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By G. H. Alani, H. T. Kennedy

One of the major difficulties in predicting the performance of oil reservoirs from their early pressure history lies in the uncertainty of estimating the volume of the liquid hydrocarbons contained in them. As a first step in filling this need, an equation was developed to determine the Inolal liquid volume of pure hydrocarbons over a wide range of temperature and pressure. The second step consisted of adapting the equation to apply to mixtures, with the heary hydrocarbons expressed as c The equatious are similar in form to van der Waals equation. hut the constants a and b tire considered as furnctions of temperature. In addition to the gas constant R, there are four constants characteristic of each hydro- When comptired with experimental values jound in the literal the. the average absolute deviation in the calculated molal volumes is found to be a Maximum of 0.33 per -cem for any of the pure liquid hydrocarbons studied. This maximum deviation was that found when comparing the calculated and observed values over a temperature range of 86° to 482°F and a pressure range from the bubbl-point ro 10,000 psis. The equations expressing the correlation for. mixrurrc were developed from 647 experimental measure-rilents of volume on 47 bouom-hole samples covering ; temperature range of 72" to 250°F and a pressure znge from bubble-point ro 5,000 psig. The average absotute deviation was found to he 1.6 per cent with the maximum for any measurement of 4.9 per cent. INTRODUCTION Accuratc information of the pressure-volume-temper-iiture behavior of hydrocarbon liquids is of considerable importance in the field of both applied and theoretical science and, especially, in the solution of petroleum reservoir engineering problems. These PVT relationships can be expressed graphically, in tabular form or as equations of state. Equations of state for gases have been developed based on the ratio of pressure, temperature and volume to the pressure, temperature and volume at the critical points of the hydrocarbons. These equations have been successful in yielding values fairly accurate for reservoir engineering purposes. For liquids, however, relations of this type are more complex and have not yielded useful results. The composition of reservoir liquids is normally expressed in terms of the moles of hydrocarbons C,? C,. C,. elc, per mole of mixture. The composition must include the fraction of a mixture such as C,,, which cannot be separated with reasonable time and effort into specific hydrocarbons. Although there are several equations of state having variable degrees of accuracy applicable to pure liquid hydrocarbons, none includes a means for estimating the volume of mixtures as a function of temperature. pressure and composition expressed in this manner.

By Edmund Davenport

THE specific aim of this work has been to study certain forms of internal deterioration which occur in tungsten filaments when subjected to high temperatures under various conditions, and to determine the cause of such deterioration. This would naturally lead to a consideration of methods of control or means of prevention of the phenomena. The deterioration was first noticed as a peculiar condition in the grain boundaries of certain tungsten filaments which had been burned? for long periods in lamps. In these cases it was noted that the grain boundaries contained a number of minute black dots which were at first thought to be non-metallic inclusions. It was demonstrated later that these dots or pits, as they were designated, could be readily produced by burning filaments in an atmosphere of flowing hydrogen. This method was convenient and adequate for the purpose, and was adopted for most of the work discussed in this paper. The evidence accumulated to date indicates that these pits are actually small voids between the grains. The purpose of this paper is to present- the information on this interesting subject gathered during a period of about 3 years. As applied to tungsten, the subject appears to be of considerable importance, experience having shown that this pitting ?is frequently associated with poor performance of filaments in lamps. The question has arisen as to whether these intergranular pits are peculiar to tungsten, or if they occur in all metals. If they are found iii all metals, the facts will be of considerable theoretical interest, as the material at the grain boundary plays an important part in most of the current theories of the properties of metals and alloys.

Jan 1, 1927

By A. U. Seybolt

Since the time this topic was originally treated in 1954, more recent French3,1 work has been published making it advisable to repeat the earlier oxygen solubility experiments, but using iron of a higher purity. Upon repeating oxygen saturation experiments with zone-refined iron, it was found that the oxygen solid solubility was at least an order of magnitude less than previously observed. SINCE the publication of an earlier paper1 (1954) on this subject by the present author, several contributions on this topic have appeared. Meijering2 in 1955 attempted to reconcile recent conflicting solubility data, without reaching any definite conclusion. sifferlen3 (1955) found that iron of high purity appeared to absorb a quantity of oxygen (0.005 to 0.025 pct) approximately proportional to the structural imperfections present, such as polygonization and grain boundary area. However, he also indicated that purity itself was a significant factor. He concluded that very pure iron nearly free of lattice imperfections would have essentially zero oxygen solubility. His second paper4 (1957) supported this contention since a zone-melted iron containing initially 0.0007 pct O analyzed only 0.0006 pct 0 after prolonged soaking at 850°C with an FeO layer on the surface. Because of the discrepancy between the results of Ref. 1 and those of Sifferlen, it seemed desirable to attempt to resolve this disagreement. EXPERIMENTAL PROCEDURE AND MATERIALS The experimental method used by sifferlen3,1 was essentially the same as that of Ref. 1. In this technique thin iron strip with a surface layer of FeO is soaked for prolonged periods at an elevated temperature in order to saturate the iron with oxygen. After two days at temperatures near 800° to 900° C, one would expect that the iron would be in equilibrium with the surface FeO. In the work reported in Ref. 1 there was evidence that two days holding at 8000to 900°C was more than sufficiently long for saturation. Sifferlen used 48 hr at 850°C. Because of the evidence presented by Sifferlen that the apparent oxygen solubility is a function of iron purity, three grades of iron were used as indicated in Table 1. The Bureau of Standards wire was used only for resistivity tests, while the other two irons were used for saturation-analysis tests of the type described above.

Jan 1, 1960

By John C. Draper

The principal object of an underground coal mine transportation sys tem is to move coal from the face where it is produced to the outside of the mine where it is prepared for market. In addition to the movement of coal, a transportation system must also move supply materials to the inside; it must move men in and out of the mine ; and it must move rock and other debris out of the mine for disposal. Usually, mine haulage is divided into three categories named for the various areas of the mine served: 1) Face Haulage. This is used at face from the mining machine to the intermediate transport system. 2) Intermediate or Secondary Haulage. Generally this is used between face haulage and main haulage. Sometimes this is merely an extension of the main haulage. 3) Main Haulage. This extends from the secondary haulage to the outside and is usually either a track or conveyor system, sometimes a combination of both. Transportation modes of coal in the various areas pose different problems, but the whole system must be synchronized. For instance, at the face the coal should be removed quickly from the various places to facilitate the movement of machines, whereas the intermediate system just passes the same coal on to the main transportation system. Selection of the transportation system must be based on the seam height, mining methods used to extract the coal, capacity required, ease of coal handling, and haulage efficiency. When driving rooms, mine cars can be used. They often simplify supply haulage and rock handling because they can also handle these items. Conveyors could be used and would have a greater haulage capacity but they cannot handle supplies easily or segregate the rock. When using a different mining method, such as longwall, mine cars cannot be used because there is not sufficient space to move the cars at the face nor can the cars haul the coal without delays which would cause excessive losses in production. As for ease of handling

Jan 1, 1973

By C. A. Stickels

A heat of electrolytic iron, to whzch alunzinutn and nitrogen had been added, was hot-rolled, cold-rolled 90 pct, and recrystallized at temperatures from 500" to 700°C. Primary recrystallization textures appear to arise from competitive growth of two types of nuclei: 1) those having orientations belonging to the "usual" primary recrystallization texture found in riming steel, and 2) those with the {111} (110) ovientation. Development of a (111}(1 10) component in the primary recrystallization texture occurs only over a certain interval of isothermal recrystallizatzon temperatures when the material is supersaturated with respect to the precipitation of AlN. Lowering the degree of supersaturation depresses the temperature interval in which a (111)(110) component occurs. An elongated, 'pancake-shaped" recrystallized pain structure and a marked delay in the start of recrystallization were found in all specimens which were supersaturated with respect to A1N precipitation after cold work, regardless of their recrystallization texture. ONE of the consequences of killing low-carbon steel with aluminum is a significant change in recrystallization behavior. About 15 years ago, Solter and eatttiel showed that this behavior was largely controlled by aluminum and nitrogen in the steel. If complete precipitation of A1N was prevented before cold rolling, an increased "recrystallization temperature" was observed in subsequent. annealing, and the recrystal-lized grains were not equiaxed. Leslie et a1.2 studied this phenomenon in some detail and clearly demonstrated the relationship between A1N precipitation, recrystallization kinetics, and the development of "pancake-shaped" grains. It has also been known for some time that aluminum-killed steels, processed to produce elongated "pancake" grains, develop a (11 I}( 110) primary recrystallization texture. This texture has not been found in iron or low-carbon rimming steel as a primary texture4j5 but has been observed following grain growth in electrolytic iron.5 The present work was undertaken to study in more detail the effect of A1N supersaturation on recrystallization textures in iron. LITERATURE REVIEW The deformation texture in heavily rolled iron has been studied in detail by Bennewitz.~ The texture consists primarily of a partial fiber texture about a (110) axis in the rolling direction, designated here as fiber texture A. It includes the range of orienta- tions (111)[110] - (001)[ 110] - (11l)[110]. A weak secondary texture also is present.6 This is a duplex partial fiber texture about two (110) fiber axes located 60 deg from the rolling direction and 30 deg from the sheet normal. The range of this texture, designated here as fiber texture B, about the [101} fiber axis is (112)[110] - near (545)[252] - (211:1[011] *The range given here follows Bennewit~.~ A few pole figures from re-crystallized material indicate a broader range than this.' However, the components which are strongest in the recrystallization texture are in this range.'________________________________________________________ Primary recrystallization textures in unkilled steels can be accounted for by growth of members of fiber texture B present in the deformed metal.5 However, while members of fiber texture B dominate the primary texture, other orientations survive primary recrystallization as well. In particular, some {111}(110) members of fiber texture A must also grow during primary recrystallization, because a well-defined {1ll)( 110) texture develops during subsequent grain growth at 700°C.5 The unusual recrystallization behavior of deformed supersaturated solid solutions has been attributed to: 1) retention of the solute in solution,' 2) formation of coherent, preprecipitation solute clusters prior to and during re~r~stallization,~ and 3) formation of a precipitate prior to and concurrent with recrystallization.'~-'~ When aluminum is supersaturated with iron, the difference in grain boundary mobility between general high-angle boundaries and certain special coincidence site boundaries is apparently eliminated.' In aluminum-killed steels, precipitation of A1N can take place at ordinary subcritical recrystallization temperatures. The rate of precipitation increases with increasing aluminum or nitrogen contents.2'13 There is some doubt, however, as to whether true precipitates form during the time at temperature needed to complete recrystallization. Leslie ef a1.2 found that precipitation in one steel was complete after about 100 min at 700GC, or after about 1000 min at 650GC, as measured by chemical analysis for AlN. Aoki et a1.,13 using internal friction for dissolved nitrogen, showed that a large fraction of the dissolved nitrogen was removed from solution within a few minutes annealing time at temperatures from 400" to 800°C. However , the rate of formation of AlN, as detected bv chemical analvsis. was much slower than the apparent rate of nitrogen removal. Hasebe,'~~ using carbon extraction replicas, has identified A1N precipitates by electron diffraction in a 0.2 C steel, solution-treated at 1300°C and annealed 2 hr at 700°C. Borchers and kim,I6 also using a replication technique, observed precipitates after annealing treatments as short as 2 min at 640°C. However, Leslie et a1.' state that no A1N precipitate can be seen while recrystallization is being inhibited in aluminum-killed steel.

Jan 1, 1967

By Walter Herd

FOR the past eight years No. 2 mine of the Cumberland Railway & Coal Co., Springhill, Nova Scotia-a subsidiary of the Dominion Coal Co., Ltd.-has had an unenviable reputation for bumps. As the workings extended in certain directions under a greater cover, these bumps increased in severity and it became apparent that some change in the system of extraction was necessary if the mine was to continue to operate. In September, 1924, following several fatalities resulting from bumps, the Mines Department of Nova Scotia requested from the U. S.. Bureau of Mines the services of George S. Rice, Chief Mining Engineer of the Bureau, to report on the conditions then prevalent in No. 2 mine, Springhill. This request was promptly and courteously granted. Mr. Rice made a full investigation and a comprehensive and helpful report, which is embodied in the 1924 Annual Report of the Department of Public Works and Mines, Nova Scotia. Prior to 1925, the room and pillar method wasp employed and in January of that year (there being a cessation of work from March to August due to labor troubles) longwall retreating on the west side, on a limited scale, and in a small section on the east side of the mine was started. The major portion of the east side was not operated on this system till August, 1926, as there was developed a considerable area ready for pillar extraction between an arbitrary boundary and a point up to which bumps of any consequence had not been experienced. In the interval development work for longwall retreating below the 5900-ft. level was vigorously pushed. This longwall retreating system was suggested by Mr. Rice as a possible remedy and was heartily endorsed by the company officials. This paper describes the conditions and happenings subsequent to Mr. Rice's report and more especially the results with the longwall retreating system of mining under the peculiar circumstances pertaining to mining No. 2 Seam, Springhill, at depth, and records the conclusions which experience with several severe bumps under this mode of extraction would suggest. Except where necessary to make the paper intelligible as an entity any duplication of Mr. Rice's report will be avoided.

Jan 1, 1929

By C. J. Frosch, J. A. May, H. G. White, C. D. Thurmond

Gallium phosphide epitaxial layers were grown from the vapor phase on undoped single-crystal galliurn arsenide substrates in silica tubes by an open-tube wet-hydrogen process. The epitaxial layers were grown over a range of water pressures at three substrate temperatures. Excess donor concentrations were determined by surface barvier capacitance measurelrzents without removing the layers from the substrates. The excess dmlor concentration, ND-NA, is fo~ind to vary approxilnately inversely with the pressure of water added to the hydrogen carrier gas. This is the relationship that would be expected for singly ionized silicon donors on gallium sites in extrinsic galliunz phosphide, with the silicon coming from the SiO generated by the reaction of hydrogen with the silica tube. An increase in the partial pressure of water in the hydrogen stream decreases the SiO pressure. The results indicate that ni, the intrinsic hole and electrmt concentration for gallium phosphide at the three substrate temperatures, is smaller than the concentration estimated from available data for the density of states effective masses and the energy gap. Mass-spectrographic measurements confirm that the dono?, introduced into gallium phosphide is silicon. The equilibrium concentrations of silicon in vapor-flown gallium Phosphide have been estimated from available thernzodynamic information that includes the solubility measurements of silicon in gallium phosphide in equilibrium with a gallium-rich liquid phase. Satisfactory agreement with the measured silicon concentrations is obtained. FROSCH1 has described an open-tube process for growing single-crystal Gap from the vapor phase by a GazO transport mechanism. The method depends upon the reaction of H20 in an H2 carrier gas with a heated source of polycrystalline Gap which provides the necessary vapor species. When the temperature of these vapor species is lowered, super saturation occurs and single-crystal Gap will deposit on a suitable substrate. Unintentionally doped single crystals of Gap grown by the wet H2 process in silica tubes are n type. Evidence is presented to show that the donor introduced is silicon, and that a qua si-equilibrium model accounts for the inverse dependence of the donor concentration on the water partial pressure and predicts the magnitude of the donor concentrations. Ainslie et al. experimentally showed a similar inverse relationship between the carrier density and oxygen pressure for GaAs. Emission-spectrographic analyses showed a decrease in the silicon concentration with increasing oxygen overpressure for GaAs. Cochran and Foster suggested the theoretical possibility of suppressing silicon contamination by using Ga20 generated by the reaction of gallium with water vapor. 1) EXPERIMENTAL The apparatus and procedures are essentially the same as those described by Frosch.' The apparatus consists of a 25-mm-ID SiO2 tube extending through a controlled high-temperature flat zone for the location of the polycrystalline Gap source and a downstream temperature gradient falling at a rate of about 14°C per cm. The latter provides the region of super saturation for the location of the single-crystal substrate. The partial pressure of water in the inflowing hydrogen stream, pA2, O was controlled by mixing me-tered proportions of dry H2 with H2 saturated with H2O vapor at 0°C. The total gas flows were about 200 cu cm per min in all experiments. The Gap sources were prepared by pulverizing boat-grown polycrystalline ingots to pass a 20-mesh sieve. The substrates were cut from an undoped single-crystal boat-grown GaAs ingot purchased from Monsanto. This ingot had a carrier concentration of about 1015 atoms per cu cm, a resistivity of about 5 ohm-cm, and a mobility of about 5000 sq cm per v sec at 25°C. Substrates with dimensions of 1 by 1 by 5 x lo-' cm were employed. The growth faces were chemically polished (111) arsenic faces. Epitaxial layers, at least 7.5 x 10-3 cm thick, were grown,. This required from 1 to 24 hr depending upon the Pii2Q values and the temperatures. In all of the runs, the source temperatures were 50°C higher than the substrate temperatures. Samples were prepared

Jan 1, 1968

By J. E. Smith, P. B. Crawford, B. L. Laudrum

A method is presented by which the displacement efficiency of a steam-injection process may be determined. The method consists of a determination of the position of the steam front at a particular time and the application of the Buckley-Leverett theory to the hot and cold regions of the reservoir with the appropriate hot or cold fluid properties. A uniform, linear flow system is assumed for this study. The method is applied to a number of reservoir conditions. The primary properties which affect the results of a steam-injection process are the oil viscosities at steam and reservoir temperatures, injection rate, pay thickness and oil saturation. The efficiency of steam injection is compared with that of water injection for a 10-acre, linearly flooded reservoir. In reservoirs where the oil viscosity is about 35 times the water viscosity, the steam process yields recoveries about 20 per cent higher than the water flood. Where the oil viscosity is near 500 cp, the steam process may recover from three to four times as much oil as a water flood. INTRODUCTION In a previous paper,' a method was suggested for evaluating a steam-injection process. Emphasis was placed upon the determination of the steam-front position in the reservoir at various times. In the present paper, the displacement process is studied in more detail. The approach is essentially that employed by Jordan, Rayne and Marshall3 in their study of hot-water injection. The steam-injection process is quite complex, and an exact description of the process has not been found; however, a qualitative description can be made. When a quantity of steam is injected into a relatively cold reservoir, the leading edge of the steam front continaally flows into cool sand, and some steam condenses. As more and more steam condenses, a bank of condensed water will form which is augmented by displaced connate water. The reservoir may be divided in three regions—(1) a region containing displaced fluids at reservoir temperatures, (2) a region contain- ing water at reservoir temperature and (3) a region occupied by steam. The reasons for the lack of a region of hot water or oil of any appreciable size have been discussed.' A method has been presented by which the location of the steam front can be determined even when heat losses to the regions surrounding the reservoir are sizable compared with the amount of heat injected. It remains to show the effectiveness of steam injection in increasing the ultimate oil recovery. To illustrate the technique for determining the increase in displacement efficiency and, hence, the increase in ultimate production, two sets of hypothetical reservoir conditions will be studied in detail.

By Josef Intrater

A dilatometric determination of the a + ß region temperature limits was performed on vacuum melted Zircaloy-2. The temperature of transformation for a-a+ß and a+ß — ß on heating and cooling as a function of rate of heating and heat treating history was studied. The limits were found to be 815° to 830°C to 975° to 995°C on heating and from 960° to 930°C to 785° to 770°C on cooling. A 5° to 15°C increase was observed for a- a + ß with increased rate of heating and a 20° to 30°C decrease for ß - a + ß with increased rate of cooling. 1 HE transformation temperature for pure zirconium has been determined by many investigators1-5 using metallography, electrical resistivity measurements, and dilatometry. The effect of the rate of cooling on the transformation temperature of zirconium has been studied by Hayes and Kaufmann6 and Duwez,7 and the effect of alloying elements by pfei18 and McGeary.13 Since the development of Zircaloy-2, the limits of the a + ß region for that alloy have been also determined. The first reported temperature for the a — a + a transformation in Zircaloy-2 was 900°C and for a + ß - ß 1000C Subsequent studies by Picklesimer and damson" indicated the beginning of the transformation at 810°C, and the metallographic study by the Technology Group of the Special Materials Section at the Westinghouse Bettis plant1' suggested that 820°to 830°C is the temperature of transformation. The dilatometric investigation by the latter group yielded 830°C for the beginning of the transformation. Thomas and Forscher12 set the beginning of the transformation at 900 °C on heating and the end of the transformation at 870°C on cooling. The above investigators stated in their paper that the dilatometric curve exhibits features caused by a eutectoid reac-

Jan 1, 1962

By K. W. Smith, E. A. Thomas

Various grades of synthetic mullite have been developed in recent years to replace or supplement natural sources of mullite deriued from the mullite group of minerals consisting of sillimanite, kyanite, and andalusite. Raw materials and heat treating processes used in making synthetic mullite are described. Chemical and physical data are given for typical grades and crystalline structure is illustrated with micrographs. Use of synthetic mullite as a refractory material in the glass and metallurgical industries is discussed. Mullite (3A12O3.2siO2), the only stable compound formed in the alumina-silica system, is usually present to some degree in all aluminum silicate ceramic products. The formation of mullite is considered beneficial to give rigidity to the structure and is dependent upon the ratio of Al2O3 to SiO2 in the original composition, particle size, degree of mixing, firing temperature, cooling rate, and the presence of auxiliary glass-forming fluxes. Mullite may also be formed at the reaction interface of fire clay or alumina-type refractories in contact with glass or slag melts. The term synthetic mullite is commonly used today to identify a class of sintered and fused aggregates or grains in the alumina-silica system having a highly developed mullite structure but derived mainly from raw materials other than the sillimanite group of minerals. Within the past 15 years extensive research has been done to develop economical processes to form sintered synthetic mullite aggregate to replace calcined Indian kyanite in super-refractories. Severa1 brands of such mullite are now being produced in commerical quantity and finding extensive use in refractories. Based on the service results of such refractories in many applications throughout the metallurgical, ceramic, and glass industry these developments have been considered successful and suitable substitutes for Indian kyanite now appear assured. EARLY DEVELOPMENT The conversion of kyanite, sillimanite and anda-lusite minerals of the sillimanite group to mullite and their use in refractories and porcelain have been discussed quite extensively in the literature by peck,' Grieg,' Riddle and Foster,3 Bowen and Grieg,4 and others and will only be mentioned here for reference to compare properties with synthetic mullite. In 1928, curtis5 reported on the development of a high temperature gas-converter process for forming synthetic mullite. The raw materials were derived mainly from lumps of high alumina clay of the correct natural composition or blends of clays and alumina that was interground and briquetted to form a suitable charge to maintain a surface combustion firing within the converter. Curtis was, no doubt, the first to illustrate by micrographs in natural color the crystalline structure of mullite derived from kyanite and mullite derived by sintering clay and alumina mixtures at temperatures above cone 32 (3123°F) and by electric fusion. In 1937, sei16 was issued a patent covering the use of a mixture of alumina-silica minerals and alumina in the proportion to form a mullite-yielding material at temperatures in excess of 3100' F. During the period from 1930 to 1940, economic conditions were not favorable for the production of synthetic mullite mainly due to an adequate supply of good grades of Indian kyanite ore suitable for conversion to mullite. Uncertain conditions on availability of the Indian kyanite during the early stages of World War II fostered further study on the development of synthetic substitutes. In 1943, McVay and wilson7 reported on an extensive investigation of domestic substitute materials. Their work covered essentially the use of mixtures of electric furnace mullite, calcined topaz, and calcined domestic kyanite. Compositions were found that gave equivalent or better hot load strength than Indian kyanite in mullite-type brick compositions; however, the calcining of the topaz presented certain physical and chemical problems on the disposition of silicofluoride and hydrofluoric acid while the high cost of electric furnace mullite was a limiting factor. In this work it was pointed out that water-quenched fused mullite was found to be unstable on reheat and gave poor hot load strength due to excessive glass present whereas the slow cooled or annealed mullite contained large crystals of mullite and corundum with little glass and gave superior results.

Jan 1, 1961

By R. C. Himes, K. Zanio, J. B. Wagner, J. W. Moody, J. F. Miller, W. Johnson

The recent research with which this paper deals has been concerned with the preparation of pure PbTe crystals suitable for control of radiative processes and othe.v electronic applications. The research has been directed toward the developrnent of methods for the preparation of puve, homogeneous, loul-ca,wier-density PbTe crystals suitable for use in the fabrication of optically pumped and electrically pumped diode lasers. Steps in the preparation of the crystals include 1) purification of the starting materials, 2) synthesis and purification of the PbTe, 3) growoth of PbTe crystals, and 4) adjustt~zertt of composition of the crystals This Paper describes the general preparation procedure employed and discusses some investigntiotzs of purification processes. THE as-received lead and tellurium are nominally 99.999 to 99.9999 pct pure. Assays furnished by the suppliers, obtained by emission spectrographic analysis, show only the presence of about 2 ppm Mg in the tellurium. Such analyses are not very informative, however, since they give no information on the concentrations of normally gaseous impurity elements such as oxygen. Both the lead and the tellurium in the as-received state usually contain appreciable concentrations of oxygen—primarily in the form of oxides on the surfaces of the material. To reduce the oxygen content, the lead is held in the molten state in hydrogen at -700°C for several hours. For this treatment, the lead is contained in a graphite boat which is rf-heated, and the hydrogen is passed through a liquid-nitrogen trap prior to use. Tellurium is subjected to multiple distillation in hydrogen to remove oxygen and other foreign impurities. If, in conducting the distillation, approximately the last 10 pct of the charge at each "stage" is left as the discard cut, purification of the tellurium proceeds as indicated in Fig. 1.l Tellurium used in this work has been distilled two or three times to reduce carrier concentration to about 10" per cu cm. The PbTe is prepared from the purified elements by reacting them in the molten state in sealed, evacuated, or hydrogen-filled silica ampoules. The charge is usually held above the melting point of PbTe (923°C) at 1000 C for 24 hr to ensure that it has been homogenized. Two methods have been employed for the growth of the required single crystals of PbTe: growth from the melt, which will be discussed first, and growth from the vapor phase. Large single crystals of p-type PbTe can be grown readily from the melt by the Bridgman method. For this method of crystal growth, the PbTe is synthesized in situ from proper proportions of the purified elements. Growth (dropping) rates in the range 1.3 to 6.5 mm per hr are employed. Material near the maximum melting composition (about 50.012 at. pct Te) is utilized to avoid composition change on freezing, and thus to obtain crystals of nearly uniform composition. Crystals prepared by use of procedures described up to this point were sufficiently pure and perfect that they could be used for the preparation of laser crystals in studies at Lincoln Laboratory.2-5 ADJUSTMENT OF COMPOSITION Good n-type crystals of PbTe cannot readily be grown from the melt. Further, growth from the melt of crystals of any compositions (n or p type) other than those near the maximum melting composition is difficult because of the large composition changes that must occur on freezing.'" However, melt-grown crystals can rapidly be brought to other desired compositions by isothermal equilibration through the vapor phase with a two-phase Pb-Te stock material, essentially as described by Brebrick and Allgaier.1 The work to be discussed has been concerned with the preparation of n-type crystals; thus, the two-phase stock which was employed contained excess lead, and all ensuing discussion is of the preparation and properties of n-type crystals. The equilibration was designed to the shift composition to the lead-rich limit of stability at the selected temperature. Initial treatment of the crystals at high temperature was employed to minimize the total time required for the equilibration. Final adjustments of the composition and state of the crystals were made by use of low-temperature heat treatment at temperatures in the range 200" to

Jan 1, 1968

By L. L. Swift

.It the present time there are four base metals being used for automo-tive bearing alloys. Of course there are numerous variations in the amounts of alloying elements added to each base metal and nearly all of these alloys have the conventional, if not classical, duplex structure; that is, they are composed of a hard constituent embedded in a soft matrix. The well-known theory is that the former will wear well, while the latter will be plastic enough to allow the bearing to be broken in and conform to the contours of the shaft. The requirements of the modern bearing have been most aptly described by W. M. Corse: In order to meet the engineering demands of today a good bearing metal must be able to carry the weight of the shaft and stand up under steady or suddenly applied loads, or even blows ill sorne types of service. A certain amount of plasticity is desired to compensate for minute irregularities in the shaft or bearing surface, and to permit yielding, thereby avoiding dangerous stresses in bearing and shaft and pre-venting overheating and rapid wear of parts. Less plasticity is required in a bearing tuetal if the surfaces of bearings and journals are machined accurately, aligned, and kept in alignment. It is desirable, of course, that a bearing metal have a low coeffi-cicnt of friction. Under most operating conditions the friction depends on the unit, pressure of the bcaring, the speed, the temperature, and the properties of the lubricant. A good bearing metal must have a low rate of wear to reduce the necessity for frequent replacements, and adjustment of the bearings. It must wear more rapidly, however, than the journal or shaft running on it, because replacement of the journal or shaft is more difficult and costly than replacement of the bearing.' The hardness of the bearing alloy is a property closely related to several of the foregoing. With a duplex microstructure, the measurement of hardness with any of the usual commercial devices means little. The Bierbaum method of measuring the hardness of the individual canstituents was developed to fill this need. MICROCHARACTER The Bierbaum MicroCharacter~,~ measures the scratch-hardness of a solid by pulling a weighted diamond point over the surface. The diamond point is ground so that it is the corner of a cube, and Mounted

Jan 1, 1939

By L. L. Swift

.It the present time there are four base metals being used for automo-tive bearing alloys. Of course there are numerous variations in the amounts of alloying elements added to each base metal and nearly all of these alloys have the conventional, if not classical, duplex structure; that is, they are composed of a hard constituent embedded in a soft matrix. The well-known theory is that the former will wear well, while the latter will be plastic enough to allow the bearing to be broken in and conform to the contours of the shaft. The requirements of the modern bearing have been most aptly described by W. M. Corse: In order to meet the engineering demands of today a good bearing metal must be able to carry the weight of the shaft and stand up under steady or suddenly applied loads, or even blows ill sorne types of service. A certain amount of plasticity is desired to compensate for minute irregularities in the shaft or bearing surface, and to permit yielding, thereby avoiding dangerous stresses in bearing and shaft and pre-venting overheating and rapid wear of parts. Less plasticity is required in a bearing tuetal if the surfaces of bearings and journals are machined accurately, aligned, and kept in alignment. It is desirable, of course, that a bearing metal have a low coeffi-cicnt of friction. Under most operating conditions the friction depends on the unit, pressure of the bcaring, the speed, the temperature, and the properties of the lubricant. A good bearing metal must have a low rate of wear to reduce the necessity for frequent replacements, and adjustment of the bearings. It must wear more rapidly, however, than the journal or shaft running on it, because replacement of the journal or shaft is more difficult and costly than replacement of the bearing.' The hardness of the bearing alloy is a property closely related to several of the foregoing. With a duplex microstructure, the measurement of hardness with any of the usual commercial devices means little. The Bierbaum method of measuring the hardness of the individual canstituents was developed to fill this need. MICROCHARACTER The Bierbaum MicroCharacter~,~ measures the scratch-hardness of a solid by pulling a weighted diamond point over the surface. The diamond point is ground so that it is the corner of a cube, and Mounted

Jan 1, 1939

By T. W. Guy

IN approaching the problems of sampling coal, a brief statement of certain facts that are more or less taken for granted may be helpful: 1. The coal-mine operator needs reliable data as to the physical and chemical characteristics of his coal in order to plan and control intelligently its mining, preparation, and marketing. The consumer needs such data in order to select the equipment and the coal best suited to meet his requirements, to check the quality of fuel delivered, and the efficiency of its use. Various government control agencies require such data as a basis for classifications and establishment of limits, for use in carrying out the requirements of federal, state or municipal laws. 91. All such data must be obtained by analyses, measurements, or tests made on samples, which are taken to represent the coal tested. It is now becoming generally recognized that, in accordance with statistical laws, test results from samples are not expected to represent the exact qualities of the lot or lots from which they are taken, except within statistical, or "expected limits. Such limits are definitely specified by some present standards of the American Society for Testing Materials and the British Standards Institution. 3. Samples that give ash within satisfactory limits are usually assumed to be sufficiently accurate for other analyses, except under special condi¬tions such as meeting close specifications for coals showing wide variability in sulphur, fusibility of ash, or other quality. 4. In modern coal sampling the increment is recognized as the basis for taking samples. For a given accuracy the number and weight of increments specified are increased with: (a) the expected ash, and (b) the top size designation of the lot to be sampled. 5. It is extremely important that every sampler recognize that: the specified number and weight of increments are minimums, and that the precautions to be used in order to take them properly are also minimums; that in the reduction of the gross sample the sizes specified for the coal after each stage of the crushing are maximum; that the quantities specified to be taken after each crushing stage are minimum; that any short cuts or failures to meet the requirements specified will reduce the statistical accuracy of the results, although it is possible that one or two checks on a few results may seem to show otherwise.

Jan 1, 1943

By C. C. Mattax, J. E. Bobek, M. O. Denekas

ABSTRACT investigations in recent years have shown that rock wettability can exert a profound influence on the displacement of oil by water from oil producing reservoirs. Core analyses frequently show oil recoveries from preferentially water-wet rock to be significantly greater than those from preferentially oil-wet rock. Thus, an accurate prediction of water-drive or waterflood oil recovery is dependent on the evaluation of reservoir rock wettability. Laboratory and field studies have been undertaken to examine and develop methods which may be used to measure rock wettahililiy, to investigate factors which may alter the wettability of reservoir rock, and to determine the wettability of specific reservoirs. It has been found that measurement of the rate and volume of spontaneous imbibition of the wet-ting phase by a rock is a reliable and reproducible test for semi-quantitarive determination of preferential rock wettability. Laboratory tests have shown that the wettability of reservoir rock may depend on both the crude oil composition and the rock type. Field and laboratory tests have indicated that coring flulids and core handling techniques can cause significant changes in the wettability of rock surfaces. However, a few fluids, brine in particular, appear not to affect core wettability and may be used when coring to determine reservoir wettability. Core handling and packing procedures have been developed which preserve core wettability during storage and laboratory testing. The wetfability characteristics of six reservoirs have been evaluated by wettabilify tests performed in the field on fresh cores cut with brine or special water-base muds. The tests indicated that all six reservoirs are water wet; however, the de-gree differed from one reservoir to another. INTRODUCTION Although surface properties of reservoir rock and interfacial characteristics of rock, crude oil, and water systems have been discussed for many years, the full significance of these properties to the production of oil is still in the process of evaluation. It is known, however, that one surface characteristic—preferential wettability of the reservoir rock—-is of paramount importance when the reservoir is being produced by water-flood or water-drive mechanisms. The importance of rock wettability has been pointed out by several authors'.',%* who have found that pref- erentially water-wet cores flood more efficiently than oil-wet cores; that is, more oil is recovered from water-wet cores in the early flooding stages than from oil-wet cores. Other authors'," indicate that waterflood oil recovery from cores of intermediate wettability may be greater than that from either strongly water-wet or strongly oil-wet cores. These recent investigations emphasize that the true wettability of a reservoir must be known before the performance of waterflood or water-drive reservoirs can be accurately evaluated. When reservoir wettability is to be determined by core analysis, precautions must be taken to maintain the original wettability which can be altered readily during coring5 nd testing.' In the coring operation the core may be partially or completely penetrated by the drilling fluid which, if it contains surface active materials, may drastically change the wettability of the core. Also, improper core handling during stcrage and testing may change its wettability because of evaporation of fluids or exposure to oxygen or surface active contaminants. One purpose of this paper is to discuss methods for obtaining, preserving, and testing cores without altering their original wettability. In addition, the results of wettability tests on fresh and preserved cores from six reservoirs are presented where special precautions were taken to obtain samples without altering their wettability during the coring operation.

By R. K. Hopkins

For a great many years fusion welding has been used in and around petroleum refineries, but it is only within six or seven years that the more important pressure vessels have been constructed by this process, because before that time the properties of fusion welds would not withstand such rigorous service. Since the adoption of fusion welding for the construction of this equipment, the refiner has required pressure vessels suitable for operation over a very wide range of conditions. On the one hand, vessels must operate at extremely high temperatures, in the range of 950" to 1000° F., and on the other vessels must be suitable for operation at sub-zero temperatures down as low as —75" F. Also, vessels are required suitable for operation at pressures upwards of 1000 lb. per sq. in., and as low as a 29-in. vacuum. In addition, vessels are required to withstand the attack of very corrosive mediums. It has been a rather difficult task for the fabricator to meet all of these requirements, but as a result of the extensive research carried on by steel manufacturers and several fabricators of class I vessels, practically all of these demands have been met. In order to meet the refiners' requirements for this wide range of conditions, the fabricator has worked closely with the metallurgist. This has enabled him to choose the proper base metal for each service condition, but it has been the fabricator's problem to develop a welding rod and welding technique, as well as a heat-treatment, that would produce in the welded vessel characteristics in and around the weld comparable to those in the base metal. Where corrosion is not a serious problem, and where the operating temperatures are not too high, ordinary carbon steel has served very well. But, when corrosion is serious, and/or when the temperatures are either very high or very low, it is necessary to use some form of alloy steel to give satisfactory service. A great deal of credit is due to the members of the Boiler Code Committee and also to the members of the Joint A.P.I.-A.S.M.E. Committee, who have formulated codes that insure the safety of the

Jan 1, 1935

By R. K. Hopkins

For a great many years fusion welding has been used in and around petroleum refineries, but it is only within six or seven years that the more important pressure vessels have been constructed by this process, because before that time the properties of fusion welds would not withstand such rigorous service. Since the adoption of fusion welding for the construction of this equipment, the refiner has required pressure vessels suitable for operation over a very wide range of conditions. On the one hand, vessels must operate at extremely high temperatures, in the range of 950" to 1000° F., and on the other vessels must be suitable for operation at sub-zero temperatures down as low as —75" F. Also, vessels are required suitable for operation at pressures upwards of 1000 lb. per sq. in., and as low as a 29-in. vacuum. In addition, vessels are required to withstand the attack of very corrosive mediums. It has been a rather difficult task for the fabricator to meet all of these requirements, but as a result of the extensive research carried on by steel manufacturers and several fabricators of class I vessels, practically all of these demands have been met. In order to meet the refiners' requirements for this wide range of conditions, the fabricator has worked closely with the metallurgist. This has enabled him to choose the proper base metal for each service condition, but it has been the fabricator's problem to develop a welding rod and welding technique, as well as a heat-treatment, that would produce in the welded vessel characteristics in and around the weld comparable to those in the base metal. Where corrosion is not a serious problem, and where the operating temperatures are not too high, ordinary carbon steel has served very well. But, when corrosion is serious, and/or when the temperatures are either very high or very low, it is necessary to use some form of alloy steel to give satisfactory service. A great deal of credit is due to the members of the Boiler Code Committee and also to the members of the Joint A.P.I.-A.S.M.E. Committee, who have formulated codes that insure the safety of the

Jan 1, 1935

By Lester W. Strock

METALLURGISTS handling lead and zinc ores have long been familiar with the spectrograph as a routine analytical tool, as its earliest regular use by American industry was in controlling impurities of zinc metal and its alloys. This application has been extended to other metal industries on an extensive scale, accompanied by refinements of procedure to such an extent that a large part of some metals produced, especially magnesium, aluminum and steel, are checked only by spectrographic methods for conformity to specifications. The spectrographic analysis of ores and other poorly conducting powdered solids presents difficulties not encountered with metallic samples, which can be arced or sparked as self-electrodes or can be readily dissolved, so that their solutions can be analyzed, as in the American Society for Testing Materials standard methods for zinc and zinc-base alloys. Spectra of powdered solid samples can be prepared by using carbon electrodes provided with a crater of suitable size, into which the sample is packed. Ore samples and many other powdered solid materials usually analyzed in the chemical and metallurgical laboratory are more complex and varied in composition than samples of metals produced in large tonnages. More preliminary work therefore is usually necessary in devising a spectrographic method for analyzing a given type of powdered sample than for analyzing metal samples, in order to use that method with confidence. The knowledge that the standard samples and unknowns produce equivalent line intensities at equal concentration is the fundamental basis of any quantitative spectrographic method. On the other hand, powdered samples have an advantage over metals in that any desired number of chemical compounds can be mixed dry in any desired ratio to produce a synthetic standard. Experience has shown, however, that spectra of elements in finely divided compounds introduced into a standard in preparing a synthetic ore sample do not always behave in the electric arc in a manner that produces spectral line intensities similar to those observed at the same concentration in a natural mineral. In ore samples minor elements frequently are contained in the crystal lattice of larger particles of an abundant ore mineral. Their dissociation and volatilization from the sample into the arc then proceeds differently in the standard and sample, with resultant differences in intensity. During the past 10 years I have devised and applied several quantitative spectrographic methods for determining various elements in rocks and minerals in connection with studies on their geochemistry,1 but the incentive has gradually changed since the summer of 1940 to the specific practical problem of searching for domestic sources of rare and strategic metals. The

Jan 1, 1945

By Walter Rosenhain

In selecting solid solutions for the subject of this lecture I have been guided by several considerations. The bodies known under that somewhat paradoxical name play a most important part in all types of alloys; consequently, a deeper knowledge of their constitution must 'be of fundamental importance to both metallurgical science and practice. Further, having been asked to deal with some of the more theoretical aspects of metallurgy, I have been tempted to describe certain considerations, which I believe to be novel, in regard to the nature of solid solutions. These considerations constitute a theory that requires much experimental confirmation, but they have passed the stage of speculations, for experimental evidence has become available and one inference after another, that can be derived from the theory, is found to be in accord with well-known facts. In putting before you these ideas and inferences, it must be understood that detailed quantitative proof of every step cannot be furnished. Our conclusions must therefore be stated with the reservation that their acceptance must depend on the manner in which the discovery of fresh facts may either confirm or confound them. If we wish to understand the structure of solid solutions we nust carefully realize the manner in which these bodies are formed in alloys. The formation of solid solutions is by no means confined to alloys, but it is desirable to confin5 attention, at the outset, to intermetallic solid solutions. It is not easy to formulate a precise definition of the term "solid solution." It may be said that a solid solution is a crystalline body formed from a liquid solution or from an intimate mixture of solids, or of liquid and solid, that retains in the solid state an admixture of the two substances (solvent and solute) as intimate as that which exists in a liquid solution. The term is undoubtedly paradoxical, for one usually associates solution with a liquid, but the difficulty cannot be evaded by using such a term as solidified solution, for this might refer to a solution that has set, or congealed, without undergoing crystallization. The German term mischkry stall avoids the difficulty and appears to

Jan 1, 1923

By Walter Rosenhain

In selecting solid solutions for the subject of this lecture I have been guided by several considerations. The bodies known under that somewhat paradoxical name play a most important part in all types of alloys; consequently, a deeper knowledge of their constitution must 'be of fundamental importance to both metallurgical science and practice. Further, having been asked to deal with some of the more theoretical aspects of metallurgy, I have been tempted to describe certain considerations, which I believe to be novel, in regard to the nature of solid solutions. These considerations constitute a theory that requires much experimental confirmation, but they have passed the stage of speculations, for experimental evidence has become available and one inference after another, that can be derived from the theory, is found to be in accord with well-known facts. In putting before you these ideas and inferences, it must be understood that detailed quantitative proof of every step cannot be furnished. Our conclusions must therefore be stated with the reservation that their acceptance must depend on the manner in which the discovery of fresh facts may either confirm or confound them. If we wish to understand the structure of solid solutions we nust carefully realize the manner in which these bodies are formed in alloys. The formation of solid solutions is by no means confined to alloys, but it is desirable to confin5 attention, at the outset, to intermetallic solid solutions. It is not easy to formulate a precise definition of the term "solid solution." It may be said that a solid solution is a crystalline body formed from a liquid solution or from an intimate mixture of solids, or of liquid and solid, that retains in the solid state an admixture of the two substances (solvent and solute) as intimate as that which exists in a liquid solution. The term is undoubtedly paradoxical, for one usually associates solution with a liquid, but the difficulty cannot be evaded by using such a term as solidified solution, for this might refer to a solution that has set, or congealed, without undergoing crystallization. The German term mischkry stall avoids the difficulty and appears to

Jan 1, 1923