Search Documents

By S. C. Sircar, B. K. Dhindaw

KINETICS and mechanism of sulfation reactions have been studied extensively. Qualitative and quantitative data are reported for the kinetics and mechanism of sulfation reaction of copper oxide pellets;''2 yet it remains a controversial Subject. The mechanism and kinetics of the sulfation of zinc oxide powder (B.D.H. analar quality) were studied by gravimetric technique. A spring of high-carbon steel wire with accuracy well within 0.2 mg was used for measuring weight change. The sample was taken in a Pyrex glass bucket, hanging freely inside a Pyrex glass tube reactor, with a gold wire attached to the spring, the reactor being surrounded by a movable furnace (double wound type) with a temperature control within *5"C. Flow of oxygen, 60 cu cm per min, and sulfur dioxide, 45 cu cm per min, were measured through calibrated flowmeters and the mixture dried over PZ05 before entering the reactor. The experimental results are presented in Figs. 1 and 2. The plot of weight change of zinc oxide, giving the amount of zinc sulfate formed, was found to be linear over the temperature range of 500" to 700° C and up to a conversion of approximately 60 pct, as beyond it they divert from linearity.' The rate of sulfation was found to be affected by total flow rate of gases at a fixed ratio of SO2/O2, up to 60 cu cm per min, and was found to be linearly dependent on quantity of total powdered sample taken. The plot of rate of sulfation of zinc oxide, 70 mg, with varying amounts of vanadium pentoxide, at a constant ratio of gases as mentioned above, and at a constant temperature of 625"C, was also found to be linear as seen in Fig. 2. Extrapolation to zero V2O5 addition gives the same rate of sulfation, as in case of pure zinc oxide, 70 mg. Vz05 was prepared by heating ammonium vanadate at 600°C for 15 min in a muffle furnace. The available literature points out that the theory of sulfation that has received the maximum support postulates the following mechanism for sulfation of ZnS: 2ZnS + 30, = 2Zn0 + 2SOZ; the ZnO formed acts as a catalyst for the reaction, 2 S02 + O2 = 2S03. This SO3 reacts with ZnO to give zinc sulfate. It is suggested here that the above widely supported mechanism is operative in the sulfation reaction and that the rate-controlling step in the sulfation reaction of ZnO is the formation of SO3 from SO, and 0,. The authors are carrying on further work in this line, and the details will be published later. The authors wish to acknowledge the facilities provided and the help extended by Prof. P. R. Dhar, Head, Department of Metallurgical Engineering, and the permission granted to publish this note by the Director, I. I. T., Kharagpur.

Jan 1, 1969

THE first session, on alloys, took place on Feb. 20, Mr. Hibbard presiding in Mr. Campbell's absence. The session covered papers on manganese, chrom-ium, and silicon-iron systems. The paper by Mr. Wohr-man was presented by title. This paper showed that manganese produced many of the effects generally at-tributed to carbon and indicated that our ideas on manganese-bearing carbon steels will have to be modi-fied. Mr. Krivobok discussed this paper at length, the gist of the discussion being that Mr. Wohrman had not taken sufficient precautions in carrying out some of his work, particularly as to the effect of silicon content. Mr. O'Neill's paper was also submitted by title and no discussion was presented. Mr. Kinzel showed an accu-rate determination of .the carbon-free chromium-iron loop obtained by means of a specially constructed tele-scopic dilatometer. The loop ends at 12.2 per cent chromium and the A-3 line at 900° is unaffected by chromium content. The A-4 line runs from 1400° to 900° at 12.2 per cent chromium as an oblique hyperbola. Mr. Armstrong noted that the brittleness in high chromium alloys is often attributed to the gamma trans-formation and, according to Mr. Kinzel's diagram, this was impossible, as the alloys contain a great deal more than 12 per cent chromium. Mr. Kinzel pointed out that the presence of carbon in the commercial alloys caused the elongation of the loop and made possible local austenite transformation. Mr. Styri discussed the relations of the coefficients of expansion as shown in Mr. Kinzel's diagram. Mr. Corson presented the iron-silicon diagram as he has worked it out, showing a pre-viously unknown intermetallic compound, Fe3Si, to-gether with characteristic martensitic microstructure varying with the heat treatment. This compound formation is the real cause of brittleness in certain re-gions of the iron silicon system. Dr. Hoyt believed some of the evidence presented by Mr. Corson to be in contradiction to the phase rule. Mr. Corson, however, explained that true equilibrium does not exist under the conditions at hand so that the diagram was accurate in spite of the discrepancies. The meetings of the subcommittee on the physical chemistry of steel making were interspersed through-out the day. Mr. Feild presided and a program of future activities was outlined. This includes plans for a symposium at the next annual meeting and methods for interesting physical chemists, particularly those in the universities, in the steel man's problems. This committee has been newly formed and bids fair to be especially active. The Iron and Steel Committee met at lunch at the Engineers' Club at noon, with Dr. Mathews presiding. After disposing of the food the report of the Nominat-ing Committee was called for, and the following were elected as officers for 1928: R. H. Sweetser, chairman; F. C. Langenberg and W. J. Priestley, vice-chairmen; and T. T. Read, secretary. The report of the commit-tee appointed at the last meeting to consider publica-tion and general policy for the committee was then called for and freely discussed, after which it was unanimously voted to instruct the new chairman to se-cure from the Board of Directors the necessary author-ization for the Committee to recognize as a Division. This action was reported to the Board at its meeting the following night and the authority granted.

Jan 3, 1928

* The greatest and richest iron ore body in the world was discovered by U. S. Steel in Venezuela in April 1947, and is disclosed for the first time in this issue (p. 178), One solid mountain of ore, Cerro Bolivar, will furnish more tonnage than the famous Hull Rust pit at Superior has, or can produce. Total resources are on the order of 2 billion tons plus. Big Steel is now moving with great speed on construction to bring out this ore, and 10 million tons are scheduled for shipment into Baltimore and Birmingham by late 1952. This ore will arrive at, Pittsburgh at a price lower than present natural ores from Superior. The Venezuelan properties will be completely mechanized. •U. S. Steel and independent companies are embarking on a taconite beneficiation program of tremendous proportions, which must be speeded to completion in the 1950's (see p. 185). By 1960 over $l.2 billion dollars will be spent on Venezuela, taconite, and Labrador to solve the United States iron ore crisis. In addition, U. S. Steel will spend another $300 million plus for a new steel mill at Trenton, N. J., before 1955. •The Deister Concentrator Co. gave $500 to the 1950 Coal Division Scholarship Fund. •Howard N. Eavenson, in analyzing the bituminous coal situation (see p. 193), suggests that anti-trust laws be extended to labor unions, disinterested trustees to administer pension funds, begin pension funds now and stop the collection of all "check-offs" for union dues or funds. •Minerals and metals worth 13.9 million dollars were produced in the United States in 1949, Secretary of the Interior Oscar L. Chapman announced. Although this value was 11 pct less than in 1948, it was the second greatest in history. Nonmetallics was the only major group that in 1949 equaled the 1948 production high. Mineral fuels decreased 12 pct and metals 15 pct. • Prospects for making gas from coal are seen to be unattractive by the Pittsburgh Consolidated Coal Co. because the success of operation depends on price and supply of coal which presently are not attractive. The company has shut down its gasification plant at Library, Pa. * Economic prospects for the immediate future in the United States are good and business probably will continue at its present high levels throughout at least the early part of 1950, Secretary of Commerce Charles Sawyer said in his year-end report to the White House based on his personal survey of business conditions. •A 467-ft well 34 miles north of Rock Springs, Southwestern Wyoming, is said to be flowing a 5 pct solution of nearly pure trona (sodium carbonate) at the rate of 10,000 barrels a day. Trona, natural soda ash, is mined for the chemical trade at Searles Lake, Calif., and from about 1500 ft underground near Green River, Wyo., and has been in short supply. •The AEC is "very much interested" in a discovery of radioactive material that has been made in Baraga County bordering Lake Superior in the Upper Peninsula of Michigan, reported F. G. Pardee, Michigan State mining engineer. The material has been identified as uranium oxide in the form of pitchblende or uraninite. The discovery, made by a geologist of the Jones & Laughlin Ore Co., is the only instance in which the commission has certified samples of Michigan rock.

Jan 2, 1950

By Jacques Steininger, Robert E. England

Single crystals of ZnTe and ZnTe1-,Sex with x up to 0.13 have been grown from the elements by temperature gradient solution zoning using excess tellurium as a solvent. Best results have been obtained with charges with the compositions 45/55 at. pct Zn, Te, for ZnTe and increasing amounts of selenium for ZnTe1-xSex. The temperature in the molten zone was maintained at about 1070°C with a gradient of about 10°C per cm. Chemical analyses of quenched ZnTe ingots show tellurium concentrations in the molten zone as high as 70 pct with concentration differences across the zone of 1 to 2 at. pct Dark dots which are observed by transmitted light microscopy in as-grown crystals can be removed by annealing in zinc vapor at 900 C. INTEREST in wide band gap semiconductors has led to a new study of ZnTe and ZnTel-xSex crystal growth. ZnTe is the only II-VI compound with a wide band gap (2.3 ev) that can be made p type with low resistivity. Attempts to make it n type with low enough resistivity to be useful for p-n junctions have so far been unsuccessful.1 ZnSe has a band gap of 2.65 ev but can be made n type only. However, ZnTel-xSex solid solutions with x as low as 0.36 have been made both highly n and p type2 with a minimum band gap around 2.12 ev3 at room temperature and appear to hold the best promise for efficient injection electroluminescence in the visible. ZnTe has the lowest melting point of the zinc chal-cogenides (1295°C) and consequently attempts have been made to grow crystals from both the liquid and the vapor phase.4 Complicated apparatus is required for growth from stoichiometric melts because of the high vapor pressures of the elements at the melting point of ZnTe and because of the problem of quartz devitrification. Small crystals have thus been grown in high-pressure equipment by Fischer5 and by Narita et a1.6 with pressures of the order of 50 atm of argon to prevent excessive evaporation from the melt. Large crystals of ZnTe can be obtained by growth from the vapor phase4 but they often present numerous dislocations and inclusions. An improvement in the quality of vapor- grown ZnTe crystals was reported by Albers and Aten7 by equilibration of mixtures of small crystals with compositions lying on either side of the solid single-phase field at fixed temperature. The same technique was later applied by Aten8 to the growth of ZnTe1-xSex crystals with less than 1 pct inhomo-geneity. Because of the higher liquidus temperatures of the solid solutions and the high vapor pressure of selenium, previous attempts to grow ZnTel-xSex from the melt have been limited and unsuccessful.9 The phase diagram of the Zn- Te system is reproduced in Fig. 1, based on data from Kobayashi10 and Kulwicki.11 Carides and Fishher12 have reported lower liquidus temperatures on the tellurium-rich side, but their data would require confirmation. The liquidus temperature on the tellurium-rich side decreases rapidly with increasing tellurium concentration and the Te2 vapor pressure over the liquidus also decreases accordingly.'3 The decrease in liquidus temperature and vapor pressure therefore makes it possible to use conventional apparatus if there is a sufficient excess of tellurium in the melt. Single crystals of ZnTe have thus been grown by Kucza,14 in a modified Bridgman technique, from solutions containing up to 60 at. pct of Te by lowering unsupported quartz ampoules through a temperature gradient at about 1200°C. Under these conditions, the phase diagram indicates that the entire charge is initially molten. Crystal growth can therefore proceed by normal freezing and rejection of excess tellurium into the melt. The modified Bridgman technique has several major limitations. Because of the rejection of excess tellurium into the melt during freezing, the melt composition and the temperature at the growth interface vary continuously. They tend to follow the liquidus until the eutectic which is very close to pure tellurium (447°C, >99 pct Te). Since the solidus composition also varies with temperature,15 crystals grown by this method are inhomogeneous. They present small variations from stoichiometry which may affect their structure and physical properties. The simultaneous increase in tellurium content and decrease in melt temperature also combine to reduce the rate of diffusion of tellurium away from the growth interface, thereby causing constitutional supercooling and possibly dendritic growth. To minimize these effects, the initial melt composition is in practice kept relatively close to stoichiometry (less than 60 pct Te). This however limits the possibilities of operating at low temperatures and pressures. This paper describes a modified method of crystal growth by temperature gradient solution zoning (TGSZ) which is an adaptation of the temperature gradient zone-melting technique developed by pfann16 and of the traveling solvent method of Mlavsky and weinstein.I7 The TGSZ method now applied to the growth of ZnTe and ZnTel-xSex crystals is characterized by its very simple experimental arrangement and sample preparation technique. Unlike the modified Bridgman technique, there is no increase in the tellurium concentration in the melt and therefore it is possible to operate at lower temperatures and pressures. This method is also suitable for maintaining a constant temperature at the growth interface.

Jan 1, 1969

By P. G. Shewmon, H. E. Collins

A study has been made to determine the sites at which sulfur adsorption occurs on copper surfaces. measurements were made of the relative torques, Ys, at the intersection of twin boundaries with surfaces near the three low-index orientations, i.e., (100), @lo), and 011), over a range of H2S/H2 ratios. HZS concerztvations j'ro~n 3 to 1500pp)n between 830" and 1050°C were used. It is concluded that sulfur adsorption occurved preferentially though not exclusively at edge sites near the (100) and (110) surfaces in the HzS range — 700 Ppm giving rise to negative torques near these orientations. Beyond this HzS range, adsorption occurred at all sites. Near the (111) surface, 7/y little with HzS concentration up to approxiwzately 75pptn. Above this range, the results indicate adsorption is occurring OH both terrace and edge sites. SCIENTIFIC interest in surfaces and their interactions with a gaseous environment dates back to the beginning of the 19th century. The scientific luminaries of that period—Faraday, Maxwell, Rayleigh, Dewar, and Gibbs—were already concerned about such processes. However, it has only been within the past several decades that adsorption on metal surfaces has been actively studied. This increased interest in adsorption has been brought about by the advent of new and improved experimental techniques and apparatus, e.g., ultrahigh vacuum, and field-emission and ion microscopes. However, most of the work done using these techniques has been carried out at low temperatures. When adsorption studies have been made at either low or high temperatures, they usually gave no indication of the particular surface orientations or type of sites on which adsorption was occurring. In the last few years, there have been a series of studies in which the surface tension, y,, and/or its derivative with respect to orientation, 7, have been studied as a function of orientation and atmosphere.'-7 Nearly all of the work on the relative torque,* ~/y, silver annealed in hydrogen and air.6 Recently Winterbottom and Gjostein" have used a modified and more accurate Mykurian method to determine the y plot of gold in hydrogen The only work in which T/~, has been measured over a range of chemical potentials for a given solute, p2, is that of Robertson and shewmon7 on the Cu-0 system. They measured T/Y, vs Po, (10"" to 10- l3 atm) at 1000°C in various mixtures of Hz0 and HZ. From this work they estimated the value of p2 at which one half of the surface sites are occupied with oxygen, pg, as being in the range 10- l6 to 10- l5 atm of oxygen. They also found that increasing Pa increased the magnitude of ~/y, near the (111) and (100) orientations. This indicates that oxygen is not adsorbed preferentially at step edges, but uniformly over all surface sites. In addition, they did one experiment on sulfur adsorption on copper surfaces, which indicated that sulfur adsorption decreases ~/y, near the (100) orientation, while not affecting ~/y, near the (111). This could be interpreted as indicating that sulfur adsorbs preferentially at step edges near the (100). In this paper the primary objective of the work has been to carry out a study of sulfur adsorption on copper surfaces over a range of temperatures and p,. In conjunction with this work, thermal grooving at grain boundaries has been examined as a method of determining the effect of sulfur adsorption on y,. METHODS Ideally, one would like to have information on the quantity of solute adsorbed on a surface and the types of sites at which it is absorbed as a function of p2. The total quantity adsorbed or the surface excess is given by the thermodynamic equation Thus data on the variation of y, with pz indicates the value of p2 at which adsorption becomes appreciable and the quantity adsorbed. The type of adsorption site is more difficult to deduce but information on this can be obtained from the variation of rz with 8, the angular deviation of the surface orientation. This is obtained from the thermodynamic equationlg Data on t and ys as functions of p2 have been obtained by the following methods. 1) Twin Boundary Grooving—By determining the effect of adsorption on the torque, 7, where T is the variation of surface energy, y,, with orientation, it is possible to obtain some indication as to the preferred sites of adsorption. Experimentally, the torque value measured is the relative torque, 7/ys The twin boundary grooving technique suggested by Mykura'' was used in this study to determine near the three low-index orientations— (loo), (110), and (111). Mykura's equation relates 7 /yS to measurements of the di-

Jan 1, 1967

By H. J. Winters

Position of the Porphyries in US Copper Supply The United States continues to be the largest producer and consumer of copper in the world. [Table 1] shows several production statistics for 1974, the most recent year that the non-communist world copper industry might consider a good year, and for 1976 and 1977. In 1974 an estimated 24% of the non-communist world's newly mined copper was mined in the US, and 87.89% of that was from the western porphyry coppers. In 1976 US new mine production was down to 22% of the non-communist world's newly mined copper, and the percentage of US new mine production supplied by the porphyry coppers had risen to 89-91%. In 1977 the statistics remained the same as in 1976. US porphyry copper production represented about 65% of US refined copper consumption in 1974, rose to 75% in 1976, and dropped back to 61% in 1977 as imports of foreign copper into the US began to swell. The financial situation of the porphyry copper mining industry continues to be very unhealthy. To see why; we can take a quick look at costs and prices.

Jan 1, 1982

By P. L. De Bruyn

The adsorption density of dodecylammonium ions at the quartz-solution interface has been Theadsorptiondensitydetermined as a function of collector concentration and pH. A ten thoushasbeenandfold range of amine salt concentration was covered at neutral pH. Experimental results show that over a thousandfold concentration range at neutral pH, the adsorption density (I) is proportional to the square root of collector concentration. Except at high concentrations, I increases with increases with increasing pH, but in general this effect is surprisingly small. . , . . A critical pH curve has been established for the flotation of quartz with dodecylammonium acetate. The conditions along the flotation curve are correlated with the adsorption measurements. THE behavior of collectors at the mineral-solution interfaces is usually explained in terms of an ionic adsorption process. Through the distribution of collector ions between the solid surface and the- co-existing solution phase the mineral is believed to acquire a water-repellent surface coating. Quantitative adsorption studies have been made on simple flotation systems1-4 only within the last few years. Such investigations were made possible by the adoption of the radiotracer method of analysis. As a consequence of these studies a new parameter has been added to aid the understanding of the flotation process. The research investigation to be discussed in this paper was undertaken to obtain a better understanding of the behavior of a cationic-type collector. This objective was approached through the determination of the distribution of dodecylammonium acetate between the quartz-solution interface and the solution as a function of the collector salt concentration and pH. To bring this investigation to focus on the more practical aspect of flotation research, an attempt was also made to correlate the adsorption results with actual flotation tests. Quartz: A —100 mesh ground crystalline quartz was infrasized; the products of the third and fourth cones were mixed together and reserved for experimental purposes. This stock material was cleaned by leaching in boiling concentrated HC1. After leaching the quartz was rinsed with distilled water until the filtrate showed no trace of chloride ian. It was then washed several times and dried. The qwrtz had a specific surface of 1400 cma per g as deterhined by the krypton gas adsorption method. Collector: The distribution of dodecylammonium acetate between the quartz surface and the solution phase was determined by the radiotracer method of analysis with carbon 14 as the tracer element. The radioactive amine salt with C" synthesized into the hydrocarbon chain5 was supplied by Armour and Co. The tracer element was located adjacent to the polar group. The radioactive salt as received had a specific activity of about 0.14 mc per g. When desired, dilution of this activity was effected by addition of non-radioactive dodecylammonium acetate also supplied by Armour and Co. ........ All other inorganic reagents used in this research were of reagent grade. Conductivity water was used for making up all solutions. Adsorption Tests: Two different experimental methods were used. In the first, to be designated as the agitation method, a weighed amount of quartz and a measured volume of amine salt solution were agitated in a 100-ml or 50-ml glass-stoppered pyrex graduated cylinder. The cylinder was filled with solution up to the stopper, since erratic results were obtained when an air space was left over the suspension. Time of agitation varied from 1 to 2 hr. Preliminary tests at different agitation times showed that the amount adsorbed remained constant for all agitation times exceeding 1/2 hr. After this conditioning period, the solids were separated from the solution by filtration through a Buechner fritted-disk funnel. The solution was re-circulated 10 times or more to allow the fused silica disk to come to equilibrium with it. Determinations of the amount of amine adsorbed on the frit itself indicated that this amount was less than 10 pct by weight of the amine acetate abstracted by 10 g of quartz. The funnel with quartz covered by a thin layer of solution was then centrifuged for approximately 5 min, at which time the moisture content of the solids was reduced to about 5 pct by weight. The wet quartz was blown into a tared beaker, re-weighed and allowed to dry at room temperature. A final weighing was then made to determine the moisture content. The second experimental method, similar to the procedure adopted by Gaudinand Bloecher,' will be referred to as the column method. Two liters of solution were passed through a bed of quartz contained in a Buechner funnel attached to a pyrex separatory funnel by means of a ball and socket joint. Preliminary tests showed that increasing the volume of solution above 2 liters does not give a measurable increase in adsorption. From 4 to 4 1/2 hr were required for 2 liters of solution to pass through the column. The moisture content of the quartz was again reduced to a minimum by centrifuging. A slightly modified column apparatus was used for experimenting with alkaline amine solutions. The same basic unit was used, but the underflow from the Buechner funnel was again fed into a Separafory

Jan 1, 1956

By Michel Elle, John Chipman

The equilibrium of gaseous H20-H2 mixtures with liquid iron-columbium alloys in the range 0.2 to 2.4 pct Cb shows that the activity coefficient of oxygen is strongly diminished by Cb. The oxide in equilibvium with the melt is identified as CbO2. The equi-librium constant at 1600 deg C is [%Cb][fo. % 0]2 = 2.9 x 10-4 where log fo= —0.14 [%Cb]. The deoxidizing power is comparable to that of vanadium, COLUMBIUM (niobium) is finding increasing use as an alloying element in steel. It forms several stable oxides and is removed from the steel bath by oxidizing slags. The specific oxide formed in steel-making is not known although Sazanov snd Shvarts-man,' in their study of its partition between slag and metal, have assumed this to be Cb2O5 It is the purpose of this study to determine its deoxidation equilibrium at 1600°c, the nature of the oxide formed and the interaction between columbium and oxygen in the melt. The investigation was based on the reaction H2 + O=H2O; Kl=ph2o/(pH2[%O]) [1] in which 0 signifies oxygen dissolved in the liquid Fe-Cb alloy. The method and equipment of recent studies2,3 were utilized. In brief, the molten alloy, contained in a small crucible, is held in a controlled mixture of steam, hydrogen, and argon until equilibrium is reached. It is then cooled quickly in a stream of helium and analyzed for columbium and oxygen, the latter by vacuum fusion.4 The solubility of the oxide in liquid iron is determined by visual observation of scum formation on the surface of the melt. Crucibles of MgO proved unsatisfactory because of partial reduction at the metal interface. Pure A12O3 crucibles were heavily blackened by the melt and could not be used at high concentrations of columbium. Silica crucibles were more satisfactory but these introduced some silicon into the melt thus necessitating an uncertain but small correction for its effect on the activities of the other solutes. In silica it was possible to observe the scum formation when the melt became saturated and there was no apparent reaction between scum and crucible. The procedure for saturated melts was as follows. The alloy charge composed of electrolytic iron and columbium grain was melted and held at constant temperature. The gas ratio H2O:H2 was progressively increased by raising the saturator temperature until a point was reached at which a bright film appeared on the surface and covered it completely. This film could be dissolved by raising the temperature of the melt and it reappeared when the temperature was lowered. Under a partial film covering, utilizing bare areas for temperature measurement, the melt was brought to equilibrium with the atmosphere by holding at temperature for about 1 hr as suggested by Dastur.5 INTERACTION IN THE MELT Several experiments were made without columbium to establish a base in silica crucibles. The results are shown in Table I. Except for one run, they agreed well with Floridis1 comparable results in other crucibles. The value of log K1 is taken from Table I as 0.58. This is slightly larger than Floridis' result, probably because of less elaborate safeguards against thermal diffusion. Results obtained in the Fe-Cb-0 series in which no scum formed are shown in Table 11. The equilibrium ratio Kl is defined as ph2o/(ph2[%O]). It is related to the equilibrium constant K1 as follows:

Jan 1, 1962

By Albert S. Trube

Increasing emphasis is being placed on the necessity for obtaining reasonably accurate estimates of the physical properties of reservoir fluids well in advance of more accurate laboratory data. One such factor is the isothermal coefficient of expansion of an undersaturated hydrocarbon liquid which may be contained in a particular reservoir. This coefficient, or liquid "compressibility", has often been assumed to be relatively insensitive and nearly constant. Although this assumption may be nearly correct in the case of high specific gravity liquids, it cannot apply in the case of medium to low specific gravity liquids. Any treatment of the nature of liquid compressibilities must give consideration to the variable nature of the isothermal expansion coefficient and the fact that it can be both pressure sensitive and temperature sensitive. The isothermal coefficient of expansion, or compressibility, of a substance is defined as -c = 1/V (?V/?p)T......(1) The value of Eq. 1 may be approximated for a finite pressure change by using the well-known relation, c = V1 - V1/Ve (p2-p1), ........(2) in which p1 > p1 and V2 > V2 and V1 + V2/2. The instantaneous compressibility may also be estimated from the slope of a curve on which log V is plotted vs pa. In this instance, it has been shown that c = In V1/V2/p2-p1 ...........(3) Eq. 3 may be used for variable compressibilities by plot-ting V vs p on semi-log paper. In this case, the instan-taneous or point compressibility is c = 2.303 m.......... . (4) in which m is the slope of the curve at a point in log cycles per psi. ISOTHERMAL COMPRESSIBILITY OF UNDERSATURATED LIQUID In the case of gases, the compressibility has been defined by Muskat' and others as Co = 1/p - ?z/z?p ..........(5) This was later generalized through application of the theorem of corresponding states' to co = 1/pr - (?z/z?pr) T8 ........(6) in which c, is defined as the pseudo-reduced compres-sibility and is numerically equal to (c.p,) and the sign is arbitrarily changed for mathematical convenience. Eq. 6 is general and applies to gases and liquids. In the case of liquids, c. = c1,pe, but if Eq. 6 is used, values of z and ?z/?p, must be determined for the liquid in question. The difficulty of obtaining accurate values of ?z/?p,, particularly in the region where T, is approaching 1.00, was pointed out in the previous paper'. This method of approach is unreliable for extension into computations of liquid compressibilities. On the other hand, c, can also be defined as follows: - Cr = 1/Vr (?Vr/?pr) Tr ......(7) and from which, Cr = 1/pr (?pr/?pr) Tr .....(8) In accordance with the theorem of corresponding states, Vr = V/Vr, p, = p/pr and pr = p/pr. Ref. 2 pro-vides an excellent source of reduced density, reduced pressure and reduced temperature data for a wide variety of fluids. For the purpose of this investigation, the set of fluids2 having ze = 0.27 was chosen because it in-cludes most of the heavier hydrocarbons usually found in those complex mixtures loosely defined as "reservoir oils". Data on undersaturated liquids in Ref. 2 were rearranged to conform with Eq. 8. To simplify the computation of cr, the isothermal p, data were plotted vs the log of pr, in which case for any straight line or tangent cr = 1/M pr pr .....(9)

Jan 1, 1958

By Charles Catlett

Some years ago the writer was struck by what might be called the remarkable vitality of the Virginia furnaces during the panic of 1893; and attention was called to the fact in the American Manufacturer of February 8,1895. From the second half of 1892, which was a period of maximum output, to the second half of 1893, when the full effects of the depression had been reached, the output of pig-iron had fallen off in Illinois 85; in New York, 66; in Ohio, 51; in Tennessee, 44; in Pennsylvania, 28; and in Virginia only 15 per cent. It seemed a reasonable inference that the State which had thus shown its marked ability to meet hard times could make and market its product with a larger margin of profit than any of the other States. This was true at that time, and to a certain extent the reasoning still holds good; but my mistake was in not fully realizing the marked effect of the Mesabi development, combined with reduced economies in transportation, and the consequent advantage to those furnaces which were so situated as to utilize these new commercial factors. The effect of these factors is seen in comparing the second half of 1894 with the second half of 1892. New York had dropped off 44, Alabama 23, Tennessee 21, Illinois 19, and Virginia 16 per cent., while Pennsylvania had increased 5 and Ohio 10 per cent. While there is no question of the great economy which has been made possible for certain interests which are peculiarly situated with reference to the ores of the Northwest, it is yet too early to say what furnaces not so fortunate will have to pay for their raw material. Already an increase of twenty cents per ton of ore has been announced, based upon increased cost of production.

Jan 1, 1900

By N. H. Darton

In the coastal plain region of the middle Atlantic slope there are no large supplies of potable surface-waters. The great rivers by which the region is intersected are tidal estuaries, and the water of their local branches is often of bad quality. The cities situated at intervals along the western margin of the region obtain a plentiful supply of excellent water from the rivers above the tidal estuaries, but out on the coastal plain surface-waters are mainly used. A few artesian wells have been sunk which afford abundant water, but their number is at present very limited. Norfolk, Newport News, and the many smaller places use surface-waters, and all over the region there is great need for purer and more abundant supplies. During the past five years I have been engaged in a study of the geology of the coastal plain for the U. S. Geological Survey, and have given special attention to the question of subterranean waters. In this communication I shall present a brief review of the geological conditions under which such waters occur in this region, and give an account of the wells which have been bored. Unfortunately the number of well-records is small, and some of the most important questions of subterranean geology are as yet far from settled. It is hoped that this paper may lead to further borings, especially as the cost of artesian wells has been much reduced by the introduction of new machinery and methods, and is now quite within the reach of the average community. In New Jersey there are many wells, and the water-bearing horizons are so definitely determined that they may almost everywhere be predicted with certainty. In Maryland and Virginia the data are less definite, but there is excellent evidence of a wide distribution of water at moderate depths.

Jan 1, 1895

By R. L. Huntington, D. T. MacRoberts, Charles R. Hetherington

Since the equation of continuity governing transient flow of gases through porous media cannot be integrated mathematically into a simple usable expression free from series terms, empirical and approximate equations have been advanced relating cumulative production and future production rates from gas reservoirs with time. In order to check the accuracy of these empirical equations and to obtain an insight into the initial conditions pertinent to the solution of the fundamental equation of continuity, experimental work has been conducted on a vertical 2-in. tube, 91.6 ft. high, packed with unconsolidated Wilcox sand. The results presented in graphical form show the accuracy of the approximate relations. Data from unsteady-flow runs on the 2-in. experimental tube are presented graphically, and are applied to obtain an equation for this specific case, and are offered as an aid in future investigations of this basic equation. The close agreement between equations calculated for steady-state flow and the experiments indicates that the decline of actual gas reservoirs may be treated by an application of these equations without serious error. Introduction The steady-state flow of gas through a porous material—that is, flow wherein the boundary conditions do not vary with time—is subject to analytical solution. Muskat1 has shown that the general differential equation is simply the La Place equation in P2. Direct solutions may be at once obtained. The unsteady state, on the other hand, is not analytically reducible. Since nearly all phenomena of practical interest in gas production involve flow in the unsteady rather than in the steady state, it has been necessary to derive approximate Solutions to the general equation. The validity of such approximations has not hitherto been adequately tested. In the experiments to be described a simple, closed, linear system is substituted for the real complex gas field. The general results, however, are independent of the geometry Of the system' The problem studied is the rate of production, and the accompanying variations in pressure, when one end of a linear porous system is opened to the atmosphere and permitted to produce to exhaustion. An approximate solution to the general differential equation, based upon the assumption of an "infinite series of steady states," is then applied to the results to determine the validity of this method of dealing with actual reservoirs. Theoretical Considerations The fundamental differential equation governing the flow of a gas through a Porous medium can be derived easily from the equation of continuity, Darcy's law, Boyle's law and a statement of the thermo-dynamic nature of the flow. For isothermal flow it is: d2P2/dx2 + d2p2/dy2 + d2p2/dz2 = 2fµ/K dP-dT

Jan 1, 1942

By R. L. Huntington, D. T. MacRoberts, Charles R. Hetherington

Since the equation of continuity governing transient flow of gases through porous media cannot be integrated mathematically into a simple usable expression free from series terms, empirical and approximate equations have been advanced relating cumulative production and future production rates from gas reservoirs with time. In order to check the accuracy of these empirical equations and to obtain an insight into the initial conditions pertinent to the solution of the fundamental equation of continuity, experimental work has been conducted on a vertical 2-in. tube, 91.6 ft. high, packed with unconsolidated Wilcox sand. The results presented in graphical form show the accuracy of the approximate relations. Data from unsteady-flow runs on the 2-in. experimental tube are presented graphically, and are applied to obtain an equation for this specific case, and are offered as an aid in future investigations of this basic equation. The close agreement between equations calculated for steady-state flow and the experiments indicates that the decline of actual gas reservoirs may be treated by an application of these equations without serious error. Introduction The steady-state flow of gas through a porous material—that is, flow wherein the boundary conditions do not vary with time—is subject to analytical solution. Muskat1 has shown that the general differential equation is simply the La Place equation in P2. Direct solutions may be at once obtained. The unsteady state, on the other hand, is not analytically reducible. Since nearly all phenomena of practical interest in gas production involve flow in the unsteady rather than in the steady state, it has been necessary to derive approximate Solutions to the general equation. The validity of such approximations has not hitherto been adequately tested. In the experiments to be described a simple, closed, linear system is substituted for the real complex gas field. The general results, however, are independent of the geometry Of the system' The problem studied is the rate of production, and the accompanying variations in pressure, when one end of a linear porous system is opened to the atmosphere and permitted to produce to exhaustion. An approximate solution to the general differential equation, based upon the assumption of an "infinite series of steady states," is then applied to the results to determine the validity of this method of dealing with actual reservoirs. Theoretical Considerations The fundamental differential equation governing the flow of a gas through a Porous medium can be derived easily from the equation of continuity, Darcy's law, Boyle's law and a statement of the thermo-dynamic nature of the flow. For isothermal flow it is: d2P2/dx2 + d2p2/dy2 + d2p2/dz2 = 2fµ/K dP-dT

Jan 1, 1942

By L. Dudley Stamp

On April 1, 1937, Burma, formerly a province of the Indian Empire, was formally separated from India and became an independent unit of the British Commonwealth. In future, therefore, statistics of oil production in India will exclude Burma and those for Burma will be separately published. The last few years have been marked by noteworthy, almost spectacular, developments in the oil fields of Burma and the Punjab. In Burma these developments have been the proving of unexpected extensions of the existing fields and not the discovery of entirely new fields. The new extensions are important not only to Burma in giving a new lease of life to her fields, but also in general as stressing some interesting geological aspects hitherto neglected. Production The production of crude oil in Imperial gallons has been: Burma India 1934 254,760,070 67,265,210 1935 251,338,974 . 71,323,362 1936 265,656,393 69,241,504 1937 (eat.) 270,000,000 70,000,000 The Chindwin Fields.—The small field at Indaw continues to produce steadily about 3,000,000 gal. a year, but no really deep test has yet been successfully carried out and resources are thus not yet fully known. The remote location of the field, inaccessible except by river and situated 22 miles from the Chindwin 270 miles up that river from its junction with the Irrawaddy, has not encouraged active exploitation. The field is worked exclusively by the Indo-Burma Petroleum Co., Ltd. (I.B.P.), using now an automatic gas-lift system, and the company formerly refined the oil at a small refinery at Pantha on the river near by. The chief market was for kerosene in upper Burma. The refinery has now been closed. The oil is stored on the field during the low-water season

Jan 1, 1938

By Perry Olcott

The Texas Gulf Coast had a rather disappointing year in the type of oil fields found. Although 17 fields were found in the area during the year, as against 21 fields in 1938, no field of major proportion was discovered. Of these 17 fields, 11 were oil fields, 4 were gas and distillate fields, and 2 were gas fields. The wildcat activity for the year resulted in about 400 dry holes, although probably 10 per cent of these were edge wells close to proved areas. During the year, 1455 oil and gas wells were completed as compared to 1637 wells in 1938, a decrease of 11 per cent. Production for the Texas Gulf Coast area for the year was 100,253,937 bbl. as against 92,530,467 bbl. produced in 1938, an increase of 8 per cent. The daily average production was 274,668 bbl. for the 365 days in the year, although only 252 producing days were allowed by the Railroad Commission; that is, 69 per cent of the time as compared to 71 days shut in for 80 per cent of the time producing in 1938. The total number of oil and distillate wells producing at the end of 1939 was 9495 as against 8451 at the end of 1938—an increase of 1044 wells, or 12 per cent. Of these wells, 6547 were flowing and 2948 pumping, or 69 per cent flowing. At the end of the previous year, 66 per cent of the wells were flowing. New Fields Angleton, Brazoria County.—The Angleton field was discovered by the completion of Glen McCarthy's No. 1 Carr in October for an initial production of 180 bbl. a day of 50" gravity oil through 11/64-in. choke with 3400 Ib. on tubing. The field is 1½ miles east of the town of Anchor. The discovery undoubtedly can be credited to the reflection seismograph, since several companies worked the area from 1933 onward with this type of exploration. The principal block was taken by the Humble company in 1934. Two deep holes by Humble revealed the presence of structure, although both were dry. The Humble and Sun companies later contributed money and acreage toward the drilling of the discovery well. The production is from a sand in the Frio, about 1700 ft.

Jan 1, 1940

By Perry Olcott

The Texas Gulf Coast had a rather disappointing year in the type of oil fields found. Although 17 fields were found in the area during the year, as against 21 fields in 1938, no field of major proportion was discovered. Of these 17 fields, 11 were oil fields, 4 were gas and distillate fields, and 2 were gas fields. The wildcat activity for the year resulted in about 400 dry holes, although probably 10 per cent of these were edge wells close to proved areas. During the year, 1455 oil and gas wells were completed as compared to 1637 wells in 1938, a decrease of 11 per cent. Production for the Texas Gulf Coast area for the year was 100,253,937 bbl. as against 92,530,467 bbl. produced in 1938, an increase of 8 per cent. The daily average production was 274,668 bbl. for the 365 days in the year, although only 252 producing days were allowed by the Railroad Commission; that is, 69 per cent of the time as compared to 71 days shut in for 80 per cent of the time producing in 1938. The total number of oil and distillate wells producing at the end of 1939 was 9495 as against 8451 at the end of 1938—an increase of 1044 wells, or 12 per cent. Of these wells, 6547 were flowing and 2948 pumping, or 69 per cent flowing. At the end of the previous year, 66 per cent of the wells were flowing. New Fields Angleton, Brazoria County.—The Angleton field was discovered by the completion of Glen McCarthy's No. 1 Carr in October for an initial production of 180 bbl. a day of 50" gravity oil through 11/64-in. choke with 3400 Ib. on tubing. The field is 1½ miles east of the town of Anchor. The discovery undoubtedly can be credited to the reflection seismograph, since several companies worked the area from 1933 onward with this type of exploration. The principal block was taken by the Humble company in 1934. Two deep holes by Humble revealed the presence of structure, although both were dry. The Humble and Sun companies later contributed money and acreage toward the drilling of the discovery well. The production is from a sand in the Frio, about 1700 ft.

Jan 1, 1940

By L. D. Jaffe, John H. Hollomon

Fox many steel parts it is desired to obtain the maximum toughness consistent with the strength required by the mechanical design. It is generally recognized that the greatest toughness at any given strength is found in steels having a tempered martensitic structure,1 and is virtually independent of the composition of the steel2 (except for carbon). The choice of the composition of a steel for the parts in question should be based, therefore, on hardenability considerations and on manufacturing facility and economy. In a recent paper3 the concept of hardenability was discussed and a somewhat new approach to the problem was suggested. The hardenability was defined in terms of the cooling conditions (speed of cooling) required to avoid the pearlite and the bainite reactions. Since all the alloying elements do not have the same effects on the two reactions, the bainitic and pearlitic hardenabilities must be considered separately. In order to design a steel for a given part, it is necessary to design a composition that has both sufficient pearlitic and sufficient bainitic hardenability. However, this requirement does not fix the combination of alloying elements to be used; an infinite number of steels would have the required hardenabilities. Other considerations limit the choice. For example, decreasing the carbon content increases the toughness at a given hardness, and for this reason low-carbon steels are often desired. Limitations or requirements of refining, casting, or forming practices often affect the level of some of the alloying elements. Price considerations enter. Frequently, however, it is very desirable to minimize the tendency toward quench-cracking while maintaining the necessary hardenability. This paper is concerned with suggesting a method for choosing compositions that will have the required hardenability together with minimum tendency toward quench-cracking. QUENCH-CRACKING Since only the case in which the entire part will transform to martensite in the particular quench employed is being considered, the analysis of the quench-cracking problem is somewhat simplified. Quench-cracking arises from the temperature gradients existing throughout the piece during cooling. Because of these temperature gradients, the contraction arising from the decreasing temperature and the expansion arising from the austenite-martensite reaction do not occur uniformly over the parts, and stresses are set up that tend to cause cracking. The temperature gradients can be reduced by decreasing the severity of quench. This, however, requires that the hardenability be correspondingly increased by increasing the carbon or alloy content. An

Jan 1, 1946

By Wm. Terry Siemers, Frank E. Kottlowski, George S. Austin

The value of industrial rocks and minerals produced in New Mexico in 1978 exceeded $227 million. The state ranked first in the nation in production of potash and perlite and was a leader in pumice production. Other commodities with sizable production in New Mexico include barite, caliche, clay, dimension stone, fuorspar, gypsum, humate, limestone, mica, salt, sand and gravel, scoria, and silica sand. Non-metallic resources are distributed throughout the state, but development and exploitation is concentrated in western and southeastern New Mexico. The value of industrial rocks and minerals within the state grew about 9% to more than $227 million in 1978. Continued growth, however, depends on continued demand, exploration, and development.

Jan 1, 1982

By D. H. Wertz, R. R. Furlong

Dry room equipment at Donora Zinc Works is of the design which prevailed at the time the plant was built in 1915. It consists of 11 adjoining rooms, each being 99 ft long, 11 ft wide, and 7 ft high and having a capacity for 1040 retorts. Heat is supplied by steam coils beneath the slatted wood floor and by warm air ducts at the ceiling. Drying practice is about the same as that generally followed in the industry except that, under normal zinc furnace operations, the maximum drying time is 45 days. During certain seasons of the year the drying process was seriously affected by varying weather conditions which frequently resulted in a scrap loss of 5 to 7 pct. Because of these unfavorable conditions, which caused uneven drying and strains in the retorts, increased retort failures in the zinc furnaces were recorded. Regulation of temperature and humidity under all conditions appeared to be the logical solution of this problem. Controlled drying had been developed for a number of ceramic products and investigation of several such drying processes in this area revealed favorable results. Along with control of drying conditions and the attendant decrease in scrap losses, plant operators also reported a material reduction in drying time. Another factor affecting the decision to proceed with this development was the drastic change in market conditions for retort clay. Curtailment of shipments from the chief source of supply made it necessary to proceed with blending of other available clays, but quality of these clays was questionable for adequate retort life in the 24 hr furnace cycle. Rapid furnace testing of new mixtures was desirable but impossible with the prolonged drying schedule. Therefore development of a controlled drying process for zinc re- torts offered the solution to the problem of rapid testing of retort mixtures. Description of Process and Equipment The freshly extruded retort is cylindrical in shape, 58 in. long, 9 in. id and has 1 1/8 in. side walls. One end is closed and approximately 2 in. thick. The moisture content of this "green" retort is about 17 pct which means a necessary removal of 30 lb of water per retort. Retorts are set on the slatted floor of the dry room with the closed end down. The controlled drying process depends upon the circulation of a large volume of conditioned air at low velocity. To provide for uniform distribu-

Jan 1, 1950

By J. S. Hromatko, L. J. Gurevich

In the course of the examination, at the BureLu of Standards, of fusible tin boiler plugs for the Steamboat Inspection Service, it became evident that an investigation should be undcrtaken to determine the precautions necessary in the manufacture of acceptable plugs. The results of the tests of these plugs show that their manufacture has improved, though at present not all of the plugs tested are, satisfactory. Table 1 gives the result of tests of some 1500 plugs from about 100 makers. Records of the tests show that several of the makers were able to produce satisfactory plugs with every pouring. The Steamboat Inspection Service has the following specifications for fusible plugs: "Fusible plugs for use in boilers of steam vessels under the jurisdiction of the Steamboat Inspection Service shall be made of bronze casing with the bore tapering continuously and openly from end to end, and filled from end to end with tin not less than 99.7 per cent. pure and to contain not more than 0.1 per cent. of lead and not more than 0.1 per cent. of zinc. The small end of the bore may be countersunk not more than 1/32 in. in depth and width, but no recess, thread, or cavity other than this countersink shall be allowed." Table 1.—Thirty-"five-mdh Testing Record of Fusible Plugs Causes of Rejection Inspection Period June-November, 1916.................. 311 32.8 47.2 3.8 11.5 15. 1 10.9 1 1.9 4.5 December, 1916-May, 1917............. 318 71.4 28.6 2.2 4.4 12.8 5.9 i ... 2.8 June-November, 1917.................. 228 73.0 27.01 ... 9.6, 5.2 9.6' ... 0.8 December, 1917-May. 1918............. 214 72.028.0 0.9 0.4 11.6 7.0 ... 7.9 June-November, 1918...............250 70.7 29.3 ... 2.0 20.0 5.2 ....2.8 December, 1918-April. 1919............ 23378.121.9 7.2 1.2 1 4.7 3.0 ... 6.0 Total 35 months....................1544.69.7 30.3 2.3 4.8 11 0 6.9 0.3 4.1

Jan 1, 1921