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By T. E. Watkins, M. D. Nelson

INTRODUCTION Deeper drilling for oil is becoming more and more the rule rather than the exception. With deeper drilling come additional problems, perhaps the greatest being those brought on by the higher temperatures encountered down the hole. particularly in the Gulf Coast region of Texas and Louisiana. Temperature gradients of the order of 1.8° to 2.0°F/100 ft are not unusual, and a gradient of 2.3"F.'100 ft is found in some areas of Texas. With a mean surface temperature of 74oF, the following temperatures could be expected for a geothermal gradient of 2.0°F; 100 ft: at 10,000 it. 271°F. 12,000 ft, 314°F: 14,000 ft, 354,oF; and 16.000 ft. 394°F. Severe gelation of lime-base drilling fluid in wells that have high bottom hole temperatures has become perhaps the most serious difficulty enconntered in drilling under such conditions. Lime-base drilling fluids have been very succesefully and widely used in the drilling of wells in the Gulf Coast region because of their inherent stability toward contaminants. their ability to suppress the swelling dispersion of bentonitic shales, and their ease of maintainance. The gradual recognition: during the past few years, that these muds were. in themselve. the cause of many difficulties experienced in drilling has led to wide-pread efforts by the drilling industry. to determine the reasons for the failure of these mud systems and to develop mud systems capable of performing satisfactorily under high-temperature conditios. MANIFESTATIONS OF HIGH-TEMPERATURE GELATION it is generally possible to recognize the symptons of high-temperature gelation early enough that advance predictions can be made of serious difficulties. in mud control, and the useful life of the drilling fluids can be extended by proper treatment. Following i.; a list of the manifestations of high-temperature gelation: (1) The drill string 'takes weight' while going in the hole after a trip. In early stages of high-temperature gelation it is possible to notice a slight reduction in drill string weight as the drill pipe is lowred near the bottom of the hole. (2) Excessive pump pressure is required to .tart the circulation of drilling fluid at or near the bottom of the hole when going hack to bottom after a trip. As the severity of the gelation increases it may be necessary to break circulation a number of times when going in the hole. (3) The drilling fluid from the bottom of the hole is thick and often granular or lumpy when pumped up after making a round trip. In a severely gelled drilling fluid system such a condition may be irreversible; that is, it cannot be stirred or chemically treated to produce a satisfactory drilling fluid. (4) Completion tool.. such as logging tools or perforating guns will not sink to the bottom of the hole. On some occasions completion tools will become stuck and require a fishing job to retrieve them if the wire line attached to them is broken. It is often difficult to determine whether the condition of the drilling fluid is responsible for sticking the tool or whether the wire line becomes key seated in a crooked hole and causes the allow difficulty. When there are 110 other symptoms of high-temperature gelation. then the difficulty may usually be attributed to the latter cause. (5) In extreme cases of high-temperature gelation it is necessary to "wash" and "ream" when going back to bottom after coming out of the hole. (6) In many -instance. it has been found to be extremely difficult and expensive to 1111 production packers 2nd tubing in moderately deep oil wells which had been drilled with a lime-base drilling fluid. In such instances-the original mud had apparently "set" to a consistency approaching that of a weak cement. CAUSES OF HIGH-TEMPERATURE GELATION Extensive test; have indicated that a lime-base mud does not develop a highly gelled condition at temperatures below 250°F. whereas above that temperature such condition often develops rapidly. (Fig. 1) concurrently. the following changes are evident ill the mud: (1) The alkalinity of the mud decreases to a very low value. with both caustic soda and lime being consumed. (2) The quartz content of the mud decreases sharply. (3) The bentonitic content of the mud decreases or di-appears, with concurrent decrease or loss of base exchange capacity of mud solids. (4) New compounds formed in the mud have been found to be cal-cium silicate, calcium aluminum silicate, and calcium sodium aluminum silicate. (5) The mud loses the ability to form a filter cake of low permeability. The above characteristics have been discussed, in part. by other authors

Jan 1, 1953

By J. H. Swisher

In measuvements of the solubility of nitrogen in fer-rilic Fe-P alloys, tile nitrogen solubility is found to be Less in pIrospliorus-bearing alloys than in pure iron. The reduction in solubility is about 20 pct in a 1.0 wt pct P alloy at 1300°C and about 30 pct in a 0.23 wt pct P alloy at 440°C. Diffusion coefficient measurements at 1150 and 585°C show that phosphorus also decreases the nitrogen diffusivity in iron. In previous work on the Fe-P-N system, phosphorus was found to reduce the nitrogen solubility in liquid iron slightly.&apos; Indirect evidence for similar behavior in a Fe at low temperature was obtained by Dickenscheid and Brauner.&apos; These authors found that phosphorus reduces the height of the internal-friction peak due to dissolved nitrogen. The results of Dickenscheid and Brauner were confirmed by J. C. Swartz of this Laboratory in a single internal-friction experiment using the same specimen stock as in the solubility measurements described below. In the present investigation, the solubility of nitrogen in a fer rite-stabilized Fe-1.0 wt pct P alloy was measured in the temperature range from 800" to 1300°C. Additional experiments were performed in the temperature range from 440° to 585°C, using an Fe-0.23 wt pct P alloy and NH3-H2 gas mixtures. EXPERIMENTAL The experiments were performed in a vertical tube furnace wound with platinum wire. For experimental temperatures of 800°C and above, a mixture of 5 pct Hz in N2 was used as the reacting gas. The gas mixture was prepurified from oxygen by passage over platinized asbestos at 450°C, and subsequently over anhydrone to remove water. Flow rates of the gases were measured with capillary flow meters. The temperature was measured before and after each experiment with a Pt/Pt-10 pct Rh thermocouple. The specimens used for the high-temperature solubility measurements were in the form of rectangular plates, 0.534 by 1.6 by 3.8 cm. The specimens were cleaned in trichloroethylene and annealed for 2 hr in hydrogen at the beginning of each experiment. In measuring the nitrogen solubility, the specimens were held in the reacting gas until equilibrated, then cooled in a water-cooled copper block at the bottom of the furnace. The time needed for equilibration at 1150°C was determined by measuring the average nitrogen content of the 1.0 pct P alloy as a function of reaction time. As will be described, the nitrogen diffusivity in the alloy at 1150°C is only slightly less than its calculated diffusivity in pure iron. At temperatures other than 1150°C, the reaction time used in measuring the nitrogen solubility was about twice the calculated equilibration time for pure iron at the same temperature. With a few exceptions, the procedure for the low-temperature solubility measurements was the same as that described above. The compositions of the NH3-H2 gas mixtures were determined by collecting gas samples from the gas train and analyzing them for NH3 by titration with HC1. The specimen thicknesses were less than those used for the high-temperature experiments, eg., 0.124 and 0.051 cm for measurements at 585° and 440°C, respectively. Nitrogen concentrations were obtained by chemical analysis, using the Kjeldahl method. The Fe-P alloys were made by adding ferrophos-phorus to electrolytic Plastiron (Type 104 A). Commercial ferrophosphorus, containing 3 pct Mn and 0.35 pct Si as the major impurities, was first purified by melting under an FeO slag. In a separate heat, the electrolytic iron was melted and vacuum-carbon-deoxidized prior to making the ferrophosphorus addition. The principal impurities and their concentrations in weight percent in the 1.0 pct P alloy are as follows: Mn, 0.01; Si, <0.01; C, 0.01; 0, 0.003; and N, 0.0012. The impurity levels in the 0.23 pct P alloy are con-

Jan 1, 1968

By WM. P. BLAKE

THE salt-beds at Salton, on the line of the Southern Pacific railway, in San Diego county, California, have been successfully worked for many years by the corporation known as the East Liverpool Salt Co., and the salt has been largely used upon the Pacific coast generally and in the interior. But the industry has lately been destroyed by the overflow from the Colorado river. The salt is dissolved, and the waves of the Salton sea now roll 50 ft. above the site of this once thriving and growing business. The salt-bed was evidently the residual accumulation from the waters of an ancient lake, which I have named Cahuilla, from the name by which a large part of the valley-the home of the Cahuilla tribe of Indians-is known. The deposit covered a comparatively small area in the lowest part of the valley, 280 ft. or more below the sea-level. This depressed area is now generally known as the Colorado desert, but has a soil of wonderful fertility wherever water can be had on its surface. The deserted beaches, and the water-lines, only a few feet above tide-level, upon the rocks of the bordering mountains, as well as a great abundance of shells in the soil, all bear decisive testimony to the former occupation of the valley by water. The depression is topographically the northern end of the Gulf of California, from which it is now separated by the delta of the Colorado river, extending practically from the mouth of the Gila river across the valley to the coast mountains on the west side. We may conclude that the imprisoned salt water was gradually displaced and freshened by the inflow and outflow of the river, so that the lake was changed to fresh or brackish water, with enough salt in it to give a bed at the bottom upon

Jan 1, 1908

By Eckhard Nembach

The phase diagram of the system Pb-In has been investigated between -27° and + 40°C, using nzainly X-ray dijfraction. In accordance with t her mo dynamic measurements by Heumann and Predel, a segregation occurs at low temperatures, though not in the form of a nziscibility gap. THE phase diagram of the system Pb-In has been the subject of extensive investigations,1&apos;1 but recently Heumann and prede13 concluded from their thermodynamic data that a new feature should occur below room temperature. These authors observed that the maximum values for the enthalpy and entropy of mixing, which occurred at a composition of 50 at. pct Pb, were +400 and —1.7 cal per g-atom deg, respectively. From this the authors estimated that a miscibility gap should occur below 30°C, centered at 50 at. pct Pb. Resistivity measurements seemed to support this view. These authors proposed the phase diagram outlined in Fig. 1. Three phases exist at 30°C: the tetragonal indium phase with c/a > 1, the tetragonal intermediate phase a, with c/a < 1, and the fcc lead phase. During an investigation of the superconducting properties of Pb-In alloys. it has been observed4 that aging a specimen with 50 at. pct Pb for 14 days at -18°C decreased the superconducting transition temperature about 0.13"K and tripled the transition width. In this paper, the results of an investigation of the Pb-In phase diagram in the temperature range from — 2T to +40°C are reported. Superconductivity and X-ray methods have been used. 1) SPECIMEN PREPARATION The materials were provided by the American Smelting and Refining Co. According to the manufacturer their purity was 99.999 pct. The weighed amounts of the constituents were sealed in quartz tubes under an atmosphere of 10 torr helium, mixed for 24 hr in a rocking furnace at 380°C, quenched in ice water, and homogenized at 20" to 30°C below the solidus line, established by Heumann and Predel. The annealing times were 144 hr for specimens containing Less than 30 at. pct Pb and 36 hr for the remainder. 2) SUPERCONDUCTIVITY EXPERIMENTS The specimens were quenched from the homogeniza-tion treatment into ice water and their superconducting transition temperatures T, measured. The procedure used has been described in Ref. 4. The transition was detected by the change of the mutual induc- tance of two coaxial coils containing the sample. T, was defined as the temperature at which 50 pct of the total change in inductance had occurred. The repro-ducibility with which T, could be measured was i0.002"K. Then the specimens with lead contents between 38 and 75 at. pct were aged for 7 days at temperatures between -30" and 40°C. If this treatment caused T, to change by more than 0.005"K or the width of the transition to increase by more than 0.002"K, it was concluded that the specimen had undergone a phase change and no longer consisted only of the fcc lead phase: as it did immediately after homogenizing. The result is shown in Fig. 2. From this one can estimate at what temperatures and concentrations phase changes occur. The X-ray measurements were based on these preliminary results. 3) X-RAY EXPERIMENTS Because of the softness of the material, relatively coarse powders. 75 p, had to be used, which were filed in a helium atmosphere from homogenized specimens. The powders were annealed at least 30 min at temperatures between 120" and 16OJC, depending on their concentration, and quenched in ice water. Then their X-ray patterns were taken at -178°C with a Picker diffractometer, model 3488K, and a cold stage. on which the specimen was in thermal contact with a liquid-nitrogen reservoir. In this way the following relation was established for the fcc lead phase: a = 4.697 + 0.00247C for 40 5 C 5 75 11 where n is the lattice constant (A) and C is the at. pct of lead. The coarseness of the powder made it impossible to use lines with 0 > 75 deg; therefore n was averaged from lines with 45 deg 5 0 5 75 deg. The results were reproducible to within i0.05 pct. Relation [I] is very similar to the one found by Heumann and Predel at room temperature. Following this, homogenized specimens with compositions between 15 and 56 at. pct Pb were aged for at least 10 days at temperatures between -27" and

Jan 1, 1970

By E. V. Potter

For a nurnber of years, it has been known that manganese made by electro-deposition under certain conditions is ductile while under other conditions it is very brittle. The ductile metal is gamma manganese normally stable only between 1100 and 1138°C1; the brittle metal is alpha manganese, stable up to 727OC. The ductile metal is not stable, but gradually changes to the brittle form; the time required to complete the transfornlation is about 20 days at room temperature. Other observations have indicated that the transformation is completed in 10 to 15 min. at about 125°C, while at — 10°C, no appreciable change occurs in 9 months. The properties of gainma and alpha Illanganese in the pure state are ordinarilj difficult to determine because the gamma structure cannot be retained by normal quenching procedures and alpha manganese is so brittle, it is difficult to obtain specimens free from flaws. In a recent investigation2 some properties of gamma and alpha manganese were determined by studying the ductile electrolytic metal and determining the changes in its properties as it transformed to the brittle alpha form. These investigations provided an excellent opportunity for following the progress of the transition and studying its mechanism. The results of a series of such investigations are reported in this paper. Procedure Various properties of manganese were determined starting with the metal in the original ductile gamma form and following the subsequent changes in its properties as the metal transformed to the brittle alpha form. These observations were made at various temperatures, the data providing information regartling the mechanism of the transformation as well as the effect of temperature 011 the transition rate. Structure and resistivity values gave the most significant results, so this paper is concerned primarily with them. The structure was studied microscopically as well as by X ray diffraction. The resistivity was determined on strips of the metal by measuring the potential drop across a given length of the specimen. Current was passed through the specimen by wires soldered to its ends, and the potential connections were made by wires looped around the specimen near its center. The current was determined by the potential drop across a standard resistor connected in series with the specimen, the potential drop being measured on a potentiometer. In the temperature range from room temperature to 100°C an ordinary drying oven was used to heat the specimen. This was entirely satisfactory except at 100°C, where the time required to heat the specimen was long compared to the transition time, making the initial section of the resistivity curve unsatisfactory. To overcome this limitation, at 100°C and higher a thermostatically controlled oil bath was used to heat the specimens. The block on which the specimen was mountetl was plunged into the hot oil at the start of each test. The heating time was thereby reduced from 5 min. to about 6 sec, and dependable resistivity values could be obtained through 160°C. At this point the whole transition, including the warm-up time for the specimen, required only about 20 sec and it was not considered worth while trying to extend the temperature range further. Aside from the heating problem, the problem of making a sufficient number of accurate resistivity determinations became more and more difficult as the temperature was raised. Using the manually operated potentiometer, 100°C was about as far as it was possible to go. At this temperature and above, a self-balancing photoelectric recording potentiometer was used. Its response was quite rapid, and it proved to be entirely satisfactory all the way through 160°C, where the tests were stopped because of the specimen heating problem rather than any limitation of the potentiometer recorder. The metal used in these tests was prepared at the Salt Lake City laboratory of the Bureau of Mines. The method of preparation is discussed in a paper by Schlain and Prater.3 The sheets were about 2 3/8 by 5 3/16 in. and varied from 10 to 16 mils in thickness. They could be cut readily into pieces suitable for the various tests. X ray and microstructure determinations were made on pieces about 1/8 to 1/4 in. wide and about 1 in. long, while resistivity measurements were made on strips as long as possible and about 55 in. wide. The thickness of each sheet was not uniform over all its surface. This had no bearing on the X ray and microstructure determinations, but sections as nearly uniform and free from flaws as possible were chosen for the resistivity determinations. The gamma manganese was electro-deposited at 30°C, the time of deposition ranging from 5 to 12 hr for each sheet. Whenever possible, the tests were started directly after the metal was stripped from the cathode; otherwise the sheet was placed immediately

Jan 1, 1950

By J. U. Messenger

A technique is described whereby the resistance of an emudian to breaking can be quantitatively determined. Produced ailfield emulsions are usually the water-in-oil type and, accordingly, do not conduct an electrical current. However, there is a threshold of A-C voltage pressure above which an emulsion will break and current will flow. The more stable an emulsion, the higher the required voltage. A Fann Emulsion Tester, modified so that low voltages (0 to 10 v) can be accurately measured, is suitable. This technique has application in evaluating the effect of a demuksifier on the stability of an emulsion. Emulsions can, in essence, be titrated with demulsifiers by adding a quuntity of demulsifier, stirring, and measuring the voltage required to cause current to flow. Any synergistic effect of two or more materials added simultaneously can be followed accurately. A demulsifier that significantly lowers the threshold voltage (from 100 to 400 v to 0 to 10 v for the emulsions in this study) is effective and can cause the enlulsion to break. A demulsifier that will bring about this drop in the threshold voltage at low concentration ir very desirable. The technique is also well adapted for rapidly screening demulsifiers. INTRODUCTION Stable emulsions in produced reservoir fluids resulting from certain well stimulation and completion procedures are common problems. The use of suitable demulsifiers can often mitigate these difficulties. At the present time, a rapid and efficient method for selecting satisfactory demulsifiers is not available. It is badly needed. Reliance is now placed primarily on trial-and-error procedures. A new test method has been developed which permits a more rapid and precise selection of demulsifiers. It involves measuring the electrical stability potential of an emulsion before and after a demulsifier has been added. This paper describes this method and shows where it should have application in field emulsion problems. NATURE OF OILFIELD EMULSIONS Two immiscible components must be present for an emuhion to form; we are concerned here with crude oil and water. An emulsifier must be present for tin emulsion to be stable. J Emulsifiers can be substances which are soluble in oil and /or mter and which lower interfacial tension. They can be colloidal solids such as bentonite, carbon, graphite, or asphalt which collect at the interface and are preferentially wet by one of these phases. Unrefined crude oils can contain both types of emulsifiers, A popular theory is that, of the two phases in an emulsion, the dispersed phase will be the one contributing most to the interfacial tension.&apos; Usually this phase contains the least amount of emulsifier. The stability of a water-in-oil emulsion is affected by the fol1owing: l) viscosity; (2) particle or droplet size; (3) interfacial tension between the phases; (4) phase-volume ratios; and (5) the difference in density between the phases. A stable emulsion is usually characterized by high-viscosity, small droplets, low interfacial tensions, small differences in density between its phases, and slow separatian of the phases. It also has low conductivity (high electrical stability potential). Water-in-oil and oil-in-water emulsions"&apos; are both common; however, oil field emulsions are predominantly water-in-oil emulsions. The emulsions which commonly occur during oompletion and stimulation operations contain a combination of several of the following: acids, fracturing fluids (oil, water, acid), and formation water and oil. Produced emulsions usually contain formation water and oil. Emulsions form in oil wells because oil and water are mixed together at a high rate of shear in the presence of a naturally occurring or unavoidably produced emulsifier. During the completion and stimulation of productive zones, and while formation fluids are being produced, oil and water are very often commingled. These mixtures are formed into emulsions by agitation which occurs when the fluids are pumped from the surface into the matrix of the formation or produced through the formation to the surface. Restrictions to flow (such as perforations, pumps, and chokes)".&apos;" increase the level of agitation; tight emulsions are more likely to form under these conditions. Often an emulsified droplet is an emulsion itself.&apos;" Therefore, emulsion-breaking problems can be quite complex. The complexity can be even greater if a third phase (gas) is included. Demulsifiers operate by tending to reverse the form of the emulsion. During this process, droplets of water become bigger, viscosity is lowered, color becomes darker, separation of the phases faster and electrical stability potential approaches zero. Any of these effects could be followed as a means of determining emulsion stability. However, electrical stability potential is the most reproducible and most easily measured parameter for following the stability of a water-in-oil emulsion.

Jan 1, 1966

By H. J. Tschirner, L. P. Davidson, R. K. Carpenter

HE electrolytic zinc plant of the American Zinc Co. of Illinois, at Monsanto, was expanded in 1943 to a capacity of 100 tons of slab zinc daily. This capacity was not attained because of inability of the leaching plant to deliver an adequate amount of solution for electrolysis. Changing the leaching method so that the acid was added to the roasted zinc material reversed the usual procedure and made it possible to attain the desired capacity. The conditions which prevented satisfactory work before this change and the difficulties which arose in reversing the usual leaching procedure are described. The "reverse" leach operation as now practiced is carried out as follows: All the calcine to be leached is fed continuously to a slurry mixing tank. About one third of the acid to be used is fed to the tank with the calcine. The slurry is discharged continuously to a Dorr duplex classifier in closed circuit with a Hardinge mill. The classifier overflow is pumped to any of six leaching tanks where the leach is completed. A finished leach is discharged through Allen-Sherman-Hoff pumps to Dorr thickeners, from which the overflow goes to the zinc dust purification and the underflow to vacuum filters. This change in leaching procedure from the usual one of adding calcine to a large amount of acid made it possible to provide an adequate amount of purified solution to the electrolyzing division and at the same time filter and dry all the residue produced. Operating savings in reagents and better metallurgical recoveries were also important benefits. The original flowsheet of the leaching plant provided leaching, sedimentation of the insoluble residue, and purification of the neutral zinc sulphate solution with zinc dust. The thickened residue was filtered and washed. The purification cake of excess zinc dust, precipitated copper and cadmium, and any insoluble residue was filtered off on plate-and-frame duplex classifier. Settlement in the thickeners was inadequate and the suspended solids in the thickener overflow gave rise to filtration difficulties after the zinc dust purification. Further, the filtration and washing of the leach residue was poor, and it became necessary to pump a large amount of unwashed or poorly washed residue to storage ponds outside the plant building. Two causes of the poor settling and filtration were determined: Soluble silica and ferrous iron in the calcine treated. The latter was a result of poor roasting and with more experience ceased to be a major problem. The silica was a normal constituent of the feed and the working out of the problem became a matter of controlling its solubility. The obvious method to render the silica insoluble was by intensive roasting. This, however, met with total failure as such roasting resulted in silicates, probably zinc, soluble in the 13 pct acid used for leaching. Attempts were made to coagulate the fine gelatinous slime with addition agents. Glue, lime, starch, beef-blood serum and others were tried without success. All the suggested tried-and-tested means of operating the thickeners gave no consistently good results. Variations in leaching time, in addition of calcine to the leaching tanks, "conditioning" of the pulp by prolonged agitation, immediate discharge of the leach upon completion to avoid breaking up flocs were all tried and given up as ineffective. Byron Marquis, of Singmaster and Breyer, worked with the plant staff on a beaker scale until a leaching procedure was developed which gave consistent results and a promise of overcoming the difficulties which had plagued the plant operation. It was suggested that the difference in solubility of silicates and zinc oxide in sulphuric acid could be made use of in a leaching method where the acidity was controlled carefully. Such control is possible when acid is added to a slurry of calcine. This process reverses the normal procedure of adding calcine to a vessel of acid, hence the term "reverse leach" was applied. In this way, the overall acid concentration can be kept very low. In the tests made, it did not exceed 0.05 g per liter free sulphuric acid. Numerous advantages were realized when no silicates were taken into solution and later precipitated as a bulky gel. The gel had made reasonable thickening and filtration of the leach pulp and practical drying of the residue impossible. When the gel was eliminated, thickening rates were increased as much as five times. The volume of residue after thickening represented about 10 pct of the total leach pulp and had been as high as 95 pct when the gel was present. The thickened pulp was filterable and the filtered cake was dried readily after washing. The zinc extraction from the calcine was slightly lower. This was more than compensated for by the increase in zinc recovered in solution from zinc which had been trapped in the gelatinous residue. The amount of copper recovered was lower. However, the amounts of other impurities, such as arsenic, antimony, and germanium, taken into solution were lower. This was particularly true of antimony. Since the inception of reverse leaching, no concentrates have failed to yield solutions free of antimony even when present in the calcine to the extent of 0.2 to 0.3 pct. Oxidation of ferrous iron is a problem of reverse leaching. Ferrous hydrate does not precipitate at pH 5.3 to 5.4 where a leach is finished. The usual oxida-

Jan 1, 1952

By T. S. Fuller

MUCH study has been given by engineers in general, and investigators in particular, to the concentration of stress which occurs under load in structural members having irregularities in section such as notches, shoulders, key ways, tool marks, etc. The result of the effect of both fresh and salt water corrosion upon the endurance properties of various metals and alloys has been ably determined and the general laws underlying these phenomena carefully pointed out by McAdam. From a practical standpoint, &apos;however, it is after all the endurance value of corroded, non-symmetrical sections which is most pertinent. In the experiments about to be described rotating cantilever specimens of nickel steel of the 3.5 per cent nickel &apos; 0.35 per cent carbon type have been used. These were machined from bars l 1/8. in. dia. and 9% in. long and were heat-treated by quenching in oil from 825 deg. C. followed by reheating to 650&apos; C. and oil quenching. The tensile and impact properties of this material so heat- treated follow:

Jan 1, 1931

By Michael P. Robinson

It has been suggested that streaming potentials are not nomlally logged because the streaming potentials known to be generated across mud filter cakes are substantially cancelled by streaming potentials generated in contiguous shale beds. Laboratory measuments of streaming poterztials acrons hand specirnens of shale have been adduced as evidence to support the suggestion. The experiments show that streanzing potential depends on the resistivity of the equilibrating solution and on pressure drop. Meizsurenlents were made perpendicular to the bedding planes of the shales. The mechanism of streaming potential generation in shale which the suggested cancellation theory iniplies has been critically examined. Conclusions reached are tested by comparing self potentials logged before and immediately after changing the resistil~ity (but not the weight) of mud in a borehole. The resultant SP change is found to equal the theoretical electrochetnical potential change, i.e., cancellation of .strearning potential is independent of mud resistivity. Since streaming po/entials generateal across mud filter cakes depend critically upon mud reistivity, shale .strearlling potential in situ must he equally sensitive. Using plausible values for the pemleahility, porosiy arzd compressibility of shale, the van Ererdingerl-Hurst approach shows that the pressure drop between horehole pressure and formation pressure in a radially honzogeneous shale is unlikely to coincide with the zone of filtrate invasion. If, perchance. this coincidence occurs with one mud a chatzge 10 a second must result in non-coincidence, i.e., a .YP logged in the second mud should show a streaming potenlial. The dilernrna may he overcome by postrrlating: (I) perrneabilities of shale7 parallel to their beddine planes greatly exceed their cross-bedding permeabilities; (2) a resistivity-sensitive mud cake of low permeability forms either on the face of, or probnhly in the lanlinations of, many shales. These postulates are examined with reference to the pres.sure and SP histories of the McClosky and Aux Vases zones in the Illinois Basin and some srcpport for them found. It is concluded that a definitive solultion to the streaming potential problem does not exist. INTRODUCTION Recently Gondouin and Scala&apos; published a contribution to the streaming potential problem which is notable particularly for the elegance of its experimental techniques. The conclusions drawn by Gondouin and Scala from their studies amplified those previously suggested by Schehck&apos;. In essence they suggested that the streaming potentials known to develop across mud filter cakes" are not normally observed on SP logs because they are largely cancelled by streaming potentials generated in adjacent shales. This suggestion appears so reasonable that many workers in the logging field will be prone to accept it. We incline strongly to the view that the suggestion is basically correct. Nevertheless, it is important to realize that the cancellation hypothesis in the form put forward by Gondouin and Scala does not appear to meet all the known experimental facts. It is the principal intention of this note to call attention to what appears to be a flaw in the relevancy of the experimental evidence adduced by Gondouin and Scala and to suggest an alternative hypothesis to remove it. The consequences of the new hypothesis are compared with field data which, we believe, are unique. A second but not less important purpose of this note is to emphasize that even the new hypothesis does not fully explain all field observations. Hence we conclude that further study of the streaming potential problem is required before it can be said that a definitive solution to it has been attained. The bare experimental bones of laboratory data on streaming potentials appear to be as follows. 1. A streaming potential is developed across a mud filter cake. This streaming potential is virtually independent of cake thickness but depends on the mud resistivity. The relationship is of the form, 2. A streaming potential is developed across a shale. This potential is independent of shale thickness but depends on the resistivity of the permeating solution if the shale has been first equilibrated in this solution. The relationship is of the form, The relationship in (1) was determined first by Wyllie3, confirmed by Gondouin and Scala and qualita-

By E. S. Bartlett, D. N. Williams

QUANTITATIVE values for the oxidation rate of unalloyed molybdenum in air at temperatures above the melting point (1460°F) of the characteristic oxide are contained in the literature as a result of previous investigations. Lustman&apos; reported values corresponding to 0.36 in. penetration per day (IPD) at 1500 and 1600°F in still air, noting essentially no variation in rate with temperature. Jones, Spretnak, and Speiser&apos; reported values corresponding to 0.14 and 0.13 IPD at 1500 and 1800°F, respectively, in still air, attributing the decreased oxidation rate at higher temperatures to a lesser accumulation of the corrosive molten oxide on the surface at the higher temperature as a result of increased volatilization rate. Harwood3 ecently summarized work in the field, presenting generalized data corresponding to 0.48 to 0.96 IPD at 1800°F and 0.55 to 0.83 IPD at 1700°F in slowly flowing air. In a recent program at Battelle, it became desirable to know more about the characteristic oxidation behavior of molybdenum under varying conditions of temperature and atmosphere. Using oxidation-test apparatus designed for dynamic, continuous recording of weight change during testing,&apos; values for the oxidation rate of molybdenum were obtained at temperatures from 1400 to 2150°F. In addition the effect of air flow on the oxidation rate was studied briefly at temperatures of 1600, 1800, and 2000°F. Exhaust of the contaminated atmosphere from the oxidation chamber was effected by an impeller pump attached to a 3/16-in.-diam opening in the oxidation chamber. The volumetric exhaust rate (cubic feet per hour) was normally maintained slightly in excess of the input rate to avoid condensation of MOO,,&apos; on the sample suspension rod. The entering atmosphere was preheated prior to admission to the oxidation chamber by a 1 1/2-in.-diam cup packed with shredded asbestos. The experimental data are presented in Table I. Comparing conditions 2 and 3 (taking into account the temperature difference) and conditions 8 and 9. shows that in the absence of forced exhaust an atmosphere of moving air results in greater oxidation rate than a stagnant atmosphere. The use of forced exhaust, as shown by comparing conditions 3 and 4 and conditions 14 and 15: resulted in an even greater increase in oxidation rate. By virtue of the size of the atmosphere input and exhaust openings, it was calculated that the exhaust velocity was about 60 times that of the input velocity for essentially equal volumetric flow rates. Because of the proximity (about 3/4 in.) of the exhaust port to the specimen, it is logical to assume that cleansing of the atmosphere immediately surrounding the specimen was accomplished much more efficiently by the exhaust flow than by the input flow at a constant-volumetric flow rate. Also, it can be seen by comparing conditions 4 through 7 and conditions 11 through 13 that increasing the rate of atmosphere flow (by increasing input velocity with a proportional increase in exhaust velocity) above some optimum value has little, if any, further effect on the oxidation rate. These results suggest that there is a maximum oxidation rate for molydenum at a given temperature which is obtained when conditions are maintained such that the partial pressure of MOO3 in the atmosphere surrounding the specimen is at a low value. By controlling the partial pressure of MOO, surrounding the sample, it is possible to control the rate of volatilization of MOO:, from the surface. This, in turn, affects the rate of oxidation, since the thickness of the MOO3 layer determines the amount of oxygen which will be able to reach the reaction surface.&apos; When the liquid oxide layer is less than some critical thickness, i.e., when the volatilization rate is high, enough oxygen is transported to the active surface to permit oxidation to proceed at the maximum rate allowed by the kinetics of the oxidation reaction. However, if the volatilization of MOO,, is suppressed, the thickness of the layer of MOO3 on the surface increases, and the diffusion of oxygen through the oxide layer becomes the rate-controlling step in the oxidation process. The lack of agreement between the present results and those of previous investigators is presumed to be due to differences in removal of the oxidation product (Moo,) from the immediate vicinity of the sample. By comparing conditions 1, 5, 10, 12 and 14, it is seen that when forced exhaust was used the oxidation rate of molybdenum increased with increasing temperature. A rapid increase was observed between 1400 and 1600°F, attributable to the effects

Jan 1, 1959

By D. G. Wilder

D.G. Wilder I found the suggestion that the amount of displacement of a fault can be numerically related to the thickness of gouge or breccia to be both intuitively satisfying and intriguing. I have long agreed that there is some type of relationship between the amount of gouge and the amount of displacement of faults. I congratulate the author for developing a numerical relationship between them. However, I am concerned that the limits for applying this relationship be fully understood. An underlying assumption in this approach is that there is either a uniform thickness of gouge or breccia along a given fault or the thickness does not vary widely. Since it is not always possible to confirm this, the displacements derived by this method should be viewed with caution unless significant fault extent can be observed. At the Nevada Test Site, in drifts constructed in granite for test emplacement of spent nuclear reactor fuel, we found a fault with 0.3 to 0.4 m (12 to 16 in.) of clay gouge. Within a few meters of this location, the fault had no clay gouge, but rather consisted of a highly fractured zone with significantly altered rock and some slickensides. Based on Fig. 1, the 0.3 to 0.4 m (12 to 16 in.) thickness of gouge would indicate a displacement in excess of 30 m (98 ft). However, no gouge thickness would indicate essentially no displacement. Based on a quartz vein that terminated on the fault, and is not identified nearby, an estimated displacement of more than a few meters was made. This estimate is consistent with that obtained using the regression line proposed in the paper if the 0.3 to 0.4 m (12 to 16 in.) thickness for the gouge is used. However, using the regression curves with zero thickness would not yield results consistent with what was observed in the field. Therefore, it is important to recognize that the suggested procedure would properly yield a range of probable displacements. ? *Work performed under the auspices of the US Department of Energy by the Lawrence Livermore National Laboratory under Contract W-7405-Eng-48. Reply by E.C. Robertson It is certainly true that the t (thickness) of gg-bx (gouge and breccia) on a fault does vary along the fault. My observations have been that near the termination of a fault, the displacement d is small and the t is also small, whereas the maximum d and t will usually be found in the central part of the fault. The information on gg-bx and t of the fault found in granite in the NTS tunnel by Mr. Wilder could be interpreted somewhat differently than he does. He speaks of the fault changing within a few meters from 0.3 to 0.4 m (12 to 16 in.) of clay gg to "a highly fractured zone with significantly altered rock and some slickensides," but no gg. The highly fractured rock may be taken to be bx, rock not so finely ground as gg but still crushed by the fault movement, equivalent to the gg in my usage, and probably occupying about the same t. Mr. Wilder&apos;s estimates for the fault in the NTS tunnel for t of 0.3 to 0.4 m (12 to 16 in.) and for d of a quartz vein, in excess of "a few meters," would place the point on the low side of the central trend line in my Fig. 1, at the lower limit. There is, of course, a problem with determining d using displacement of only one planar surface. It would be greater or lesser depending on the rake of the movement. Finally, estimating the d of a fault from its t should be made with awareness of our present uncertainties, as pointed out by Mr. Wilder. Although the central trend line in my Fig. 1 has a ratio of d/t of 100, I have put the limiting ratios at 10 and 1000. Understanding of the values of the ratio will be improved only with collection of more data, for which the discussion of Mr. Wilder is much appreciated. ? G.C. Waterman E.C. Robertson&apos;s paper provides significant information to a geologist attempting to deduce fault offset by noting the products of structural dislocation. However, considerable mapping in underground and open-pit mines, and examination of structures produced in different geological settings, have convinced me that gouge and breccia thickness are controlled by geological conditions and fault movement. The following paragraphs suggest geological variables that control them. 1. Depth of Loading A near-surface fault resulting from tensional stress has more breccia/gouge than is produced by a similar stress at considerable depth. A deep-loaded compressional stress may produce a linear zone of schist, or structural dislocation may occur along an earlier formed belt of schist. Such "shear zones" are common in Canadian mines in precambrian rocks. In neither case can offset be directly deduced by an analysis of the minimal gouge/breccia in the shistose rocks. At greater depth, stress may be partially to wholly relieved by flowage. I vividly recall first noting the regional "Midas Thrust" in the Lark mine, Bingham Mining District, UT (where we called the structure the North Fault). My recorded notes, as I remember them, showed a narrow gouge streak separated the "Jordan" and "Commercial" limestone units from impure, muddy limestone beds of uncertain stratigraphic position. The visible structure did not indicate the great importance of this premineral fault

Jan 1, 1985

By Milton E. Wadsworth, T. D. Chatwin

Bulk density variations can usually be minimized by properly mixing the material before moisture measurement. The measuring of moisture on material being with- drawn directly from storage bins requires some form of bulk density correction. In Bethlehem&apos;s pellet plants continuous automatic bulk density correction and uniform feed-rate control are obtained with Bethlehem&apos;s patented Bin Level Control System. With this sys- tem a single probe, suspended or inserted in the bin, senses whether material is at the proper level in the bin and automatically regulates filter speed to control the filter-cake discharge rate to maintain this level. The level of concentrate in the filter-cake bin can thereby be controlled to within ± 1/2 in. of the point of contact between the concentrate and the probe. Material thickness on the conveyor does not have to be controlled accurately and mix compositions can vary widely as long as they do not contain variable amounts of water-soluble electrolytes. In sinter plants, errors caused by changes in normal feed rate and bed height are minimized by counter-weights that permit the free-floating to maintain a uniform contact pressure on the mix. Large changes in mix resistance can be taken care of either by resetting the control point or by adjusting the calibration control.

Jan 9, 1968

By W. E. Bron, E. S. Machlin

GRAIN boundary migration in V-shaped thin specimens of high purity silver was studied. Each specimen contained two crystals having the relative orientation: (111)A/(111)B; (ll0)A/(101)B. The boundary between these two crystals varied between a continuous curved and an alternating two plane interface. The plane interfaces were oriented parallel to (101)A/(011B) and (121)A/(211)B. Traces of these planes are shown in Fig. 1. Evidently the two plane interface, although of higher area, comprises lower total interface energy than the average curved boundary it replaced. The plane boundaries were found to move at 650 °C to consume the broad segment of the V opposite to the direction of interface area and energy decrease. On investigation, using the thermal etching technique of Hendrickson and Machlin,1 it was found that the outer grain contained 8.3x108 more dislocations per cm" than the grain at the apex of the V. Consequently, the boundary moved to decrease the strain energy associated with the difference in dislocation density across the boundary. The rates of motion of specific {110} and {112} boundaries were measured during interrupted anneals at 650°C by referring the position of the boundaries to each other and a fiducial line on the specimen surface. The measured rates of motion are 0.075 and 0.025 mm per hr for the {110} and {112} boundaries, respectively. Plots of grain boundary motion vs time of annealing show straight lines with little deviation of data points from these lines.

Jan 1, 1957

By Donald Warren, J. F. Libsch

HIS investigation originated as a result of a pre-vious experimental study&apos; of the magnetic properties of Fe-Co alloys fabricated by the powder metallurgy technique. Densities of powder compacts prepared for the magnetics investigation varied from 7.45 to 7.70 g per cu cm or from 93 to 95 pct of the experimental value of 8.08 g per cu cm for a fused alloy of the same composition.&apos; While this range of density is considered sufficiently high for most applications, the highest possible density is to be desired for maximum magnetic properties. By applying a technique similar to the one described above to a pure electrolytic iron powder, Rostoker³ was able to achieve a density of 7.895 g per cu cm, which is the highest density ever reported for sintered iron. While Rostoker&apos;s work involved the sintering of an elemental powder rather than a mixture, it was believed that higher densities should also have been obtained for alloys using the above technique because of the recoining operation and the high sintering temperature. Consequently, it was decided to investigate the various factors affecting the density of this alloy with the idea that such a study might lead to higher densities and, as a result, powder alloys having magnetic properties identical with those of the fused alloys. It was believed that the principal reason that near-theoretical densities for the powdered alloy were not obtained was the interference of gases with the normal sintering mechanism. When present during the sintering operation, gases can exert several harmful effects: they can remain on the particle surface and interfere with surface diffusion and plastic flow; they can be released and, under certain conditions, expand the void spaces through gas pressure; or they can remain trapped in the pores and exert a hydrostatic pressure that retards elimination of the pores. Jones,4 Rhines,5 Goetzel," and others have given the effect of gases in the sintering of powder compacts an extensive treatment. Among the more important sources of gases in the sintering process are dissolved gases, adsorbed gases, air entrapped during pressing, and gaseous products of chemical reactions. During sintering adsorbed gases are partly released at a relatively low temperature, while those gases entrapped during pressing cannot escape until their pressure is increased sufficiently through increasing temperature to expand the interpartjcle openings. The remaining adsorbed gases, gaseous reduction products, and dissolved gases produce a similar effect at the higher temperatures. If, in the sintering process, gas evolution occurs after the interpore channels have been sealed, an exaggerated expansion of the void spaces results. This is particularly true if the temperature is high enough for extensive plastic flow. In his fabrication of powder bars from tantalum, Balke7 had to consider the effect of adsorbed hydrogen and provide for its escape during sintering by limiting the compacting pressure to a maximum of 50 tons per sq in. The effect of gases entrapped during pressing was first noted by Trzebiatowski8 when he found that gold and silver powders decrease in density with increasing sintering temperature if pressed at 200 tsi, while they exhibit the usual increase when pressed at 40 tsi. Recent investigators9-11 have also noted that entrapped gases have an effect on the expansion of copper compacts during sintering. Proper provision for the escape of gaseous products of reduction must be made in order to avoid deleterious effects. Myers" states that in the sintering of electrolytic tantalum powder, the temperature was gradually raised to 2600°F with a pause at 2000°F to permit reduction of the oxides. Experimental Details For the present study, 50 pct Co-50 pct Fe compacts in the form of circular disks 1½ in. in diam and 0.15 in. thick were fabricated by the pressing and sintering of a mixture of the elemental powders. It was decided to follow the sintering process by means of liquid permeability measurements, because it was thought that such measurements might serve as a measure of relative pore sizes, as well as a possible indication of the point at which most of the interpore channels become sealed. However, since the permeability as measured by the flow of a liquid, such as ethylene glycol, does not give an absolute indication of the point where the pores have become isolated, a method for determining the percentage of pores connected to the surface was set up. As an additional cross check on the permeability measurements, metallographic methods were used to study the relative pore size. Finally, the property of ultimate interest, the density, was measured. Raw Materials: The powders used consisted of an annealed, 99.9 pct pure, —150 mesh grade of electrolytic iron powder, and a 98 pct pure, —200 mesh grade of reduced and comminuted cobalt powder. The cobalt powder was not further processed either by hydrogen reduction or annealing. The screen analyses for the iron and cobalt powders are given in Table I, while the chemical analyses for each type of powder are listed in Table 11. Table 111 gives the hydrogen loss measurements for the powders according to the M.P.A. Standard Method and for a higher temperature as well. Preparation of Compacts: Equal amounts of the elemental powders were mixed by rotation for 1 hr and then pressed into compacts approximately 0.15

Jan 1, 1952

"The mines of Butte, in addition to the square timber used, consume each year large quantities of round timber, which are called stulls. The Stull business is an important industry, as will be seen from a brief description of the operations of the Mines Timber Co., which institution furnishes most of the stulls and lagging poles used in the Butte mines.Timber produced by the Mines' Timber Co. is mostly cut on the government forest reserve, on California gulch, American gulch and French gulch. To bring the timber to market, a flume 16 miles long has been constructed from Big American gulch to Mill creek. The flume, which heads on Big American gulch, on the Atlantic slope, crosses the Continental Divide at an elevation of 6,525 ft., and delivers timber at Mill creek on the Butte, Anaconda & Pacific railway, which is on the Pacific slope. Timber is loaded on cars at Mill creek and shipped to the Butte mines, a distance of twenty-six miles. There are 29 trestles on the flume line over 25 ft. high. The highest trestle is 78 ft. and the longest is 775 ft. The longest tunnel on the line of the flume is 565 ft. from portal to portal."

Jan 1, 1913

By R. R. Jones, R. W. Kraft

Zn-Mg2Znn eutectic alloys nzay freeze willr either rodlike or lanzellar rnorphology. Alloys with slighlly more than /he eutectic arrzount of rnagnesillrn usually contain three-cnned dendrjles of MgzZnll in a eutec-lic ttlulris. All three morphologies haue the same cryslallographic orientution relationship: (0UOl) zn - 11 (111) Mg2Znll and (2310)Zn 11(101) Mg2Znll, but u3ith different prej-erred groulth direclions. The lurnellae lo rods transifion in con/rolled ingols qf euleclic cotnposition occurs because lhe large kinelic undercooling due to MgzZnll minirrzizes /he ejj-ecl of the solid-solid inlerface energy. The eutectic morphology is influenced by the presence of lhree-nned dendrites 0-f MgzZn11 which may conlrol /he rricroslrccture by acting as nuclealion sites. In recent years there has been much interest in eutectic solidification and several theories have been proposed. One of the confusing factors is the existence of various morphologies in which the solidified phases may form. The lamellar microstructure seems to be most common in metal eutectics, and it has been claimed&apos; that all regular eutectics should be lamellar if sufficiently pure. However, there still remain eutectic alloys which are not lamellar or which change their morphology as a function of growth conditions. The eutectic between zinc and the intermetallic phase Mg2Znll was chosen for this investigation because it has been found to solidify in more than one morphology. The diagram in anssen&apos; locates the eutectic point at 3.0 wt pct Mg and 367°C. lliott gives 364°C as the eutectic temperature, leaving the phase compositions unaltered. Since the growth conditions determine the micro-structure of the solidified alloy, the factors controlling the transition from one morphology to another could be studied. The lamellae to rods transition is of particular interest. PROCEDURE Alloys were prepared from carefully weighed portions of 99.999 pct Zn and 99.97 pct Mg by melting in Pyrex containers under argon and casting into graphite boats. The resulting ingots were remelted under argon and solidified unidirectionally in a horizontal tube furnace at growth rates ranging from 2.0 to more than 50 cm per hr under a temperature gradient, measured over a 5-cm length, of 9" to 14°C per cm. The solid-liquid interface appeared to be planar at all growth rates although no attempt was made to confirm this by decantation or quenching. A few ingots were allowed to freeze uncontrolled. Most alloys were of the nominal eutectic composition, 3.0 wt pct Mg according to Hansen2 and lliott, but some contained as much as 3.35 wt pct Mg. Chemical analyses were not run since metallographic examination confirmed that the desired composition was achieved. Specimens were cut from the middle portion of the ingot normal to the growth axis, polished mechanically, and etched with 2 pct Nital. Suitable areas were selected for the determination of crystallographic orientation relationships by a tiontechniqueof described previously by one of the authors.4 The (2310) planes of zinc and the (8701, {944}? (1032) planes of Mg2Znll were found suitable for orientation determination; experimental error was on the order of 2 or 3 deg. RESULTS Three different morphologies were found in the unidirectionally solidified alloys: lamellar eutectic, rod-like eutectic, and a structure whose most predominant characteristic was the presence of three-vaned (cellular) dendrites of Mg2Znll. These dendrites were only found in alloys with more than the eutectic amount of magnesium. In some ingots fine hexagonal needles of Mg2Znll surrounding a core of MgZn2 were observed. They were probably due to incomplete alloying and seemed to have no effect on the eutectic morphology. In addition hexagonal spirals like those discussed by Fullman and wood5 and Hunt and acksonh ere observed in some ingots frozen without directional control. Both MgZZn,, and MgZnz were detected by X-ray diffraction in these alloys. Since the morphology could not be grown unidirectionally and no characteristic orientation relationship between the phases was found, further study was limited to the lamellar: rodlike, and three-vaned dendrite morphologies. Alloys of Eutectic Composition, No Dendrites. The mcrostructures of allovs with no three-vaned dendrites were either lamellar or rodlike depending on the growth rate. At rates below 10 cm per hr the morphology was lamellar, consisting of two sets of parallel plates intersecting at about 54 deg like the Mg-MgzSn eutectic described by raft.7 At growth rates faster than 14 cm per hr the microstructure showed rods of zinc in a matrix of MgnZnll, while intermediate rates yielded mixtures of rods and lamellae in small groups. The lamellar "grains" were often several millimeters in cross section, but contained small irregular areas which divided each grain into perfect islands 100 or 200 p in diam. Lamellae were parallel to each other throughout the grain in spite of these defects in the structure, Fig. 1. Rods, on the other hand, could only be produced in small groups arranged like fish scales and separated by irregular areas of appreciable thickness, Fig. 2. Alloys Not of Eutectic Composition, With Dendrites. In alloys with 3.1 to 3.35 wt pct ME,-. three-vaned dendrites bf MgzZnll were usually found surrounded by eutectic. At growth rates slower than about 10 cm per hr the dendrites were separated from each other by small areas of both lamellar and rod eutectic, Fig. 3.

Jan 1, 1969

By Tuncel M. Yegulalp, Malcolm T. Wane

In general, many problems relating to the exploitation of mineral deposits are probabilistic in nature. This derives from the fact that the geologic universe is inherently random. Probability theory and statistics have been found useful for forecasting the behavior of natural events that occur in the geologic universe. The objective of this paper is to illustrate the application of the theory of extremes to this fore-casting problem. For example, it is customary for design purposes to determine the rupture strength of geologic materials. The theory of extremes is exceedingly useful in describing that portion of the frequency distribution of rupture strength which contains the least strengths. Parameters describing the distribution of the least strengths are more important to the designer of mining excavations than parameters describing the total distribution. The basic principles of the theory of extremes will be detailed and illustrated. Any person required to work in the laboratory of nature is aware that uncertainty is a salient feature of all mining enterprises. A mining engineer required to plan the most efficient, practicable, profitable, and safe mine finds himself face to face with numerous ill-understood and often unquantifiable states of nature. Basic information necessary for adequate planning is often lacking or derived from incomplete tests on samples or experience of doubtful validity. The planning procedure usually takes the form of determining a feasible layout with the intent of determining an optimal layout when and if the necessary details and information become available. The crux of the entire procedure is the choosing of numbers to put into the operational and structural models which encompass the plan. Many times these numbers must be assigned qualitatively from past experiences and are called the "most probable ones." At other times, load records, performance records and material tests provide a basis for extrapolation. In any event, the numbers are chosen from a distribution or set of all numbers. Since each number in the distribution represents a possible state, the choice of any particular value is based upon a decision rule. To illustrate, consider the design of an underground structure or the design of a rock slope. The initial step is the formulation of the various possible structural actions which result from the geometry of the layout. For a given structural model various intensities of behavior are possible depending upon the load, deformation, and material characteristic spec-trums, respectively. Of particular interest to mining people is the failure behavior or condition, i.e., when there is a complete collapse of structural resistance by either structural instability or fracture. A necessary feature of the analysis is the "rupture strength" of the material. Information on the rupture strength is derived from testing either in situ or in the laboratory and the usual outcome is a variation in the test results. The methodology used to overcome this variation is to construct a frequency distribution of rupture strengths, and then determine a measure of central tendency and variability. The main idea involved is that the central tendency number will be used in the failure calculations and the measure of dispersion will be used to estimate the probability of failure. In particular if the distribution of rupture strength is normal, the mean rupture strength is the central tendency number and the standard deviation of the rupture strength is the measure of variability. Suppose the mean value of rupture strength is 1000 psi and the standard deviation is 200 psi. Insertion of 1000 psi into the failure calculation produces results that are unsafe, hence a common decision rule is to reduce the mean value by a "factor of ignorance" so that the failure calculation will produce a "safe result." If two is chosen as a factor of ignorance, this means the value inserted in the calculation is 500 psi or 2.5 times the standard deviation. The next step is to determine the percentage chance that failure will occur from a design created on this basis. Tables on the normal distribution function show that this percentage chance is 0.621% or approximately 7 times out of 1000. In practice, however, the situation is more complicated than represented by the foregoing illustration. The laboratory or field testing program usually constitutes a pathetically small sample of the geologic universe of interest and not enough testing is carried out to determine the exact form of the distribution of the test results. The normal, Cauchy and Student&apos;s T distributions are strikingly similar, and it becomes a matter of mathematical convenience to assume the normal law for phenomena which follow other laws.

Jan 1, 1969

By C. S. Sivaramakrishnan, Manjit Singh, Rajendra Kumar

Regarding liquid nzetals structurally as a suspm-sion of clusters , having derivated solid-state coordination, in truly liquid atoms, the recently developed Kuvlar-Samarin technique of centrifuging- in liquid state enabled the determination of the cluster sizes inAl-Cu mid Pb-Sn systems. It is shown that the colutne fraction of the clusters does not exceed 9 pct and the energy of their formation in Al-Cu is about 5.5 kcal per g-atom and in Pb-Sn eutectic alloys about 25 kcal per y-atoni. STRUCTURAL investigations of liquid state have principally followed the following three courses: i) studies with X-ray, electron, or neutron diffraction; these investigations have shown that there is a certain amount of regularity in the structure of liquid metals which can be defined by a coordination number and that the structure is a derived function of that in the solid state; ii) thermodynamical investigations which are based on the concept of ideal behavior; these describe the liquid state in terms of free-energy values and other thermodynamic functions; although these investigations are of help in the study of the general effects of alloying, they do not provide any structural insight into the precise atomic distribution in liquid state; iii) measurements of surface tension and viscosity; although it is natural to expect that the viscosity is related to the structure in liquid state, these investigations have so far only provided information which can be used by the foundry technologists and has been little utilized in formulating models of the structure of liquid state. As it happens, investigators in the three groups have worked almost independently of each other and there is practically no structural correlation between the results of one group with those of another. The purpose of the present paper is to indicate that the experimentally measured parameters of these three groups of research are closely related to the structure in the liquid state. STRUCTURE OF LIQUID METALS Although atomic distribution in solid and gaseous states is rigorously known, that of the liquid state is only appreciated on the fringes. There is no universal model of atomic distribution in liquid state, but two diverse models are at present hotly contested. The first, largely expounded by ~ildebrand,&apos; regards the liquids as condensed gas since many of their properties and much of their behavior can be adequately described by regarding them as fluids. The second mode12j3 considers that some form of near-solid as- sociation of large number of atoms exists in the liquid state. On the other hand, ~ernal&apos; was able to predict rather precisely the radial distribution functions in liquids on the basis of statistical geometric approach which considered that liquids are "homogeneous, coherent, and essentially irregular assemblage of molecules containing no crystalline regions or holes large enough to admit another molecule". He introduced the concept of pseudonuclei in the otherwise random structure as aggregates of closely packed tetrahedra which gradually merge into irregularity and continually replace each other. To what extent the pseudonuclei can be regarded as regions of near-solid association is indefinite but Bernal suggested that the concept of pseudonuclei can be compromised with the latter model if the near-solid associations are regarded as extremely dense and not necessarily crystalline. The difficulty in projecting the structure of liquid metals arises because they exhibit duplicity of character as some of their properties are closer to those of crystalline solids and others to fluids. There is an increasing tendency to discuss the structure of liquid metals in terms of the second concept according to which the structure of liquid metals may be conceived as consisting of i) clusters of atoms where the aggregation is a close derivative of that in the crystalline state, ii) individual atoms which behave like true liquids in respect to degrees of freedom and iii) excess number of vacancies. It is noteworthy that the introduction of only 5 pct vacancies is sufficient to transform crystalline matter into the liquid state. At any instant of time thermodynamic equilibrium exists between i, ii, and iii, but the relative proportion of the clusters and random atoms is not known. That this is so can be appreciated by the fact that, when liquid metal is rapidly cooled, liquid state vacancies may condense in the form of dislocation loops and vacancies in excess of their equilibrium number in solid state. These dislocation loops have been observed in thin foils of aluminum prepared from rapid cooled aluminum. As temperature increases above melting point the number and volume fraction of clusters decrease but those of vacancies and random atoms increase. Clusters are transient in nature. In pure metals the cluster is an aggregation of the metal itself. In alloys, however, the nature of the cluster largely depends on the interaction between solvent and solute atoms. If the interaction between unlike atoms is greater than between like atoms: the clusters are then aggregates of unlike atoms. Examples of this kind of system are A1-Cu, Mg-Pb, and so forth, i.e., systems which exhibit negative departures from the Raoult&apos;s law. In systems where the interaction between unlike atoms is smaller than be-

Jan 1, 1968

By JOHN MARKLE

JOHN MARBLE, mining engineer, coal operator, philanthropist, member of the Institute since 1879, vice-president in 1903-04, has been paid the well deserved tribute of Honorary Membership. The presentation of the diploma was made at a luncheon in New York on Feb. 13, the citation reading: "In recognition of his work as an engineer and administrator of mines and his services to mining engineering education." Within the last month Lafayette University dedicated the new John Markle Mining Engineering Building, the gift of the eminent alumnus for whom it is named. In addition, Mr. Markle has contributed a maintenance fund for the carrying out of far-reaching plans for improving the mining courses to be given at the Institution. One of his theories is that quality rather than quantity of engineering graduates is the need of the profession. John Markle was born in Hazleton, Pa., in 1858. He received his degree of M. E. at Lafayette in 1880, and married Mary Estelle Robinson in New York City in 1884. Since 1880 he has been associated continuously with the firm of G. B. Markle & Co., and its successor companies. He has also been an official of numerous other important companies, although he is now retired from active business life.

Jan 1, 1930

By John W. Burd

A system is described for the simultaneous deposition of epitaxial layers on as many as eight substrates. A high degree of uniformity of both physical and electrical characteristics is achieved in the films. Variation of film thicknesses is consistently less than ±10pct within a wafer and from wafer to wafer within a run with the variation typically on the order of 55 pct. Composition variation of GaAs1-x PX layers within a wafer and from wafer to wafer within a run is consistently less than 51 pct. Electrical evaluation of the films by several techniques indicates excellent doping uniformity within a wafer and from wafer to wafer within a run. Mobilities for lightly doped GaAs films at 300°K are consistently >6000 cm2 v-1 sec-1 and mobilities > 7000 cm2 v- 1 sec-1 are regularly attainable. Techniques for the preparation of material with carrier concentrations from 1 x 1015cm-3 to 1 x 1019 cm-3 n-type and 5 x 1016 to 5 x 1018 cm-3 p-type are discussed. METHODS for the preparation of 111-V compounds by vapor phase reactions have been extensively reported in the literature.1-6 Almost all of the apparatus described for these various methods are suitable for processing one or at the most a very limited number of wafers simultaneously. With the recent rapid advances in the use of vapor grown GaAs for microwave oscillators and GaAs1-xPx as visible light emitters the requirements for these materials are steadily increasing. In order to satisfy these requirements it is necessary to move from a laboratory scale apparatus to one which is capable of processing a large number of wafers simultaneously. Desirable features would be a high degree of uniformity among the wafers and good reproducibility from run to run. The apparatus to be described fulfills these requirements very well. DISCUSSION The various methods reported in the literature can be classified under three headings: 1) closed tube, 2) open tube, and 3) the close-spaced method. Of these three the open-tube method is the most amenable for scale-up to a manufacturing process. It is the most versatile and the various operating conditions can be more precisely controlled than with the other two methods. A number of chemical reactions may be used to achieve vapor-phase growth of 111-V compounds. Sev-era1 of the more generally used reactions are shown in Fig. 1. All of these reactions have the following points in common: 1) generation of a volatile group III(Ga) species by the reaction of the transport agent (halide or HC1) with either Ga or GaAs, 2) introduction of the Group V(As and/or PI component, 3) a method of adding dopant, if desired, and 4) a region in which deposition from the vapor will occur and form as a single crystal epitaxial film on the substrates. The laboratory scale reactors permit the hot re-actant gases to flow into the relatively cooler deposition zone and pass successively over the several substrates which are arrayed along the long axis of the tube parallel to the gas flow. With this arrangement the composition of the reactant stream is continually changing as solid material is deposited on each successive substrate. As a result of this changing gas composition the reaction driving force also changes from substrate to substrate and the degree of uniformity of layer thickness, doping level, and so forth, is poor. This effect can be partially overcome by imposing a controlled temperature gradient along the deposition region to compensate for change in gas composition. However, even when this is done variations in layer thickness on the order of 30 to 40 pct are common and as high as 50 pct are frequently experienced between adjacent wafers in the tube. To expand this arrangement to a large number of wafers would only increase the nonuniformity from the first to last wafer in the line. From the above discussion the two undesirable features of changing gas composition and temperature gradient become evident. A reactor system which eliminates or minimizes these undesirable features is one in which the apparatus is mounted vertically as shown schematically in Fig. 2. The vertical mounting permits the disposition of a number of substrates on a suitable support so that all wafers are at the same vertical height in the furnace and hence at essentially the same temperature. By using only a single row of wafers the reactant gas mixture passes over only one substrate in its path through the reactor. Thus the two undesirable features of changing gas composition and temperature gradient are minimized. An additional design feature which further minimizes temperature variations is rotation of the substrate holder. Rotation serves to integrate any radial temperature gradient existing around the resistance heated furnace. A photograph of a reactor assembly at the completion of a run is shown in Fig. 3. MATERIAL PREPARATION Apparatus. Although any of the several chemical systems shown in Fig. 1 are adaptable for use in this apparatus the one generally used is System 2, the hydride synthesis system. This system has been de-

Jan 1, 1970