were conducted on core samples to determine fracture phenomenology and parameters and to verify material properties. The fracture parameters were obtained from posttest measurements of fracture distributions and correlation with stresses calculated by a wave propagation code. Model development was guided by these experiments and similar experiments in various materials performed by other agencies. The validity of the modeling, parameters, and scaling was evaluated by comparing fracture patterns from field tests with calculational simulations.

Jan 1, 1982

By J. H. Swisher

The rate of internal sulfidation of austenitic Fe-Ti alloys in H2S-H2 gas mixtures is controlled primarily by sulfur diffusion, with counterdiffusion of titanium playing a minor role. At temperatures below 1100°C, enhanced diffusion along grain boundaries becomes important. The rate of internal sulfidation at 1300°C is approximately equal to the rate computed from the sulfur diffusion coefficient. The diffusion coefficient of titanium in y iron has been determined from electron microprobe traces in the base alloy near the subscale interface. The solubility of sulfur in Fe-Ti alloys has been measured in the temperature range from 1150° to 1300°C. The equilibrium sulfur content is found to increase with titanium content, due to the large effect of titanium on the activity coefficient of sulfur. The Ti-S interaction becomes stronger as the temperature decreases. TITANIUM as an alloying element in stainless steels is an effective scavenger for interstitial impurities, carbon in particular. Titanium is known to form stable sulfides; however extensive thermodynamic data on the Ti-S system are not available. Schindlerova and Buzek1 have shown that the Ti-S interaction in liquid iron is moderately strong. There have been no previous studies of the Ti-S interaction in solid iron. Internal sulfidation of Fe-Mn alloys was the subject of a recent investigation by Herrnstein.2 He found the rate of internal sulfidation to be an order of magnitude greater than predicted from available solubility and diffusivity data. A satisfactory explanation for the discrepancy could not be given. In the present study, the solubility of sulfur in austenitic Fe-Ti alloys was measured using a standard gas equilibration technique. Fe-Ti alloy specimens were also internally sulfidized. The rate of internal sulfidation was measured as a function of temperature and alloy composition. Supplementary electron micro-probe measurements were made to provide additional information on the nature of the internal sulfidation process. EXPERIMENTAL The starting materials were alloys containing 0.12, 0.24, 0.38, and 0.54 wt pct Ti. The alloys were made in an induction furnace by adding titanium to electrolytic iron that previously had been vacuum-carbon-deoxidized. The major impurity in the alloys as determined by chemical analysis was carbon. The carbon content of the alloys averaged about 100 ppm; metallic impurities were presented in concentrations of 50 ppm or less. Specimens were made in the form of flat plates, 0.03 by 2 by 4 cm for the equilibrium measurements and 0.5 by 1.5 by 3 cm for the rate measurements. The experiments were performed in a vertical resistance furnace wound with molybdenum wire and containing a recrystallized alumina reaction tube. In the gas train, flow rates of the reacting gases were measured using capillary flow meters. The source of H2S was a mixture of approximately 2 pct H2S in H2, which was obtained in cylinders from the Matheson Co. A chemical analysis was provided with each cylinder. The H2-H2S mixture was diluted with additional hydrogen to obtain the desired ratio of H2S to H2, and the resulting mixture was diluted with 30 pct Ar to minimize thermal segregation of H2S in the furnace. Argon was purified by passage over copper chips at 350°C and subsequently over anhydrone. Hydrogen was purified by passage over platinized asbestos at 450°C and then over anhydrone. The H2-H2S mixture was purified by passage over platinized asbestos and then over Pas. The samples used in the solubility measurements were analyzed for sulfur by combustion and iodometric titration. The subscale thickness in the internally sulfidized samples was measured on a polished cross section, using a microscope with a micrometer stage. Electron microprobe traces for titanium in solution were made on several samples that had been internally sulfidized. A Cambridge microanalyzer was used, and the known titanium content at the center of the specimen was used as a calibration standard. The procedure for the microprobe measurements will be described further when the results are presented. RESULTS AND DISCUSSION Equilibrium Data. Fig. 1 shows the sulfur concentration as a function of gas composition for three alloys equilibrated at 1300°C. The dashed line is based on data published by Turkdogan, Ignatowicz, and pearson3 for pure iron. The breaks in the curves are the saturation points for the alloys. The fact that the initial slope decreases with increasing titanium content indicates that titanium interacts strongly with sulfur in solution. To obtain information on the composition of the precipitating sulfide phase, the measurements described in Fig. 1 were extended to higher sulfur partial pressures. These results are shown in Fig. 2. (The initial portions of the curves are reproduced from Fig. 1.) The highest PH2s /pH2 ratio used is believed to be below the ratio required for the formation of a liquid sulfide phase. Time series experiments were used to study the approach to equilibrium in the samples. It was found that equilibrium with the gas phase was reached in less than 4 hr at 1300°C.

Jan 1, 1969

By W. M. Robertson

The rate of crack Propagation thvough a solid meta1 in the presence of a liquid metal has been calculated. The crack is assumed to propagate by solution of the solid in the liquid under the influence of an applied stress, with volume diffusion of the dissolved solute through the liquid controlling the propagation. The calculated velocities can be tens of centimeters per second or higher. THE embrittlement of normally ductile solid metals by liquid metals has been the subject of extensive study, as summarized in the book by Rostoker, McCaughey, and arkuus.' In experimental studies of liquid-metal embrittlement it is usually concluded that the observed crack-propagation rates are too high to be accounted for by diffusion processes. Diffusion is considered to be an unimportant factor and various other mechanisms are invoked to account for the experimental observations. The similarities of liquid-metal embrittlement to stress-corrosion cracking, to hydrogen embrittlement of steel, and to low-temperature embrittlement of bcc metals are frequently used as analogies for these mechanisms.1"3 The present paper assesses how rapidly a crack could propagate by a mechanism of volume diffusion through the liquid metal. We assume that the crack propagates by solution of the solid in the liquid at the crack tip under the influence of the applied stress and diffusion of the dissolved solute away from the crack tip. The model uses only macroscopic thermodynamic, kinetic, and elastic concepts. The calculations indicate that this dissolution-diffusion mechanism can give high crack velocities. In some previous treatments4'' of crack propagation in a liquid-metal environment the fundamental step has been the breaking of atomic bonds at the crack tip. The liquid greatly decreases the energy necessary to break these bonds. The present model assumes the crack is filled with liquid metal; the presence of the liquid is essential because diffusion through the liquid is assumed to control the rate of propagation. With proper modification this model could also apply to stress corrosion in a liquid environment. THEORY Consider a crack in a homogeneous elastic continuum, ignoring all the structural details of the solid. This neglects a host of metallurgical details which can be significant in the problem of liquid-metal embrittlement;' but this simple assumption is a useful approach in evaluating the role of diffusion through the liquid. The stress distribution around the crack tip establishes a gradient in the chemical potential at the tip, which causes a diffusion flux through the liquid away from the tip. The solid-liquid interfacial tension works against crack propagation, since propagation requires creation of interfacial area. From these two considerations we derive the diffusion flux, which then yields an expression for the velocity of the crack tip. The concentration of the solute in the liquid, C, is equal to the equilibrium concentration in the presence of an unstressed, flat surface, Co, plus the excess concentration due to the stress, AC(a), plus the excess concentration due to capillarity, AC(y): We calculate AC(o) and AC(y) and then obtain the diffusion flux. Consider (Fig. 1) a long flat crack of length 2L, thickness 2r, and tip radius r, where r remains constant as the crack propagates in the positive x direction. There is no stress ay in the y direction across the flat surfaces of the crack. The magnitude of the stress at the crack tip due to the applied stress, a,, is given by the relation6 ^=^[l-2^] 12] which, for long narrow cracks, becomes The stress increases the chemical potential in proportion to the strain energy.? The excess chemical potential due to the stress, Ap(a), is given by where 52 is the atomic volume of the solid and E the Young's modulus. Inserting Eq. [3] gives Now consider the crack to be filled with a liquid metal. The excess solubility due to stress, hC(a), is given by the excess chemical potential due to capillarity, Ap(y), is given by8 where y is the solid-liquid interfacial energy, and v1 and YZ are the two principal radii of curvature of any surface point. At the crack tip, r1 = -r and vz = m, so TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AIME

Jan 1, 1967