Search Documents

By L. I. Cothern

The introduction of mechanized mining has created a demand for long working faces. It has also prompted mining men to contest the old theory that longwall methods can be used only where roof conditions are ideal and where pack-wall material is plentiful. "Longwall" as used in this paper means "modified longwall," "semi-longwall," or any of the various ''wall" or "long-face" methods of mining. Many mines are now using long conveyor faces that differ only in their methods of development, types of roof support and method of loading coal onto the conveyor. Some types of longwall operations are being carried on successfully under conditions heretofore considered impossible by men experienced in longwall mining. With possibly one or two exceptions, long-face methods in Alabama are a direct result of the need for lower mining costs. The advantages over room-and-pillar systems were clearly expressed in an article by Messrs. Fies and Lacy of the DeBardeleben Coal Corporation1 as follows: (1) increased tonnage per miner; (2) increased percentage of lump coal; (3) reduction in cost of development; (4) elimination of the cost of room yardage; (5) reduction in the cost of haulage, from ability to use larger cars; (6) reduction in the cost of machine cutting; (7) reduction in cost for tracks; (8) reduction in the cost of deadwork; (9) reduction in the cost of supervision. An attempt on the part of the operator to gain these advantages by changing from room-and-pillar to longwall requires considerable courage, and credit should be given to those men who have done their bit to meet the competition of rival fuels. The initiatory problems to be solved are in reference to: (1) retreating or advancing system, (2) length of wall, (3) method of roof support, (4) method of entry development, (5) type of conveyor or loader, (6) hand vs. machine loading (onto conveyors), (7) hand vs. machine loading in entries, (8) control of roof pressure,

Jan 1, 1940

By C. G. Dunn

IDENTIFICATION Of the kinds of orientation relationships that may exist among crystals is an important problem in the metallurgical field. As an aid to its solution standard orientations of several orders of twins would be very useful for rapid analyses to discover high-order as well as low-order twin relationships. Although data have been published that give orientations for three generations of twins, these data are not readily useful in the form presented; i.e., in a stereographic projection with one pole per orientation.1 However, accurate data based on calculations of the positions of all {100} planes for such groups would be very useful when presented in tabular form. Therefore, calculations have been made for a group of four orders of twins and the data are listed in Table 3. Illustrative applications are considered briefly, with the idea of pointing out what may be done with large groups of orientations. METHOD OF COMPUTING ORIENTATION OF A TWIN It is common practice to describe the orientation of a crystal in terms of the positions on a stereographic net of the poles of certain planes of the crystal. A single position on a net may be given it terms of two angle variables, two sets of which appear in the following equations: [Polar NetWalff Net x=rsinOocos4pyx=rcos0. y=rsinB,sin4,ny-rsin0.cos¢,, z=rcos0,,z=rsin0.sin4,,] The three numbers x, y and z determine a length r as well as a direction [(0, 0)] in an X, Y, Z coordinate system. In the present case, r will be set equal to (h2 + k2 +12)1/3, where h, k and 1 are the usual Miller indices for a crystallographic plane, a restriction that facilitates determination of the positions of poles of new planes from those of old or known ones,2 as will become evident later. Furthermore, since twinned lattices have certain planes in common, it is an easy matter to determine the orientation of a twin of a crystal if the orientation of the crystal itself is known. We start therefore with a crystal of known orientation (positions of three {100} poles given) and determine where the cube poles occur in first, second, third and fourth-order twins. Methods for identifying twinned lattices and for making the calculations to find the orientation of a twin have been published.3 4 Reference 4 will be illustrated in the calculation of the orientation of a twin, even though this method differs from the one used by the writer in obtaining the following data on four orders of twins. Consider a crystal S and its twin A1, A1 being one of the four {112} or {III}

Jan 1, 1945

By J. C. McKinnell

The appraisal of an oil lease may often be mad,? through production decline analysis, which requires description of the functional relationship between the oil production rate and either cumulative production or time. Heretofore, attempts to define the function appropriate to a given set of production data have depended to some extent on subjective procedures. The purpose here is to introduce an objective solution, obtained by combining the principle of least squares with the theory of equations. MATHEMATICAL ANALYSIS The fundamental differential equation appropriate to a general class of decline curves may be written. Solution of Eq. 1 for general boundary conditions may be written in terms of either the cumulative oil production or time: These equations constitute the mathematical expression of the so-called hyperbolic decline. Their complete description for a given set of production data requires the numerical evaluation of the three parameters1.', n, D, and (go),. For the special case of n = 0, Eq. 2 becomes q. = (q.), - DiN with the corresponding expression in terms of time being q. = (qa),e...........(5) Similarly, for the special case of n = 1, Eq. 3 becomes with the corresponding expression in terms of cumula- tive oil production being q. = (q.),e " '.......(7) Eqs. 4 and 5 constitute the mathematical description of the so-called exponential decline; Eqs. 6 and 7 are the mathematical description of the harmonic decline.',' Returning to the hyperbolic expressions, Eqs. 2 and 3 may also be written, q: = sNp + b........ (8) and where a = 1 - n; s = (n— 1)D,(q0);"; b = (go):-"; a'=-n;s/= nD,(qo);"; and b' = (go);-. Note that both Eqs. 8 and 9 are linear in either time or cumulative production with respect to an exponential function of the production rate. In other words, a straight line relationship results for both variables when associated with the appropriate power of q,. This fact is of prime importance in the application of statistical analysis. . STATISTICAL ANALYSIS For a given oil lease, the time, production rate and cumulative production are recorded records. To establish predictive formulas from Eqs. 2 and 3, it remains to determine numerical values for the three parameters [n, D, and (q,) .] through an investigation of the past history. Upon interpreting a, s and b as parameters, Eq. 8 may be expressed for every time interval of interest, i, over the past history as follows. (q,): = s(Np), + b........(10) In general, Eq. 10 will not be satisfied exactly, because of the assumptions in the expression of Eq. 1, and the errors and anomalies universally associated with production data. It will instead define the residual, s(Np), + b- CO=d......(11) Squaring both sides and summing over all the data points, m, under consideration yields

By Benjamin C. Craft

Oil and gas development in Louisiana during 1935 brought this state at the close of the year up to fourth place in the nation as a producing area. A review of development in North Louisiana centers around Rodessa, the most important reserve discovered in this area in many years. While the producing limits have not been defined, this discovery is one of the major developments of the year. New gas fields were discovered in Lincoln, De Soto and Bossier parishes. The Lincoln Parish discovery, completed flowing a highly saturated gas from the Glen Rose, further indicates the importance of deep-seated prospects in the interior salt-dome area. Minor extensions were made at Sligo and Pine Island. During the year, 126 oil wells and 103 gas wells were completed in North Louisiana as compared with 144 oil wells and 68 gas wells during 1934. The North Louisiana oil production was 9,617,405 bbl. as com-pared with 9,274,050 bbl. during 1934, an increase of 343,355 bbl., while the gas production increased 18 billion cu. ft. in 1935 over its 1934 figure. The Louisiana Department of Conservation gage of Nov. 1, 1935, shows an open-flow capacity of 4,563,725,000 cu. ft. per day from 941 wells in the Monroe field and 682,770,000 cu. ft. from 159 wells in the Rich-land field. A great deal of leasing continues in North Louisiana as a result of the Lincoln Parish discovery and development in the Rodessa field, especially in Bossier, De Soto, Winn, Lincoln, Bienville, Webster, Ouachita and Richland parishes. South Louisiana's position as an area of important reserves was further proved during the past year. Increased drilling resulted in the discovery of seven new fields: Lafitte, Garden Island Bay, Tepetate, Bunkie, St. Martinsville, Jeanerette and Big Lake. New sands or producing horizons proved productive in 15 of the proven fields. The total oil production for South Louisiana during 1935 was 40,731,-056 bbl. as compared with 23,255,437 bbl. during 1934. There were 222 oil and gas wells completed in South Louisiana during 1935 as compared with 214 oil wells during the previous period. Drilling during

Jan 1, 1936

By Benjamin C. Craft

Oil and gas development in Louisiana during 1935 brought this state at the close of the year up to fourth place in the nation as a producing area. A review of development in North Louisiana centers around Rodessa, the most important reserve discovered in this area in many years. While the producing limits have not been defined, this discovery is one of the major developments of the year. New gas fields were discovered in Lincoln, De Soto and Bossier parishes. The Lincoln Parish discovery, completed flowing a highly saturated gas from the Glen Rose, further indicates the importance of deep-seated prospects in the interior salt-dome area. Minor extensions were made at Sligo and Pine Island. During the year, 126 oil wells and 103 gas wells were completed in North Louisiana as compared with 144 oil wells and 68 gas wells during 1934. The North Louisiana oil production was 9,617,405 bbl. as com-pared with 9,274,050 bbl. during 1934, an increase of 343,355 bbl., while the gas production increased 18 billion cu. ft. in 1935 over its 1934 figure. The Louisiana Department of Conservation gage of Nov. 1, 1935, shows an open-flow capacity of 4,563,725,000 cu. ft. per day from 941 wells in the Monroe field and 682,770,000 cu. ft. from 159 wells in the Rich-land field. A great deal of leasing continues in North Louisiana as a result of the Lincoln Parish discovery and development in the Rodessa field, especially in Bossier, De Soto, Winn, Lincoln, Bienville, Webster, Ouachita and Richland parishes. South Louisiana's position as an area of important reserves was further proved during the past year. Increased drilling resulted in the discovery of seven new fields: Lafitte, Garden Island Bay, Tepetate, Bunkie, St. Martinsville, Jeanerette and Big Lake. New sands or producing horizons proved productive in 15 of the proven fields. The total oil production for South Louisiana during 1935 was 40,731,-056 bbl. as compared with 23,255,437 bbl. during 1934. There were 222 oil and gas wells completed in South Louisiana during 1935 as compared with 214 oil wells during the previous period. Drilling during

Jan 1, 1936

By J. E. Burke

Recent investigations have elucidated many of the phenomena of the grain growth process, but have also revealed some conflicting and unexplained results. Beck and his co-workers 1,2,3 have shown that grain growth continues with continued heating at one temperature until the average grain size approaches the thickness of the specimen. Plotting the logarithm of the average grain diameter, D, against the logarithm of the annealing time, t, they find the straight line relationship given by the equation: D = Ktm [,] with possible small deviations at short annealing times. K and n are constants at constant temperature. On the other hand, Wa1ker4 finds that, in alpha brass) the rate of growth falls off more rapidly than indicated by Eq i after long annealing, so that an equilibrium grain size is approached. Burke5 showed, using Walker's data, that time and temperature for grain growth are apparently related through an activation energy, H, according to the relationship: ] where h and tz are the annealing times necessary for the average grain size to increase from Do to D at temperatures T1 and T2 and R is the gas laws constant. In the case quoted, H had the value 60,000 cal per mol. The apparent validity of this relationship, at least up to 700°C, and the approximate value of H were later confirmed by Beck3 The results obtained by Beck Kremer, Demer and Holzworth2 for aluminum and aluminum-magnesium alloys could not be satisfied by such a relationship, since the slope of the isothermal curves increased with increasing temperature. These data indicate and Beck, Holzworth and HuV ater demonstrated expcrimentally that the only apparent factor controlling the rate of grain growth at constant temperature is the grain size. While many of the phenomena have been elucidated, a reasonably quantitative explanation of the process is lacking. There exists uncertainty even as to the primary driving force for grain growth, although there is a considerable body of indirect evidence that the interfacial energy of the grain boundary is responsible.7,8,io Making implicit use of this assumption, several authors14,16 have pointed out that grain boundaries should migrate toward their center of curvature. Harker and Parkerg have advanced this concept furthest, and show that one can expect grain boundary migration to occur only when the grain faces are curved, or when they meet at non-equilibrium angles. When the face is curved toward a grain A, for example, the atoms in the surface of grain B, on the other side of the boundary7 are on the average more surromded by the atoms of their lattice than the atoms on the surface of grain A. Because of thermal motion, the atoms at the interface will sometimes be attached to grain A and

Jan 1, 1949

By Jose A. Ruiz

INTRODUCTION For heterogeneous non-catalytic solid-gas reactions carried out in fluidized bed reactors, nominal bed temperature is an average value between gas and solid. For highly exothermic reactions, actual particle temperature can be up to hundred degrees above termocouple temperature, since heat dissipate at slower rate than heat generation during some steps of transformation. These micro instabilities at particle level can displace thermodynamic equilibrium from the desired phase to others. This effect is important when relatively narrow range of phase stability exists, like in sulphation roasting of sulphides, where bed discharge contains, in addition to the desired sulphate others metastable phases such as basic sulphate and ferrite. For example, for copper-iron sulphide concentration roasted below 680°C, no cupric ferrite is formed, as shown by Jakob et al., therefore the separate Kellogg's stability phase diagrams Cu-S-O represent the roasting (Fig.l). At temperature above this one, like 760°C for example, phase stability changes from CuSO4 to the basic sulphate Cu0•CuSO4. Solid state reaction between Cu0•CuSO4 and Fe203 also occurs to form cupric ferrite, Cu0•Fe2O3, therefore the Cu-Fe-S-O Kellogg's phase diagram of Fig. 1 (continuous line) represents this condition of roasting. Although both Cu0•CuSO4 and Cu0•Fe2O3 are metastable phases under normal operating conditions of sulphation roasting(1-10% SO2, 1-10% 02 and 680°C, points A and B,Fig. 1) sulphation of these species and particularly ferrite are slow and limited due to diffusional control. This explain why reactors discharge contains several phases: CuSO4, Cu0•CuSO4, CuO•Fe203 plus small amounts of CuS and FeS due to the baclonixed conditions of fluidized bed reactors. The presence of cuprous ferrite due to reducing conditions inside individual particles also occurs, but in very limited extent at the reaction interface, as it is demonstrated by the low soluble iron levels of calcines. On the other hand, the presence of cupric ferrites can be explained only due to the higher temperature achieved by particles, since below 680°C cupric ferrite formation does not take place. [ ] This phenomena also occurs for others non-ferrous metal sulphides concentrates roasted under sulphation conditions, such as 7n, Co and Ni. Therefore the prediction of discharge composition of fluidized beds is not possible based only on kinetics and mechanistics models alone or purely thermodynamical considerations, since all factors should be integrated to describe the overall phenomena. SINGLE PARTICLE TRANSFORMATION Assuming a first order reaction with respect to the gas and zero for solid, such as

Jan 1, 1984

By H. E. Elliott, R. S. Busk, A. T. Peters

ONE of the problems of the fabricator of metals and alloys is the propensity of some composition ranges toward abnormal grain growth during certain stages of fabrication. In this respect magnesium alloys are no exception among alloys. Fortunately, convenient foundry control methods have been developed by which the abnormal grain growth possible in certain magnesium-alloy castings can be suppressed. An unusual characteristic of magnesium alloys, however, is that castings of some composition ranges are subject to local grain growth during heat-treatment without the necessity of intentional mechanical stressing of the part prior to heat-treatment. This effect occurs only under certain critical casting conditions, and only in certain alloys of greater than about 8.5 per cent aluminum content, such as C alloy (Mg, o per cent Al, 2 per cent Zn, 0.2 per cent Mn) and G alloy (Mg, i0 per cent Al, 0.2 per cent Mn). The first observation of this phenomenon in cast magnesium alloys occasioned much surprise, since it is not observed in other metals. Jeffries and Archer' have stated that "the grain size of cast metals, provided they have not been plastically deformed, cannot be changed by heating below the melting point." The study of the conditions leading to abnormal grain growth in cast magnesium alloys, and of the mechanism of this phenomenon, has led to some very interesting observations. Perhaps the most significant of these was the observation that stresses originating from cooling contraction in magnesium-alloy castings are the only stresses necessary, under certain conditions, to cause local recrystallization and subsequent grain growth in the casting during heat-treatment. of abnormal local grain growth was a definite problem in the production foundry on C alloy sand castings. Illustrated (Fig. r) is a picture of a casting scrapped because of this defect. A mottled effect is produced in coarse-grained areas by suitable etching solutions. The properties of metal in the affected area are much impaired by such grain coarsening. Ultimate tensile strengths of half the normal value have been measured in metal of this nature. In this paper are described the techniques that have been developed by The Dow Chemical Co. for studying, and in large measure solving, this production problem. Also discussed are studies of the mechanism by which excessive grain coarsening occurs, and the fundamental conditions that produce this effect. The abnormal grain growth discussed in this paper will be referred to as "germination," since this term has been defined' as any process leading to an abnormally coarse grain size. This paper deals only with abnormal local grain growth that may occur during the solution heat-treatment of certain magnesium-alloy castings, as dis-

Jan 1, 1945

By Robert Bakish

VARIOUS aspects of structure-sensitive corrosion of single crystals and polycrystalline aggregates of Cu,Au have been presented in papers by the author, in association with W. D. Robertson. Prompted by some observations in the course of these studies, a new approach to the problem was undertaken. Results of these new experiments are reported here. Thin slices, less than 2 mm thick, were prepared from single crystals 3.5 mm in diam grown by the Bridgman technique. The crystals were homogen- ized for 300 hr at 850°C. Crystals with no deformation, crystals deformed in tension to the yield point, and crystals deformed 20 pct in excess of the yield point were used. Crystals of several different orientations were studied. Slices were immersed for one month in 2 pct aqueous solution of FeCl3 and, subsequent to this immersion, were subjected to bending. Immersion and bending were carried out at room temperature. The size and geometry of the crystals did not permit accurate data on the loads involved. A most unexpected result was obtained in the process of bending these slices of Cu3Au crystals normal to the (110) plane. Completely brittle be-

Jan 1, 1958

By Henry Howe

FIG. 1 shows a volute aging break which developed spontaneously in a hardened and tempered steel helmet between 19 and 38 days after it had been tested ballistically. A similar break, shown in Fig. 2, developed spontaneously in a similar helmet about 40 days after the ballistic testing. In this case the rupture occurred abruptly and with a loud report. The path of rupture in this second case, though much the less regular, is the more interesting of the FIG. 1. FIG. 2. two, in that it is an approximation to two parallel volutes centered at the point of impact of the projectile, just below D. Several weeks later, after the photograph for Fig. 1 was taken, a similar doubling of the volute crack occurred in this helmet, starting from the end of the eyelash crack near A and spreading thence to the left contra-clockwise for about ½ in. The negatives from which these pictures are made have not been touched up in any way, save writing the letters on them. In both cases the trajectory of the bullet was normal to the initial surface at the point of impact, and in both the helmet passed the ballistic

Jan 2, 1919

By W. S. Owen, T. Bell

The variation ox the M, temperature with nitrogen concentration has been determined experinzentally. The free-energy difference between martensite and the parent y Phase at the M, temperature,is computed for Fe-C and Fe-N alloys using recent solubility data fm the Fe-N system and new data for the variatim of the activity of the interstitial solute in the y phase with concentration. The "geometric model" is considered also, and the importance of Zener ordering is noted. It is shown that, although at any chosen concentration the M, temperature and the activity are significantly different in the two alloy systems, the free-energy duference is the same within the limits of experimental error, thus Providing further evidence of the very close similarity between the martensite transformations in Fe-C and Fe-N alloys. TO estimate the free-energy change accompanying the martensite transformation in binary interstitial alloys it is necessary to know the variation of the Ms temperature with interstitial solute concentration and some thermodynamic data. To date, only the Fe-C system has been discussed because this was the only system for which relevant experimental measurements had been made, but even in this case the data available are insufficient to permit the free-energy change to be calculated without the assumption of a thermodynamic model for the y and a solid solutions. The last comprehensive discussion of the topic was by Kaufman, Radcliffe, and Cohen in 1.960.' Since that time Ellis, Davidson, and Bodsworth2 have redeter mined the activity of carbon in y iron as a function of carbon content and Atkinson3 has measured the activity of nitrogen in Fe-N austenite. The M, temperature of Fe-N is reported in the present paper. Thus, it is now possible to assess the free-energy change accompanying the martensite transformation in Fe-N alloys on the same basis as that used to assess the change in Fe-C alloys. This comparison is of interest because it has been shown recently4 that the structure of the martensite formed in Fe-N alloys changes with nitrogen content in a manner exactly parallel to the changes in structure in the Fe-C series and that the strain associated with the distortion of the iron lattice in either the y or the a phase by a nitrogen atom is the same as that produced by a carbon atom. The work to be described tests whether or not this close similarity between the two systems extends to the thermodynamics of the martensitic transformations. THE Ms TEMPERATURES FOR Fe-N MARTENSITE Bose and Hawkes5 found the M, temperature of a eutectoid Fe-N alloy (2.35 wt pct N) to be 35°C. This single determination appears to be the only reported measurement of the M, temperature of an Fe-N alloy. In the present work a series of more than fifteen different specimens containing between 0 and 2.7 wt pct N were prepared by controlled nitriding of pure iron wire 0.010 in. diam. The iron was supplied by B.I.S.R.A. and was designated ACN2. The nitriding procedure, all aspects of which are critical, has been described in detail elsewhere.' Each specimen was quenched from the austenitizing temperature into brine at 20°C without removing the specimen from the ammonia-hydrogen atmosphere in which it was ni-trided. Alloys containing up to 0.7 wt pct N were fully martensitic. More concentrated alloys contained progressively more retained austenite. At 2.34 wt pct N the specimen was completely austenitic after quenching to 20°C. The M, temperature of specimens with M, temperature above 20°C (those containing less than 2.35 wt pct N) was determined by a thermal arrest technique. For the more concentrated alloys (2.35 to 2.70 wt pct N) the variation of electrical resistance with temperature down to -196°C was used. Unlike Fe-C alloys, Fe-N alloys cannot be reaus-tenitized in vacuum or in an inert atmosphere because excessive loss of nitrogen occurs, even in short times, at high temperatures. Consequently, the alloys were reaustenitized in the ammonia-hydrogen mixture corresponding to nitrogen equilibrium at the temperatures used. The specimens were quenched in a blast of cold hydrogen gas and the temperature, measured by a thermocouple welded to the 2.5-in.-long specimen, was recorded on a high-speed recorder. In the first experiments 0.002-in.-diam chromel-alumel wire thermocouples were used but it was found that these gave erroneous readings due to contamination by nitrogen pickup. Pt-Pt 13 pct Rh wires of 0.002 in. diam were found to be satisfactory. Further details of the experiments are available in the original thesis.7 The cooling rate was controlled between 400° and 4000°C per sec by adjusting the hydrogen pressure. At least three cooling curves were obtained for each composition. Each specimen was analyzed for nitrogen after quenching. To aid in the accurate location of the martensite arrest points a series of cooling curves of 0.010-in.-diam platinum wire were recorded and these, which did not contain an arrest, were used as comparison standards. Four specimens, each in the form of a 3-in. loop, were prepared from each of the four alloys containing more than 2.35 wt pct N. One specimen was used for nitrogen analysis, one for X-ray diffraction, and two for resistance measurements below 20°C. The latter specimens were quenched from 20°C into constant-temperature baths at selected lower temperatures.

Jan 1, 1968

By Stanley D. Michaelson, Norman Weiss

This was a year of realization. Some years are for planning and development, some for designing and building, others for fulfillment. With greater hopes and plans for the future than ever before, the year 1954, nevertheless, will be remembered principally because of project completion. Among copper mines, for example, there were Silver Bell, Copper Cities, Bisbee, Yerington, and White Pine. In iron, there were the Humboldt, Coleraine, Cerro Bolivar, and Eagle Mountain. In asbestos, Johns-Manville's new mill at Asbestos, Que. In uranium, completion of the ninth mill on the Colorado Plateau-Kerr-McGee's at Shiprock, N. M. In research, 1954 marked the completion of Kennecott's Research Center in Salt Lake City, one of the historic forward strides in the science of minerals beneficiation. The year was fruitful in other directions as well. Investigations of a fundamental nature were on the upswing, and pilot plant projects have also increased in size and number. Progress in new reagents and equipment was greater than normal. It can already be conservatively predicted-from the technological point of view-that 1955 and 1956 will be tremendous years.

Jan 3, 1955

By F. W. Jessen, James N. Howell

The accumulation of paraffin deposits in tubular goods has been recognized as a major production problem since the inception of the petroleum industry. This problem is not limited to any particular geographical area nor is it limited to a specific type of crude oil.' Generally speaking, "paraffin" deposition pertains to the deposition of any predominately organic material in flow lines, and possibly even at the sand face, which would hamper the production of oil. In some fields, a continuous effort is required to remove deposits of paraffin and in order to accomplish this, many unique methods have been devised. The best solution to this problem, however, is to prevent the formation of such deposits. One method which has been tried in a number of fields is the use of plastic pipe. The purpose of this investigation is to compare the relative effectiveness of several plastic materials to aid in the reduction or prevention of paraffin accumulations in surface flow lines. COMPOSITlON OF PARAFFIN DEPOSITS By definition, paraffin deposits are those materials which are insoluble in crude oil at the prevailing producing conditions of temperature and pressure. Such deposits1 s usually consist of small particles of petroleum wax intermixed with resins, asphaltic material, and crude oil. They may also contain a variety of foreign materials such as sand, silt, water, various metal oxides, sulfates and carbonates of iron. barium, and calcium. The petroleum waxes deposited in flow strings usually consist of both a "hard" and a "soft" wax fraction. These waxes are largely aliphatic hydrocarbons with smaller amounts of aromatic and naphthenic compounds. Nathan' has classified the hard and soft wax fractions. The aliphatic hydrocarbons present are those of high molecular weight with high melting points. Reistle3 pointed out that these high molecular weight compounds first separate from the oil due to a sharp decrease in solubility as the melting point increases. The identification of the resins and asphaltic materials rests, at present, on an arbitrary solubility procedure. Under certain conditions, materials which are insoluble in pentane (ASTM D-893) are defined as resins and asphalts. Subgrouping of these materials is made on decreasing solubility in benzene and carbon disul-fide. Shock' found some correlation be-tween the solvent response and the pentane insoluble content of paraftins: higher pentane insoluble fractions are less soluble in any of the commonly used commercial solvents. PARAFFIN CONTROL METHODS The methods used in oil fields to prevent and remove paraffin accumulations can be grouped into four general classes: (1) operative methods, (2) physical methods, (3) chemical methods, and (4) combination of any of these. Operative methods attempt to prevent the formation of paraffin deposits while the other methods are concerned primarily with the removal of these deposits. Plastic coated pipe has been used for a number of years to prevent cor- rosion in wells, and in manv instances paraffin deposits have -been greatly reduced. Field observations have indicated that plastic coated pipe not only reduced paraffin accumulation but in some cases eliminated deposition completely; however, data are needed to demonstrate the relative effectiveness of plastic materials. Deposition Apparatus The pipe used to determine the effect of velocity on rates of deposition was %- and 2-in. nominal diameter, and 5 ft in length. Steel, butyrate, rigid PVC, kralastic resin-type plastic pipes, epoxy coated pipe, PVC lined glass fiber pipe, and aluminum pipe were tested. Steel pipe was used as a control. Fig. 1 is a schematic diagram of the apparatus showing the relative position of the separate units making up the equipment. In order to facilitate the installation and removal of the test pipes in the apparatus, O-ring seals capable of sustaining pressures of 50 psi were provided at each end. Test pipes were submerged in a cold water bath maintained at or below room temperature by circulating water through copper cooling coils packed in ice. A hot water bath equipped with immersion-type heaters, stirrers, and a thermoregulator was used to maintain the temperature of the oil prior to introduction into the piping manifold. The capacity of the oil reservoir was 30 gal. A 33-gal/min centrifugal pump, capable of producing turbulent flow velocities in the test pipes, was used to circulate the oil through the system when using %-in. pipe; and a 70-galjmin centrifugal pump was used in later tests using 2-in. pipe. A by-pass arrangement made it pos-

By William L. Boyd, Eugene L. McCarthy, Laurance S. Reid

Proper control of the moisture content of natural gas is essential to reliable operation of gas transmission and distribution facilities serving northern markets. The moisture content of natural gas is usually determined by dew point measurement at the existing pressure. For any gas of constant moistrire content. the dew Point varies with the pressure. A correlation of the data of several investigators is prezented in graphical form by the authors. These data were correlated by the authors and F. M. Townsend, C. C. Tsao. M. I). Rogers. Jr.. and J. A. Porter. graduate students in chemi(.a1 engineering at the University of Oklahoma. Of articular interest are the hitherto unpublished low temperature data observed by Wickliffe Skinner. Jr., which are included in this correlation. PRESENTATION OF DATA The problem of interpreting water dew points, or saturation temperatures. of natural gas in terms of specific moisture con-tent has increased in importance during the past decade bec.arl.;e of extensive development.; in the transmission and petro-chemical phases of the natural gas industry. Virtually all gas transported to northern and eastern markets must be dehydrated to a low water vapor content to prevent hydrate formation in transmission and distribution lines and resultant interruption.; in gas deliveries. Complete dehydration is required in certain phases of tile petro-chemical industry involving low-temperature operations. It is a well-known fact that the water vapor content of pure hydrocarbon vapors and their mixtures at superatmospheric pressures cannot be predicted with accuracy by assuming validity of the ideal gas laws." Earlier interest in the general problem was concentrated on the water vapor content of pure hydrocarhons and hydrocarbon mixtures in the pressure and temperature ranges common to gas and oil producing reservoirs in order to obtain fundamental data for the improvement of production techniques and the furtherance of reservoir studies. Excellent data are published for pressures ranging from atmospheric to 10,000 psig and for temperatures ranging from 100° to 460° F4,9,10,11 and are found to be in close agreement. However, experimental data at high pressures and temperatures below 100°F are comparatively limited in scope. Experimental data in the lower temperature range have been reported by Laulhere and Briscoe.8 Deaton, et al,2,3 Hammerscllmidt,5,6 and wade," In general, the pressures employed in these investigations ranged from atmospheric to 1.000 psig while temperatures ranged from 32° to 120°F; i.e., the usual conditions encountered in gas transmission line operations, Additional data were reported by Russell, et al,12 at pressures as high as 2.000 psig and covering a rather narrow atmospheric temperature range. In 1947, Hammerschmidt published a correlation of all available data,' in which the water vapor content of gases at saturation. under high pressure and low temperature. was predicted by extrapolation. In 1948, Wickliffe Skinner. Jr.. presented data on the moisture content of a low nitrogen content gas at low temperature and at pressures ranging upward to 1.500 psia.1-3 Comparison of Skinner's experimental data with the extrapolated data of Hammerscllmidt revealed an appreciable variation in the lower temperature range. emphasizing the need for a new correlation which would rely on Skinner's data at lower temperatures. Careful scrutiny of available data suggested that presence of an appreciable quantity of nitrogen in a gas mixture may affect its saturated moisture content so that data obtained from gases with more than three per cent nitrogen were not used in this correlation. CORRELATION OF DATA Data employed in this correlation are presented in Table I. The data of Dodson and Standing.4 McKetta and Katz,9 and Olds, Sage and Lacey10 were compared and found to be in close agreement so that the data of Olds. et al, re-plotted in a more convenient form by the Humble Oil and Refining Co.,' were used for temperatures of 100°F and above. Skinner's data were used for temperatures below 40°F. Between these intermediate temperature limits, the data of Hammerschmidt.7 Wade" and extrapolated data of Olds. et al.1 were tabulated

Jan 1, 1950

By E. T. Turkdogan, M. L. Pearce

The rates of sulfurization and desulfurization of calcium aluminate, silicate, and ferrite melts by CO + CO2 + SO2 mixtures at 1550°C are reported. It is shown that for melts 10 to 15 mm deep transport of sulfide ions within the melt controls the rate of sulfur transfer. The rate data from shallow melts, i.e., 1 to 4 mm deep, have been analyzed on the basis of a diffusion or a reaction controlled process and indications are that the both processes may play a part in controlling the rate of sulfur reaction. The rates of desulfurization of silicate XVEACTION equilibria between metals, metal oxides, and gases have received considerable attention in recent years. However, the understanding of and aluminate melts increase with increasing PCO2/PCO ratio in the gas stream, the effect being most marked for aluminate melts. The sulfide equilibrium data obtained from the present work are shown to be in accord with the results of previous studies. It is shown that carbon dioxide has a measurable solubility in silicate, aluminate, and ferrite melts. Consideration is given to the partial equilibria which control the directions and the rates of reactions occurring simultaneously in complex heterogeneous systems. the kinetics of heterogeneous reactions, particularly those occurring at elevated temperatures has not been improved appreciably. Almost all the metallurgical reactions occur in heterogeneous systems involving two or more phases. Although in many authoritative text books and original Papers the basic principles concerning the kinetics of heterogeneous reactions are clearly underlined, they are seldom used to the best advantage in kinetic studies, particularly those involving the metallurgical reac-

Jan 1, 1963

By E. M. Norris

THE Western phosphate deposits extend over a large area in the Rocky Mountain region, comprising portions of south central Montana, southeastern Idaho, northeastern Utah, and southwestern Wyoming. A limited acreage of these deposits passed into private ownership prior to Dec. 9, 1908, at which time 7000 sq. mi. of land in these phosphate fields was withdrawn from public entry by direction of the Secretary of the Interior. Under the Act of Feb. 25, 1920 (41 Stat. 437) title to all phosphate lands in the public domain was reserved to the United States with provisions for leasing portions to citizens, corporations, states, etc. The above act, in effect, created by law a Western phosphate reserve of approximately 2,269,055 acres.

Jan 1, 1944

By W. L. Fink, R. S. Archer

This paper describes results obtained on aluminum-beryllium alloys and aluminum-beryllium-copper alloys in the preparation of which aluminum of 99.95 per cent. purity was used. The constitution and structure of the high purity binary alloys are given. The aluminum-beryllium eutectic occurs at 0.87 per cent. beryllium and 645° C. The solid solubility of beryllium in aluminum at 631° C. is 0.05 per cent, beryllium, and at room temperature is less than 0.013 per cent. beryllium. The densities of the alloys are substantially the same as the values calculated on the assumption that the densities of the elements are not changed by alloying. All of the alloys age-harden at room temperature after a solution heat treatment, and the chill cast aluminum-beryllium-copper alloys age-harden at room temperature without a prior solution heat treatment. Hardness and tensile properties are given. Salt spray corrosion tests on sheet specimens are described. It is shown that beryllium docs not lower the corrosion resistance of aluminum to salt spray provided the alloy has received a solution heat treatment. Commercial Possibilities of Beryllium Alloys Beryllium has certain properties such as low density, high hardness, good corrosion resistance, low thermal expansion and fairly good electrical conductivity, which would indicate that it is worthy of consideration as an ingredient of light alloys. It was not until recently, however, that beryllium could be produced with sufficient ease to encourage research along this line. The production of beryllium by electrolysis from a fluoride bath has now developed to the stage where it could be used commercially if there were sufficient demand for the element. Claims made in certain newspapers and technical articles in regard to thc strength and corrosion resistance of thc aluminum-beryllium alloys are not justified by experimental results. Moreover, beryllium is an expensive metal ($200 a pound at the time this work was done) and, on account of the nature of its ore and the consequent difficulty of its extraction, it will in all probability continue to be a relatively expensive metal, although the cost would undoubtedly be a great deal less than $200 a

By Ralph W. Smith

Development of the lime industry in Ste. Genevieve County began in a crude way in 1840. According to information furnished by the Missouri Bureau of Geology, in the early days small vertical kilns built of stone were used, and wood was the fuel. Modern development began in 1904 when one company introduced steel shells lined with firebrick. Within a few years two more companies erected similar plants, and in 1925 a fourth company began operations. Thus there arc today four lime companies at Ste. Genevieve, all operating at high capacity and with a gradually increasing production. Geology The limestone of Ste. Genevieve County, which has the chemical composition and purity required for lime burning, is the upper 80 or 90 ft, of Spergen formation. The Missouri Bureau of Geology, in its geological map of Ste. Genevieve County, gives the Spergen formation a total thickness of 160 ft., but only the upper portion is pure enough for lime burning, with an average raw-stone analysis of 98.7 per cent CaCo3; 0.35 SiO2; 0.3 R2O3; 0.35 MgCO3; 0.3 SO3. The Spergen, one member of the Meramac group, Iowa series, of the Mississippian system, underlies an area approximately 12 miles long north and south, by 5 miles wide east and west (Fig. 1) in Ste. Genevieve County. The entire eastern two-thirds of Ste. Genevieve County is sedimentary, the formations dipping gently toward the east on an average grade of about 4 per cent, or 2 1/2°. Thus the outcrops of the various sedimentaries run approximately north and south. A line running west from Ste. Genevievc crosses the outcrops of the sedimentaries, ranging from the top of the Mississippian to the Ozarkian geological system in a space of 12 miles. Thus with the gentle dip of 2 1/2° the 160-ft. thickness of the Spergen formation stretches out in its outcrop so that it is approximately one mile wide. The early quarry and lime developments at Ste. Genevieve mere in this easily obtained surface rock of the Spergen outcrop.

Jan 1, 1938

By Ralph W. Smith

Development of the lime industry in Ste. Genevieve County began in a crude way in 1840. According to information furnished by the Missouri Bureau of Geology, in the early days small vertical kilns built of stone were used, and wood was the fuel. Modern development began in 1904 when one company introduced steel shells lined with firebrick. Within a few years two more companies erected similar plants, and in 1925 a fourth company began operations. Thus there arc today four lime companies at Ste. Genevieve, all operating at high capacity and with a gradually increasing production. Geology The limestone of Ste. Genevieve County, which has the chemical composition and purity required for lime burning, is the upper 80 or 90 ft, of Spergen formation. The Missouri Bureau of Geology, in its geological map of Ste. Genevieve County, gives the Spergen formation a total thickness of 160 ft., but only the upper portion is pure enough for lime burning, with an average raw-stone analysis of 98.7 per cent CaCo3; 0.35 SiO2; 0.3 R2O3; 0.35 MgCO3; 0.3 SO3. The Spergen, one member of the Meramac group, Iowa series, of the Mississippian system, underlies an area approximately 12 miles long north and south, by 5 miles wide east and west (Fig. 1) in Ste. Genevieve County. The entire eastern two-thirds of Ste. Genevieve County is sedimentary, the formations dipping gently toward the east on an average grade of about 4 per cent, or 2 1/2°. Thus the outcrops of the various sedimentaries run approximately north and south. A line running west from Ste. Genevievc crosses the outcrops of the sedimentaries, ranging from the top of the Mississippian to the Ozarkian geological system in a space of 12 miles. Thus with the gentle dip of 2 1/2° the 160-ft. thickness of the Spergen formation stretches out in its outcrop so that it is approximately one mile wide. The early quarry and lime developments at Ste. Genevieve mere in this easily obtained surface rock of the Spergen outcrop.

Jan 1, 1938

By William E. Ford, Edward Salisbury Dana

I. Sul~harsenites, Sulphantimonites, etc. In these sulpho-salts, as further explained on p. 320, sulphur takes the place of the oxygen in the commoner and better understood oxygen acids (as carbonic acid, H2COs, sulphuric acid, H4S04, phosphoric acid, H3P04, etc.). The species included are salts of the sulpho-acids of trivalent arsenic, antimony and bismuth. The most important acids are the ortho-acids,

Jan 1, 1922