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By K. Takahashi, I. Iwasaki

The methyl stretching vibrations for a series of normal xanthates, isoxanthates and normal amines were determined with the aid of an infrared spectro-photometer, and the results were compared with published information on the corresponding alcohols. The frequency shifts of methyl stretching vibrations may be attributed to the inductive effect of polar groups. The hydrogens in the shorter chain alkyl groups are somewhat polar and can be expected to interact with water molecules by hydrogen bonding. Contact angle, surface tension lowering, solubility, and critical micelle concentration appear to be related to the induced polarity of the alkyl groups. Traube's rule states that in homologous series of compounds solubility decreases and surface activity increases regularly with the size of the hydrocarbon group. Analyzing the work of transfer of a solute from solution to surface, Langmuir' interpreted this rule to mean that each CH2 group added to a molecule produced its effect independently of the others. It is also well known2 that the maximum equilibrium contact angle with sulfhydryl collectors is independent of the polar groups and of the sulfide minerals, and that it increases to a certain limit with the number of carbon atoms in the alkyl group. This observation is thought to demonstrate the orientation of the collector molecules at the sulfide surfaces. The dependence on the hydrocarbon chain length is usually explained as due to the screening of the force field of polar mineral surfaces.3-5 Here again, Langmuir's principle of independent surface action appears to be implied. Heteropolar compounds consist of nonpolar and polar groups, the former being the hydrocarbon group and the latter containing such electronegative atoms as O, N, S, P, or halogens. According to Palit6 the hydrogens in the alkyl groups are more electroposi- tive than in the paraffins owing to the negative inductive effect of the polar groups and a possibility that a hydrogen bond with water molecules ensues. Goto and Takenaka7 provided direct evidence of the inductive effect by measuring the shift of the C-H stretching vibrations of alcohols, acids, and alkyl bromides with an infrared spectrophotometer. Their approach appeared to be directly applicable to the studies of surface activity both at air-water and water-mineral interfaces encountered in flotation systems. The present article attempts to relate the C-H stretching vibrations of alkyl xanthates, alcohols, and amines with such flotation chemistry parameters as contact angle, surface tension lowering, solubility, and critical micelle concentration. MATERIALS AND METHODS Normal xanthates from methyl to octyl inclusive and the isopropyl, isobutyl, and isoamyl xanthates used in this investigation were prepared in the usual manner.8 Normal amine hydrochlorides with carbon chain lengths of 1, 2, 4, and 6 were from Distillation Products Industries, of 8 from Archer-Daniels-Midland Co., and of 10, 12, 14 and 16 from Armour and Co. Normal propylamines, pentylamines and heptylamines from Distillation Products Industries were used both as received and as hydrochloride formed by converting the amines according to the procedure described by Li9 Perkin-Elmer Model 521 and 621 infrared spectro-photometers were used to investigate the spectra in the frequency region of 3050 to 2800 cm-' with frequency scale expansion. The accuracy of the frequency readings was within + 1 cm-1. The KBr micropellet technique was used to prepare the xan-thate samples for measurements, and the halocarbon mull technique was used for amines and amine hydrochlorides. EXPERIMENTAL RESULTS Fig. 1 shows the CH3 asymmetric stretching vibrations as a function of the number of carbons in the alkyl group for normal xanthates, isoxanthates and amines. Also included in the figure are data for normal alcohols and isoalcohols taken from the article

Jan 1, 1970

By Edward Chapman

IN the Leadville district toward the close of the "intermediate mesothermal period" of mineralization, there occurred a stage of ore deposition marked by a rather complex mineral association. As bismuth minerals formed in many places during this period, it is here called the "bismuth stage" for convenience of description. The minerals so far identified with this stage, listed roughly in the order of prominence, are: chalco-pyrite; several varieties of galena, differing slightly from one another in their small contents of silver, bismuth and tellurium; altaite; hessite; galenobismutite; alaskaite; aikinite; gold; tennantite; argentite; and perhaps sphalerite and arsenopyrite. With the exception of gold, the age relations of these minerals are difficult to determine. As shown in their descriptions, they all appear contemporaneous and hypogene. Gold may be in part contemporaneous, but most of it is distinctly later. Where minerals of this stage occur so that they can be mined alone, as at the Tucson mine, they constitute high-grade ore. Elsewhere their presence in small amounts has served to increase greatly the value of what otherwise would be low-grade pyritic or zinc-lead sulphide ore. The distribution of the bismuth ores corresponds closely to the distribution of gold ores, though not so general. It seems probable that most of the gold in the district was deposited during the "bismuth stage." These ores occur relatively near the supposed centers of mineralization in Breece and Printer Boy Hills or deep down along the Tucson-Maid fault, which is one of the well recognized channels of mineralization in the Iron Hill and Graham Park areas- Consideration of the high-grade nature of this mineralization and the fact that it appears to be found relatively close to the source of mineralization suggests that prospecting along some of the known channels, even deeper than they have yet been prospected, may offer hope of commercial success.

Jan 1, 1939

By W. F. Chiao

Ultrasonic attenuation, a, measurements in the frequency range of 5 to 55 mc per sec have been studied to determine their quantitative relationship with the following three variables of mixed microstructures in steels: 1) the volume percent, XF, of polygonal fer-rite in mixed structures of martensite and polygonal ferrite in Fe-Mo-B alloys: 2) volume percent, XA, of retained austenite plus martensite aggregates in high-carbon steel; and 3) substructural differences between 100 pct bainitic ferrite structures formed at various temperatures. The quantitative relationship obtained in the first two conditions by plotting a us the known structural parameters can be expressed, respectively, as: where al, a 2 and C1, Cz are constants. In the third condition the nature of the attenuation depends on the state of dislocations generated at the transformation temperatures and also on the alloy composition. From these measured results, the mechanism of ultrasonic attenuation caused by these mixed microstructures can also be studied. MUCH interest has recently been shown in the application of ultrasonic attenuation and wave velocity measurements to the study of the microstructural characteristics of steels. The general aims of most of the investigations in this field can be grouped into two categories: one is to study the mechanisms of ultrasonic losses caused by the characteristic phases in the microstructure of steel,''' and the other is to develop nondestructive test methods and applications for quality control.~' 4 Apparently no work has been done on the evaluation of ultrasonic attenuation meas -urements as a means of quantitative determination of a given phase in the microstructure of a steel. It is well-established that the decomposition of austenite results in four main microstructural constituents—polygonal ferrite, pearlite, bainite, and martensite—and that each phase has different mechanical properties. Thus, when a steel consists of mixed microstructures, the mechanical properties can often be related to a quantitative measure of the volume percent of each phase present. This study relates ultrasonic attenuation measurements to: 1) the volume percent of polygonal ferrite in mixtures of martensite and polygonal ferrite in Fe-Mo-B alloys; 2) the substructural differences between 100 pct bainitic ferrite structures formed at various temperatures; and 3) the vol- ume percent of austenite in austenite plus martensite aggregates in a high-carbon steel. The choice of the specimen materials was based on the laboratory stocks which were suitable to produce the required mixed microstructures for this study. EXPERIMENTAL PROCEDURES Materials and Heat Treatment. Polygonal Ferrite Plus Martensite Structures. This mixture of phases was produced in a vacuum-melted Fe-Mo-B alloy. The alloy was hammer-forged at 1900" ~ to a -f-in.-sq bar. By isothermally heat treating the alloy at 1300° F for various times and then water quenching, variations in the amount of polygonal (or proeutectoid) ferrite can be controlled in a microstructure in which the balance of the material is martensite. In the present work, four different times of isothermal transformation were adopted; after heat treatment, the four specimens were machined for ultrasonic measurements. The compositions, heat treatments, and dimensions of the four specimens are listed in Table I. 100 pct Bainite Structures Formed at Different Temperatures. It has been well-established by Irvine et al.= that the presence of molybdenum and boron in ferrous alloys can retard the formation of polygonal proeutectoid ferrite and expose the bainitic transformation bay, so that a more acicular or bainitic ferrite can be obtained over a wide range of cooling rates. Their investigation6 also showed that the mechanical properties of fully bainitic steels are usually closely dependent on the substructural characteristics of the steels. For studying the substructural characteristics in completely bainitic structures, six Fe-Ni-Mo alloys, of which five were free from carbon addition and one with 0.055 pct C addition, were selected so that a wide range of hardness values for 100 pct bainitic ferrite structures could be produced by normalizing at 1900" F followed by air cooling. The different bainitic transformation temperatures were recorded during air cooling. All of the alloys were vacuum-melted and then forged at 1900" F to square bars. Data on the six specimens of these structure series are summarized in Table 11. Austenite Plus Martensite Structures. The high-carbon steel used to study austenite plus martensite structures was vacuum-melted and then forged into Q-in.-sq bar. The series of mixed structures of austenite plus martensite was produced by quenching the specimens from the austenitizing temperature to room temperature and then refrigerating them at various temperatures within the range of martensite transformation to produce different amounts of retained austenite. Data on the four specimens of this series are listed in Table 111. Quantitative Analysis of the Microstructures. The microstructures containing martensite plus polygonal ferrite were analyzed by the point-counting technique.

Jan 1, 1969

By John G. Hall

MANY millions of tons of raw materials are removed each year from open pit mines in the eastern U. S. These materials are used by industry to produce aluminum, asbestos, barite products, building stone, cement, crushed stone, copper, coal, dolomite, garnet, iron, limestone, mica, phosphate, phyrophyllite, titanium products, and wollastonite. Improvements in open pit mining techniques through the years have made open pit mining more and more attractive as compared to underground methods. Today ore deposits that formerly would have been mined underground have proven to yield more profit if mined by open pit methods. Ever-rising labor and material costs have made equipment capable of high-volume production and low-unit cost-and supplies rendering low-unit costs-not only attractive to open pit operations, but essential to their economic existence. During the past year, the major advances have been in drilling and blasting operations, and the application of large capacity materials handling equipment. Mining men from the Great Lakes, Northeast, East Central, and Southeastern regions of our country tell in the following articles of the trends in open pit mining in their areas during 1956.

Jan 2, 1957

By T. E. Leontis

The specific effect of various rare-earth metals on the room- and elevated-temperature properties of magnesium has been evaluated. Alloys containing didymium exhibit the highest tensile and compressive strengths at room and elevated temperatures. All the rare-earth metals increase the creep resistance of extruded magnesium at temperatures in the range of 400° to 600°F, but the degree of enhancement depends on the temperature and on the concentration of the added metal. THE effects of rare-earth metals on the properties of sand-cast magnesium were discussed in some detail in earlier paper by the author.' The present paper deals with the effect of the same alloying elements on the properties of extruded magnesium. This investigation also had as its aim the development of a wrought alloy having a better combination of room-temperature strength and ductility and elevated-temperature strength and creep resistance than is found in magnesium-Mischmetal-manganese alloys, which have been reported earlier.2-5 The only known attempt to study wrought magnesium alloys containing pure cerium instead of Mischmetal was made by Mellor and Ridley.6 They found that in the form of rolled bars there is a definite, optimum cerium content for creep resistance at 200 °C and that the creep resistance of these alloys at 200 °C is significantly Improved by heat treatment at 550" to 580"C. In the present investigation the compositional variation in mechanical properties of the following alloy systems is presented: I—magnesium-Misch-metal. 2—magnesium-cerium-free Mischmetal. 3— magnesium-didymium. 4—magnesium-cerium. 5— magnesium-lanthanum. Alloys containing predominately praseodymium are not included in this series because of the lack of this material. Experimental Procedures The alloying ingredients used in preparing the alloys described herein are the same as those reported in the earlier paper.' Cerium-free Mischmetal is the rare-earth mixture remaining when the cerium is removed from Mischmetal, which contains all the rare-earth metals as they occur naturally in mon-azite sand, the ore from which Mischmetal is produced. Removal of both cerium and lanthanum from Mischmetal leaves what is commonly called "didym-ium," consisting predominantly of neodymium and praseodymium. Although the composition of the particular batch of each metal used may differ somewhat from the analysis presented previously, these differences are not great enough to warrant repeat- ing the specific composition of each material. The electrolytic magnesium used as the starting material in these alloys has the same typical analysis as that given in the earlier paper.' The alloys were prepared in small laboratory melts applying all the necessary precautions for alloying rare-earth metals with magnesium described by Marande.' Most melts were large enough to cast one 3 in. diam billet 10 in. long. In a few cases, particularly the didymium-containing alloys, the lack of sufficient amounts of the rare-earth metal limited the size of the billet to 6 to 8 in. All billets were scalped to a diameter of 2 15/16 in. and faced to a length of 9 ¼ in. as limited by the size of the extrusion container. The alloys were extruded into ½ in. diam rod on a 500-ton direct-extrusion press using a 3 in. container. The details of the extrusion step are: billet preheat, 925°F (2 hr); container temperature, 900°F; die temperature, 900°F; extrusion speed, 10 ft per min; reduction ratio, 36:1; and percent reduction, 97.3. The lower melting point of alloys containing didymium' necessitated reduction of the extrusion speed to 5 ft per min in order to prevent hot shorting during extrusion. Adequate lengths were cropped from both ends of each extruded rod to assure that all the material used for tests was extruded under uniform conditions. Tensile and compressive properties at room temperature are reported in the several conditions of heat treatment. The ASTM designations are used to distinguish these conditions as follows: T5—Direct age at 400°F (16 hr) T4—Heat treat at 950°F (4 hr) for alloys containing didymium T4—Heat treat at 1050°F (4 hr) for all other alloys T6—T4 + age at 400 °F (16 hr) The lower heat-treating temperature for alloys containing didymium is necessitated by the lower melting point of these alloys. All heat treatments were conducted in electrically heated, circulating-air furnaces. A protective atmosphere containing 0.5 to 1.0 pct sulphur dioxide was used for the high temperature heat treatments. Tension and creep specimens 6 Yz in. long and compression specimens 1½ in. long were cut from the extruded rod. A reduced section of ? in. diam was machined on the tension specimens, whereas on the creep specimens a reduced section of 0.450 in. diam

Jan 1, 1952

By C. Graeme-Barber, R. L. Bell, T. G. Langdon

An analysis is made of the formulas and ,methods used to estimate the contribution of grain boundary sliding to the overall strain of a polycrystal. The errors involved in the approximations and/or ,mistakes in earlier work are assessed quantitatively so as to make possible the critical use of previously published data. SINCE it has been found that, under conditions of very slow creep, the strain due to grain boundary sliding (?gb) may contribute as much as 80 pct of the total creep strain,1,2 it is obviously important to have reliable methods for estimating this grain boundary strain. In two recent papers Stevens3,4 has drawn attention to the pitfalls encountered in assessing ?gb. He criticizes 1) the assumptions made in the derivation of some of the formulas for ?gb, and 2) the indiscriminate averaging procedures used for obtaining the quantities substituted in these formulas. These and further criticisms of earlier work are mostly valid. Unfortunately the only formulas and procedures recommended are either impossible or very difficult to apply in practice. Furthermore no attempt is made to assess the errors involved by the earlier approximations or mistakes, and so it is not possible to make critical use of any of these early dab. The present article attempts to improve on these shortcomings by reference to empirical verification of easily applied formulas whose theoretical derivations involve some otherwise unjustifiable assumptions, and by a quantitative assessment of the errors in previous work. DEFINITIONS First it is necessary to define the terms and symbols to be used. The choice of symbols preferred here is a logical combination and extension of the v introduced by McLean5 and the u by Brunner and rant.' In Fig. 1 the two grains X and Y are displaced by the sliding vector AC. u is the component of sliding resolved along the stress axis, v is that measured perpendicular both to the stress axis and to the specimen surface, and w is that measured perpendicular to the stress axis but in the plane of the surface. Two angles define the orientation of the grain boundary: 8, between the stress axis and the surface trace of the boundary, and +, the internal angle on a longitudinal section cut perpendicular to the surface. In computing the strain resulting from the boundary displacement at all the in- dividual boundaries in a polycrystal the components u, v, or w are sometimes averaged along a longitudinal line (i.e., parallel to the stress axis), sometimes along a transverse line, and sometimes at randomly chosen boundaries. Averages obtained in these three ways are given subscripts 1, t, and r, respectively. Stevens rightly calls attention to the possibility of non-equiaxed grain shapes either at the start or at the end of deformation. In this article all values of numbers of grains per unit length will refer to measurements made before deformation. The subscripts 1 and t will be used for the number of grains per unit length obtained along longitudinal and transverse lines, r for that obtained by averaging along a number of randomly directed lines. FORMULAS FOR ?gb ?gt, as a Function of u. An obvious truth is that cgb can, in principle, be obtained by summation of all the v components at the boundaries intersected by a longitudinal line of known length I, viz.: where nl is the number of grains per unit length, parallel to the stress axis, in the unstrained specimen. There are assumptions in the analytic derivation of Eq. [I] due to Brunner and rant' but ~achinger' arrived at Eq. [la] by a rigorous method. Unfortunately the experimental procedure required by Eq. [ la] proves very difficult as boundary migration tends to obscure the points at which the longitudinal line meets the grain boundary and the errors on such measurements tend to be large, see Fig. 2. For example, on a specimen of Magnox AL 80 at a creep strain of 9.7 pct, 300 measurements of u obtained from the points of intersection of a longitudinal line with the grain boundaries gave ul = 8.95 ± 3.58 pm, or an error of ±40 pct, at the 95 pct confidence limit. These large errors due to migration may be avoided by measuring u from the separation of the segments

Jan 1, 1968

By K. G. Davis

Dilute alloys of silzer in tilz haz been solidzjzed a1 controlled rules, in lzorizontal tubes 2 mrz and 0.5 rn in diam. Radioactive; tracer techniques we?-e used to study solute distvihutions along llze specimens and irmpurity substructures, as functions of the conditions growth. The results have heen mzalyzed using Burton, Prim, and Slichter's tnodel for the solute disty-ihution in the liquid ahead of an advancing solid-liquid interface. DECANTING techniques have been used to establish criteria for the formation of impurity substructure during solidification in several alloy systems An analysis equating the appearance of impurity substructure with the incidence of constitutional supercooling was developed,= in which diffusion was assumed to be the predominant mode of solute mixing in the liquid. Substitution of experimental data into the equations derived from the diffusion analysis gave reasonable values for solute diffusivity in the liquid. However, in these investigations solidification rates of 10 cm per hr and over were used, to minimize the effect of natural conection, whereas for crystals of high perfection lower solidification rates are needed, usually between 1 and 5 cm per hr. A knowledge of the conditions under which impurity substructures will be formed at low growth rates, and the degree of segregation to be expected, is therefore of interest. In the present investigation, radioactive-tracer techniques have been used to study the effect of growth rate, initial solute concentration, and size of specimen on the formation of substructure in uni- directionally solidified rods of dilute silver in tin alloys, over a range of growth rate between 0.5 and 10 cm per hr. Criteria for the formation of substructure were established by auto radiography. This was believed preferable to the decanting technique, for the relationship of the structure on a decanted interface with that of the freezing interface is not clear, since a layer of liquid is left on the surface following decanting.' The effect of substructure on the distribution of solute along the rods was also investigated. EXPERIMENTAL The procedure for sample preparation has been described in detail by einber. Alloys were prepared from tin of 99.999 pct purity and silver of 99.99 pct purity. A"', an emitter of both y and 0 radiation, was used as tracer. Samples of the alloys were drawn up into silica tubes with inside diameters 0.5 or 2 mm, remelted in a horizontal furnace, and solidified at controlled rates. A few centimeters of the samples were left unmelted for a measure of the initial concentration. Total sample length was approximately 20 cm. The temperature gradient in the furnace was kept constant at 36°C per cm in the region corresponding to the melting point for tin. To find how well this corresponded to the actual temperature gradient in the melt, a thermocouple of 38-gage wire was electrically insulated with a thin layer of Sauereisen cement and placed within one of the 2-mm-diam tubes, which was then filled with tin. The maximum diameter of the coated wire was 0.5 mm, the bead of the thermocouple junction being no larger than the diameter of the wire. A plot of temperature vs distance traveled by the furnace is given in Fig. 1 for a rate of furnace travel of 1 cm per hr. The temperature gradient in the liquid

Jan 1, 1967

By J. B. Clark, A. S. Yue

The zone-melting technique can be adapted for the de-termination of the eutectic composition in complex metal systerrzs. The application of this method is demonstrated in a simple eutectic system, Mg-AE, in which the eutectic composition is known and in a complex ternary system, Mg-Al-Zn, in which the literature is uncertain as to the composition of the ternary eutectic. The advantages and limitations of this unique approach for the determirution of the eutectic composition are discussed. ThE eutectic composition in phase diagrams is usually determined by thermal analysis of a series of arbitarily selected alloy compositions. The temperatures of the liquidus and eutectic arrests for each alloy are plotted and the eutectic composition is estimated by extrapolation to the entectic temperature of the curve formed by the liquidus arrest temperatures for the series of alloys. Although this approach readily yields the eutectic temperatures, several dekrminations are needed to estimate the eutectic composition, even in a simple system. In a complex ternary system, a great many determinations are often necessary to estimate, even approximately, the ternary eutectic composition. Thus, the conventional method is inherently tedious and time consuming. The application of zone melting provides a relatively efficient method of determining the eutectic composition.' As an illustration, consider the zone melting of an alloy composition C, in the simple eutectic system A-B, shown in Fig. 1, under the ideal conditions of infinitely rapid diffusion in the liquid, no diffusion in the solid, and ease of nucleation of both phases. As the zone moves along the bar, the composition of the zone is enriched by solute rejected during the freezing of the a phase and the zone composition approaches the eutectic composition CE.Once the zone composition attains the lowest melting composition, i.e., the eutectic composition, it remains at this composition as the zone moves along the bar and finally freezes as such at the end of the bar. Chemical analysis of the end of such a zone-melted bar then should yield the eutectic composition CE of the system A-B. A corresponding analysis can be made for a ternary eutectic system. Under the ideal conditions noted above, only one pass of the molten zone is required to yield the eutectic composition. Experimentally, however, a solute-rich layer forms at the solid-liquid interface2 and the composition of the zone does not attain the eutectic composition as rapidly or as uniformly as in the ideal case outlined above. But with agitation of the melt, the ideal conditions can be approximated experimentally. Also, as shown below, zone melting permits a cumulative build-up of the solute at the end of the bar to the eutectic composition. The purpose of this paper is to demonstrate this unique method for determining the eutectic composition. The method is here applied to two systems: first, to the binary Mg-A1 system, in which the composition is well established, and second, to the complex Mg-Al-Zn system in which there is doubt concerning the composition of the ternary eutectic. EXPERIMENTAL PROCEDURE The zone-melting apparatus used in this study is described in detail elsewhere.3 Briefly, the binary alloy rods (5/8 in. in diam and 9 in. long) and the ternary alloy rods (5/8 in. in diam and 6 in. long), with the compositions given in Table I, were zone

Jan 1, 1962

By S. A. Bradford

Internal-oxide precipitates in decarburized a iron alloys were studied by microscopic and X-ray methods. Diffusion of oxygen is primarily trans-granular, although large amounts of manganese or PhosPhorus cause preferred grain boundary dimsion at temperatures below 1450OF. Transgvanular internal oxidation follows the parabolic rate law with an apparent activation energy of 60 kcal per g-atom for decarburized rimmed steel and around 50 kcal per g-atom for higher alloy contents. The internal oxide is (Fe,Mn)0. Evidence was found for a miscibility gap in the FeO-MnO system. UNTIL very recently, the internal oxidation of metals was studied primarily as a scientific curiosity or, in a few cases, as a means of strengthening alloys by precipitation hardening. However, with the recent development of low-carbon enameling sheet steel, internal oxidation has become a problem of practical importance to the steel industry. For example, in 1961 it was reported1 that internal oxidation of steel can occur during decar-burization by open-coil annealing and will reduce the notch ductility of the sheet unless the process is carefully controlled. The present study was therefore undertaken to learn more about the rates and mechanism of oxygen diffusion and oxide formation in iron alloys. BACKGROUND The process of internal oxidation has been well-defined in the literature:',' oxygen dissolves in an alloy, diffuses inward from the surface of the metal, and reacts to form a precipitate with the alloying element that will provide the most stable oxide. he growth of the finely divided so-called subscale, i.e., the internal-oxidation zone, depends on the diffusion rates of both the oxygen and the reactive element.4 Investigators have generally found that increasing the temperature increases the size of the oxide particles, the rate of subscale growth, and the tendency to transgranular diffusion. With very few exceptions, the square of the thickness of the internal oxide layer is directly proportional to the reaction time. Given two conditions easily satisfied for iron systems— a) an oxygen solubility much less than the concentration of the alloying metal and b) an oxygen-diffusion rate to the oxide boundary much faster than that of the alloying element—then the general expression developed by Rhines and co-workers5 for the parabolic growth rate of the internal-oxide zone can be simplified to the following form: where Co and CM are, respectively, the solubility of oxygen and the concentration of the alloying element, DO is the diffusion coefficient of oxygen, O/M is the weight ratio of oxygen to metal in the precipitated oxide, and x is the thickness of the internal-oxide zone after an annealing time t. Both the oxygen solubility and diffusion coefficient can be approximately expressed as functions of temperature by Arrhenius-type equations: in which H and Q are, respectively, the heat of solution and the activation energy of diffusion. Consequently, the apparent activation energies calculated from Arrhenius plots are the sum of the heat of solution of oxygen in iron and the activation energy for diffusion of oxygen. The data, if not the interpretation, of Schenck et al.8 bear out the fact that oxygen diffuses in the atomic form. The general rate law for atomic diffusion is: the reaction rate being proportional to the square root of the pressure at low pressures. Benard and Moreau8 studied both the surface oxidation of Fe-Ni alloys and the gradual penetration of oxygen into the metal. They observed that oxide particles first form along grain boundaries and then grow to form continuous films that eventually envelop the grains. The parabolic rate law does not usually apply in these cases, especially at the higher temperatures. The oxide formed is wustite which gradually transforms into Fe3O4 and finally into Kennedy and coauthors8 examined Fe-Ni alloys with 26, 75, and 84 pct Ni oxidized at 800°C and

Jan 1, 1964

By Alfred V. de Forest

We are now assembled in this hall for the eighteenth lecture in honor of the memory of our greatest American metallurgist, Henry Marion Howe. Many of his most intimate contemporaries, led, as was fitting, by Professor Sauveur, have described his vital accomplishments in three fields: as a leader in technical industrial development; in theoretical research; and finally as a teacher and source of inspiration for nearly two generations of students. In 1914 Professor Howe had retired from active teaching, but maintained his laboratory at Columbia University under the care of Arthur G. Levy, with whom he published many of the papers that later were incorporated into his last book, " The Metallography of Steel and Cast Iron." My position at the time was that of personal assistant to Professor Campbell—no pay, no duties, but the great privilege of preparing specimens, taking pictures and attending to some of the current consulting work. Whenever possible, I visited Howe's laboratory to chat with Levy and gather ideas about the wonderful field of metallography—in which I was a rank amateur, rescued by the quiet enthusiasm of Donald Smith of Princeton from an instructorship in civil engineering. Levy let me act as a fly on the wall during the Professor's occasional visits. Busy as he was, Professor Howe took the time and trouble to encourage my interest, as he had done for hun- dreds of others. He told me how he went about gathering his own information speculating as to causes, considering experiments, and verifying his conclusions. I ventured to mention some tests I had run on the irregular stretching of wires of different metals. He read the small volume I had prepared of ill-assorted facts and fancies and remarked: "Nobody cares for your theories or the history of your tests. Describe what you found as briefly as possible and perhaps I can help you to publish." Curiously enough, among my discards were some autographically recorded load-versus-electrical-resistance measurements. Taken with inadequate knowledge and equipment, these curves did not reproduce consistently, but if the relationship between strain and resistance had then been explored, the latest type of strain gauge might have been in useful service for the past 25 years. Professor Howe was a gifted teacher, perhaps because he was primarily an ardent and assiduous student. His own eagerness to learn and his willingness to revise and extend his opinions constantly encouraged those of his environment to be diligent and painstaking in the pursuit of knowledge. In honoring his memory, I also wish to bring to mind the kindly, humorous and quiet Levy, and join his name again, as it was for too brief a space in the past, with that of many-sided Henry Marion Howe. Factors oF Impact Strength The subject chosen for the Howe Memorial Lecture by Dr. Gillett last year

Jan 1, 1941

By G. T. Pruitt, T. L. Irby, P. B. Crawford, H. Ferrell

In water flooding peripheral, center-to-edge, line-drive or water-encroachment patterns the question has arisen, "when should a producing well be converted to a water-injection well?". It is realized that, if the producing well is shut in when water breakthrough occurs, some oil could be left in an unswept area. Yet, operation to high water-oil ratios may require processing much additional water. If a well is shut in, "where should the allowable be transferred?". A review of the literature indicates that very few data are available to the engineer to assist him in answering these questions. It is the purpose of this paper to present information which may be of value in selecting the flooding technique and the injection and producing wells and in scheduling injection and production rates. Certain phases of these problems can be studied in the laboratory. The Potentiometric model is well suited for studying many waterflooding problems. This model assumes that steady-state flow exists, that the mobility ratio is equal to one and that gravitational effects are neglected.'-' The three-phase sand model also has been recognized as an effective means for studying certain reservoir problems. Both models were used in making the study reported here. This paper discusses seven cases utilizing various waterflooding techniques. Data for the first five cases were obtained on the potentiometric model. Data for Cases VI and VII were obtained by constructing and flooding an unconsolidated sand pack (a three-fluid-phase system) and by determining the swept area and cumulative oil recovery for various types of operations. APPARATUS AND PROCEDURE The potentiometric model reservoir was 30 in. long X 10 in. wide by about 1/2 in. deep. Four wells were equally spaced in a line array along the lateral center line. (See Fig. 1.) Well No. 1 initially was an injection well for each of the patterns reported. The cases studied with the potentiometric model and sand model are described herein. The laboratory sand model reservoir was a 30- 10-in. rectangular Lucite vessel packed with sand to a depth of about 0.65 in. Four wells were equally spaced in a line array along the lateral center line. The reservoir material was an unconsolidated sand into which the reservoir fluids were mixed to yield fluid saturations of 55 per cent oil, 25 per cent water and 20 per cent gas. The water was added to the sand and the material mixed, after which the oil was added. Kerosene and water, the fluids used, gave a viscosity ratio of 1.64:1. In packing the reservoir, care was taken to assure constant fluid saturations and constant porosities. A new mixture was prepared for each run. During water flooding, a colored water was injected by a constant rate pump. The injection rate was 1.1 B/D/ft of sand thickness. For this series of tests, each of the producing wells was open to the atmosphere and, as in the potentiometric model study, Well No. 1 initially was an injection well for each of the patterns. KESULTS OF POTENTIOMETKIC MODEL STUDlES Two cases (Cases I and 11) involving equal pressure injections were studied, with the following results. Case Water injection was initiated at Well No. 1; the producing wells (Nos. 2, 3 and 4) were operated at constant and equal bottom-hole pressures. When water broke through at Well No. 2 and achieved the selected water-oil ratio, Well 2 was converted to a water injection well, resulting in two injection and two producing wells. The injection pressures at Wells 1 and 2 were maintained equal and constant; pressures at the producing wells were held equal, but they were lower than those at the injecting wells. A similar process was repeated when water broke through at Well No. 3. The flood was terminated when

By R. A. Greenkorn, R. C. Smith

Hele-Shaw cells are used to model creeping flow through porous media (where Darcy&apos;s law is valid). The effects of inertia on flow about obstructions in a Hele-Shaw cell can be calculated by a perturbation method if one can determine a solution to Laplace&apos;s equation. Results of a computer solution for flow about circular, square and elliptical obstructions are presented. These results show that or a modified Reynolds number of less than I, the inertia terms are small; and for values of less than 3, the average streamline predicts the ideal flow. Therefore, the analogy might be used for studying flow in porous media up to a modified Reynolds number of at least 3. INTRODUCTION The nature of fluid flow in porous media is of interest in the fields of soil mechanics, ground water flow, petroleum production, filtration and flow in packed beds. Because it is very difficult to study the phenomenological behavior of flow in porous media, homologs and analogs are used to study flow characteristics. A Hele-Shaw model, made of two closely spaced plates - usually glass — is often used as an analogy to two-dimensional flow in porous media. Hele-Shaw2 showed experimentally that the streamline configuration for creeping flow around an obstacle located between two closely spaced parallel plates is the same as for two-dimensional, ideal flow about the same obstacle. Stokes7 verified these observations mathematically. The usual equation of motion for flow in porous media is Darcy&apos;s law. The form of the mathematical statement of Darcy&apos;s law is identical, within a multiplicative constant, to the expression for the average velocity over the plate gap in the plane of a Hele-Shaw model. These models may be used to describe flow in both homogeneous and heterogeneous porous media. In the mathematical proof of the Hele-Shaw analogy it is assumed that the convective terms in the Navier-Stokes equations are negligible and that the equations of motion degenerate to Laplace&apos;s equation, with pressure the dependent variable. Whenever a Hele-Shaw model is used as an analogy to flow in porous media, .the validity of this assumption is in question. Riegels5 showed that if convection is not neglected, the velocity distribution around a cylindrical obstruction in the flow field depends on a Reynolds number, the plate spacing, and a dimension characteristic of the obstacle. Riegels&apos; solution, a perturbation solution, uses the boundary condition that the flow rate into the obstacle averaged over the plate gap at any point on the obstacle is zero. The method requires that a solution to Poisson&apos;s equation for the perturbation pressure be found. Riegels evaluated this solution for the case of the cylindrical obstruction. His method may be simplified by eliminating the need for solving Poisson&apos;s equation for the perturbation pressure. Instead, an analytic expression for the perturbation pressure gradient is obtained (valid for arbitrary shapes) and used to eliminate pressure from the equations for the perturbation velocities. The results show, for symmetrical shapes, that if NRe < 1, the convective acceleration terms are small, and that the average velocities represent ideal flow up to at least NRe = 3, where: L is a characteristic dimension of the obstacle perpendicular to flow, b is the plate spacing, u is viscosity, v, is velocity of approach and p is density. THEORY* Incompressible fluid flow through a Hele-Shaw model and a porous medium are analogous because the equations for the average velocity components in two-dimensional flow are identical if:

Jan 1, 1970

By Bradley Stoughton

The regular, bottom-blown Bessemer converter of the present day is a modification of previous forms, and most of the latest proposed modifications of it are merely returns to former types which Ressemer discarded. That he tried almost every conceivable method of blowing iron, with tuyeres at almost every possible position or angle, is well known; and it is to be supposed that he was familiar with the advantages of each type, since he finally settled on that form which has not been improved upon hitherto, for the purposes for which converters will generally be used. Modifications have been tried along two lines: In the arrangement of tuyeres, and in the manner of carrying out the process with tuyeres still blowing vertically upward through the bath. While they have all failed in general competition with the regular modern type of vessel, some of them have found special fields in which they have held their own. The most notable example is in the steel-casting industry, and especially in that part of it concerned with the manufacture of castings which require very hot or very fluid metal, or supply a demand of constantly varying physical or chemical requirements. In this industry the small converters occupy a field between that of the crucible-process and that of the open-hearth process, arid have won a place for themselves in France, England, America, Russia and other countries, which they bid fair to retain until either a new method is discovered of producing cheaply very hot, fluid steel, or the open-hearth process is so improved that very hot steel may be made with it at lower cost of repairs to lining arid roof.

Jan 1, 1903

By G. R. St. Pierre, M. J. Pool, R. Speiser

The activities of chromium in solid Cr-Ti solulions contaitning from 10 to 90 at, pct Cr were measured over the temperatutre range 1250" to 1380°C. The Knzudsen effusion technique with direct weighing of the Knudsen cell was used. This was possible because the vapor pressure 0f chromium is about 600 times greater than the capor pressure of titanium so that the amount 0f titanium effusing could be neg-Lected. the activities of titanium were determined by g-raphical integration of the Gibbs-Duhertz equatiotz. The solutio~ls sllcdied exhibited positive deviations from Raoult&apos;s law, but they approached ideality as the temperature was raised from 125 to 138t C. The integral free energy of mixing was calclated from the activity values. AF has a maximum value of - 1.66 kcal a1 1390°C and a composition oj 55 at. pcl Cv. The free energy of formation of &apos;TiCr, is —0.76&apos; lzcal a1 1250°C. The heats and entropies of mixing usere determined using the second law and thus tile mlues could be in error by a considerable amount. The Cv-Ti system is not a regular solution. ThE increasing emphasis on application of various models to alloy formation and solution behavior has led to an intensified interest in the thermochemistry of alloys. In a majority of the cases where different models have been applied the alloy system used was a simple one. However, the amount of data available on more complicated systems is small and in order to fully understand the behavior of metallic solutions more experimental work has to be carried out on these systems. The Cr-Ti system is reasonably complex and even though this system was being investigated as early as 1937 by Kroll,&apos; no previous work has been done on the thermodynamic properties of either the liquid or solid state. This research was undertaken to determine the thermodynamic properties of solid Cr-Ti alloys. EXPERIMENTAL PROCEDURE The experiments on the Cr-Ti system were carried out in a water-cooled metal vacuum system. This system is composed of a brass vaporization chamber wound with copper tubing for cooling purposes, a brass liquid-nitrogen trap, an oil diffusion pump, and a Duo-Seal forepump. The pressure in the system is measured with an ionization gage. The interior of the vaporization chamber is shown schematically in Fig. 1. The Knudsen cell is supported by the molybdenum tripod, and a magnetically operated shutter is provided to protect the Pyrex sighting glass against deposition of metallic vapors in the intervals between temperature measurements. Heating is accomplished by means of a 20-kw 450-kc Westinghouse oscillator. The susceptor in this case is 10-mil tantalum seamless tubing which also forms the outside of the sample container. The remainder of the sample container consists Of an im~ervims re-crystallized alumina crucible and a 10-mil-thick tantalum lid. Two holes are drilled in the lid. The diameters of these holes were measured with the calibrated stage of a "Tukon" microhardness tester. The thicknesses were measured with a micrometer. A Leeds and Northrup disappear ing-filament optical pyrometer was used to measure the temperature. This is sighted through the smaller of the two holes in the lid and corrections for the emissivity of the sample were not necessary since the ratio bf cell length to hole diameter was large enough to insure a hohlraum. The pyrometer was calibrated at the ~~t~~~l Bureau of Standards, and the correction for the Pyrex sighting window was determined in the laboratory. The titanium used in this investigation was obtained from Mallory-Sharon and the chromium from The Union Carbide Metals Co. The reported purities were

Jan 1, 1968

By Albert J. Phillips

IT is a privilege and a pleasure to deliver this, the Twenty-sixth Annual Institute of Metals Division Lecture. Eleven years ago C. A. Edwards addressed this audience on the subject "Gases in Metals." In spite of this relatively recent presentation, I propose to, present to you some quantitative considerations of industrial significance on the separation of gases from molten metals because recent observations and measurements, presented in the literature, have made it possible to evaluate mathematically the gases or gas-forming elements and to develop an understanding of the mechanism of gas separation that should permit, in many cases, the control of this baffling phenomenon. DEFINITIONS Before becoming involved in the subject it seems desirable, for the sake of clarity, to state certain definitions and axioms: I. We are dealing only with gases that separate from the molten metal either during cooling or in the transition from liquid to solid. Gases injected by the liquid stream and trapped in the solidified metal, or those forced into the solidifying metal from the mold due to either thermal or cher4ical effects are not considered. Neither are we concerned with the separation of gases within the metal after solidification is complete for the data on this subject are at least complete enough to permit the practicing metallurgist to satisfactorily control the phenomenon. 2. Only where there is a decrease in solubility or a change in equilibrium of either a gaseous element or an element that reacts to form a gaseous compound, can there be a separation of a gaseous phase from the liquid or solidifying metal. 3. The amount of gas separating from the liquid during solidification can be computed directly from the amount of the element contained in the liquid when freezing commences less the amount of the element found in the solid either as a separate solid phase or in solid solution. 4. There can be no separation of gas bubbles unless the told pressure of the gases in the liquid meld exceeds atmospheric pressure plus the hydrostatic pressure of &apos; the liquid metal head. (In addition, pres- sure resulting from surface tension in- creases the total pressure requirement for initial gas separation. Probably the remarkable differences in appearance caused by different gases in the same host metal are influenced greatly by the rate of diffusion of the gas in the liquid metal balancing the decrease in pressure as the gas bubble size increases and the surface tension effect decreases. Thus hydrogen with its high diffusion rate in liquid copper separates in the form of relatively coarse cavities for a given rate of heat extraction.) 5. Gas separation can take place at less than atmospheric pressure in the voids created by the shrinkage from liquid to solid, but since the voids are not caused by the gas the presence of gas in the voids is of importance only where it

Jan 1, 1947

By Roger V. Pierce

INTRODUCTION IN the last few years, much study has been devoted to increasing stoping efficiency. The reasons for this are shortage of manpower, shorter working hours, operating regulations, and shortages of essential materials. More efficiency in mining methods is needed to offset these adverse factors. In the past, attention has been centered upon haulage, hoisting equipment, mill flowsheets, etc., but recently the spotlight has been focused on the cost of stoping and the cost of handling materials. Scrapers and scraper hoists have thus assumed greater importance. In order to make it possible for certain ore bodies to be mined at a profit, it has been necessary to apply assembly-line practices to the streamlining of mining methods. All cycles of the mining operation must balance, and the sooner broken ore is removed from the working face, the sooner another round can be started. Since the introduction of scraper hoists in metal mines more than thirty years ago, much progress has been made in their design and application. Alert operators are now constantly watching for methods in which to apply scrapers. The saving of manpower in development work and the changing of mining methods that once employed manual handling of materials are increasing vital wartime tonnages. Essential ores from newly discovered ore bodies are moving rapidly from stopes to reduction plants-because it is now possible to develop an ore body and place it in production with a minimum of manpower and development work. Today, speed is one of the prime essentials of mining. Everywhere, there is a concentrated effort to use experienced miners in breaking rock, in timbering, and in carrying out the various phases of mining that require many months of training. Much effort is being made to mechanize the working places because experienced men naturally prefer to work where the majority of materials are handled mechanically. In line with this policy, many new men are being taught the details of scraper work, because even green men can quickly become acquainted with scrapers and thereby release older heads to perform the more skilled phases of mining. In some places it has been found economical to change from one system of stoping to another that more readily allows the application of mechanical muck-handling equipment. Where blocks are worked faster, the cost of materials, time, and labor is cut drastically. This favorable situation allows more manpower to remain on straight breaking and timbering-or straight production mining. More-over, when blocks are mined faster, more floors can often be mined vertically before the mucking or wheel floor is moved. This results in several direct savings. There are cases where it has been proved that by working a given block faster more area, longitudinally or vertically, could be mined at one time, thus permitting the reduction of development cost. (Fig. I.)

Jan 1, 1943

By T. L. Joseph

It is a distinct privilege to participate in this meeting convened to honor the memory of Henry Marion Howe, a distinguished scientist and metallurgist. Many have added to our rapidly growing fund of metallurgical knowledge but few have made the unique contribution of formulating basic concepts essential to an over-all comprehensive view of the subject of metallography. Of those previously selected to deliver this lecture, several have added a personal touch to their discourse because they were able to refer to their associations with Dr. Howe. It was not my good fortune to know him or to enjoy his inspiring influence. Like most of you, my contact has been with his published works, which are outstanding in that they provide lucid, detailed expositions of the nature and behavior of metals and alloys. His deep understanding and clarity of expression have greatly accelerated our progress in metallography and in the use of metals. The degree to which a man&apos;s thinking, experimentation and writing contribute toward an understanding of basic laws and phenomena determines whether his life&apos;s work is of transitory or permanent value. This occasion appropriately recognizes the fundamental importance of Dr. Howe&apos;s pioneer work in the field of metallurgy.. On two former occasions, gray iron was selected as a subject for discussion. The fact that the production of pig iron has not been discussed before does not reflect any lack of interest on the part of Dr. Howe or former lecturers in the process that underlies the production of steel. Although Dr. Howe&apos;s work in his later years centered around metallography, his earlier publications show a considerable interest in the production of iron and steel. He recognized that in the ascending spiral of metallurgical advancement we are not winding a single thread but are weaving a complex fabric. Specific evidence of his interest in the production of pig iron may be found in his book&apos; on The Metallography of Cast Iron and Steel. In explaining why blast furnaces have been in constant use for about 600 years, he says: "The process is economical because it utilizes with extraordinary completeness the calorific power of the coke due to the thorough transfer of heat from the gaseous products of combustion to the charge." This emphasis on heat transfer, overlooked in many more extended and more recent discussions of the blast-furnace process, illustrates Professor Howe&apos;s ability to see the essentials. Other distinct advantages of the blast furnace, such as the removal of- much of the sulphur and practically all of the oxygen, were mentioned. It was also stated that although the blastfurnace process is complex in nature, its outward form is comparatively simple, thus permitting large-scale production at small labor costs. All who contemplate the production of metallic iron from its ores by any other process might well consider the

Jan 1, 1947

By William C. Hagel

Oxygen-18 exchange between gaseous oxygen, held at a pressure of 125 mm Hg in a PL-IORh chamber, and splzeres of a Fe2O3 containing three or less grains was determined from 9000 to 1250°C. Isotope equilibrum on crystal surfaces appears to be quickly established, and the rate-determining factor is self-difiusion confbvrning to the relation D = 2.04 esp(- 77,900/RT) sq cin sec-&apos;. Changing sphere diameters caused no detectable variation in diffusion coefficients. Oxygen ions diffuse faster than cations at low temperatures, but a crossover may occur at about 1150°C. INVESTIGATIONS by Davies et al.&apos; and Himmel et al2 have suggested that the mechanism of iron oxidation above 600°C involves a predominance of cation migration in the wüstite (FeO) and magnetite (Fe301) layers and oxygen-ion migration in the hematite (a Fe2O3) layer. Evidence for little cation migration during hematite growth consists of: 1) the disappearance of radioactive-silver markers, presumed to vaporize from the oxide-gas interface, and 2) a large discrepancy between parabolic rate constants for magnetite oxidation and those calculated from Lindner&apos;s3 data for cation self-diffusion, D:, using Wagner&apos;s theory.4 Reversing the calculations gave anticipated self-diffusion coefficients, D:, for oxygen ions of 3.6 x 10-9 sq cm sec-1 at 1100°C and 5.9 x 10-10 sq cm sec-1 at 1000°C. Since then Kingery et a1.5 reported three values for oxygen-ion diffusion in polycrystalline, sintered hematite. These were obtained near 1200°C, at an oxygen pressure of approximately 150 mm Hg, and could be represented by the Arrhenius expression, Dg = 1 x 10 11 exp(-146,000/RT) sq cm sec-1. Extrapolation to temperatures below 1100°C infers that oxygen ions are less mobile than cations. This contradicts the aforementioned oxidation evidence and also coble7s study of the initial sintering of hematite. From the latter, apparent diffusion coefficients for the slowest rate-controlling species could be calculated, and fair agreement was found with an extension of Lindner&apos;s data for cation diffusion. Fig. 1 depicts such comparisons graphically. Three points have been included for the determinations of Himmel et al. on cation diffusion in large, natural hematite crystals surrounded by pure oxygen at atmospheric pressure. No dependence on crystal log raphic direction was noted. Since the value of 10-l4 sq cm sec-&apos; at 1000°C actually represents an upper limit, one might interpret that there is a small decrease in D: when single crystals are employed. On the whole, however, cation diffusion appears relatively well-defined,* while the few results tension to lower temperatures. After having gained experience measuring oxygen-ion diffusion in certain glasses7 and in the corundum oxide, a Cr2O3, the purpose of this work was to determine D; values for hematite and thus possibly assist a mechanistic understanding of the kinetics of the oxidation and reduction of solid iron oxides. I) EXPERIMENTAL PROCEDURE A) Material. Hematite powder of moderately high purity was received from the Columbian Carbon Co. An accompanying lot analysis listed 0.03 H2O, 0.008 weight percents, with the remainder Fe2O3. Subsequent treatments were ball milling, drying, prepressing, and hot-pressing for 60 min at 1350°C under 5000 psi. Since graphite dies coated with a slurry of alumina were used for hot-pressing, the surrounding atmosphere at temperature was sufficiently reducing to form some magnetite on the outer surface of each cylinder. After removing any attached alumina, a stabilizing anneal of 50 hr at 1300°C in oxygen was added. The final product was nonmagnetic and exceeded 97 pct of the density (5.24 g cm-3) usually given for FezO3. On polishing cylindrical ends, counts were made of the number of grain boundary intercepts per

Jan 1, 1967

By I. B. Cadoff, J. C. Bilello, R. Rosenberg

Diffiusion of magnesium into the surface of LiF crystals to controlled depths and subsequent heat treatments provided a wide range of surface zone harahesses and structure, The bend strength of the LiF crystals was increased by as much as an or-dev of magnitude. Ductility was achieved when dislocation generation occurred in the diffusion zone or when dislocations penetrated to the surface from the intevior. A critical surface hardness of 130 to 140 kg per sq mm was found helozu which generation could take place in the diffusion zone and ahoue which the zone was impenetrable, This hardness was obtainable by several methods, among them the aging of quenched MgF2 -LiF solutions to produce MgF, precipitation. Maximum hardness was ohtained in quenched specimens with no visihle evidence of MgF,. Diffusion-zone formation followed a parabolic rate law and an activation energy of 20.9 kcal per mole was obtained for the process. RECENTLY, the properties of ionic crystals as related to surface condition have been receiving much attention, specifically the transitions between ductile and brittle behavior. Originally Joffe 1 showed that NaCl crystals could be made ductile by immersion in water and related this to the elimination of surface microcracks. Aerts and DeKeyser 2 and Gorur 3&apos; have subsequently shown that ionic crystals are inherently ductile and are embrittled through contact with air. Machlin and Murray4 hypothesized that a layer of NaCIO3 produced by contact of ozone with NaCl induced embrittlement by acting as a barrier to outward dislocation flow. westwood,&apos; Rosenberg and Cadoff,9 and Bilello and cadoff&apos; have reported surface strengthening of LiF crystals by coating with a magnesium compound and then heat treating for adherence. The major effect of the coat was to inhibit dislocation-slip lines from reaching the specimen surface. westwoods showed microcrack formation and fracture to be caused by slip-band interactions at the surface. The material presented in this paper is an extension of the work reported earlier by Bilello, Rosenberg, and cadoff&apos;6,7 and illustrates the wide range of surface properties and bulk behavior obtainable by use of heat-treated magnesium-diffused surface regions in LiF crystals. EXPERIMENTAL PROCEDURE The LiF single crystals were obtained from the Harshaw Chemical Co. Some batch to batch variation was observed; therefore all specimens for a given test series were cleaved from the same crystal. The typical dimension used was 1 by 0.1 by 0.40 in. Surface damage resulting from cleavage was removed by chemically polishing in a 2 pct NH4OH solution. Each group of specimens was given a vacuum anneal at 700°C for 4 hr to provide a base standard for measuring comparative effects of various surface treatments. To produce the reacted surface zone, the annealed specimens were immersed in a boiling suspension of MgF, in doubly distilled HzO, agitated slbwly for 30 sec, removed, and dried at room temperature. Uniform coatings of MgF, were deposited with a thickness of approximately 5 mils. It should be noted that this technique can be modified for use with crystals which are soluble in water by using boiling absolute alcohol as the dissolving medium. This was found effective for the coating of NaCl with MgF2. The diffused surface zone was obtained by annealing the coated samples at elevated temperatures in a vacuum of lob4 mm Hg. Penetration depth was controlled by varying the annealing time from 1/2 to 28 hr. After heat treatment, the samples were tested for bend strength and hardness. Load was applied by four-point bending in a hard-beam testing jig. Four-point rather than three-point bending was used to provide a wide area of constant stress and to minimize the effect of localized inhomogenities in the specimen. The deflection rate was 8 x min-&apos; and the distance between knife edges was 1/4 in. Load-time curves were obtained from a chart recorder coupled to the machine and converted to resolved shear stress on the shear plane vs deflection, as plotted in the figures. The unstressed portions of the sample outside of the two outer knife edges were used for the microhardness studies. Microhardness measurements were made with a Bergsman tester attached to a Reichert metallograph. All hardness impres-

Jan 1, 1964

By Pol Duwez, H. E. Martens

The high temperatures encountered in the operation of jet engines have imposed most drastic requirements upon the materials used in their construction. There are two different approaches to the materials problem connected with the design of parts in contact with high temperature gases. The first approach is to use a material which will perform satisfactorily at a temperature comparable to that of the gas. The second approach is to use a cooling system so that the material is maintained at a temperature appreciably lower than that of the gas. Besides the conventional method of cooling by means of a liquid in contact with the material exposed to a high rate of heat transfer, a less orthodox method consists of making the part to bc cooled of a porous material&apos;, so that the cooling fluid can be forced through the pores, In this scheme, the temperature of the coolant moving in a direction opposite to that of the heat flow increases gradually while passing through the porous material, and the coolant forms a protective layer on the surface exposed to heat, This method, referred to as ((sweat cooling," was pro- posed at the Jet Propulsion Laboratory in September 1944, and the experimental work on the preparation of porous metals was started early in 1945. The sweat cooling method opens new lines of research in powder metallurgy by extending the field of application of porous metals. The porous metals available at the present time are used mostly as bearings or filters, and a rather limited number of alloys are made for these applications. In addition, the fabrication of bearings or filters does not require a very close control of the permeability, while in the case of sweat cooling such a control is of primary importance. In designing a sweat cooled part it is imperative to assure a given rate of flow of coolant under certain conditions of Pressure drop. Generally, the Proper pressure drop and the rate of flow of coolant are deduced from heat transfer and design considerations, and consequelltl~ the Permeability of the Porous metal to be used is also determined. It is therefore necessary for the designer to have available a continuous series of porous metals covering a range of permeability as wide as possible. Contrary to the requirements established in the fabrication of filters, the actual pore size of a porous metal intended for sweat cooling is of little consequence, except for its effect on permeability. The tensile strength is likely to be of great importance for some applications. Since the tensile strength of a porous alloy decreases with increasing porosity, an important problem is to develop porous alloys having the maximum permeability with minimum porosity.

Jan 1, 1949