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By G. T. Davis, C. C. Mattax, M. O. Denekas

The effects of crude oil cornponents on the wellabil-ities of sandstone and limestone were investigated. Fractions containing cornponents differing in molecular weight and molecular structure were obtained from crude oils by distillation, extration and chromatography. Individual fractions were then tested for their effects on rock wettability. Tests indicate that sundstone wetta-bility may he changed by a complex variety of surfactants varying both in molecular structure and molecular weight. Limestone appears to be particularly sensitive to basic, nitrogenous surfactants. INTRODUCTION Investigations in recent years have shown that petroleum reservoir rock wettability can exert a significant influence on the efficiency with which oil can be produced by water flooding. While most reservoirs are presumably water-wet, they niay range in their degree of water-wettability from near-neutral to strongly water-wet.'" Reservoir wettabilities other than strongly water-wet are likely to be induced by adsorption of surface-active components froni the crude oil on the pore walls of reservoir rock.:' Little is known, however, about the nature of the surface-active materials which are likely to be adsorbed by the reservoir rock. Due to the complexity of crude oils. attempts made in the past90 isolate these surface-active components have met with only limited success. It is probable that many different types of surface-active materials arc indigenous to crude oils and that many of these may be adsorbed to varying degrees by reservoir rock. This was cxolored in the studies discussed in this paper. The over-all objective in these studies is to ascertain whether the wettability of a given reservoir can be determined by examining the surfactant content of the reservoir crude. To this end, crude oils were examined to determine the variability of indigeneous surfactants with regard to chemical type and molecular weight. Crude oils were separated by distillation into fractions differing principally in molecular weight, by chroma-tography into fractions containing compounds differing in polarity, and by solvent extraction into nitrogenous and non-nitrogenous fractions. Individual fractions were then tested for their effects on the wettabilities of sandstone or limestone rock samples. EXPERIMENTAL PROCEDURES Fractionation of the Crude Oils Samples of Miocene, Eocene and Jurassic crudes were distilled at temperatures not exceeding 200°C. The final stages of distillation were completed in a molecular still at pressures down to three microns of mercury. Fifteen to 30 fractions were obtained from each crude oil. These cuts were sufficiently broad that separation can be considered to have been effected principally on the basis of the molecular weights of the constituents of the crude oil. A considerable portion (20 to 40 per cent) of the crudes would not distill under these conditions. The residues were recovered and tested with the other fractions. Fractions differing in polarity were separated from a crude of Pennsylvanian age and an extracted sample of Miocene oil by chromatography, using a solid adsorbent. Since surfactants are, for the most part, polar compounds, chromatography should separate many of the surfactants from the crude oil. Such a separation should provide fractions containing compounds differing in molecular structure. Nitrogeneous compounds were extracted from Miocene crude oil with a solution of sulfuric acid in meth-anol. The residual oil was further processed by chonia-tography. Each of the fractions obtained by thesc procedures was dissolved in a non-polar solvent (xylene) and diluted to its original concentration in the crude oil. No attempt was made to maintain an anaerobic atmosphere above the samples while they were being dissolved. These solutions of the fractions were then tested for their effects on the wettability of sandstone and limcstone as discussed in the next section. Measurement of the Effects of Crude Oil Fractions on Rock Wettability No entirely satisfactory method for measuring rock wettability has yet been developed. All methods used are empirical. The imbibition test was used in these studies. This test is based on the tendency of a rock to imbibe the wetting phase spontaneously. For example, if a strongly water-wet rock is first saturated with oil and then placed in water, the water will quickly invade the rock by capillarity and much of the oil will be displaced. If the rock is slightly water-wet, water irnbibition will proceed more slowly and, in many instances, considerably less oil will be displaced. A water-saturated, oil-wet rock will imbibe oil. The initial rate with which water (or oil) imbibition takes place indicates, qualitatively, the degree of water (or oil) wettability of the rock.

By Thomas Fraser

BECAUSE of the present interest in the subject of sulfur in coal and its removal, such information as is available in the coal-washing literature on the various factors that determine the adaptability of a coal for wash- FIG. I.-COAL-WASHING TABLES OF ONE-FOURTH COMMERCIAL SIZE. ing have been collected and are presented here together with some observations based on results of experimental work carried out in the coal-washing laboratory of the mining department of the University of Illinois, and investigative work at Illinois washeries in connection with the work on reduction of the sulfur content of coal, being carried on at the Urbana Station of the.U. S. Bureau of mines. This investigative

Jan 9, 1919

By R. P. Rothwell

AT this our first meeting I beg to call the attention of the members of our Institute to what is certainly a question of the greatest possible importance to the industries we represent; and more particularly to the welfare of the coal and iron trades : I refer to the enormous waste of coal in mining and in its preparation for market, as now practised in our anthracite coal-fields. It is a fact which many of you can certify to, that we are wasting fully one-ha f of all the coal in the veins we are now working, and there are cases, which might be mentioned where this proportion, immense as it is, has been greatly exceeded. The popular belief that our deposits of anthracite coal are "practically inexhaustible," is very far from being founded on facts. On the contrary, supposing the present rate of increase in the production to be maintained, it is probable that a maximum yield for our coal-fields would be attained in about fifteen years ; there are in fact some of our smaller basins where the principal veins are nearly exhausted and the production has already attained its maximum. There are others, again, where the depth attained-and it must be borne in mind that we commenced working at the surface outcrop-moderate though it is (scarcely ever reaching eight hundred feet), has so increased the cost of mining as to imperil the capital invested, and though it requires but little foresight to predict the time when the difficulties of mining will be very considerably increased by reason of the greater depth, greater quantity of water, fire-damp, and other fruitful sources of cost, yet, ignoring these recognized facts, we continue to waste more than one-half of the coal where it is obtained with the least danger, expense, and trouble, that is, near the surface-either above water-level or at a moderate depth below it. The inspection of almost any accurate mine map will satisfy you that, on an average, we leave fully one-third. of the coal in the ground as pillars to support the roof; in some places more than one-third thus remains, while it is very rare that less than one-quarter is left. In almost every case this coal is absolutely lost, for it will very rarely pay to reopen gangways and lay roads to it after that portion of the mine has been abandoned. Is it necessary in all cases to support the roof, and where it is, may not some artificial

Jan 1, 1873

By Jean Howard, E. V. Walker

ManY papers have been published during the last few years on the formation of cube texture in 3 1/4 pct Si-Fe, e.g., those of Assmus, Detert, Dunn, and Walter.1,5 All are concerned with the formation of the texture by a process involving secondary re-crystallization and the relative surface energies of (100) and other planes under certain conditions of annealing. The authors have found that cube texture can also be produced by heavily cold rolling strip in which the cube-on-edge texture has first been formed. Cube texture develops on annealing, but in this case it is not accompanied by secondary recrystallization. The starting material is a sintered compact, the preparation of which has been described elsewhere. Using a conventional processing schedule employed for producing commercial silicon-iron with the cube-on-edge texture, the sintered compact is cold rolled to such a thickness that, after annealing in pure hydrogen for 24 hr at 1350'~ to produce the cube-on-edge texture, the final thickness required can be obtained by giving a further cold reduction of 85 pct. Cube texture is developed by annealing at -900~~ in pure hydrogen: it has been produced in strip up to 0.024 in. thick. The microstructure of the strip consists of a mass of small primary grains within the boundaries of the much larger secondary grains which ex- hibited cube-on-edge texture before the final cold roll. If the strip is annealed at -1000 after the 85pct reduction, secondary recrystallization begins to take place, provided a strong cube texture is present. On raising the temperature more secondaries grow, complete secondary recrystallization being obtained on annealing at -1150'. From this it is concluded that the secondary crystals are produced by the texture inhibition mechanism: they show (110) and (111) planes in the surface of the strip, the former being the more numerous. It has been observed that the more perfect is the (110) [001] texture prior to cold rolling by 85 pct, the further from the ideal is the (100) [oo].] texture. A similar treatment applied to high quality commercial grain-oriented silicon-iron strip failed to produce cube texture. The tilt and rotation of the [loo] from the rolling direction was less than 10deg, but (to within a few degrees) the planes (130), (450) and (210) lay in the surface of the strip. Acknowledgment is made to the Engineer-in-Chief of the British Post Office for permission to use the information contained in this note.

Jan 1, 1962

A. O. GATES, Salt Lake City, Utah (communication to the Secretary*).-The writer is delighted by the results shown in Mr. Bell's paper, which prove in an experimental way different from that followed by the writer' that "the work clone in crushing is proportional to the surface exposed by the operation," per Rittinger's Law. Mr. Bell's work was all clone in commercial types of crushing machines, while my work was clone in a testing machine; his work represents fully one hundred times the expenditure and time that my work represented; a great number of tests were made by his organization to determine single points, while I was obliged to depend on the general trend of a curve for results; we agree absolutely that "Kick's law," for which Mr. Stadler was sponsor, does not apply to rock crushing. While my work indicated the reliability of Rittinger's theory, Mr. Bell's work clearly establishes the reliability and makes it Rittinger's law.

Jan 5, 1917

By L. A. Wright

Union Carbide Corp.'s Pine Creek mine in California is the largest known tungsten deposit in the West, and the producer of well over five million tons or ore to date. Located 21 miles northwest of Bishop on the eastern slope of the Sierra Nevadas, the mine is also a source of molybdenum and copper and it was the quest for the molybdenum which caused the mine management to undertake a pillar recovery program. GEOLOGY For a full discussion on the geology of the Bishop tungsten district and the Pine Creek mine, reference is made to Special Report 47, Calif. Div. of Mines. The deposit lies along a 3000 ft segment of the contact between quartz monzonite and the marble that flanks the west side of the north portion of the Pine Creek pendant. All the components of a typical contact metamorphic tungsten deposit are developed; these consist of tactite, light colored calc-silicate rock and quartzose rock.

Jan 5, 1964

F. G. SMITH.-Probably someone will ask whether I discovered why the bottoms of the large shells broke out. I did not, as a result of this investigation. An experiment was made along the lines indicated in this paper, to determine whether abnormal grains greatly affected the physical properties of brass. Two ordinary test bars were annealed for 1/2 hr. at 750° C. and physical properties determined on one. The other was covered with indentations made with a peen hammer and then reannealed. for 5 hr. at 750° C. It was found in the tensile test to be made up of large grains 1/4 to 1/2 in. in diameter. The physical properties, however, differed from those of the first bar only as much as might be expected after a 5 hr. anneal under normal conditions. It appears then that the large grains produced in this manner do not ruin the physical qualities of the brass.

Jan 12, 1919

Manganese ore from the Black Rock, Kramer, and Black Jack mines in Tooele and Jaub Counties, Utah, are of acceptable grade, the U. S. Bureau of Mines has announced. Payment of a premium price of 252¢ per lb to the Copper Range Co., of Michigan for the output of its White Pine mine, has been agreed to by the DMPA. The contract will be limited to $28.6 million worth of copper. The agreement follows an RFC loan grant of $57 million to bring the White Pine property into production within three years. Increases of 5 to 6 cents over the Lake copper ceilings have been granted to the Calumet & Helca Consolidated Copper Co., for operation of "high cost" deposits, according to Jess Larson, DMPA administrator. Mr. Larson expects the move to add about one million lb of copper per month to the supply. The agreement can be cancelled on 60 days notice and is terminated automatically in the event copper ceilings are removed.

Jan 1, 1952

By K. Tajrych

Time and again, lives are lost in underground cave-ins only be- cause there is no quick, sure way of locating the victims. When such accidents happen, rescuers must usually depend on the testimony of eye- witnesses for information on the whereabouts of trapped miners. Seldom is this information reliable. The witnesses themselves have just been through a traumatic experience that has distorted or destroyed their sense of time and place. A far more reliable method of finding men underground has recently been developed by the Coal Mining Research Institute of Ostrava, Czechoslovakia. With this system, a miner can be located with adequate precision even if he shows no sign of life. For the system to work, the miner need only have his electric cap lamp somewhere nearby. The system consists of a minute radio transmitter operated by the lamp battery (Fig. 1). This tiny transmitter continuously emits high- frequency electromagnetic waves that can be picked up by a sensitive direction-finder receiver in case of accident.

Jan 8, 1969

By Arthur Knapp

THE economics of fuel oil must be considered in two aspects; viz., fuel oil as one of a number of competitive fuels and fuel oil as a refined product of petroleum. "Fuel Oil" is usually defined as that product of petroleum which is used in furnaces for the generation of heat by simple combustion. It is true that any product of petroleum used in an internal combustion engine is essentially a fuel oil, but such oils are not included in the class known as "Fuel Oil." FUEL OIL AS ONE OF SEVERAL FUELS For a number of years, the petroleum industry has believed that the petroleum reserves were very limited and that petroleum products would begin to become scarce within a few years. The industry has believed FIG. 1.-DAILY AVERAGE CONSUMPTION OF FUELS BY PUBLIC UTILITY POWER PLANTS. that there would be a gradual but continual rise in prices as a result of this impending scarcity.

Jan 1, 1928

By R. H. Migliaccio, M. B. Kahle

The railroad haulage system was started at Kennecott's Bingham Mine in 1906 and has remained a prime mover of ore and waste for the succeeding sixty years. As the stripping ratios increased contract stripping on the upper levels of the mine was introduced employing truck and shovel methods. The ore production then was 90,000 tpd. Analysis of expanding the ore production to 108,000 tpd revealed that the increased ore production and continually rising stripping ratio would result in waste production requirements that exceeded the capacity of the rail haulage system above 6290 level. The advent of larger haulage trucks (65-100 tons) in the early 1960's made available to the Bing- ham Mine economic and operating factors which showed truck haul- age to be the best replacement for rail haulage on the upper levels of the mine. As part of that analysis it was concluded that company stripping would replace the contractor stripping in the top area of the mine.

Jan 7, 1973

By George T. Bator

If confronted with the problem of pumping a mixture of slime-free sand, gravel and boulders up to six in. in diameter, at the rate of 175 tons per hr in one single-stage pump against a static head of 90 ft and a total head of 140 ft, of which 20 is on the suction side, an engineer might be forgiven for backing away from the job, especially if he were also told that the pump wearing parts must have a minimum hardness of 550 Brine11 for the sake of abrasion resistance. Yet precisely that feat has been accomplished in the gravel pit of John B. LaGarde, Inc., near Anniston, Ala. The pump used is of decidedly novel design and its successful operation since installation 1.5 years ago suggests that it may be of timely interest in numerous other applications in the mining industry, such as pump transportation of coal washer refuse or rock from open-pit's without unduly fine crushing.

Jan 9, 1950

By George L. Lyle

WITH the advent of World War II, the need for agricultural products rose phenomenally and caused a similar increase in demand for plant foods of which phosphate rock is one of the more important raw materials. By the close of the war or shortly thereafter, all of the operating companies were expanding their production facilities. Many companies installed modern bulk material handling facilities. Designs varied, but were generally of the overhead trestle type of storing conveyors. American Cyanamid studied these various installations but was not satisfied with the conventional system because of high initial cost, increased maintenance problems in the way of painting structural steel that might be submerged in stored materials, and because of slightly increased operating costs. As a consequence of these economic analyses, conferences were held with the various conveyor manufacturers to develop a better method of storing and reclaiming. After considerable engineering study, one conveyor manufacturer suggested the unique system which was installed in 1950.

Jan 8, 1954

By Ralph Sherman

IN these days of intense competition for the domestic fuel market much is heard of the low efficiencies with which solid fuels, and most particularly bituminous coal, are burned in domestic heating equipment. In contrast to the every-day operating efficiencies of 85 and 90 per cent in large, central, electric-generating stations, efficiencies of 50 per cent and lower are cited for the hand-fired home furnace. Just as the miles per gallon of gasoline is only one of the factors that determine the cost of operation of an automobile, so the thermal efficiency is only one factor in the cost of domestic or other heating. The purpose of this paper is to analyze the total costs of domestic heating by various fuels and types of equipment, to determine the relative importance of efficiency and other factors, and to discuss what this signifies relative to the future of the use of fuels in the home.

Jan 1, 1933

By Z. M. Zavodni

The stability of waste dumps depends to a great extent on the physical properties of the underlying foundation. These physical properties are evaluated through surface geotechnical surveys, subsurface exploration, and field and laboratory testing. Sufficient information must be obtained to define and assess the strength, consolidation, distribution, topographic and hydrogeologic properties for these materials. Important foundation data collected in the field include: surface infiltration rates, downhole hydraulic conductivities, ground water levels, bedrock structural parameters, soil types and soil thickness. Laboratory testing should identify the classification, strength, moisture content, hydraulic conductivity, attenuation and consolidation characteristics. Summarized in this paper are procedures and typical results of porphyry copper leach dump foundation investigations. Laboratory properties and design recommendations for potenia1 foundation liner materials are described. Back analysis and laboratory foundation strengths are compared. The topographic effect of the foundation on dump behavior is discussed and a foundation pore pressure monitoring experiment at the toe of an active waste dump is described.

Jan 1, 1985

By Dorsey Hager

THE possibility of oil and gas production in Alabama has been little considered as yet. Gas and some oil have been found in northwestern Alabama, near Birmingham, in the Pennsylvanian beds, but the oil and gas possibilities in the Cretaceous beds are not generally appreciated. The recent activity of oil companies in that State has attracted much attention, and in this paper the main structural and the general stratigraphic features are described. Four favorable areas are outlined. These contain folds of major interest. There are other favorable areas which have not been mapped. Commercial pools discovered in this area would have the advantage of being near tidewater. Mobile, Ala., on the Gulf, of Mexico, would be the logical site for refineries and shipping facilities. A pipe line could readily be laid to that city from the Hatchitigbee and the Jackson areas. The logical outlet for the Geneva and the Gordon areas would be Panama City, Fla., on the Gulf of Mexico.

Jan 2, 1918

By T. W. Healy, P. Somasundaran, K. Ananthpadmanabhan

Hydrolyzable surfactants such as fatty acids and amines undergo, in addition to micellisation and precipitation, various associative interactions in aqueous solutions to form ionomolecular complexes such as acid-soap, dimers, etc., depending upon the solution conditions such as pH. The interaction of these collector species with the mineral surface and with other dissolved species in solution will play a significant role in determining the interfacial processes such as adsorption and flotation. Marked differences in the hydrophobicity imparted to the mineral surface depending upon the solution conditions such as pH can be attributed to possible differences in surface activities of the foregoing complexes. This aspect of solution chemistry of flotation system is discussed here for two widely used collectors, namely, oleic acid and dodecylamine. Equilibrium species distribution diagrams, based on the available literature data and on estimates of energy of interactions between molecules, have been obtained for oleic acid and dodecylamine solutions.

Jan 1, 1980

By Homer E. Harris, William C. DeSieghardt, William A. Burgess

Under sponsorship of NIOSH, Eastern Associated Coal Corp., with the Harvard School of Public Health acting as a subcontractor, has determined for the first time the effective protection provided to working underground coal miners wearing approved half-mask dust respirators. This was done by conducting 187 man-shifts of in-mine testing in four different coal mines; included in this testing were 37 different test subjects representing 11 different job classifications and 5 different models of respirators. Presently available respirators on average provided significant protection levels to working miners even though on an intermittent use basis. However, "average" protection values were well below those achieved under laboratory conditions. Protection levels varied from man to man in a given work crew and from day to day for a given man. In addition, some of the factors affecting use and effectiveness of presently used respirators are discussed, as are areas in which improvements are needed, and the need to consider these improvements in context of a systems approach.

Jan 1, 1975

By D. E. Ranta, M. W. Ganster, A. D. Ward

An ore zoning technique developed by Climax geologists during the past forty years has been used to contour drill-hole assay values on cross-sections for fourteen porphyry molybdenum deposits in western North America, including the Climax and Henderson orebodies. Detailed geological studies of these large, complex deposits are essential in determining ore controls, which are the factors most critical to the zoning of MoS2 and to conceptualizing geologic model s. The technique provides a detailed representation of the size, shape, grade distribution, and geologic continuity of the individual deposits. It demands a disciplined approach and adheres to rigorous rules while maintaining flexibility for adaptation to widely varying geologic conditions. By defining the limits that guide and control manual, computer-assisted conventional, and geostatistical reserve estimates, it exerts a strong geologic influence on the estimation process. A combination of ore zoning and geostatistical analysis of molybdenum deposits produces a significantly more accurate, precise, and defendable geologic reserve estimate than other methods.

Jan 1, 1984

By Shiro Ban-ya, John Chipman

Equilibrium in the reaction was investigated at temperatures of 1500°, 1550°, and 1600°C for sulfur concentrations up to 7.2 wt pct. Multisample crucibles contained the liquid alloys in a resistance-heated furnace using a technique especially designed for the study of more complex alloys to be reported separately. Modern free-energy data are used to correct the H2S:H2 ratio for dissociation of H2S and calculalion of the partial pressure of S2. Published data on the equilibrium are similarly corrected. Thermodynanzic treatment of the data employs the composition variable zs = nS/(nFe — nS) and the activity coefficient Gs = as/zs The data at 1500" and 1550°C are fitted by the equation log s = —2.30zs. Within the limits of experimental error the same coefficient is applicable to the data at higher temperatures. Equations are given for the free-energy change in Reaction [I] as well as for the solution of S, gas in the metal. The heat of solution of 1/2 s2 is -32.28 i2.5 kcal. Uncertainty in the free energy is very much smaller. For dilute solutions of interest in steelmaking, the activity coefficient of sulfur is unchanged from that listed in Basic Open Hearth Steel-making. DETERMINATIONS of the thermodynamic properties of sulfur in liquid iron by Morris and williams1 and by Sherman, Elvander, and chipman' provided a basis for control of sulfur in steelmaking processes. From the standpoint of understanding the chemistry of metal plus nonmetal in liquid solution they left several questions unanswered. The activity of sulfur in dilute solution at about 1600°C was well-established but temperature coefficients were uncertain, due at least in part to the use of the optical pyrometer and uncertainty regarding the effect of sulfur on emissivity. It appeared that deviation from Henry's law increased with increasing temperature, a most unusual behavior requiring either confirmation or disproof. These studies were based on experimental determination of equilibrium in the reaction: At high temperatures H2S is partially dissociated so that the gas mixture contains HS, S2, and S in addition to HS. At the time of the earlier studies the free energies of these constituents were unknown and it was therefore impossible to make adequate correction for dissociation. Observations on the effects of alloying elements by Morris and coworkers1, 3 and by Sherman and Chip-man4 enable us to assess the effects of alloying elements on the activity and to make corrections for incidental impurities in the binary liquid. These studies as well as a number of more recent investigations will be reviewed in detail after out own experimental results have been presented. It was our purpose in planning this study to avoid uncertainties regarding the emissivity of alloys and the errors of thermal diffusion which plagued some of the early attempts,5 by using a resistance furnace and thermocouple in preference to induction heating and optical pyrometer. Modern data on free energies of the gaseous species are to be applied to our data and to those of other investigators to obtain corrected values of K1 and of the activity coefficient and ultimately to relate the sulfur content of the bath to the equilibrium partial pressure of S,. Extension of the study to include ternary and complex solutions will be described in a later section. EXPERIMENTAL METHOD a) Preparation and Calibration of H2-H2s Gas Mixture. The source of hydrogen sulfide was a preparer mixture of 43 pct H2S, balance hydrogen, contained in a large aluminum cylinder. This was passed through anhydrone and through a microflowmeter. Hydrogen was passed through platinized asbestos, ascar-ite, and anhydrone, and through a capillary flowmeter. Argon was passed through copper wool at 500°C, then through ascarite, anhydrone, and a flowmeter. The flow rate of hydrogen was kept constant at 200 ml per min, to which an arbitrary amount of the hydrogen-hydrogen sulfide mixture was constantly added and then the prepared gas mixture was introduced into the reaction tube through a gas mixer. In certain experiments 200 ml per min of argon was added to the hydrogen-hydrogen sulfide gas mixture to increase the total flow rate of gas. The ratio of hydrogen-hydrogen sulfide in the inlet gas was checked for each run by chemical analysis. A sample of the gas taken from a bypass was bubbled through zinc and cadmium acetate solution (4 pct zinc acetate, 1 pct cadmium acetate, and 1 pct acetic acid) to remove hydrogen sulfide from the gas mixture, and the flow rate of the remaining hydrogen was measured by a soap bubble method to determine the volume of hydrogen. The amount of hydrogen sulfide absorbed in solution was determined by titration with iodine against sodium thiosulfate, with starch used as the indicator. The ratio of hydrogen sulfide to hydrogen in the inlet gas could be kept within ±2 pct in the range from 10-2 to 5 x 10"4 which corresponds to from 0.2 to 7.0 wt pct sulfur in liquid iron. b) Furnace Arrangement. Fig. 1 shows the furnace arrangement and the shape of the alumina crucible used in this experiment. A vertical-tube silicon carbide electric resistance furnace contained the reaction tube which consisted of two parts, the gas-tight

Jan 1, 1969