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By Raymond J. Kujawa

For general purposes, insulating materials may be any of those mineral substances that provide a barrier between a desired human environmental feature and an unwanted condition. In this sense, radiation shields, electrical insulations, cryogenic insulation, and acoustical barriers would qualify. For this chapter only the thermal and acoustic insulations used for the median range of normal comfort control will be covered. Because of their magnitude and complexity the other fields are left to other chapters. In another sense, this section deals only with the ultra-lightweight aggregates and insulations, rather than the multitude of light-weight structural materials. Definitions and Uses The insulating materials covered in this chapter are the three groups of mineral products that provide thermal or acoustic barriers through the median temperatures encountered in home and industry. The three mineral categories are perlite, vermiculite, and the silicate wools whether they be categorized as glass, mineral, or rock. Perlites are those amorphous aluminum silicates with minor impurities that take the form of a felsitic, glassy lava possessing a pearl-like luster and concentric cracking. In a more commercial sense the term is used to describe either the natural or processed acidic, volcanic glass, containing from 2 to 5% combined water, that may be converted to a frothy mass by heating rapidly to the softening point. Vermiculites are micaceous, hydrated magnesium iron aluminum sheet silicates of varying composition. Commercial vermiculites are any of these sheet silicates that are capable of sufficient expansion on rapid heating to make an acceptable, highly porous product. Mineral wools, rock wools, silicate cottons, glass fiber are generic names for manufactured fibers in which the fiber forming substance may be slag, certain rocks, or glass. The fibers may be made by a blowing or spinning process. The resultant fibers may be felted or matted or gathered in the manner best suited to the use. The three groups may be used competitively to insulate ceilings and walls. The fibers have strong advantages in this area as they may be manufactured in batts that are stable in residential wall construction. The perlites and vermiculites are more suited to insulate cores and cavities of masonry walls and as plaster and concrete aggregates for thermal insulations. Vermiculite is widely used for insulating attic floors. Because of manufacturing techniques and controls, the glass fibers have made great strides as composites in the plastics industry but only a few of these uses classify in the insulation category.

Jan 1, 1975

By J. Parke Channing

We are accustomed to think that we are efficient in the United States, particularly with respect to such things as mining and manufacturing. The conduct of the war has demanded in England and in France a complete readjustment of manufacturing methods and plans, and today England, is probably as efficient a country as there is in the world, not even excepting Germany. This is all the more remarkable because it has been notorious for years that England has been inefficient in her manufacturing and the country has been flooded with things "Made in Germany.'' Today England is almost a socialistic community and the State is doing almost everything. England is now in such a position that practically everyone in the country is engaged in industry necessary for the conduct of the war, and this has been accomplished by increasing the efficiency both of her tools and of her man power. In the United States we certainly have been efficient so far as machines and perhaps so far as methods have been concerned, but we have not been efficient in the utilization of our man power. Before the war, our labor was undoubtedly far more efficient than that of England, but it certainly was not so highly efficient as it should have been, and the problem that confronts us today, and will all the more confront us after the war, is to make our man power efficient. England has had a taste of what you may call State Socialism, and her laboring men are not going to be content to return to the old order of things. There is one feature of the labor problem in England which has permitted her to reach this condition of state socialism with comparative rapidity; this is that practically all of her laborers are English; she has little or no foreign population. While an Englishman may be a strong union man and ready to fight his employer tooth and nail, at heart he is still a British subject, and when his country was in danger he rose to the occasion. In the United States we have such an admixture of unassimilated foreigners that the problem is more difficult, and as yet we have not been brought to that point of stress which has arrived in England. But if

Jan 1, 1919

By T. A. Pollard, C. R. Sandberg, E. B. Elfrink

This paper presents an evaluation of compressibility factor data and a discussion of their application to the estimation of gas reserves. A correlation is presented which provides compressibility factors for use in both two-phase and single-phase hydrocarbon systems. Accuracies comparable to those obtained previously for single-phase systems only can be expected. A simple means of predicting the presence or absence of a liquid phase in a condensate system of known composition is illustrated. The correlation is based on 1,030 compressibility determinations from 21 hydrocarbon samples taken from eight oil fields. Of the data used, 75 per cent were from California, 15 per cent were from the Mid-Continent area, and 10 per cent were from South America. The average numerical deviation of the experimental data from this compressibility chart is 1.22 per cent. Charts and tables are included and discussed which illustrate the errors involved through the misuse or nonuse of compressibility factors in estimates of gas-in-place. INTRODUCTION The compressibility factor is a coefficient which expresses the deviation of a gas of given composition from the Perfect Gas Laws. A factor such as this is necessary in any calculation involving volumes of gaseous mixtures, and finds extensive application in the estimation of natural gas and condensate reserves. It is used in the decline curve, the volumetric, and the material balance methods of gas reserves estimation. The behavior of gases at high pressures has been investigated extensively in recent years and considerable data have been assembled on the compressibility characteristics of a number of gases. Notable among the investigators of high pressure gas relationships are Kvalnes and Caddya, Kay" Sage and Laceys, and Brown, Standing" and Katz4. Other contributors are Smith and Watson, Roland and Kaveler', and Stevens and Vance". The data on compressibility factors assembled by these investigators have been presented and correlated in numerous ways; particularly noteworthy is the method first presented by Kay5 which relates compressibility factor "Z" to pseudo-reduced temperature and Pseudo-reduced pressure. Other investigators have used this empirical relationship successfully and numerous charts covering a large number of gases have been constructed on this basis. It is the purpose of this paper to evaluate compressibility factor data and to illustrate the importance of their proper use in the estimation of gas-in-place for both gas and condensate reservoirs. EVALUATION OF COMPRESSIBILITY FACTOR DATA The compressibility chart presented by Standing, Katz, Brown and Holcomb in 1941 is probably the most recent and reliable chart for natural gases. The reliability of the Katz chart has been investigated by the writers for a fairly large number of gases (single-phase) in the pressure range from 500 to 10,000 psia and temperature range from 80 to 400°F. A summary of this comparison is presented in Table I. The numerical average deviation of the chart compressibility factors from the experimental compressibility factors is 1.05 per cent, and the algebraic deviation is -0.28 per cent. The Katz correlation appears to be quite accurate for single-phase hydrocarbon systems. It was based on single-phase systems and does not necessarily provide a means of accurately predicting the behavior of two-phase systems which might be encountered in condensate work. Data published recently by Sage and Oldsl' have enlarged the knowledge of phase behavior in condensate systems by covering extensively the Compressibilities of systems in the two-phase as well as single-phase regions for a wide range of temperatures, pressures and gas-oil ratios. An evaluation of these data indicates that conditions can arise, especially in condensate systems having fairly low gas-oil ratios, in which two phases occur and the usual gaseous compressibility factors do not accurately apply. The measured PVT data of Sage and Olds covering two-phase systems have been correlated with additional such data from the Mid-Continent area and South America; these are presented in Fig. 1. This chart is the result of 1,030 compressibility* determinations from 21 hydrocarbon samples taken from eight oil and condensate fields. Of the data used, 74.75 per cent were from California, 15.45 per cent were from the Mid-Continent area, and 9.80 per cent were from South America. The chart construction is based on the original

Jan 1, 1949

By C. R. Sandberg, T. A. Pollard, E. B. Elfrink

This paper presents an evaluation of compressibility factor data and a discussion of their application to the estimation of gas reserves. A correlation is presented which provides compressibility factors for use in both two-phase and single-phase hydrocarbon systems. Accuracies comparable to those obtained previously for single-phase systems only can be expected. A simple means of predicting the presence or absence of a liquid phase in a condensate system of known composition is illustrated. The correlation is based on 1,030 compressibility determinations from 21 hydrocarbon samples taken from eight oil fields. Of the data used, 75 per cent were from California, 15 per cent were from the Mid-Continent area, and 10 per cent were from South America. The average numerical deviation of the experimental data from this compressibility chart is 1.22 per cent. Charts and tables are included and discussed which illustrate the errors involved through the misuse or nonuse of compressibility factors in estimates of gas-in-place. INTRODUCTION The compressibility factor is a coefficient which expresses the deviation of a gas of given composition from the Perfect Gas Laws. A factor such as this is necessary in any calculation involving volumes of gaseous mixtures, and finds extensive application in the estimation of natural gas and condensate reserves. It is used in the decline curve, the volumetric, and the material balance methods of gas reserves estimation. The behavior of gases at high pressures has been investigated extensively in recent years and considerable data have been assembled on the compressibility characteristics of a number of gases. Notable among the investigators of high pressure gas relationships are Kvalnes and Caddya, Kay" Sage and Laceys, and Brown, Standing" and Katz4. Other contributors are Smith and Watson, Roland and Kaveler', and Stevens and Vance". The data on compressibility factors assembled by these investigators have been presented and correlated in numerous ways; particularly noteworthy is the method first presented by Kay5 which relates compressibility factor "Z" to pseudo-reduced temperature and Pseudo-reduced pressure. Other investigators have used this empirical relationship successfully and numerous charts covering a large number of gases have been constructed on this basis. It is the purpose of this paper to evaluate compressibility factor data and to illustrate the importance of their proper use in the estimation of gas-in-place for both gas and condensate reservoirs. EVALUATION OF COMPRESSIBILITY FACTOR DATA The compressibility chart presented by Standing, Katz, Brown and Holcomb in 1941 is probably the most recent and reliable chart for natural gases. The reliability of the Katz chart has been investigated by the writers for a fairly large number of gases (single-phase) in the pressure range from 500 to 10,000 psia and temperature range from 80 to 400°F. A summary of this comparison is presented in Table I. The numerical average deviation of the chart compressibility factors from the experimental compressibility factors is 1.05 per cent, and the algebraic deviation is -0.28 per cent. The Katz correlation appears to be quite accurate for single-phase hydrocarbon systems. It was based on single-phase systems and does not necessarily provide a means of accurately predicting the behavior of two-phase systems which might be encountered in condensate work. Data published recently by Sage and Oldsl' have enlarged the knowledge of phase behavior in condensate systems by covering extensively the Compressibilities of systems in the two-phase as well as single-phase regions for a wide range of temperatures, pressures and gas-oil ratios. An evaluation of these data indicates that conditions can arise, especially in condensate systems having fairly low gas-oil ratios, in which two phases occur and the usual gaseous compressibility factors do not accurately apply. The measured PVT data of Sage and Olds covering two-phase systems have been correlated with additional such data from the Mid-Continent area and South America; these are presented in Fig. 1. This chart is the result of 1,030 compressibility* determinations from 21 hydrocarbon samples taken from eight oil and condensate fields. Of the data used, 74.75 per cent were from California, 15.45 per cent were from the Mid-Continent area, and 9.80 per cent were from South America. The chart construction is based on the original

Jan 1, 1949

By Lawrence H. Van Vlack, Otto K. Riegger, Gerald I. Madden

The microstructural variations of periclase (MgO) in the presence of oxide liquids are examined under the steelmaking variables of: 1) temperature, 2) liquid composition, and 3) FeO additions under different oxidation levels. Attention is given to the distribution of the phases, both liquid and solid, and to the growth of individual crystalline grains. Silicate liquids penetrate more extensively between individual periclase grains than do liquids containing high percentages of Fe2O3 Higher MgO solubilities in the liquid and lower MgO contents of the solid favor more rapid grain growth. The presence of a second solid phase reduces the periclase grain growth rate and increases the amount of the solid-to-solid contact within the oxide microstructures at high temperatures. The service suitability of a refractory depends on many factors. Two are of major importance and include 1) the thermal resistance to melting, and 2) the mechanical resistance to loads at service temperatures. Neither is a simple consequence of the service temperatures because service conditions will alter compositions, produce partial melting, and induee phase changes. Consequently, the equilibrium phase relationships have been rather thoroughly studied and give a knowledge of the thermal resistance to melting, but do not give full information about the mechanical properties because two refractories with the same types and quantities of phase may have different microstructures. Although variations of microstructures with time, temperature, and composition have been subjects for extensive investigation in metals, only a limited amount of comparable microstructural work has been performed for refractory materials.' This study was an attempt to evaluate some of the consequences of service parameters upon the microstructures of refractories so that bases may be established for the analyzing of high temperature mechanical properties. Periclase (MgO) was chosen as the refractory oxide; variables included those which are encountered under steelmaking conditions such as 1) temperature, 2) liquid composition, and 3) FeO additions under various oxidation levels. Specific attention was given to the distribution of the phases, both liquid and solid, and to the growth of individual crystalline grains. The most closely related work on microstructures of polyphase materials is that of Van Vlack and Rieg-ger2 on the microstructure of magnesiowüstite [(Mg,Fe)O] in the presence of silica. In that work which pertained to solid solutions with less than 40 pct MgO, most of the quantitative work was performed on FeO microstructures. The chief conclusions concerning these relatively low-melting oxide solids were as follows: 1) the rate of crystalline grain growth is inversely proportional to the grain diameter, 2) grain growth proceeds more rapidly at higher temperatures but is slightly retarded by additional liquid content, and 3) a Silicate-containing liquid penetrates as a film between the individual magnesiowüstite grains independent of time, temperature, amount of liquid, or the MgO/ FeO ratio. The above observations are in contrast to prior work3 on the microstructure of silica in the presence of iron oxide-containing liquids where the liquid does not penetrate as a complete film between solid grains. The phase relationships for the compositions of the present work are shown in Fig. 1 which is a summary of the work of several investigators.4 Of importance is the fact that CaO forms a more stable structure with SiO2 and Al2O3 than do either MgO or FeO. The oxygen potential has little effect on periclase unless iron oxide is also present. The iron oxide is ferrous at moderately low oxygen levels, changing to ferric as the Oxygen potential is increased so the spinels, magnetite, and magesioferrite are formed.5 These two phases are relatively stable in air at steelmaking temperatures. I) EXPERIMENTAL PROCEDURE ractory were made with reagent grade Oxides. The magnesium oxide used was 99 pct MgO after ignition, and the iron oxide raw material had a minimum content of 99 pet Fe2O3. The CaO, SiO2, and A12O3 were also reagent grade raw materials. After mixing, the required compositions were pressed into pellets at a minimum pressure of 5000 psi to insure compaction of the raw materials and prevent excess void content. A silicon carbide element tube furnace was used with thermocouple control for sin-

Jan 1, 1963

By Howard Martens, Pol Duwez

IN two papers published in 1949, alloys of chromium with the refractory metals tungsten, molybdenum, tantalum, and columbium were investigated in view of their possible use as high temperature resisting materials. For the Cr-Ta system, a partial phase diagram was presented and the only intermediate phase was identified at Ta2Cr3. A phase of the same composition was also observed in the Cb-Cr system. The X-ray diffraction data presented in these papers, however, were insufficient for crystal structure determination. It is shown in the present study that the only intermediate phase in both the Ta-Cr and the Cb-Cr systems corresponds to the ideal stoichiometric ratio TaCr2, or CbCr2. Both structures are cubic, MgCu, type. At high temperature, however, TaCr2 has a hexagonal MgZn, type structure, which can be retained at room temperature by fast cooling. The alloys were prepared by melting in a helium arc furnace on a water-cooled plate. The design of the furnace was essentially the same as that described in ref. 3. Some alloys were also obtained by sintering compacts made of the mixed powders pressed at 80,000 psi. The sintering was carried on for 4 hr at 1375°C. The tantalum and columbium powders were supplied by Fansteel Metallurgical Corp., North Chicago, 111. The tantalum powder was the reagent grade, with a particle size smaller than 400 mesh and a total impurity content less than 0.1 pct. The columbium powder was smaller than 325 mesh and contained approximately 0.1 pct C and traces of Fe, Ti, and Zr. The electrolytic chromium powder from Charles Hardy, Inc., New York, was smaller than 300 mesh and contained about 0.1 pct Na, 0.05 pct Ca, and traces of Cu, Al, Mg, Si, and Co. Powder diffraction patterns were obtained with a 14.32 cm camera, using copper Ka radiation filtered through nickel foil. The powder pattern of the TaCr2 alloy obtained by sintering at 1375'C was different from that obtained on the same alloy rapidly cooled from the melt. Contrary to this result, the powder pattern of CbCr2 was the same, whether the alloy was made by sintering at 1375°C or by melting, and was similar to that of the TaCr, sintered. It was also found that the structure of the TaCr2 specimen obtained by melting was retained after heating for 4 hr at 1590°C, but transformed into the structure found in the sintered specimen after heating for 4 hr at 1375°C. Hence, the structural change of TaCr2, appears to be a reversible polymorphic transformation. CbCr2 and ToCr2 Structure, Low Temperature Form By using large scale Hull-Davey charts, the powder pattern of CbCr, and of the low temperature form of TaCr2 were readily interpreted on the basis of a face-centered cubic lattice with a parameter of approximately 6.95 kX. The indices of the reflections together with the values of sin' 0 are given in Tables I and 11. From this list of observed reflections, it appears that the (200), (600), (024), (046), and (028) reflections are missing. The lack of (h00) reflections for h 4n indicates a four-fold screw axis. The missing (Okl) spectra for k + 1 An indicate the existence of a diamond glide d. The combination of these symmetry elements can be found in the O— Fd3m space group, which is therefore the most probable one. After having determined the approximate density of TaCr, by the immersion method, the number of molecules per unit cell was calculated and found to be nearly eight. This information, added to the fact that the most probable space group is O leads to the consideration of a structure of the MgCu2 type, in which the atoms have the following positions: 8 magnesium in a and 16 copper in d. On the basis of this structure, intensities were computed by means of the usual formula: 1 cos'20 I a sin2 cos where F is the structure factor; 8, the Bragg angle: and p, the multiplicity factor. As shown in Tables I

Jan 1, 1953

By H. C. Fiedler

The development of cube-on-edge secondary re crystallization texture in Si-Fe strip depends upon the ability of inclusions, such as manganese sulfide, to restrain nomal grain gvowth. The ability of inclusions to perform this function is shown to depend upon their size and distribution. The desired uniform dispersion of many small inclusions is obtained by controlling the cooling rate from above the solution tempmature of the inclusions or, alternatively, by drastic 'quenching from above the solution temperature followed by heat treating at a lower temperature. The development of the cube-on-edge secondary recrystallization texture in Si-Fe strip depends upon both establishing the proper primary recrystallization texture and having inclusions to restrain normal grain growth. It has been suggested that the first requirement is met with a texture which, though weak, is near (110)[001]. A mechanism for secondary recrystallization originally proposed by ielsen' is consistent with the presence of this primary texture. It is visualized that a secondary grain appears where two adjacent grains happen to be sufficiently similar in orientation to be capable of behaving as a single large grain. This pair of grains will grow at the expense of its smaller neighbors as a consequence of its having lower grain boundary free energy. Other explanations of the origin of the secondary recrystallization texture have been offered,' and it can be concluded that the mechanism is not fully understood. Nevertheless, it is apparent that operationally the necessary primary recrystallization texture is obtained simply by interposing an anneal during the cold reduction to final gage. The role of inclusions in the development of the secondary recrystallization texture has been demonstrated by May and Turnbull4 in a comparison of a high-purity heat and a heat containing manganese sulfide. They showed that the driving force for secondary recrystallization is inversely proportional to the diameter of the matrix grains and that the function of the inclusions is to maintain a small matrix grain size. Other inclusions, such as various sul- fides,')' silicon nitride,8 and vanadium nitride,' titanium carbide,'' and vanadium carbide," have been shown to be effective in promoting secondary recrystallization to the cube-on-edge texture. There is also evidence that silica inclusions in Si-Fe strip made by powder-metallurgy techniques perform this function.' This report is concerned with the second of the two requirements for secondary recrystallization, namely the importance of the metallurgical control of the size and therefore number of inclusions. While the concepts involved are simple, they are fundamental to the making of this material. EXPERIMENTAL PROCEDURE A heat containing 3.27 pct Si, 0.026 pct S, 0.06 pct Mn, and 0.004 pct C was made in an air induction furnace from electrolytic iron, 98 pct ferro-silicon, electrolytic manganese, and iron sulfide. The heat was divided between graphite and baked-sand molds with a cavity 2-5/8 by 5 in. and with walls 2-3/4 in. thick. Slabs, 1 in. thick and 2-5/8 by 5 in., were cut from the ingots and hot-rolled either in the as-cast condition or after one of the heat treatments described later. After pickling, the 80- to 100-mil-thick hot-rolled band was, unless otherwise noted, heat-treated for 5 min at 900°C before being cold-rolled to 25 mils. After a heat treatment of 1 to 3 min at 860°C, the strip was cold-rolled to 12 mils, the final thickness. The percent cube-on-edge texture was determined by dividing the maximum torque as averaged from four samples by the maximum torque of a 3-1/4 pct Si-Fe single crystal having the (110) plane in the plane of the sample. The torque measurements were made in a field of 1000 oe on 1-in.-diam disks. RESULTS AND DISCUSSION The importance of the thermal history of the ingot is evident in Fig. 1 from the appearance of strips heat-treated in a temperature gradient. The sample

Jan 1, 1964

By D. E. Light, J. Y. Somnay

The use of alkyl acid phosphates and their alkali salts as collectors for the uranium minerals brannerite and uranothorite was investigated. In particular a detailed flotation study was carried out using isooctyl acid phosphate as a promoter. Tests were conducted on an Elliot Lake ore analyzing 0.11% U 3 O 8, chiefly as brannerite, and approximately 9% pyrite. Pyrite was floated with conventional reagents; the flotation of brannerite from the sulfide tails was studied to determine the optimum pH and pulp density to employ with isooctyl phosphate. 4 uranium recovery of over 90% was possible with a selectivity index of 8.95 when these tails were floated at 17% solids and a pH of 1.7. The effect of various modifying agents was also investigated. Aluminum sulfate, lactic acid and sodium silicate improved the selectivity of collection yielding selectivity indices of 9.5 to 11.5. Ferric chloride was found to be a depressant for brannerite. A Bancroft ore which analyzed 0.13% U308, and contained uranothorite was also amenable to flotation using isooctyl acid phosphate. The composite uranium concentrate obtained assayed 0.41% U308 at a recovery of 95.3% and a ratio of concentration of 3.24. Previous investigations1,2 on the flotation of brannerite, pitchblende, uraninite and/or uranothorite from various Canadian ores showed that fatty acids, including oleic acid and tall oils, petroleum sulfo-nates and alkyl acid phosphates, were suitable collectors for these uranium minerals. Additional work carried out by the Mines Branch in Ottawa on brannerite ores from the Elliot Lake area3 used the tall oil Acintol FA-1, or FA-2, as a collector. A recovery of 92% of the uranium in a concentrate which contained about 55% of the weight and assayed 0.2% U3O8 was obtained from a feed of 0.1% U308 in this latter instance. Eigeles et a1.4 carried out flotation on pitchblende ores and found that the most promising results were obtained with alkyl acid phosphates and their alkali salts as collectors. Within the homologous series of alkyl phosphates, the best flotation characteristics were displayed by isooctyl phosphates. Further, isooctyl phosphate derivatives were much less sensitive to hardness forming salts than oleic acid, enabling all flotation tests to be made with tap water. This paper describes tests employing alkyl acid phosphates for the flotation of ores containing brannerite and uranothorite. The flotation work described herein was conducted in conjunction with the development of a leaching process for Elliot Lake, Ontario, brannerite ores. In this process pyrite in the ore was concentrated by flotation and roasted, providing sulfur dioxide which was used to produce sulfuric acid in situ in a liquid-solid extraction process. A 40% conversion to sulfuric acid was indicated at a leaching temperature of 80°C; this resulted in the extraction of 93% of the total uranium after a contact period of 6 hr. A rotary kiln was used as a leaching vessel. Preconcentration by flotation was studied in conjunction with the above process to reduce the bulk of solids for leaching and, consequently, capital expenditure. The materials and methods used in this study will be described initially. Then the results will be presented in two sections, the first dealing with the brannerite ore, and the second with the uranothorite. Finally an economic analysis of the results on the brannerite material will be made. MATERIALS AND METHODS The two ore samples examined were from uranium-producing mines. One was a brannerite ore, a uraniferous quartz pebble conglomerate from the Elliot Lake area, which contained 0.11% U3O8, 4.3% S and 4.5% total Fe. Mineralogical studies of similar samples indicated the presence of quartz, microcline, sericite, pyrite and minor quantities of rutile, pyrrho-tite and zircon. The other ore was from a biotite-rich pegmatite in the Bancroft area; feldspar, quartz and biotite formed the major gangue components. Uranothorite was the principal uranium mineral; the head assay was 0.13% U 3 O 8. Preparation of Feed: The ores were crushed to —10

Jan 1, 1963

By Gerhard Derge

THE introductory paper1 of this series described the potential behavior of tin in sodium carbonate and bicarbonate solutions whose pH ranged from 8.4 to 11.2 and demonstrated that significant and reproducible results could be obtained by proper attention to experimental technique. In examining the corrosion of tin under such conditions, it is desirable to know the effects of anions, aside from carbonate, that are likely to be present in commercial materials packaged in tin. Therefore, in this paper the potential behavior of tin in carbonate solutions to which sodium fluoride, chloride, bromide, iodide, sulphate, nitrate, monobasic phos-phate, dichromate, perborate and acetate have been added will be described. For most of the additions, solutions containing 0.001 and 0.01 .moles of the added material were studied. The experimental procedure was exactly the same as that described in the first paper; the pH of the electrolyte was controlled by adjusting the ratio of carbonate to bicar-bonate as follows: pH 0.1 M NaHCO3 8.4 2 parts 0.1 M NaHCO3, 1 part 0.1 M Na2CO3 9.5 1 part 0.1 M NaHCO3, 2 parts 0.1 M Na2CO3 10.0 0.1 M Na2CO3 11.2 The reagents used were all of C.P. grade. The anions studied may be divided into three groups: (1) anions that had little or no effect upon the potential curves-sulphate, nitrate, and acetate; (2) those that helped to prevent corrosion at low pH only-fluoride, chloride, bromide, and iodide; (3) those that helped to prevent corrosion at high pH also-phosphate, perborate, and chromate.

Jan 1, 1939

By Thomas Cox

The following compilations are made from a series of investigations and are used to present the subject in an unbiased manner, as the writer does not represent any company or financial interest. The present situation is complex. The producers are hard pressed by reason of the low price of crude, while the independent refiner is little better off, because of the corresponding cut in price of refined products, except on occasional contracts. If the real costs are analyzed, it will be seen that the land speculators and the lessors—royalty owners—make the larger profits and not the struggling legitimate operator or independent refiner. The present-day (October, 1922) posted prices per barrel for crudes are Kansas, Oklahoma, Mexia, Gulf Coast, and Louisiana..... $1.25 Healdton............................................. 0.75 Northern Texas and Central Texas...................... 1 . 50 Pennsylvania......................................... 3.00 Wyoming, Elk Basin.................................. 1.25 Wyoming, Salt Creek................................ 0.70 California Base..................................... 0.60 These prices are at the well. In addition, crudes must be gathered and transported to refinery (by pipe line or tank cars), refined, and the refined products marketed. These crudes are of various gravities, ranging within a narrow margin for each field or district, so that averages are not difficult to deduce, and it is these averages that really determine the average operating conditions. In order to show the present realizations, the prices and costs now obtaining are listed against the average yields; the figures are also adjusted VOL. urn.----71

Jan 1, 1923

By Thomas Cox

The following compilations are made from a series of investigations and are used to present the subject in an unbiased manner, as the writer does not represent any company or financial interest. The present situation is complex. The producers are hard pressed by reason of the low price of crude, while the independent refiner is little better off, because of the corresponding cut in price of refined products, except on occasional contracts. If the real costs are analyzed, it will be seen that the land speculators and the lessors—royalty owners—make the larger profits and not the struggling legitimate operator or independent refiner. The present-day (October, 1922) posted prices per barrel for crudes are Kansas, Oklahoma, Mexia, Gulf Coast, and Louisiana..... $1.25 Healdton............................................. 0.75 Northern Texas and Central Texas...................... 1 . 50 Pennsylvania......................................... 3.00 Wyoming, Elk Basin.................................. 1.25 Wyoming, Salt Creek................................ 0.70 California Base..................................... 0.60 These prices are at the well. In addition, crudes must be gathered and transported to refinery (by pipe line or tank cars), refined, and the refined products marketed. These crudes are of various gravities, ranging within a narrow margin for each field or district, so that averages are not difficult to deduce, and it is these averages that really determine the average operating conditions. In order to show the present realizations, the prices and costs now obtaining are listed against the average yields; the figures are also adjusted VOL. urn.----71

Jan 1, 1923

By Colin G. Fink, Leslie G. Jenness

Tantalum and columbium occur together in tantalite and columbite ores, which may be considered as ferrotantalate (FeTaz06), with part of the iron and tantalum replaced by manganese and columbium respectively, the general formula, therefore,becoming (Pe, Mn)O.(Ta, Cb)2Os. The ratio of tantalum to columbium is not fixed; the amount of tantalum may vary from one-third to three times that of columbium. Minerals having a high content of tantalum are called tantalite, while those possessing larger amounts of columbium are classified as columbite ores. These minerals are found in pegmatites and often occur in veins associated with cassiterite and wolframite, and may contain small amounts of tin, tungsten, titanium and si1ica. l Methods of Extraction Several methods have been proposed for the extraction of tantalum and columbium from their ores, among them being: 1. Fusion with Potassium or Sodium Bisu1fate.—The finely ground ore is fused with potassium bisulfate, after which the mass is boiled with water and the fusion repeated several times. The residue finally resulting is digested with ammonium sulfide to remove traces of tin and tungsten, boiled with hydrochloric acid, filtered and washed. These oxides are then dissolved in hydrofluoric acid, the silica evolved as silicon tetra-fluoride and the hydrofluoric acid solution used for the potassium double fluoride separation of tantalum. 2. Fusion with Sodium Carbonate and Sodium Nitrate.2—This fusion renders the tantalum and columbium soluble, and they are extracted

Jan 1, 1931

By R. A. Meussner, R. T. DeHoff, F. N. Rhines

ZINC diffuses through copper more rapidly than does tin. Accordingly, when a ternary diffusion couple is made, by bringing an 0 copper-zinc brass into contact with an a copper-tin bronze at fixed high temperature, it is to be expected that zinc will diffuse into the bronze faster than tin diffuses into the brass. Adjacent to the brass side of the couple the total alloy content (zinc plus tin) should diminish, therefore, while next to the bronze side the alloy content should increase. Since the path of compo- sition change must be continuous, in a single-phased alloy, it should follow a curved and, in general, an S-shaped course. The realization of this prediction is demonstrated in Fig. 1, where the composition paths of two ternary diffusion couples are plotted on the appropriate isotherm of the copper-tin-zinc phase diagram. The diffusion couples were both made from a binary copper-tin alloy analyzing 5.0 pct tin placed against binary copper-zinc alloys analyzing 18.9 and 29.3 pct Zn, respectively. These alloys were produced from electrolytic grades of copper and zinc and a pure grade of straits tin, melted under borax in clay-graphite crucibles and cast in a vertical iron mold. Cylindrical pieces 1 in. in diam and 1 % in. long were machined from the casting and were faced by metallographic polishing to good matching end surfaces. Pairs of the cylindrical pieces were held

Jan 1, 1959

By R. W. Smith, M. E. Brookes

The temperature at which th: quenched 0' (ordered bcc) phase transfo.rms to the ( (complex hexagonal) phase on heating has been examined for certain Ag-Zn and Ag-Au-Zn alloys using an electrical resistivity method. The transition temperature decreases by approxinzately 7°C as the zinc content is reduced by 1 at. pct. The critical temperature, Tc, for long-range order has also been measured for a number of Ag-Au-Zn alloys. Extrapolation to zero gold content suggests that Tc decreases by approximately 5°C per 1 at. pct reduction in zinc content. The 0 phase of the Ag-Zn system exists over a narrow range near the composition Ag zn,' Fig. 1, and has a bcc structure which is disordered above 272°C. Slow cooling to temperatures below the range 274"/258"C allows the complex hexagonal phase, r° to form.2 This is the stable structure at room temperature.3 Upon quenching 0 -phase alloys from high temperatures, it is found that the 0 — (' transformation is suppressed; but ordering takes place (i.e., 0 -0'). This ordered structure can also be obtained by the room-temperature aging of cold-worked (0.4 Deformation of the 0' phase gives rise to a fur- ther hexagonal phase ( (of nearly ideal axial ratio) which reverts to b' within a few hours.= In view of this, it has been suggested that the equilibrium struc-

Jan 1, 1969

By W. A. Tiller, W. C. Johnston

A theoretical analysis of alloy solidification in which the effective partition coefficient, k, of the solute is allowed to vary as a function of interface position is performed. A variety of solute distm'butions in the solid is predicted depending upon the functional dependence of k with interface position. Conversely, the variation of k with interface position required to produce a particular solute distributzon in the solid can be calculated. These preciictions have been tested by controlling the width of the momentum boundary layer in the liquid as a function of interface position with a rotating mugnetic field. One of the objects of controlled solidification is to utilize the freezing process for the preparation of crystals of specific materials containing a predetermined distribution of solutes. For example, a thermoelectric power generation material may exhibit a figure of merit, 2,' as a function of temperature, T, and solute concentration, C, as illustrated in Fig. 1. If we wish to use this material in a device between the temperature limits T1 to T2 a significantly greater efficiency will result from the device if the thermoelectric element illustrated in Fig. 1 consists of a range of solute concentrations appropriately located with respect to the temperature distribution rather than using a sample of constant solute concentration. For this reason and many others2 we are interested in programming and controlling the solute distribution in a single crystal

Jan 1, 1962

By Emile Hiertz

THE first press was installed in June, 1910, and the second in March,1911. They produce 1,000 briquettes per hour, weighing 5 kg. (11.05 1b.) each, under a pressure of about 400 kg. per square centimeter (5,689.2 lb. per square inch). The chloride of magnesium is received from the potash mines at Hanover in tank cars in approximately a 35 per cent. solution. The quantity of solution added to the flue dust varies between 2 and 3 per cent., so that the briquettes contain about 1 per cent of MgCl2. To fresh dust as much as 10 per cent. of coke breeze may be added and bri¬quettes made that still have a crushing strength of from 25 to 30 kg. (377 to 426.6 lb. per square inch) after 36 hr., and 45 kg. (639.9 lb. per square inch) after six days. After having treated 140,000 tons of the material, the reports of the blast furnaces show that the briquettes improved the action of a furnace and produced less dust than did Minette ore. As much as 35 per cent. of briquettes is added to the furnace charge without bad effects on operations. The presence of chlorine did not produce any corrosion in the furnace, downtakes or other piping. The presence of a certain amount of chlorine in the dust reduces the amount of chloride of magnesium which it is necessary to add for briquetting.

Jan 12, 1913

By J. E. Chappelear

We are concerned with the problem of calculating the forces produced by passing waves on a submerged object (in particular a drilling barge) located on the ocean floor. We employ the linearized theory of waves (the Airy1 theory), since solutions are generally more easily obtained in such a theory. It will be indicated how an approximate solution to the problem can be obtained for waves of finite height by use of a linear combination of Airy waves. We shall assume the submerged object has an infinite length, thus neglecting diffraction and making the problem two-dimensional. We find that there is not a considerable difference between our solution and the usual engineering solution. The force, as a function of time, is plotted in Figs. 4 and 5, together with the usual solution for easy comparison. So far, no experiments have been found to compare with the results. As will be shown, the calculations can be extended to waves of finite height (Stokes2-Struik3 waves) in an approximate fashion. This can be done by calculating the force produced by each Fourier component of the wave, separately, and omitting the coupling between the various harmonics produced by Bernoulli's theorem. The problem and its boundary conditions will be briefly stated. We seek a function, +, the velocity potential, which is harmonic, ?2?=0...........(1) and which satisfies the boundary conditions ??/?n =0 .......(2) (the normal derivative of + is zero) on the ocean floor and the sides of the barge, and s??/?y = ?..........(3) on the ocean surface, where s = g/w2........(4) The physical reasons for these choices and an interpretation of ? are given by Lamb.' As previously stated, we assume also that the problem is two-dimensional. We set up our coordinates such that x = 0 is the center of the barge and y = 0 is the ocean floor. The coordinates are shown in Fig. 1, together with the location of the barge on the bottom. Our solution may be decomposed into a function which is symmetric about x = 0,?e, and one which is antisymmetric, +,, ? = ? + ?o...........(5) Thus directly above the barge we have as boundary conditions that for x = 0, ?o = 0, ...........(6) and ??e/?x = 0........(7) Now, far from the barge, we have that (for x positive and assuming the waves are incident from the left) ?e ? Ae cosh ky cos k (x + a) , . . . (8) and ?e ? Ao cosh ky cos k (x + ß) . . . . (9) where + means ". .. approaches ... for x large." Let us put Ae, Ao, and k equal to one, and remember that, in accordance with the derivation of Eq. 3, a sinusoidal time factor is to be supplied. Then we may rewrite Eq. 8 for ?e, and we find that

Jan 1, 1958

By Morris Muskat

Analytical calculations have been carried out on the effect of casing perforations on the productivity of wells, and formulas have been derived for general types of perforation patterns. The numerical calculations, however, show that the resultant well productivity is essentially independent of the perforation pattern, but is determined mainly by the total perforation density. Thus, for example, for a density of three perforations per foot of casing, the well productivity will be cut to one third of that of the uncased well for a perforation radius of 1/8 in., and to approximately one half for a perforation radius of 1/4 in., regardless of the detailed manner in which the perforations are distributed over the casing surface. The analytical theory is also extended to include wells completed with slotted liners. It is shown that the reduction in productivity due to such liners will be relatively small as compared with that due to perforated casings. The increasingly important role being played by productivity factors of wells in determining well potentials and in the general evaluation of producing formations lends interest to the analysis of all the various factors that may infuence the productivity of a well. In recent papers1 the results have been given of theoretical studies made to determine the effect on the productivity factor of a well of the gas-oil ratio of the production and the connate water within the sand. These have served to show that both of these factors may, under suitable conditions, materially reduce the effective productivity factors below those that would be anticipated on the assumption that the wells produce homogeneous fluids. In this paper will be presented the results of the analysis of an entirely different factor influencing the productivity of a well. This refers to that resulting from the increased use of the method of completing wells by setting casing opposite all of the productive strata and then gun-perforating the particular zones of immediate interest. The practical success of this method of completion would appear to be an answer to the question as to whether it seriously reduces the well productivity or materially cuts down the ultimate oil recovery that may be derived from the producing section. Nevertheless, it is of interest to examine just how great the effect of the restricted flow channels, represented by the gun perforations, may be in increasing the over-all effective sand resistance. Of course, to the extent that the well potentials are severely restricted by proration regulations, minor reductions in well productivities are even less serious than if the wells were to be allowed to produce wide open. On the other hand, even under these circumstances there may be at least the academic interest in such calculations in being able to correct and evaluate the effect of the perforations in order to carry

Jan 1, 1943

By Morris Muskat

Analytical calculations have been carried out on the effect of casing perforations on the productivity of wells, and formulas have been derived for general types of perforation patterns. The numerical calculations, however, show that the resultant well productivity is essentially independent of the perforation pattern, but is determined mainly by the total perforation density. Thus, for example, for a density of three perforations per foot of casing, the well productivity will be cut to one third of that of the uncased well for a perforation radius of 1/8 in., and to approximately one half for a perforation radius of 1/4 in., regardless of the detailed manner in which the perforations are distributed over the casing surface. The analytical theory is also extended to include wells completed with slotted liners. It is shown that the reduction in productivity due to such liners will be relatively small as compared with that due to perforated casings. The increasingly important role being played by productivity factors of wells in determining well potentials and in the general evaluation of producing formations lends interest to the analysis of all the various factors that may infuence the productivity of a well. In recent papers1 the results have been given of theoretical studies made to determine the effect on the productivity factor of a well of the gas-oil ratio of the production and the connate water within the sand. These have served to show that both of these factors may, under suitable conditions, materially reduce the effective productivity factors below those that would be anticipated on the assumption that the wells produce homogeneous fluids. In this paper will be presented the results of the analysis of an entirely different factor influencing the productivity of a well. This refers to that resulting from the increased use of the method of completing wells by setting casing opposite all of the productive strata and then gun-perforating the particular zones of immediate interest. The practical success of this method of completion would appear to be an answer to the question as to whether it seriously reduces the well productivity or materially cuts down the ultimate oil recovery that may be derived from the producing section. Nevertheless, it is of interest to examine just how great the effect of the restricted flow channels, represented by the gun perforations, may be in increasing the over-all effective sand resistance. Of course, to the extent that the well potentials are severely restricted by proration regulations, minor reductions in well productivities are even less serious than if the wells were to be allowed to produce wide open. On the other hand, even under these circumstances there may be at least the academic interest in such calculations in being able to correct and evaluate the effect of the perforations in order to carry

Jan 1, 1943

By B. H. Caudle, A. B. Dyes, R. A. Erickson

The study of the influence of fluid mobilities on the sweepout pattern resulting from the injection of gas or water has been extended to cover the production period which follows breakthrough of the injected material. Mobility ratios over the range common in field operations (0.1 to 17) were studied for several pattern floods (five-spot, staggered, and direct line drive). The experimental data required for these studies were obtained by the use of the x-ray shadowgraph technique using miscible oil phases of different viscosities in porous plate mode1s of a reservoir element. From the shadowgraph pictures obtained before and after breakthrough of the injected fluid, flowing ratios at the producing well and cumulative volumes injected were calculated. The method for applying such data in predicting field behavior is illustrated for a water flood of a five-spot. For this case a range of mobility ratios of 0.5 to 5.0 results in: (I) nearly complete (95 to 100 per cent) sweepout pattern efficiencies at abandonment conditions, (2) production after breakthrough being responsible for as much as one-third of the total recovery at the lower mobility ratios, and (3) a twofold variation in the operating life of the reservoir. In determining the merits of a secondary recovery operation, the fraction of the reservoir which is ultimately to be swept by the injected fluid is of major importance. Because of its significance a large amount of research has been applied to the study of areal sweepout efficiency. Muskat, Wyckoff and Botset1,2 have presented the classic analysis of the pattern efficiency at breakthrough for several injection patterns in which the mobility of the fluids ahead of the injected phase front was equal to the mobility of the fluids behind the front. Aronofsky3 as extended this analysis of recovery at breakthrough through numerical computations and by the stepwise use of the potentiometric model to include the effect of different fluid mobilities ahead of and behind the invasion front on the line drive performance. Fay and Prats' have also employed numerical computations to show the influence of one other condition of fluid mobilities on the five spot flood. In a previous paper' a new method of attack on this problem which employed x-ray and porous plates was described. At that time experimental results were also presented which described the effect of fluid mobilities on the reservoir area contacted by the injected fluid at breakthrough for the five spot and direct line drive patterns. Most of the literature pertaining to sweepout pattern efficiency has emphasized the pattern which is obtained at breakthrough of the injected phase. The increase in the sweepout pattern which occurs after breakthrough

Jan 1, 1955