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By Marshall B. Standing, Donald L. Katz

DENSITY data are reported on 16 saturated hydrocarbon vapors at pressures ranging from 1000 to 8220 lb. per sq. in. and at temperatures ranging from 35° to 250°F. These data have been used to extend the compressibility-factor chart for natural gases up to 10,000 lb. per sq. in. The relatively large quantity of high-boiling constituents present in high-pressure vapors in equilibrium with crude oils makes it necessary to include in the analysis of the gas the molecular weight, density, and possibly boiling range of the heptanes and heavier fraction. Relationships have been presented by which the density of gases may be obtained directly from the temperature, pressure, and gas gravity provided the gases have a common source or are similar in composition. INTRODUCTION The densities of natural gases are necessary in many engineering computations in petroleum production and utilization. Gas reserves, changes in reservoir pressure, gradients in gas wells, metering of gases, pipeline flow, and compression of gases are typical problems requiring the density of the gas. A decade ago, engineering computations used ideal gas laws with deviations up to 500 lb. per sq. in.4 Recent discoveries of pools having pressures up to 7500 lb. per sq. in., and installation of pressure-maintenance and recycling plants, have increased the need for data on gas density at high pressures. METHODS OF COMPUTATION The accepted method of computing the density or specific volume of natural gases is the use of the ideal gas law corrected by a compressibility factor. The method proposed by Kay7 of correlating compressibility factors for gaseous mixtures on pseudocritical properties5 appears to be satisfactory for natural gases.2 The methane-compressibility factor has been shown to deviate systematically from the behavior of natural gases2 and a chart giving these corrected factors is available. A method of computing specific volume of gaseous mixtures from partial molal volumes has been reported by Sage and Lacey.8 Complete data for the computation are not yet available for all hydrocarbon gases. Most of the reported data on gas densities have been in the single-phase region removed from the dew point or saturation condition. Since most gases in the reservoir or while on contact with liquid during flow are saturated, the determination of densities under conditions of saturation is particularly important. Although there is no reason to believe that the saturated gases differ in behavior from those considerably removed from their dew points, the usual experimental determinations find difficulty on approaching the dew-point conditions. This paper reports the density of 16 saturated gases in equilibrium with crude oils. The relationships developed to compute the density of gases to high pressure' have been modified and enlarged. A simplified method of obtaining gas density is presented in the form of charts, which apply for specific groups of gases.

Jan 1, 1941

By E. V. Potter, H. C. Lukens

In general, during all electrowinning processes, large volumes of gas are liberated at the cathodes of the electrolytic cells. Most of this gas escapes from the electrolyte, but much of it may be absorbed or entrapped in the metal being plated. In many cases, this is not objectionable, but since it is liberated when the metal is heated, it is a potential source of trouble where the metal has to be heated or melted. Since this gas is principally hydrogen, in escaping from a melt it may cause minor explosions and scattering of the molten metal, while in other cases it has been reported to make the metal rise in the molds when cast. Therefore such metals would be more generally useful if all or most of the gas were removed before they were used. In an earlier investigation1 the gas content of electrolytic manganese was determined and methods found for removing most of it without detrimentally affecting the properties of the metal. In this paper results of a similar investigation on electrolytic chromium are presented. Apparatus The apparatus used in these investigations is essentially the same as that used in the manganese work1 and is shown in Fig I. It consists of sample chamber A, vacuum or pressure gauge B, volume gauge C, vacuum pump D, hydrogen container E, auxiliary gas chamber F, and furnace G. The pressure in the system is measured by the mercury manometer B. Changes in gas volume are measured by volume gauge C which is essentially another mercury manometer in which the volume of the mercury column is large and can be varied by raising or lowering the well H. In this apparatus the tube had a volume of 100 cc for a 60 cm length. Larger changes in gas volume can be accommodated by auxiliary containers attached to the system at F. The sample is heated by furnace G, the temperature of which is regulated within 5°C by an automatic controller. The only change in the apparatus was the sample container which was made smaller because of the chromium metal's containing more gas than the manganese metal and a smaller sample was used. Method The measurements were made as follows: The complete system when cold was evacuated and refilled with H2 until all the air was removed. It was then refilled with H2 to the desired pressure, as indicated on manometer B. The temperature was then raised to the desired value and as gas was either liberated from or absorbed by the sample, the height of well H was changed to alter the volume of the system so as to keep the pressure constant. In determining rates of liberation of gas, volume readings were taken at convenient tirne intervals depending on the rapidity with which the gas was liberated. In determining total volumes, the specimen was held at constant temperature and pressure until

Jan 1, 1949

By W. D. Potter, E. T. Peters

Single-crystal films of boron have been prepared by thermal reduction of purified BCl3 with subsequent deposition of boron onto oriented silicon substrates. The structural properties of films prepared under various experimental conditions have been determined by light microscopy and "grazing-" angle electron-diffraction analysis. An orientation relationship is proposed for silicon and a-rhombo-heclral boron which can be described as: (111)Si (112)B; [110]Si [110]B ElEMENTAL boron is known to have a high energy gap* and consequently has potential value as a high- *Energy gaps of 1.35 to 1.55 ev1-3 and 2.0 ev4 are reported for ß-rhombohedra1 and a-rhombohedra1 boron, respectively. temperature semiconductor.5 Exploitation of this property, however, has been hampered by the unavailability of pure, single-crystal boron. Two recent symposia6,7 have treated the subjects of purification, crystallization, crystal structure, and properties of boron and provide a foundation for further investigation in these areas. The structure, lattice constants, and observed ranges of stability for four reported polymorphs of boron8°12 are listed in Table I. The rhombohedral structures are generally accepted as true polymorphs whereas the tetragonal structures are believed to be transient. Most currently available single crystals of boron are grown by Czochralski and floating-zone methods. Unfortunately, these crystals generally contain numerous defects and are highly strained as a result of the polymorphic transformations and thermal contractions which accompany cooling. Recently, Armington, Potter, and Tanner13 have reported the formation of single-crystal films of boron on silicon single-crystal substrates through thermal reduction of BC13 by hydrogen. Boron E. T. PETERS, Junior Member AIME, is Senior Scientist, ManLabs, Inc., Cambridge, Mass., and W. D. POTTER is Research Chemist, Air Force Cambridge Research Loboratories, L. G. Hanscom Field, Bedford, Mass. formed at temperatures near 1000°C was identified as the a-rhombohedra1 form, consistent with expectation. The present paper describes a continuation of this work with specific reference to characterization of the structural features of the deposited boron films. The ultimate goal of this program is to produce large-area single-crystal films of a-rhombohedra1 boron to be used for electrical and optical studies by other workers. PREPARATION OF BORON FILMS The experimental procedure of preparing thin films is similar to that described by Theuerer14 for the epitaxial growth of silicon by thermal reduction of SiC14 and has already been described as applied to the preparation of boron thin films.13 Briefly, a mixture of BCl3 vapor and dry hydrogen is passed over a heated silicon substrate. Thermal reduction of the BC13 allows deposition of boron on the substrate. The substrates were {111}-oriented, single-crystal silicon. Square specimens 0.63 cm on an edge by 0.1 to 3.0 mm thickness were prepared by

Jan 1, 1965

By Theron Wasson

The discovery of eight new oil fields, two of which may be of major importance, was the outstanding record in Michigan this year. These new fields have helped to support the declining production from old areas and place the total of 18,559,000 bbl. in line with the past six or seven years. Thus, it appears that Michigan is doing its part in maintaining the production of the country in the third year of the war. The new fields are in the central basin area where oil was first discovered in Michigan, thus tending to focus attention on the deeper part of the lower peninsula of the state. Through 1944 the state of Michigan has produced a total of 222,-641,580 bbl. of crude oil from 100 pools, many of which arc relatively small. Among the previous1y discovered fields Reed City is still the outstanding producer, with Fork, Headquarters, and Adams following in the order named. The Reed City pool produced a little over 5,000,00 bbl., which was more than one third of the state's total for the year. Almost two thirds of the year's total oil production came from fields discovered in the past five years. Maps A map of the oil and gas fields of Michigan in 1943, published in the A.I.M.E. report for 1944,* shows the main producing areas and should be referred to if information in regard to their location is desired. The producing zones are shown in the columnar section in the same publi- cation." The data in Tables I and 2 have been carefully ' checked and every effort has been made to show as complcte information as possible. New Discoveries and New Developments Eight new producing areas were discovered during 1944 which, in order of importance, are: Deep River Field.—The discovery well in the Deep River field was drilled by Don Rayburn and others, and should be listed as a chance discovery, as, from a geological standpoint, it was not considered favorable until oil was found at a depth of 2838 ft. in a dolomitic layer in the top of the Dundee limestone. The first well was completed in January 1944, with an initial production of 2500 bbl. By the end of the year 15 wells had been completed, proying an area 2 1/2 miles long and 1/2 mile wide. Coldttater Field.-The Coldwater field was discovered in August 1944, by the Sohio Oil Co. Production is from secondary dolomite at the top of the Dundee at a depth of 3703 ft. To the end of 1944 nine wells had been drilled on 40-acre spacing. Essexville Field.—Essexville field was discovered by United Drillers and Producers, Inc. Eight wells had been completed to the Dundee lime by the end of 1944, and prospects were good for further development during 1945. Hilliards Field.—Hilliards field was discovered by Cook and Fortney. Production is from the Traverse lime at an average depth of 1588 feet,

Jan 1, 1945

By Dorsey Hager

North Central Texas has recently become a center of interest for the oil men of America. The bringing in of the McClosky well at Ranger, Eastland County, and the shallow pool at Brownwood, Brown County, in 1917, has stimulated interest in this area to fever pitch. Oil men from all over the United States are now investing there. The area of present interest is shown by the accompanying map (Fig. 1). The money spent in leases runs into millions of dollars. It is no exaggeration to say that a strip of country 200 miles (321 km.) long and 125 miles (201 km.) wide, comprising some 15,000,000 acres (6,070,310 ha.), has been leased practically solid at a cost for rentals and bonuses of at least $1 per acre. The test holes contracted for will certainly number 400, at a cost of at least $5,000,000. From what has been done in the past six months, $20,000,000 at least will be spent. To pay returns on this amount of money, new production to the extent of at least 12,000,000 bbl. must be obtained. At present, the production from new fields will not average over 5000 bbl. per day; three wells at Ranger are producing 3000 bbl.; 250 wells at Brownwood produce 1000 bbl.; and the Gray well, Coleman County, is as yet an unknown factor. However, at Ranger there is every indication of developing a good pool covering from 1500 to 2000 acres (607 to 809 ha.), more or less, but the wells are deep, 3400 to 3800 ft. (1036 to 1158 m.), and cost $35,000 to $40,000 to drill. Large wells are necessary to pay for such expensive holes. As new wells are drilled, the gas pressure will be lowered rapidly, and large production need not be expected. For those oil men who expect a second Cushing or an Eldorado, Ranger holds little of promise. At Brownwood, Brown County, there are some 250 shallow wells (depths from 200 to 350 ft.) averaging 4 to 7 bbl. per day. There is a chance of an extensive producing area for these shallow sands to the southwest, and the opening of several thousand acres of shallow oil territory, and also some promise of deeper oil horizons in the Ranger horizon, but probably all under 2500 ft. At present, the lease brokers and speculators, and only a handful of oil men, have made any money. More fields must be developed, and it is more particularly with these possibilities that this paper deals. Lack of water for drilling purposes has undoubtedly held back development so far this year; this part of Texas has had a drouth for two years and there is an actual scarcity of water. Geological investigations so far undertaken cover nearly all the area outlined, and while pakt of the

Jan 1, 1920

By W. I. Duvall, D. E. Stephenson

A theoretical solution is given for the energy that is radiated outward when either a cylindrical or spherical cavity located underground in a uniform stress field is suddenly created or enlarged. The method of derivation shows that the stress field in the solid rock surrounding the opening does work on the rock because of elastic displacements that result when the size of the cavity is increased. The amount of this work is sufficient to account for both the increase in the strain energy in the rock surrounding the opening and the seismic energy that radiates outward. Thus, the source of the radiant seismic energy is mainly the gravitational potential energy and not the strain energy stored in the rock. The amount of the radiant seismic energy is directly proportional to the volume of the rock removed from the opening or relieved of stress. Seismic energies from rockbursts are compared with earthquake energies. Also, the amount of gravitational potential energy released by underground explosions is calculated and found to be small compared to the seismic energy generated by the detonation of the explosive. A review of the early literature on rockbursts shows that a number of investigators calculated the amount of energy released by rockbursts. 1-5 However, none of these papers give the formula used to make these calculations or a reference to the derivation of any formulas. The general impression that one obtains from these early papers is that the main source of the seismic energy released by rock-burst is the strain energy stored in the rock before it is fractured. However, a few of the early papers appear to have considered the solid rock at a distance from the mine opening as a possible source of the seismic energy. Recently Black and starfield7 gave a theoretical solution for the strain energy in a stressed plate with and without a circular hole. Also, Press and Archambeau8 gave the theoretical solution for the seismic energy released when a spherical cavity is created in rock subjected to a three-dimensional stress field. Both of the above theoretical papers start with the condition of no opening and calculate the strain energy before and after the opening is suddenly formed. Neither of these papers appear to have calculated the work done by the applied stress field as the cavity is enlarged. The rockburst problem associated with deep mining is concerned with the failure of the solid rock surrounding an underground opening. Therefore, it seems appropriate to consider theoretically the problem of suddenly enlarging the size of an existing opening. The purpose of this paper is to present the theoretical solution for the energy that is available for release as seismic energy when an underground circular tunnel or spherical cavity is suddenly enlarged in diameter. To keep the mathematics as simple as possible, a uniform radial applied stress field is assumed and the rock is assumed to be isotropic, homogeneous and perfectly elastic.

Jan 1, 1965

By John P. Dolan, Charles A. Einarsen, GiIman A. Hill

his paper discusses how the following formation characteristics can be determined mathematically from drill-stem test pressure charts: true formation pressures, effective permeability of the entire section tested, well productivities, wellbore damage, and possible detection of barriers (faults, pinchouts, etc.). This paper also presents a practical method for im-mediate determination of eflective permeability and well-bore damage from successful double shut-in pressure tests. A list of recommendations for improving the reliability of drill-stem rest pressures is also presented. INTRODUCTION A drill-stem test is a temporary completion designed to sample the formation fluid and to establish the possibility of commercial production. Early pressure recording devices were used merely to verify proper operation of the testing tool. Until recently the accuracy of the pressure gauges has been insufficient for any reliable quantitative use of the recorded pressures. In view of the need for more reliable formation evaluation and as a result of the recent interest in exploration work employing the concept of hydrodynamic en-trapment,1,2,3,4 better pressure recording gauges are now in use. These devices can record pressure within 1 per cent above 1,000 psig and can detect differential pressures as low as 1/2 psig. In addition to formation pressure, several other reservoir characteristics can be determined from DST charts; namely, well productivity, formation permeability, wellbore damage, and the possible existence of bar- riers (faults, pinchouts, changes in permeability, etc.). This paper presents a practical method to interpret DST pressure charts for formation pressures and many other reservoir properties, a method that has been developed in analyzing approximately 4,000 DST charts during the last five years. The techniques used are a composite of published articles on drill-stem testing5,6, together with well-known pressure build-up analysis methods. THEORY It has been shown7,8 that the following equation may be used for analysis of pressure build-up curves: Po - Pw = 162.6 qu/kh log ( to + ?/?) .....(1) When this equation is applied to the curves obtained in drill-stem testing, the assumptions and boundary con-ditions are more nearly realized than in conventional flow and build-up tests on producing wells. Zak and Griffen9 have recently discussed in detail the use of this equation in analyzing DST charts. One of the problems with DST curves is the lack of reservoir data for precise analysis. Therefore, it is necessary to develop empirical rules and field methods for analyzing DST charts in quantity. For this reason, the empirical methods presented in this paper have been developed, and their derivation is found in Appendices A and B. METHOD USED FOR ACCURATE READING OF DRILL-STEM TEST CHARTS In order to apply the pressure build-up theory to DST charts, it is necessary to obtain a digitized expression for the pressure and time data recorded by the pressure gauge. These data may be either provided by the service company or interpolated by projecting a

Jan 1, 1958

By James R. I. Henagan, William O. Crego

The Mamou Field, located in Evangeline Parish, La., is an elongated anticlinal structure on the downthrown side of a major east-west fault with oil and gas production from the upper part of the Wilcox formation. Two main producing horizons occur at an approximate depth of 11,500 ft and have been designated the Morein sand and the Deshotels sand. The upper sand (Morein) had an original bottom-hole pressure of 6,788 psig, which is some 1,500 psi above the normal pressure for that depth. Oil production with high gas/oil ratios and fluid analyses giving high shrinkage factors prompted a study of the reservoir in its early stages. The results indicated a closed reservoir producing under solution gas drive with low expected ultimate oil recovery. The early study of the Wilcox formation and its contained hydrocarbons resulted in the presentation of the data to the Department of Conservation of the State of Louisiana. with suggestions for field rules and a request for permission to inject extraneous water into the Morein sand. The water injection plans eventually led to complete unitization of working and royalty interests, to the construction of a gasoline plant, and to a central tank battery installation for the field. Deshotels sand wells were reworked to the Morein sand, and the water injection system was installed and ready for continuous operation in the early part of 1949. The injection of water was started in time to arrest the bottom-hole pressure decline at or near the bubble-point pressure. This injection was calculated to increase the ultimate recovery and to conserve natural resources. Pressure maintenance, the extraction of LPG products, and the sale of residue gas (early 1950) represent an attempt to produce an oil field with utmost efficiency. INTRODUCTION The two principal Wilcox oil horizons in the Mamou Field are the Morein sand and the Deshotels sand, occurring at 11,500 ft and 11,700 ft subsea, respectively. Minor oil production has been encountered in Morein stringer sands. (Fig. 1.) This paper deals only with the Morein sand, which is blanket over the Mamou Field. It is, however, segmented by the northwest-southeast "E" fault as shown in Fig. 2. The west segment is the area involved in the water injection pressure maintenance program. To date the east segment has operated largely under the influence of a strong water drive. The paper presents (1) a brief history of field development, (2) a resumé of reservoir conditions which led to the decision to inject extraneous salt water into the principal producing horizon, and (3) a summary of reservoir analysis and performance. FIELD DEVELOPMENT The Mamou Field is located in Evangeline Parish, La. The discovery well (J. B. Morein No. 1, now Unit No. 5) was completed in December, 1945, after penetrating 200 ft into the Wilcox formation. Initial production from the Morein

Jan 1, 1951

I. PRESIDING OFFICER, At all business meetings of the Institute the President, or, in his absence, the First Vice-President, or, in the absence of both of them, any other Vice-President or Director, chosen by the meeting, shall preside. At all other meetings of the Institute the President, or, in his absence, one of the Vice-presidents shall preside. If none of these be present the meeting shall elect a Chairman. The President shall do and perform such other duties as may from time to time be assigned to him by resolution of the Board of Directors of the Institute. II. ORDER OF BUSINESS. At each business meeting of the Institute the order of business shall be as follows: 1. Reading of minutes of preceding meeting. 2. Report of the President, 3. Report of the Treasurer. 4. Report of the Secretary. 5. Election of Directors. 6, Reports of Standing Committees. 7. Reports of Special Committees. 8. Special Orders. 9. Miscellaneous business. This order of business may be changed at any meeting, by a vote of a majority of the Members and Associates present. At all sessions of the Institute, other than business meetings, the order of proceedings and the time of adjournment shall rest in the discretion of the presiding officer. III. SECRETARY OF THE INSTITUTE. The Secretary shall keep a record of the proceedings of all the meetings of the Institute, He shall be custodian of the corporate seal, of the minute books and of all the legal documents belonging to the Institute. He shall have charge on behalf of the Institute of all correspondence. He shall notify all Officers and Directors and all members of committees of their election and appointment; shall issue notices of all meetings of the Board, and of the annual and other business meetings of the Institute; and shall, in calling special meetings of the Directors, specify the objects of such meetings. He shall act as clerk at all the meetings of the Board of Directors and at all meetings of the Institute, The Secretary shall be custodian of all technical or scientific papers submitted to the Institute for its consideration and shall have general charge and supervision of the editing and proof-reading of all material published by the Institute, and of the distribution thereof. The Secretary shall be the custodian of all back numbers of the Transactions and other publications of the Institute. There shall be kept under his direction an account in ledger form of all such back numbers, He shall on the first day of January of each year submit to the Library Committee a statement of the number of copies of Transactions, magazines and other publications printed during the preceding year, giving the number distributed and remaining undistributed; also a statement covering additions to and withdrawals from the total stock of Institute publications, with the number 'remaining on hand at date of statement,

Jan 1, 1928

By Paul L. Burkhart

THOUGH at an earlier period brief studies had been made by the Lehigh Navigation Coal Company Inc., it was not until 1924 that J. B. Warriner, then general manager, called for a comprehensive study of timber treatment, treating solutions, and related operations. Because of the impossibility of procuring accurate costs and other pertinent treating data, the American Wood Preserving Co. agreed to treat a car of mine timber at the Port Reading plant of the Reading Railroad. Fig. I shows the treating data collected at the treating plant on this timber, which was installed in two of the Lehigh mines in 1925. Table i.—Results of Timber Survey in 1925 before Treated Timber Was Introduced Length of tunnels and gangways ft..... 522,987a Length of tunnels and gangways timbered, ft.................................. 224.880 Number of steel mine sets in use......... 2,412 Number of timber sets in use............ 63,834 Number of timber sets with evidence of rot 50: 419 Number of timber sets with evidence of squeeze..... ...................... I3,415 Percentage of all timber sets showing evidence of failure: BY wet rot........................ 6.0 By dry rot........................ 73.0 By squeeze....................... : Average life of wood set in Panther Valley, years............................... 5.3 • 99.05 miles. In the latter part of 1925, a survey of the tunnels and gangways of the company's Panther Valley mines was made to determine the proportion of gangways or tunnels timbered, cause of timber failures, approximate life of the average wood set and the approximate percentage of treated timber that it would be profitable for the company to use. Results of this survey appear in Table I. Because of the high percentage of timber that gave evidence of failure by rot, as noted in Table I, and a further study of the life of the sections where timbering was necessary, it was deemed advisable to fill 25 per cent of the yearly gangway timber requirement with treated timber. Quantities and Treatments OF Treated Timber Purchased In the early days of the program, none of the large treating companies would accept orders for small quantities of treated timber and the company was compelled to state the quantity of timber it would require at each operation in each month of the year. Table 2 is an example of the tabulation given to the various treating companies to assist them in making a yearly bid on the minimum quantity of timber required by the company during the year 1931. A bill of timber was calculated for each car, the weight of which would be between the minimum and maximum weight permitted for railroad-car loading. The treating company was paid for timber upon delivery at the operation specified. As extra cars of timber were required, they were ordered from the treating company, and payment was required On their receipt, on the basis of the piece or tonnage

Jan 1, 1942

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

IT is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investigators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from 1100° to I700°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxidation of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous clays burned to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,5 the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery6 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the clay, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid,i.e., the sulphur was in combination with the silica. Orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By Paul L. Burkhart

THOUGH at an earlier period brief studies had been made by the Lehigh Navigation Coal Company Inc., it was not until 1924 that J. B. Warriner, then general manager, called for a comprehensive study of timber treatment, treating solutions, and related operations. Because of the impossibility of procuring accurate costs and other pertinent treating data, the American Wood Preserving Co. agreed to treat a car of mine timber at the Port Reading plant of the Reading Railroad. Fig. I shows the treating data collected at the treating plant on this timber, which was installed in two of the Lehigh mines in 1925. Table i.—Results of Timber Survey in 1925 before Treated Timber Was Introduced Length of tunnels and gangways ft..... 522,987a Length of tunnels and gangways timbered, ft.................................. 224.880 Number of steel mine sets in use......... 2,412 Number of timber sets in use............ 63,834 Number of timber sets with evidence of rot 50: 419 Number of timber sets with evidence of squeeze..... ...................... I3,415 Percentage of all timber sets showing evidence of failure: BY wet rot........................ 6.0 By dry rot........................ 73.0 By squeeze....................... : Average life of wood set in Panther Valley, years............................... 5.3 • 99.05 miles. In the latter part of 1925, a survey of the tunnels and gangways of the company's Panther Valley mines was made to determine the proportion of gangways or tunnels timbered, cause of timber failures, approximate life of the average wood set and the approximate percentage of treated timber that it would be profitable for the company to use. Results of this survey appear in Table I. Because of the high percentage of timber that gave evidence of failure by rot, as noted in Table I, and a further study of the life of the sections where timbering was necessary, it was deemed advisable to fill 25 per cent of the yearly gangway timber requirement with treated timber. Quantities and Treatments OF Treated Timber Purchased In the early days of the program, none of the large treating companies would accept orders for small quantities of treated timber and the company was compelled to state the quantity of timber it would require at each operation in each month of the year. Table 2 is an example of the tabulation given to the various treating companies to assist them in making a yearly bid on the minimum quantity of timber required by the company during the year 1931. A bill of timber was calculated for each car, the weight of which would be between the minimum and maximum weight permitted for railroad-car loading. The treating company was paid for timber upon delivery at the operation specified. As extra cars of timber were required, they were ordered from the treating company, and payment was required On their receipt, on the basis of the piece or tonnage

Jan 1, 1942

By L. S. Castleman, H. A. Froot

A study was made of the growth kinetics of B-brass layers in a-brass us y-brass diffusion couples in which both phases were saturated in the 6 phase. It was found that useful estimates can be made of the difhsion coefficients at the ß-phase interfaces from interface displacement data, which are relatively easy to measure experimentally; also, a useful estimate can be made of the mean heat of activation for diffusion from layer growth data. The effects of pressure on layer growth kinetics were explored and found to be consistent with a vacancy model for diffusion in 6 brass in both the disordered and ordered temperature range. 1 HE study of multiphase diffusion receives relatively little attention in comparison with that devoted to diffusion in homogeneous materials. Of the hundred or so papers on diffusion written each year,' only a few are devoted to the subject, and it is the rare review article2,3 that devotes any space to multiphase diffusional phenomena. This is unfortunate, since the metallurgist frequently encounters practical situations involving cementation processes such as cladding, protective coating of metals, and so forth in which he needs guidance of a fundamental nature. The investigation of multiphase diffusion phenomena is complicated by the fact that one must consider reactions at phase interfaces as well as the migration of atoms within the individual phases; these reactions cause the interfaces to be displaced within the diffusion zone. The relative displacement of two adjacent interfaces corresponds to the growth of an intermetallic layer, and it is not difficult to determine experimentally the kinetics of layer growth. In the past few years it has been pointed out4,5 that valuable fundamental information may be gained about diffusion coefficients and the concentrations at interfaces through a study of their motion. Accordingly, it is the purpose of this paper to report the results of an investigation of interface motion in a simple multiphase binary system. In the work reported herein, attention was focussed on the growth of a 6 -brass layer in a diffusion couple prepared from a- and y-brass compositions saturated with respect to the 6 phase. This particular system was chosen for a number of reasons. First, the bcc ß-brass phase is disordered for all compositions at temperatures above 468°C and becomes increasingly long-range ordered for all compositions at temperatures below 454° C;6,7 thus, the effects of a variation in order on interface displacement could be determined. Second, diffusion coefficients have already been obtained as a function of temperature in the ß phase both in the ordered and disordered Re- and a theoretical picture of the mechanism of diffusion in this and other ordered solutions is emerging.11'12 Third, some thermodynamic data are available for the a-, ß-, and ?-brass phases,13,4 and these data could be used to gain insight into questions of phase equilibria and concentrations at phase interfaces.

Jan 1, 1963

By A. W. D. Hills

This paper describes the development of a generalized integral-Wofile method for the analysis of heat transfer dwing solidification. The method is extremely flexible, and can be applied to a wide range of situations. This flexibility has been achieved by characterizing the solid metal layer in terms of two parameters, and by developing two simultaneous nonlinear differential equations for these parameters in terms of the heat fluxes crossing the boundaries of the solid layer. The use of these equations is illustrated in a series of examples which involve the solidification of pure metals at zero superheat cooling under different conditions. The simplicity with which the method can be extended to treat more complicated jwoblems is illustrated in a further example which involves natwal convection effects in the liquid metal. ThE rate at which molten metal solidifies in an industrial casting process, and the structure of the cast product, are both controlled by the rate at which heat can be removed from the casting. A knowledge of heat transfer rates is thus essential to the control of the process and to the control of the structure and soundness of the final casting. Heat transfer rates during real solidification processes cannot be predicted by formal mathematical techniques, however, because nonlinear boundary conditions are involved. Approximate methods are normally used, and these have included electrical and hydraulic analogue techniques, finite difference methods, and the integral-profile method. Considerable effort has been devoted to the development of the first two techniques, but the integral-profile method has been used very little so far. This is unfortunate because the method is capable of providing relatively accurate solutions for the heat transfer equation during solidification without involving large amounts of computer time. A further advantage of the method is its flexibility, although this is not apparent from the integral-profile solutions that have been developed to date. These solutions have been derived for the solidification of molten metal at zero super-heat under cooling conditions involving either a constant heat flux from the cooled surface;' a constant heat transfer coefficient at the surface,'-3 or a specified variation in the surface temperature.4,5 A generalized integral-profile method is presented in this paper which can be used to predict unidirectional solidification rates under a very wide range of more realistic cooling conditions. The use of the method is illustrated in a series of problems involving pure metals, or skin forming alloys, solidifying at zero super-heat. However, the principal advantage that this method has over the previous integral-profile methods is the ease with which it can be extended to treat more complicated solidification problems. This is illustrated by considering a problem in which super-heat is liberated from the liquid metal by natural convection during the solidification process. In the final section of the paper the generalized method is compared with previous methods used to predict solidification rates and its extension to more complicated solidification problems is briefly discussed.

Jan 1, 1970

By Leendert de Witte

A review is given of the principles on which recently proposed methods of electric log interpretation in shaly sands are based and of the evidence brought up in support of the theoretical derivations. It is. pointed out that the qualitative techniques suggested to date have a tendency to be too pessimistic in the prediction of the presence of commercial hydrocarbon accumulations. In the quantitative treatment, a new concept is introduced, namely that of strongly reduced activity of the double layer counter ions which are present near the negatively charged rock surfaces. This lemmu when applied to the calculation of the equilibrium concentratiotls of interstitial waters yields a set of very simple relations. The resulting expressions for electrochemical potentials across rock samples appear in satisfactory agreement with laboratory experiments. The formulae obtained for the electrical conductivity of shaly formatioris are of the same form as those arrived at empirirally by previous workers. Combination of the expres.riorls for potentia1s and conductivities gives a direct proof of the Tixier relation which states that for shaly water sands the product of apparent formation water resistivity and apparent formation factor equals the resistivity of the sand 100 per cent .saturated with formalion water and which was verified by the work of Wyllie and Perkins and their co-workers. The relations for the resistivities and spontaneous porer11inI.s have been extended to the case of hydrocarbon hearing shaly formations, thus laying a formal basis for the quantitative interpretation of electric logs in shaly oil sands. INTRODUCTION The presence of disseminated clays in porous rocks saturated with electrolytic solutions has a strong influence on the transference of ions taking place under electrical or chemical potential gradients. Both the electrochemical emf's in evidence on the SP curves of electric logs and the electrical conductivity measured on resistivity logs arc directly dependent on the ionic transference in the interstitial waters of the formations traversed by boreholes. A large number of researches have been carried out on the nature and magnitude of the effects of clays on ionic transference. The most recent of these have been described in papers by McCardell and Winsauer,1 2 Wyllie and Southwick,3 poupon, Loy, and Tixier,4 and by Perkins et al.5 Most of these authors consider the effects of the clays as due to the fixed negative charges on the clay lattice. These charges cause the formation of diffuse surface layers with a high concentration of positive ions. The internal solution of the shaly reservoir rock has therefore a different ionic composition and concentration than the electrolyte with which it is in equilibrium (connate water produced from the formation or mud filtrate by which the formation is invaded). To calculate the equilibrium concentration of the internal solution, use is made of the Donnan6 relation, which states that the mean ionic activities of the internal solution and of the external electrolyte must be equal. From this and the

Jan 1, 1956

By A. J. Phillips, A. A. Smith, J. S. Smart

THE preparation of a sufficient quantity of high-purity copper for extensive laboratory use in the study of impurity effects has been an integral part of a research program in progress at the Central Research Laboratory of the American Smelting and Refining Co. for the past several years. Initially the degree of purity desired was that necessary to meet two essential requirements for experimental accuracy: (I) no impurity was to be present in the copper in an amount capable of producing a detectable effect on the properties to be studied, (2) even the minor changes in properties caused by the addition of extremely small amounts of individual elements were to be measured without significant interference from contaminants. In the course of the investigation, evidence has accumulated to justify the conclusion that this copper is of exceptional purity; in fact, no impurity can be detected by any chemical method or spectrographic technique known to the authors. The present paper describes the method of production of the copper and presents some of its properties. PREPARATION OF HIGH-PURITY COPPER The elimination of impurities from commercial electrolytic copper is accomplished by a three-step purification process. The first operation consists of an electrolysis through a purified CuS04-H2SO4 electrolyte using bagged anodes, low current .density (5 amp. per sq. ft.) and low temperature (25°C. max.). The electrolyte is prepared from commercial Cu2SO4 and is purified by heating the solution and adding I gram Fe as Fe 2(S04)3 to each 100 grams dissolved copper; sufficient hydrated oxide of copper, prepared from Cu2SO4 and NaOH, is supplied to precipitate Fe(OH)3, which carries down arsenic, antimony, tin, selenium, tellurium and other minor constituents. Silver and remaining traces of lead are removed by addition of Na2S to the acidified filtrate, which is then refiltered after standing hot overnight. The cold solution is made up to 30 grams per liter Cu and 150 grams per liter H2S04 and introduced without addition agents into the electrolytic system, which consists of a double row of hard-rubber battery boxes with the inside webbing and partitions removed, arranged in seven steps of ascending height. Electrolyte is uniformly supplied to the two highest cells by glass siphons operating from a constant-level reservoir, and flows by gravity through the bank of seven cells, entering each at the bottom and leaving at the top. Glass air lifts continuously supply the returning liquid to the constant-level reservoir for recirculation. Each cell contains three 434 by 43a by I-in anodes cast from high-quality electrolytic wire bar copper, various lots of which have been used with equal success. The anodes are pinned to sheet copper hangars shaped to prevent crawl of the electrolyte to the multiple-wired bus bars-which would result in fouling of the contacts and hang inside wool flannel bags stretched over open wood frames. The deposit

Jan 1, 1941

By H. A. Saller, F. A. Rough

Studies of the V-U system have been made to determine the constitutional diagram. The diagram is fairly simple, since no intermediate phases are formed. Additions of vanadium lower the uranium melting point and allotropic transformation temperatures. The maximum solid solubility of vanadium in uranium is 12 atomic pct and the maximum solid solubility of uranium in vanadium is about 4 atomic pct. WITH the advent of high purity iodide vanadium,' it became of interest to study the alloying characteristics of vanadium and uranium. Alloys were prepared covering the entire system and were studied using a combination of metallographic examination and thermal and X-ray analyses. As a consequence of this work, the V-U constitutional diagram was evolved. In order to prepare suitable alloys for equilibrium-phase studies, it is desirable to have the purest possible starting materials. For this investigation, calcium-reduced vanadium, de Boer process crystal-bar vanadium, and good Mallinkrodt Chemical Co. uranium were used. The first work was done using the best vanadium then available, that being calcium-reduced vanadium produced at Knolls Atomic Power Laboratory. Subsequently, the important features of the diagram were checked using alloys made with crystal-bar vanadium produced at Battelle. These checks are in agreement with the earlier work. Analyses of the starting materials are contained in Table I. Only minor amounts of any impurities were present in either the vanadium crystal bar or uranium. Nevertheless, care was exercised in selecting the uranium for the alloys. The procedure followed was to section the stock into suitable pieces for melting, and macroetch each piece. Only those pieces which appeared to be clean by macroetch examination were used for alloying. Experimental Procedure Melting: Alloys with 0 to 50 atomic pct V were induction melted in beryllia (BeO) crucibles under vacuum of 10 microns pressure or better. A number of remelts was frequently required to insure uniformity of the individual ingots. Although no visible reaction between the alloy and crucible was found in any of these operations, the alloys were checked by spectroscopic analysis. Only trace amounts of beryllium were detected in the alloys. Alloys containing 50 to 100 atomic pct V were arc melted in a water-cooled copper crucible under an atmosphere of helium. A tungsten electrode was used. Ingots of 10 to 15 g were produced readily by turning and remelting a few times. Such small ingots were necessary because high purity vanadium was not available in appreciable quantities at this time. After melting, the ingots were examined metal-lographically for segregation and were consolidated by remelting before fabrication was attempted. Spectroscopic analyses showed that only small amounts of tungsten were picked up during the arc-melting process. Fabrication of Alloys: Alloys containing up to 20 atomic pct V could be fabricated by rolling in air at 600°C with 5 min between passes. After each pass through the rolling mill the alloys were returned to

Jan 1, 1954

By Henry F. Hebley

This paper brings within the compass of one comparatively brief article a general description of the situation concerning the nation's water resources. It touches upon the phenomenal growth in the demand for water supply and emphasizes the problems facing the coal industry both with regard to acid mine water drainage discharged from active and abandoned mines and the suspended solids discharged to the stream system from wet coal preparation plants. IT must always be remembered, with regard to the problem of water-borne industrial wastes, that stream pollution from any cause is just one factor in the comprehensive problem of water supply in modern times. Industries nonexistent 25 years ago are now flourishing, and supplies of water piped to homes and apartments, as well as the greater number of plumbing fixtures per dwelling and per building, have created an ever growing demand on the country's water resources. Indication of this rapid growth in demand is shown in Table I, which is quoted from Abrams. of Texas increased 287% and the water consumption 7000 per cent." The domestic load varies greatly, depending on the extent of the available supply and the habits of the community. According to the report of the President's Water Resources Policy Commission' the United States Public Health Service reported a national average of 127 gal per capita per day, varying from 60 gal in communities of 500 persons to 140 or 150 gal in cities of 10,000 or over. Other critical areas may be cited to illustrate the inter-relation between new industrial processes and the demands for water in the area where the new enterprise is located. Powell and Wilson have pointed out that during World War 11, in the vicinity of Louisville, Ky., a rapid expansion of industry took place, consisting of numerous synthetic rubber plants. The demand for water increased from 37 million gal per day in 1937 to 62 million gal in 1943. These heavy requirements drew down the supply stored in the water-bearing aquifers to such an extent that urgent plans for recharging were considered. Similar situations have developed in the Los Angeles area and in the vicinity of Texas City. Warne4 has drawn attention to the situation in Los Angeles area, where in the West Basin the withdrawal of ground water in 1945 was 90,000 acre-ft, almost double the amount of the natural fresh water recharge. The draw down has been so severe that the level of the ground water is now below sea level, and sea water is invading the West Basin aquifers at rates up to 300 ft per year. In the Report of the Engineers Joint Council it is pointed out that in the area of Texas City the ground water table has been critically lowered. In 1930 the daily withdrawal from the water-bearing aquifer was 0.5 million gal. By 1945 the quantity withdrawn

Jan 1, 1954

By L. L. Newman

As soon as the Congress recognized the alarming rate at which our domestic oil resources were being depleted during the war, it took action to step up the rate of research and development which the Bureau of Mines had been conducting for several years on the production of synthetic liquid fuels from coals. Under Public Law 290, approved April 5, 1944, funds were authorized for the Bureau to proceed with research, development, design and construction of demonstration plants for the hydrogenation of coal, the synthesis of oil from carbon monoxide and hydrogen, and the distillation of oil from shale. During the latter part of 1944, when it became evident that the collapse of Germany was near, a Technical Oil Mission was organized to study the German techniques of synthetic oil production. Since the cost of hydrogen or synthesis gas is one of the major factors of expense in the operation of hydrogenation or synthesis gas processes, the Bureau of Mines considered it of prime importance to include on the mission gas engineers whose instructions were to examine closely the methods employed by the Germans in solving the problem of providing low-cost hydrogen or synthesis gas for their very extensive operations on synthetic liquid fuels. The Solid Fuels Mission and the Utilities Mission, as well as the Army and Navy Missions, also included teams for the study of German gas production. Although their objectives naturally differed from those of the Technical Oil Mission and from each other, it was recognized that there was considerable overlapping of their fields of investigation. Duplication of effort, however, was largely avoided through the close cooperation between the group leaders of these missions. For example, although I went to Europe as a member of the Technical Oil Mission, my first Gcrman assignment was actually made by Dr. Harry F. Yancey, leader of the Solid Fuels Mission— to investigate the brown-coal gasification methods in central Germany. The art of gasification in the United States and England, and to a large extent in the proximity of the coking-coal regions of Germany and the rest of continental Europe, depends essentially on two stages of operation; namely, carbonization and intermittent water-gas generation. As far as the United States is concerned, complete gasification in a single stage of operation is rarely practiced, except in gas-producer operations where the product is a relatively lean gas consumed close to the point of manufacture, and for water-gas production with anthracite as a generator fuel. Complete gasification of bituminous coal has been the subject of numerous investigations. Many relatively simple modifications of the water-gas generator have been tried to permit the direct gasification of low-cost bituminous coal instead of high-cost coke and anthracite for the production of water gas. Although varying degrees of Success have been achieved and the water gas produced generally has been higher in

Jan 1, 1947

By E. N. Mazza, H. S. Kalish

The effect of sintering types 302, 3028, and 430 stainless steel powder compacts in hydrogen and dissociated ammonia was investigated. It was found that sintering in dissociated ammonia resulted in as much as 0.5 wt pct increase in the nitrogen content of stainless steel even though the dissociation of the gas was complete. Sintering in hydrogen, on the other hand, reduced the nitrogen content of the stainless steel to less than 0.01 wt pct. In the case of the 302-type stainless steel, the low nitrogen content resulted in a material that was largely ferritic, whereas the high nitrogen content rendered the material fully austenitic. Sintering in dissociated ammonia resulted in lower density, generally lower tensile strength, less ductility, and higher hardness than sintering under equivalent conditions in hydrogen. The reduction of oxides on both stainless steel and iron particles was found to be effected by hydrogen partial pressure in the sintering atmosphere. Compacting pressure was found also to effect oxide reduction during sintering. DISSOCIATED ammonia often is used as a substitute'.' for hydrogen in sintering and in annealing, since economic advantages sometimes can be obtained by such a substitution. In addition, anhydrous ammonia contains very little impurity. Thus, dissociated ammonia gas is very dry whereas tank hydrogen often must be freed of oxygen and water vapor prior to use in many applications. The sintering of stainless steel powder compacts as well as bright annealing is well recognized as requiring a hydrogen atmosphere and for the foregoing reasons dissociated ammonia is frequently substituted. It has generally been overlooked, however, that the nitrogen in dissociated ammonia might have an important effect on the sintering process and on the properties of stainless steel compacts. Considered an inert gas in many applications, nitrogen, on the other hand, is very reactive with cer- tain metals. Dissociated ammonia could not be used for hydriding zirconium or titanium. Nitrogen reacts with columbium, tantalum, chromium, uranium, thorium, and many other active metals. Iron and iron-base alloys are, for the most part, inert in nitrogen but there are many borderline cases. It has been reported that stainless steel stabilized with columbium or titanium should not be sintered in dissociated ammonia.3 olybdenum has been reported as reacting with dissociated ammonia to a minor extent.' Although most of the reactions with iron-base alloys are attributed to the action of un-dissociated ammonia and the action of nascent nitrogen, Uhlig4 showed how readily pure molecular nitrogen reacts with and diffuses into 18-8 stainless steel at 1150°C. He also pointed out how readily nitrogen diffuses out of 18-8 stainless steel when heated in pure dry hydrogen, and these thorough investigations on the subject show that commercial stainless steels are nitrogen-bearing, since they are melted in air. The effects of nitrogen in stainless steel, particularly the 18-8 Cr-Ni type, previously have received considerable attention." In 1926, it was pointed out

Jan 1, 1956