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By S. C. Jones, J. A. Davis

This paper describes displacement mechanisms of micel-lur solution slugs, displuced by a thickened water "mobility buffer", in a glass micromodel and in consolidated Berea sandstone cores. Colored motion pictures, taken through a microscope, recorded interactions on a pore-to-pore bash in the micromodel. Production and differential pressure data from consolidated cores previously waterflooded to residua1 oil saturation revealed displacement mechani.sm.s macroscopically. Oil is displaced miscibly, while interstitia1 water is displaced immiscibly by the injected micellar. solution slug. Part of this water is dispersed and carried near the lead ing edge of the .slug, and some may remain as a residual saturation. Thickened water displaces any residual water. It also emulsifies with the. slug material, thereby displacing it. The displacement sequence forms banks of oil and water with relatively constant fractional flows, saturations, and mobilities. The mobility of oil and water flowing ahead of the .slug defines .slug viscosity required for stable displacement. Equations are presented that describe. several aspecis of the displacement flow behavior: oil breakthrough, oil cut during production of the stabilized bank, breakthrough of banked water and the resulting decreased fractional flow of oil, fluid mobilities, etc. Breakthroughs, calculated from the equations, are compared with experimental data. Slugs of micellar sollution, ranging from 1 to 5 percent PV, produced unusually high oil recoveries (up to 100 percent) in previously waterflooded consolidated cores. Investigation of the effect of mobility buffer size on oil recovery indicated that recovery is reduced in 3-in. X 4-ft cores for mobility buffer sizes .smaller than 50 percent of the pore volume. Introduction A new oil recovery process,* conceived in 1962, utilizes a slug of micellar solution' that has sufficient viscosity to avoid an unfavorable mobility ratio with respect to the oil and water it displaces. These micellar solutions are composed of hydrocarbons, water, and surfactants, and may contain electrolytes and co-surfactants. The micellar solution is displaced by a "mobility buffer". The mobility buffer is a bank of reduced-mobility fluid, preferably an aqueous polymer solution. The entire system is displaced by unthickened water. This paper describes some of the microscopic and macroscopic displacement mechanisms observed during laboratory development of the fluids for a potential field test. Microscopic phenomena were observed photographically in a specially constructed glass flow model and macroscopic data were taken from constant rate, tertiary displacements conducted in Berea sandstone cores. Qualitative Description of Micellar Solution Flooding This section qualitatively describes displacement mechanisms that occur when a slug of micellar solution is injected into a previously waterflooded core. The slug completely removes oil from the portion of core it contacts, and banks oil in the process. The oil saturation in this bank and the flowing WOR reach definite, fixed values that are determined by water and oil mobilities and slug characteristics. This zone of constant WOR and oil saturation will be called "stabilized oil bank" in the following discussion. When this stabilized bank reaches the outlet end of the core, the oil cut jumps from zero to a constant value equal to the fractional flow of oil. Saline water has little or no solubility in the slug. Because of this. the slug displaces in-place brine immiscibly. During slug injection, most of the brine is displaced ahead of the slug, some is carried along in the leading portion of the slug, and part of the brine may become immobile. The immobile, residual brine is later miscibly displaced by thickened water. Displacement of all the oil and only part of the water during slug injection results in a higher fractional flow of oil ahead of the slug than occurs when all the water is displaced after injection of thickened water is begun. The slug spontaneously emulsifies fresh (low-salt content) water. By emulsification, the slug can become infinitely diluted, and hence totally displaced, by thickened water. Fluid saturations in the core are shown schematically in Fig. 1. Parts A and B show conditions before and after the start of the thickened-water injection, respectively. Since thickened water displaces any residual brine by-

Jan 1, 1969

By Walter V. Knopp, Laurence Delisle

INTRODUCTION THE aim of this work was the preparation of nickel-steels from elemental metal powders by powder metallurgy techniques. It was known that plain carbon steels could be made from a mixture of iron powder and graphite and that the effect of carbon on iron in powder form was of the same nature as that produced in fusion metallurgy. The problem in making nickel steels from elemental powders consisted therefore in finding out whether sufficient diffusion of the nickel and other incidental metals normally present in such steels could be induced in the solid state to modify the properties of plain carbon steels made from powders and produce the beneficial effect of alloying. The composition selected originally was that of an S.A.E. 2330 steel. Metal powders, in the proportion corresponding to that composition, were mixed with graphite, pressed, and heated at different temperatures for different periods of time, to produce bonding of the metal particles and mutual diffusion of the various elements without melting. Temperatures up to 1325°C and sintering periods as long as 6 hr were first investigated because it was expected that such conditions would produce maximum diffusion with an accompanying improvement in the properties of the alloy. It was found that, although diffusion proceeded to a large extent under the conditions investigated, it would not be complete unless sintering were carried out at a high temperature for much longer than 6 hr. Relatively high temperatures and long sintering times are objectionable from a practical point of view, particularly when a low cost material is to be produced, because they necessitate the use of special, costly equipment. Work could be done to improve the diffusion of iron and nickel by changing conditions other than the sintering temperature and time, i.e., finer primary or alloy powders could be used. However, a marked change in the properties of the steel had been observed even with only partial diffusion. It was thought, therefore, that instead of trying to improve the diffusion, advantage might be taken of its incompleteness to produce a special structure consisting, in the unquenched condition, of a hard constituent, rich in nickel, dispersed in a tough pearlitic matrix. Steels with such a structure, not readily obtainable by fusion, should have desirable mechanical properties. Besides, it should be possible to prepare them from elemental powders under economical conditions. This latter alternative was therefore adopted for the second phase of this work. This report is divided into four parts: 1. General Procedure. 2. Effect of Sintering Temperature. 3. Effect of Varying the Nickel Content. 4. Effect of Alloying Elements. GENERAL PROCEDURE The general technique of cold pressing as used in powder metallurgy was applied.

Jan 1, 1948

By H. M. St. John

MAINTAINING a satisfactory structure in brass and bronze castings has always been a foundry problem of great practical importance. While metallurgists and scientific investigators have not entirely ignored this matter, it has received less of their attention than has been given to iron, steel and the wrought copper and aluminum alloys. Investigation in this field has probably been discouraged to some extent by the complicated nature of the alloys involved. Hundreds of alloys are in more or less common use, most of them containing copper, zinc, lead and tin in-widely varying proportions. They also contain appreciable percentages of iron and antimony as impurities, and often phosphorus, which has been added as a deoxidizer and fluidifier. Small amounts of sulfur are usually present. It is not uncommon to find nickel, sometimes in rather substantial quantities. Traces of other metals are frequently present. So complicated and variable a mixture obviously offers difficulties in. any investigation of the various factors that influence the structure and other properties of the casting.

Jan 1, 1930

By H. W. Becker, C. C. Frye, A. V. Degau, A. Masuda

Natural gas containing 25.65 per cent hydrogen sulfide and 4.75 per cent carbon dioxicle is gathered frorn eight \veih arid tratzsporrcd 26 miles at a flow rate of 160 MMcf/D and at operating pressures of frotrl 1,200 to 1,800 psig. Dry desiccant dehydrators at each wellsite tnaintaitz the dew point of the gas below 17F. Telemetering facililies permit control of field operations from a central instrunlent console. Corrosion control ineasures, design coilsiderations and material specifications pertainitz to these specia1 conditions are cliscussed. INTRODUCTION Natural gas containing 25.65 per cent H2S and 4.75 pcr cent CO, is produced from the Pine Creek field, Alta. It is dehydrated at wellheads, gathered at 2.200 psig and transported 26 miles to the Windfall field where it is delivered to the inlet of injection compressors at 1,800 psig. The daily average volume of gas transported is 160 MMcf. The project is believed to be unique in its combination of percentage of hydrogen sulfide, operating pressure and transportation distance. This paper describes the project and presents details of some of the design features, corrosion control program and centralized automatic operational control. The Pine Creek field project is one phase of a joint operation of two fields—thc other being the Windfall field. The two fields lie about 30 miles north of Edson, Alta. and 20 miles west of Whitecourt, Alta., respectively, as shown on the map (Fig. 1). They are owned by the same interests and operated according to a plan for maximum economic recovery of products. The Windfall Leduc D-3 reservoir contains a rich condensate-bearing gas containing 15.5 per cent HIS. The gas from the Pine Creek field contains only very small quantities of butane and heavier products. The Windfall reservoir is being cycled to obtain maximum condensate recovery using gas from the Pine Creek field as the displacing fluid, while producing the residue sales gas for both fields from the Windfall field. The Pine Creek field development and gas-gathering facilities are shown on the map (Fig. 2). The producing formation is the Leduc D-3 reef at a depth of 11,300 ft. The original reservoir pressure was 4,590 psia at 7,400 ft subsea and the temperature is 245F. Eight wells are equippcd with dry desiccant dehydrators with the following capacity ratings: three at 35 MMcf/D; three at 20 MMcf/D; and two at 10 MMcf/D. WELLHEAD EQUIPMENT Dry desiccant dehydrators were designed to reduce the water content of the saturated wellhead stream to 2.5 lb of water/MMcf at 2,000 psig. This specification was necessary to prevent hydrates and corrosion forming in the pipeline which will operate at temperatures as low as 20F. A typical flow diagram is shown in Fig. 3, and Fig. 4 is a photograph of one of the wellhead installations. Some of the design details given below are subject to modification in the field. The well-stream flowing temperatures range from 135 to 170F. Wellhead flowing pressures up to 3,200 psig are reduced to the dehydrator-operating pressure of about 2,100 psig by throttling through a pressure control valve. The gas is then passed through an aerial cooler where its temperature is reduced to 105F. thus removing over half

By P. H. Metzger, D. W. Fuerstenau

The activation of sphalerite was found to occur at a much lower rate with Pb++ then with Cut++ or Ag+. To prevent activation with Pb++, the ratio [m in solution must approximate 103. An example is given illustrating how this condition is met in practice through the addition of zinc sulfate and soda ash. In selective lead-zinc flotation, the mill operator, especially the one who is concentrating a partially oxidized ore, often must add zinc sulfate and/or soda ash for effective depression of the sphalerite. In the present paper the authors show how this practice prevents the activation of sphalerite in the presence of Pb++. A number of years ago Gaudin (1) postulated that Zn++ might control the activation of sphalerite with Pb++ through competitive adsorption. However, recent experimentation has shown the activation of sphalerite with Ag+ and Cut++ to be a chemical reaction in which silver or copper ions replace zinc in the sphalerite lattice through the formation of a more insoluble sul-fide (2,3,4) Thus, if activation with Pb++ is similar to that with Ag+ or Cu t+, zinc salts should control the activation of sphalerite not through competitive adsorption but because the ratio of [zn++/Pb++] in solution regulates the extent of the chemical exchange between Zn++ and Pb++ in the solid phase. The objective of this investigation has been to study the kinetics and equilibrium conditions for the uptake of Pb++ by sphalerite and to investigate the prevention of lead activation with zinc salts. BASIC PRINCIPLES Sphalerite activation has been shown to be a replacement reaction wherein a less soluble compound is formed at the expense of the more soluble zinc sul-fide (2,3,4) For example, if sphalerite is placed in an aqueous silver nitrate solution, ZnS gives to the solution more S= than can exist together with Ag+, and hence the following reaction takes place: ZnS + 2 Ag+? Ag2 S + Zn ++; k = [zn ++]/[Ag ++]2 = 10 26 (1) Therefore, ZnS will dissolve in the presence of Ag+ and activation of sphalerite with Ag+ will proceed after monolayer coverage by solid state diffusion until equilibrium conditions are reached in the system (2, 4) Because of the large difference in the solubility of ZnS and Ag2S, zinc salts cannot affect the reaction unless a complexing agent, such as cyanide ions, is present to complex Ag+ more tightly than Zn++ . By complexing Ag+ and Zn++ in solution, the uptake of Ag+ by sphalerite can be regulated by controlling the ratio m. . Experimentally (2) it was found that the activation of sphalerite by Ag+ could be prevented through the addition of NaCN if this ratio reached a value of approximately 10 26. The mechanism of sphalerite activation with copper salts is given by the following reactions: ZnS + Cu ++ ? CuS + Zn + + ; (2) k = [Zn++]/[Cu++] = 10 11 ZnS + Cu + ? Cu2S+ Zn++; (3) Experimentally Mao (3) found that the activation of sphalerite with Cu++ or Cu + was prevented if the ratios expressed in Equations 2 and 3 were approximately l09 and l022, respectively, with cyanide ions as the deactivator. Although zinc salts do not affect the activation of sphalerite with silver or copper ions in the absence of a complexing agent, activation with lead ions theoretically can be controlled by the addition of zinc salts because of the relatively small differences between the solubility of ZnS and PbS (5). Equilibrium

Jan 1, 1961

PROF RICHARD ÅKERMAN Stockholm, Sweden DR FRANK DAWSON ADAMS Montreal, Canada PROF RICHARD BECK Friberg, Germany ANDREW CARNEGIR New York, N.Y. DR. JAMES DOUGLAS New York, N.Y. PROF HATON DE LA GOUPILLIERE Paris, France SIR ROBERT A. HADFEILD London, England PROF HANS HOFFER Leoben, Austria HERBERT C. HOOVER Leoben, Austria JAMES FURMAN KEMP New York, N.Y. PROF HENRI LOUIS LE CHATELIER Paris France EZEQUIEL ORDONEZ Mexico City, Mexico DR ROSSITER W, RAYMOND New York, N.Y. PROF RICHARD H, RICHARDS Boston Mass. DR. ING H. C. EMIL SCHROEDTER Dusseldorf, Germany JOHN E. STEAD Middlesborugh, England PROF DIMITRY CONSTANTIN TSCHERNOFF St Petersburg, Russia PROF TSUNASHIRO WADA Tokyo, Japan CHARLES D WALCOT Washingtion D.C.

Jan 1, 1923

By G. Howell Clevenger

FORMERLY great divergence of opinion existed in regard to the influence of copper in steel, as affecting its various physical properties. More recently the investigations of Stead,1 Breuil,2 Wigham,3 Burgess and Aston,4 Ball and Wingham,5 Miiller,6 Dillner,7 and others have shown fairly good agreement in the major points. Copper steel has been shown by these investigators to possess special properties which make it valuable for certain uses. The general range of composition of the useful alloys of copper and iron, and of copper, iron, and carbon, has been quite definitely established, for the former by Burgess and Aston,8 and for the latter by Breuil 9 and Stead.10 Stead 11 has removed one difficulty in reconciling certain of the earlier data by calling particular attention to the influence of carbon in copper steels. Another point which caused confusion in the earlier investigations, particularly in regard to " red-shortness," was the presence of sulphur. Failure to note the presence of sulphur often led to attributing " red-shortness " to the presence of small amounts of copper. Turner 12 has called attention to the fact that where copper exists in an iron ore it often occurs as the sulphide, so that the presence of copper in steel made from such ores might also, necessarily, mean the presence of sulphur. It is evident that the effect in this case might be quite different than where pure copper was added.

Jan 10, 1913

By T. S. Jr. Sligh

OF all the qualities that are essential in a good cigar tobacco none is quite so important as the burn. This term is general and includes many points, the most important of which are evenness of burn, color of ash, firmness and coherence of ash, and fire-holding capacity. The fire-holding capacity refers to the length of time the leaf or cigar will continue to, glow after ignition. Chlorides tend to prevent complete combustion and products are formed thereby that are injurious to the flavor and aroma. On the other hand, the carbonates of the alkalies, particularly of potassium, aid the combustion and increase the fire-holding capacity. Barth1 thought that the harmful effect of the chlorides was due to their fusing and coating the tobacco, thereby preventing complete combustion. Schlosing,2 Nessler,3 and Garner,4 suggested widely different theories to account for the favorable action of potassium salts. In order to study carefully the action of the various salts upon the course of combustion of the cigar a knowledge of the temperature of the burning cigar is necessary. Lehmann5 who seems to be the only investigator who has made any attempt to determine the temperature of a burning cigar gives 480° C. as the maximum temperature which he recorded. It is evident, however, that his measurements were in error, probably on account of the method and apparatus used, since the lowest visible red corresponds to a temperature of about 575° C.

Jan 9, 1919

By C. H. Mathewson

MicrOscopic metallography has been exploited quite well enough to bring about a very general understanding that the typical metal or alloy is composed of minute crystalline particles blended into a coherent rnicrostructural rnosaic. One does not have to be a specialist in metallography to realize that the properties of such an aggregate are essentially a summation in appropriate form of individual effects derived from the shape, size, placement or orientation and cohesive characteristics of the component particles. It is clearly of great importance to consider the various forms of discontinuity which may occur at the boundaries between these crystalline particles. When a number of particles each possessing the same orderly arrangement of atoms are brought together into a close-fitting system of purely haphazard contacts, not unlike a handful of snowflakes compacted into a snowball, the particles are said to possess random orientation. There are no generally accepted views concerning the arrangement of the atoms or the constitutional reaction between atoms where one crystal meets another, but these contact regions are characterized by strength rather than weakness and it is customary to require the presence of many rather than few boundaries in preparing metal for useful service. Under certain circumstances all of the particles in a metal may be nearly alike in orientation. Other general tendencies of orientation may be associated with particular forms of mechanical and thermal treatment. In contrast with these cases of fortuitous or statistical diversity of orientation, we often find adjacent particles united along a plane which possesses a grouping of atoms belonging equally well to both structures. This, of course, determines a fixed relationship between the two orientatjions and it is always possible to derive one from the other by some form of- rotation or reflection prescribed by the symmetry of the crystal structure under consideration. Particles united in this manner are known as twin crystals although the term refers to the form of association rather than the number of individuals concerned.

Jan 1, 1928

By O. D. A. Pease, C. D. Young, C. H. Strand

In an effort to employ cast steel of a stronger structure than that found in the annealed steel casting, the possibilities of heat treatment which will increase the strength without materially decreasing the ductulity may be resorted to.

Jan 1, 1915

By Jay F. Smith

The Alan Wood BOF Shop consists of two 140 ton furnaces with a rated yearly capacity of 1-1/4 million ingot tons, he hot metal for the BOF Shop is supplied by two 18 foot blast furnaces which produce an average of 2000 tons per day, To achieve the rated ingot ton capacity with this limited supply of hot metal, the preheating of scrap is necessary. This is accomplished in the furnace by using an oxygen-natural gas burner. Piping Arrangement The natural gas and oxygen are piped into the Shop through 8-inch lines to their respective valving stations. As can be seen from Figure 1, the flow of natural gas passes through a flow control valve which is common to both furnaces, after which it divides into two 6-inch lines forming two identical and independent gas control lines, one for each furnace.

Jan 1, 1972

By C. E. Mills

STUDIES of ground movement and subsidence resulting from mining operations cover a broad field. It is also a very important consideration and one that eventually affects nearly every mining operation of any extent. The damage to surface buildings, removal of mine surface plants and replacements of main hoisting shafts must reach an astounding expenditure were these cost figures available over a period of years. Were the subject one of mathematical formula and dependent only on the angle of draw of the walls or country rocks, the problem would be relatively simple. Consideration must be given to depth and extent of workings; structural conditions of the orebodies and enclosing country rock; physical properties of these same rocks, including schistosity, bedding, jointing, slips, dikes, faults, and other structural weaknesses. The method of mining, extent of openings, supporting pillars, and amount of moisture or water underground are other pertinent factors. With such a large number of variable factors, it is apparent that the subject of subsidence is one that must be based largely on experience and results at other mines where conditions are somewhat comparable. In presenting this paper, it is the intent to describe the progressive results of past ground movements at the United Verde, to bring out physical conditions largely responsible for this movement, but to refrain from theorizing on the ultimate extent of subsidence resulting from future mining operations.

Jan 1, 1934

By E. D. Gardner

The Synthetic Liquid Fuels Act (58 Stat., 190; 30 U.S.C. Sup., Secs. 321- 325) was approved by Congress April 5, 1944; it directed the Bureau of Mines to build demonstration plants to produce synthetic liquid fuels from coal, oil shale, and agricultural products. The most important oil-shale de- posits in the United States are in the Green River formation of Colorado, Utah, and Wyoming. The oil shale of western Colorado generally is more amenable to exploitation, more persistent, and apparently richer than elsewhere in the Rocky Mountain Region. It occurs at the top of a high plateau surrounded by bold, nearly vertical escarpments 500 to 600 ft in height. The top 400 to 500 ft of these escarpments comprises an oil-shale measure that averages 15 gal of shale oil per ton; the bottom 70 to 100 ft of the measure, called the Mahogany Ledge, averages over 30 gal per ton. The full measure in a 1000-square-mile area is estimated to contain 300 billion barrels of shale oil;' the Mahogany Ledge is estimated to contain 100 billion barrels of oil. These estimates are based on numerous surface samples and on core-drill holes drilled by the Government and by private enterprise. The oil-shale beds are undisturbed and lie nearly horizontal. The name

Jan 1, 1949

By Albert Hill Fay

IN giving a sketch of the geology and mining of the tin-deposits of Cape Prince of Wales, a short description of the geographic and climatic conditions may be of special interest on account of this being a part of the world of which very little is known, even by the reading public. As shown in Fig. 1, the location of the Cape is lat. N. 65° 35' and long. W. 168°. It is bounded on the north by the Arctic ocean ; on the west by Bering strait and on the south by Bering sea. It is the western-most point of the mainland of North America, and to the west, across the strait, one can see East Cape, Siberia, which consists of a rugged, steep coast of granite cliffs. The climatic conditions are of interest because of the part they have had in the surface geology, and also because they affect mining from an economic standpoint. In connection with the climate and geography, it does not seem out of place here to quote a few lines from the prologue of The Wandering Jew, written by Eugene Sue, under the caption '1 The Land's End of Two Worlds."

Sep 1, 1907

By W. F. Durfee

In the year 1862 the author of this paper was called upon to design and superintend the erection and working of the machinery of an experimental works for the production of steel by a process

Jan 1, 1884

By J. A. Ede

The object of the writer is to call attention to a rather unique aggregation of economic products distributed over a line of succeeding formations about 3 mi. long, to be seen within a few miles of La Salle, Ill. Fig. 1 is an ideal section of the stratification exposed and exploited along a distance of 3 1/5 mi. in a southwesterly direction from the quarry of the Utica Hydraulic Cement Co. located near the historic site of Kaskaskia village to the Oglesby shaft at Oglesby. No attempt has been made to cover the whole field, special mention only being made (with the exception of two places) of the operations found along the course or parallel to the direction assumed in the ideal section. I have used Fig. 2, after J. R. Bent and De Witt Kelly, to locate the relation of the La Salle anticline to the coal mines of this district and to show the operation of No. 1 and 3 mincs of the Illinois Zinc Co. Anticline and the Rock Formations Owing to the structural deformation between La Salle and Utica, the older rocks of the state are exposed to the surface along the northern embankment and the bottoms of the Illinois River valley near the latter place. At; the Illinois Zinc Co. works, Sec. 16, Tp. 33, R 1, a well for water mas sunk 1828 ft. and samples taken every 10 ft. of the ground penetrated; duplicates were sent to Mr. Cady of the Illinois Geological Survey. A general compilation or synopsis study of this section is here presented. As the well is over 1 mi. west of the Western limb of the anticline, the section affords some reliable data. These samples were studied and interpreted by H. M. DuBois as Lower Magnesian, and by G. H. Cady as the Lower Magnesian. The results are given in Fig. 3. The most interesting geological feature of this district is the La Salle anticline. In 1865, Leo les Quereux, looking at Split Rock, asked how it happened that the upper coal measures overlie strata of the Lower Silurian and what has become of the formations which are generally found intermediate—the Upper Silurian, the Devonian and sub-carboniferous, and the lower member of the coal measures?

Jan 1, 1920

By Hansheinz Portisch, Harold Margolin

A surface expansion was found to occur sometime after etching in Ti-A1 alloys containing 9.5 to 12.5 wt pct Al. The structure formed, grew, and disappeared with tzrrze. The surface expansion was followed by microscope observations and interferometric and lattice parameter measurements. Activation energy measurements for the growth of the "expansion structure" and chemical analysis indicated that the phenomenon occurred as a result of hydrogen pzckup during etching. It is proposed that hydrogen initially enters octahedral sites of Ti3Al coherent with a Ti and later shifts to the tetrahedral sites. It is postulated that expansion occurs when hydrogen enters the tetrahedral sites. The expansion structure disappeared, it is proposed, because of diffusion of hydrogen from the surface into the body of the alloy and because of loss of coherency of Ti3Al. In examining Ti-A1 alloys, Ence and arolinl observed markings on the surface of specimens. These markings did not appear after electropolishing only, but rather appeared only after etching. The markings appeared to grow as a function of time after etching and later seemed to disappear. Although the markings had some similarity to precipitates, showing, frequently, a Widmanstatten type of arrangement, the observation that other microstructural markings continue to be seen within the new structure suggested that it was actually not a precipitate. The source of this structure was unknown and an attempt was made in the present investigation to develop some understanding of its nature. It has been labeled expansion structure. 1) EXPERIMENTAL PROCEDURE A) Alloys. Alloys in the range 6.5 to 14.5 wt. pct A1 were studied. Bars, 4 in. sq, forged from Bureau of Mines (73 Bhn) titanium consumably arc-melted 4-lb ingots,' as well as 50-g arc-melted buttons of desired aluminum contents were used. The 50-g buttons also used Bureau of Mines titanium (73 Bhn) and aluminum of 99.99 pct purity. Buttons containing up to 8.5 wt pct A1 were hot-rolled from a furnace at 900' . Those with higher aluminum contents were hand-forged on a titanium anvil, and heated with an oxygen-hydrogen torch in the region of 1200" to 1300°c. Frequent reheating kept the samples at the desired temperature range. After a reduction of about 30 pct, the samples were water-quenched. To eliminate any contamination picked up either during hot rolling or forging, at least 1 mil of the surface of the sample was taken off. B) Heat Treatment. Prior to heat treatment all alloys were vacuum-annealed to remove hydrogen. Samples were annealed at 900' until a vacuum of 10'5 mm Hg was established. After this treatment, the samples were wrapped in molybdenum sheet and heat-treated in argon-filled quartz capsules, which were broken under water or iced brine at the conclusion of the heat treatment. All heat treatments under dynamic vacuum were performed in a rapid-quench furnace. This consisted of a molybdenum-lined quartz tube attached to a vacuum system and through a stopcock to a beaker of water. At the completion of the heat treatment the vacuum stopcock was closed, the furnace shut off, and dropped below the quartz tube. Then immediately the inlet stopcock was opened and water admitted until the tube was filled. The steam formed was allowed to escape through the inlet stopcock. This method was used in heat treatments up to llOO°C. C) Metallography. Specimens for metallographic examination were ground, then electropolished using a Disa Electropol machine with a perchloric acid electr01te. Specimens were etched with R-etch.3 A standard etching time of 3 min was used, with the specimen being agitated during immersion. D) Sample Preparation for X-ray Analysis. Samples 0.2 to 0.5 mm in diam were produced from heat-treated rods which were turned to 2 mm diam on a lathe and then rotation-etched. An etchant consisting of 1 pt HF, 7 pt HN03, and 12 pt HzO was satisfactory. With the rod rotating in a vertical position at 50 to 100 rpm, a needle with uniform dimensions could be obtained. Care had to be taken to insure that the rod was at the center of rotation, otherwise cavitation developed. If a small unevenness developed, it was possible to grind it off with a fine emery paper. E) X-ray Diffraction. All X-ray work was done on a North American Phillips X-ray diffraction apparatus and a Jarrell Ash microfocus X-ray unit. The Phillips unit was used with a copper target and nickel filter. The Jarrell Ash unit was fitted with a cobalt target and iron filter. For the Phillips unit 35 kva and 20 ma were used, whereas for the microfocus unit with the 100-p fixed-focus gun 40 kv and 1.5 ma were used. It was found that alignment of cameras on the Jarre11 Ash unit was very critical. The X-ray beam contains an intense area which is not the beam center. The cameras were aligned with the intense region by monitoring the beam coming out of the camera with a Geiger counter. Adjustments were made until a maximum intensity was obtained. A Phillips diffractometer with a Brown chart recorder furnished some of the lattice parameter data. The divergence slit up to 80 deg 28 was I deg; above 80 deg, a 4-deg opening was used, while the scatter slit was1 deg and the receiving slit had a 0.003-in. opening. The general scanning rate was 1 deg per min, while peaks of special interest were rescanned at -j deg per min. For elevated-temperature X-ray diffraction a Uni-cam High Temperature Camera with a film diameter

Jan 1, 1969

By R. E. Fryxell, E. C. Duderstadt, P. K. Conn

Permeation rates for nitrogen through are-cast tungsten were measured in the temperature range 1800° to 2600°C at nitrogen pressure differentials of 1.0 and 0.1 atm. Gas chromatography was used to measure the quantities of nitrogen which permeated through 0.26-and 0.53-mm-thick membranes. Permeation rates were proportional to the difference between the square roots of the nitrogen pressure on each side of the membrane and inversely proportional to membrane thickness, indicating that atomic nitrogen was the difjusing species and that diffusion was the rate-limiting step of the process. Permeation coefficients calculated from the rates may be represented by the equation: where P is expressed in the units cu cm (stP)-mm per 1/2 sq cm-min-atm"' and 70.0 * 0.8 is the activation energy in kcal per mole of permeating species. In a previous paper' permeation rates were reported for hydrogen and for oxygen through tungsten. The permeation cells used for the hydrogen measurements were suitable for measuring nitrogen permeation under similar conditions, so the study was extended to include nitrogen. Permeation rates of nitrogen through the polycrys-talline arc-cast tungsten membranes were measured in the temperature range 1800" to 2600°C using two membrane thicknesses and two nitrogen pressure differentials. Permeation coefficients were calculated and the activation energy of the process determined. THEORY For diatomic gases which dissociate prior to diffusion, the quantity of gas which permeates through a membrane or wall at an elevated temperature where bulk diffusion is the rate-limiting step of the process is given by the equation: where: q = total amount of gas permeating a membrane, P = temperature-dependent permeation coefficient, A = area of membrane, t = time, p1 = gas pressure of high-pressure side, p2 = gas pressure of low-pressure side, and d = thickness of membrane. When bulk diffusion is the rate-controlling step, and the solubility of the gas obeys Henry's law, a further relationship is that, for any given temperature and pressure, the permeation is the product of diffusivity and the amount in solution. The permeation coefficient, P, is temperature-dependent according to the equation: where: Po = permeation constant, Q = activation energy, R = gas constant, and T = absolute temperature. EXPERIMENTAL PROCEDURES Cell Design and Experimental Apparatus. Two of the permeation cells used for the previous measurements of hydrogen permeation are shown in Fig. 1. Each consisted of a cylindrical chamber divided into two parts by a permeation membrane fabricated from high-purity (>99.9 pct W) wrought tungsten sheet made from vacuum arc-cast tungsten. The membrane in one cell was 0.26 mm thick and the other was 0.53 mm. The fabrication of these cells was described previously.' The permeation cells were mounted vertically in a high-temperature tungsten resistance furnace and the membranes and the center portions heated to test temperatures. Temperatures were measured by sighting an optical pyrometer on the edge of the membrane through a small hole in a tungsten plate which was fastened to the side of the cell. This arrangement provided an approximate black-body condition and eliminated the need for emittance corrections. Appropriate corrections were made for the quartz window through which the temperatures were measured. Argon gas flowed through the 10-liter volume of the furnace at the rate of 4.7 liters per min. An impurity

Jan 1, 1969

By C. E. Coleman, D. Hardie, A. E. Wraith

A photoguaplric method of measuring crack velocities has been applied to an examilzation of- the effect of hydrogen on the impact properties of zirconium. Results indicate that the crack in hydrided zirconit travels at about 26 m per sec whereas that in the uacuum -annealed is dependent on the speed of the hammer. RECENT work on the effect of hydrogen on zirconium reveals that when hydrided zirconium is tested in slow bending the crack producing failure can be unstable. The mode of fracture seems to involve the crack linking up broken hydrides by a ductile mechanism in the zirconium matrix.2" In order to compare the fracture of zirconium with that of other metals which show unstable crack propagation, notably steel, the rate of the crack spread must be known. As the methods previously used for measuring crack growth are either unsuitable for the present work5-'' or very costly," a simple technique has been devised in which the maximum crack velocity is derived from a series of crack position-time measurements. EXPERIMENTAL PROCEDURE The experimental arrangement is shown schematically in Fig. 1. The flash unit12 was triggered when the Charpy hammer touched the specimen and the 6-psec flash of the lamp delayed by a preselected time interval in the range 100psec to 10 msec. The camera was left on open shutter during the test. From direct measurement on a calibrated photographic print, Fig. 2, the position of the crack and the specimen was found at a known time after impact and, from a series of such tests using an appropriate range of flash-delay times, the crack velocity was estimated. Preliminary experiments were carried out on mild steel above and below its transition temperature. Vacuum-annealed zirconium, and zirconium hydrided to 100 ppm H were then tested at 20" and 150°C. For comparison, Zr-2.6 pct Nb alloy (in the 0 + transformed /3 condition), vacuum-annealed or hydrided to 100 ppm H, was tested at 20 C. The chemical analyses of these materials are given in Table I. For the high-temperature tests a fine chromel-alumel thermocouple was spot-welded onto each specimen close to the notch. The test piece was heated up to 200°C to allow enough time for preparing the apparatus while the specimen cooled to the testing tem- perature. It was assumed that the specimen cooled uniformly. The accuracy of the flash-delay time was better than i2 pct i 5 psec. The crack length was taken as its maximum distance traveled normal to the length axis of the specimen. Errors in these measurements arise as a result of the uncertainty in the location of the crack tip and the difficulty in defining the exact position of the crack starting point. The latter was due to the bonding and large amounts of deformation at the hammer contact point, especially in the vacuum-annealed specimens tested at 150°C. The maximum error in the measurements was however estimated to be about 5 pct. DISCUSSION OF RESULTS From the trial experiments using mild steel above its transition temperature it can be seen from the plot of crack length against time after impact, Fig. 3. that a reasonable estimate of the maximum crack velocity at the surface of the specimen may be made. Other features of note are the initiation time before the crack is first seen and the slowing down period

Jan 1, 1967

By Russell W. Dayton

The metallurgical polarization microscope has been utilized in several researches in the last few years, thus attaining a fair degree of prominence, but little has been written in a manner suitable to a metallurgist concerning the theory of this instrument. In this investigation the theory was carefully studied, and the results are presented here in a detailed manner, yet as simply as possible. The theory is discussed with particular reference to the three chief functions of the instrument: (1) determination of anisotropy; (2) effect of strain; and (3) identification of inclusions. Each of these is investigated experimentally, with especial attention to the mechanism of producing any effect. Where possible, the discussion is supplemented by photomicrographs. The instrument used had numerous defects as a polarization microscope; these and their remedies are discussed. In the microscopic study of transparent mineral sections (chalcography) the use of polarized light has aided tremendously in the identification of a mineral. The determination of strain in transparent substances (photoelasticity) by the use of polarized light has lately become a commercial process, used in testing finished glass articles. The success of the use of polarized light with opaque materials has not been so great. The magnitude of the effects obtained is much less than that of the corresponding effects with transparent materials, and the mechanical difficulties are much greater. Königsberger,"' i in 1909, was the first to apply polarized light to the microscopic study of opaque substances; Endell and Hanemann(2) were the next, in 1913. In 1919 and 1920, Wright(3,4) prepared two papers on the subject. In the first he developed the detailed mathematical theory from the viewpoint of the electromagnetic theory of light, and in the second described the various methods in use, giving improvements of his own. Schwarz(5)

Jan 1, 1935