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By Nicholas J. Grant, A. W. Mullendore, Paul Predecki

The Duwez technique of splat cooling in which a molten droplet of metal is accelerated and made to impact on a cold, highly conducting substrate was investigated.- An apparatus for producing "splat" was constructed employing an explosive powder charge to accelerate the molten metal. Transport of the molten metal just prior to impact with the substrate was studied by means of high-speed photography. The molten particles are small spherical droplets from about 1 to 50 µ diameter. The average cooling rates for aluminum, silver, and a gold alloy splatted on nickel substrates at room temperature were determined experimentally and were found to vary from 18 to 5 x 10' C per sec. The heat-transfer coeficients for pure aluminum and pure silver splats cooled on nickel substrates at room temperature were found to be 2.7 to 6.8 and 13.6 to 54.2 cal per sec sq cm 'C (2 to 5 x 104 and 1 to 4 x 18 Btu per hr sq ft OF), respectively. Solidification rates in pure aluminum and silver splats were calculated. "SPLAT cooling" is a term describing a technique for extremely rapid freezing and cooling of molten metals and alloys to room temperature or below. The technique was developed by Duwez et al.' in 1960, and after refinement2 consisted in transferring a few tenths of a gram of molten metal to near sonic velocity to strike a suitably placed cold copper surface. Upon impact, the metal spread into a thin nonuniform film called a splat, about 10-4 cm thick. The splat particles produced in this manner were thin enough in some areas to be suitable for transmission electron microscopy, without further treatment, and, together with X-ray data, yielded a variety of structures which would be classified as follows: 1) supersaturated solid solutions (increase in solubility limit), 2) metastable crystalline stoichiometric and non-stoichiometric intermediate phases ( in Au-20.5 at. pct Si and in Au-14 at. pct Sb, respectively), 3) amorphous alloys, 4) retained high-temperature phases, 5) alloys having equilibrium phases present, but with unusual, markedly altered structures. The crystalline phases present in splats were usually extremely fine-grained and had low dislocation densities. Present interest in splat cooling centers around a study of the unusual structures produced by the technique, their contribution to alloy theory, and the possibility of the development of new or unusual properties. In addition, the technique is being examined for the production of bulk quantities of new high-strength alloys for low- and high-temperature use. Although a number of alloy systems have already been investigated by the technique, relatively little is known about the mechanism of splat formation and the physical conditions encountered by the metal during solidification and cooling. The purpose of this work was: 1) to determine the velocity, shape, and size of the molten metal droplets just prior to impact with the cold substrate; 2) to try to estimate or measure solidification rates, heat-transfer coefficients, and cooling rates in splats. EXPERIMENTAL TECHNIQUE Splatting Apparatus and Procedure. An apparatus similar to the type originated by Duwez et a1.,2 but employing an explosive charge to accelerate the molten metal, was used. A "Ramset" fastening tool (a gun normally used for driving studs into concrete, steel, and so forth) was mounted vertically above a resistance-heated graphite crucible as shown schematically in Fig. 1. A splat product was produced by melting a few tenths of a gram of metal at the position shown in Fig. 1, and then exploding a powder charge in the breach. The shock wave thus generated traveled down the barrel into the furnace, ejecting the molten metal through the 0.06-in.-diameter hole at the bottom of the crucible. The ejected metal was impacted on a high-conductivity metallic substrate where it formed a splat. High-Speed silhouette Photography. In order to investigate the size and shape of the ejected, molten metal just prior to impact with the cold substrate, high-speed silhouette photographs were taken, and are shown in Figs. 2 and 3. These photographs were obtained with the aid of an Edger-ton, Germeshausen, and Grier microflash unit and a submicrosecond flash drive equipped with a variable time delay. Two types of triggers were

Jan 1, 1965

By T. H. Alden, H. W. Schadler

The strain rate dependence of the flow stress of the eutectoid Zn-Al alloy has been determined as a function of mechanical processing, microstructure, and temperature. The best superplastic properties result from the ultrafine, equiaxed structure produced by solution treatment and isothermal transformation at 0°C. Lamellar structures produced by isothermal transformation and coarse equiaxed structures produced by annealing also exhibit strain rate sensitivity in excess of 0.5, but at higher stresses and lower strain rates than the finest structure. Solution treatment and isothermal transformation eliminate the effect of prior processing history. Small composition variations in the binary alloy do not influence the mechanical properties. Below the eutectoid transformation temperature (.275C) increasing temperature lowers the flow stress at all strain rates. The data do not favor any of the present proposals for the mechanism of superplastic flow. ALLOYS of zinc and aluminum, near the eutectoid composition, have been investigated for: 1) the flow stress-strain rate and elongation behavior,1, 2) the transformation kinetics,3 and 3) structure,3"5 but the structure sensitivity of the mechanical properties is poorly understood. Using a near eutectoid alloy water-quenched from 380°C, Backofen et aL2 estab- high and increases with increasing strain rate. They found a correlation between strain rate sensitivity and tensile elongation as expected from the increased resistance to necking that a high strain rate sensitivity provides.296 The large elongation at high strain rates is attractive for metal forming. Since most other superplastic alloys7-l3 do not show high strain rate sensitivity at such a high strain rate (for the exception see Ref. 12) there is the possibility of a unique deformation mechanism for this alloy. The sensitivity of the mechanical properties of the eutectoid alloy to thermal history1 suggests a structure sensitivity that has not been demonstrated. Gar-wood and Hopkins3 identified a lamellar product for material transformed between 200" and 260°C. The size of the lamellae decreased with decreasing temperature. They also demonstrated that an unresolved transformation product formed below 200°C. A granular two-phase material was resolved for specimens quenched to below 150°C by Mitbauer and sauerwald4 who observed coarsening of the structure after annealing. The role of grain boundaries in superplastic deformation is suggested by the strong effect of grain refinement in encouraging this phenomenon at high strain rateS7-11, 13 and is emphasized in several proposals about rnechanism7, 8, 12 and in a theory14 of high-temperature deformation. Alden8 showed metallographic evidence that grain boundary sliding is occurring extensively at strain rates where m is large but less at high strain rates where normal plasticity is observed. Holt and Backofen10 have shown that sliding also oc-

Jan 1, 1969

The Secretary : The work of Mr. A. E. Outerbridge, Jr., of Philadelphia, first made known in his paper on " The Mobility of Molecules of Cast-Iron," read at the Pittsburgh Meeting of the Institute, in February, 1896, has been reviewed by the Committee on Science and the Arts of the Franklin Institute, whose report, dated May 5, 1897, is accompanied with a table of tests made by the Committee, and amply confirming the statements of Mr. Outerbridge. Concerning the originality and novelty of his investigation, the Committee says: " The fact that a certain molecular change takes place in cast-iron in the course of time has been known and recognized by many persons for a long time, and that this change tends to relieve the internal strains and render the casting tougher has often been noticed and acted on, although in a very crude way; but, so far as the sub-committee has been able to learn, Mr. Outerbridge has been the first to make a careful study of this, and to note that the change may be hastened by impact, and the whole effect produced in a short time, and also to make a scientific study of the phenomenon. We believe great credit is due him for the initial observation and the careful work dependent thereon. The results were first given to the public in a paper read before the American Institute of Mining Engineers, on February 20, 1896. This aroused a wide-spread interest and discussion among users of cast-iron, and so far as the sub-committee has been able to determine, it has not been shown that anyone, either in this country or abroad, has antedated Mr. Outerbridge in his work in this line. The Franklin Institute therefore recommends the award to him of the John Scott Legacy Premium and Medal." This report has not been published, hut I have had the opportunity to read it in manuscript. The table of testa accompanying it comprises 91 tests of " rumbled" and an equal number of " not rumbled" companion-bars of cast-iron, 26 by 2 by

Jan 1, 1898

By H. W. Highriter

THE method developed and used in this laboratory for the production of metallic uranium of such purity that it is ductile and can be cold-worked to fine wire or thin sheet by rolling has already been described1. It consists, briefly, in the electrolysis of potassium uranous fluoride (KUF5) in a molten bath composed of equal parts of sodium and calcium chlorides. The bath is contained in a graphite crucible, electrically heated to about 775° C., the crucible serving as the anode for electrolysis. The uranium deposits in finely divided form mixed with salts upon a molybdenum cathode suspended axially in the crucible. Upon com-pletion of the electrolysis the cathode is removed and cooled, the deposit broken and leached to remove salts. The metal powder is washed with water and dilute acetic acid and dried in vacuo to reduce oxidation. Suitable amounts are then pressed into pellets and heated in vacuo by high-frequency induction, using a thoria crucible. The uranium melts and flows away from the pellet, leaving a shell, which is largely oxide. In general, this method produced a satisfactory metal, although at times the uranium was not ductile. The investigations recorded here were made to find the cause of this embrittlement. It was known that the metal generally contained carbon, derived from disintegration of the graphite crucible in which electrolysis is conducted, in amounts dependent upon the thoroughness of washing the metal powder. Accordingly, analyses of several samples, both ductile and brittle, were made by combustion and absorption of C02 in Ascarite, using air instead of oxygen to reduce the temperature and rate of oxida-tion. Several of these metals were made with special precautions to reduce carbon content. The results show no relationship between ductility and carbon content in the range investigated (Table 1).

Jan 1, 1935

By T. S. Spicer

The relationship of coal characteristics to the principal types of firing equipment has been known to the coal combustion engineer, but is not as familiar a subject for purchasing agents, salesmen, consumers, and executives of coal-producing and consuming companies. This general survey of characteristics determined by standard laboratory tests, of major types of combustion techniques, and of the relationships between the two is directed toward the latter audience. It will also serve as a review for those actively engaged in the combustion of coal. Although the relationship of coal characteristics to the principal types of firing equipment is well known to the experienced coal combustion engineer, apparently there is need for a summary article on this subject. The author has received numerous requests for such a paper from purchasing agents, coal salesmen, coal customers and executives of coal-producing and consuming companies. Consequently, the scope of this paper will be directed to this audience, with the hope that it may serve also as a review to others actively engaged in the combustion of coal. The magnitude of this subject is so great that only a brief general treatise is possible. The author realizes that because there are so many special cases and exceptions to the generalities which follow, he is in jeopardy of contradicting himself. It is the hope, however, that the many references cited will prove valuable to those who wish to study the details excluded by necessity, due to space and time limitations. Hence, the characteristics of coals as determined by standard laboratory tests will be discussed; the major types of combustion techniques reviewed; and then the characteristics and firing will be related. CHARACTERISTICS OF UNITED STATES COALS The coals of the United States range from lignite to anthracite and each has its own general characteristics. The extensive coal fields of the U. S. are shown in Fig. 1 and the estimated reserve according to rank for each state is illustrated in Fig. 2. Coals may be classified according to rank as shown by Table I from the ASTM Standards on Coal and Coke, D-338-38.1 The basis of this classification is ac- cording to fixed carbon and heating value (Btu per pound) calculated to a mineral-matter-free basis. The high-rank coals are classified according to fixed carbon on the dry basis; and the low-rank coals according to Btu on the moist basis. Agglomerating and slacking (weathering) indices are used to differentiate between certain adjacent groups. While rank is not itself a characteristic it does signify certain characteristics that accompany a class of fuel. Anthracite, for example, immediately implies a hard, free-burning, smokeless coal of low volatile matter, usually having an ash of high fusibility. Coals may also be classified according to grade as described by ASTM Designation D-398-37.1 This quality classification is determined by size, calorific value, ash, ash-softening temperature, and sulfur. This type of classification is not used as extensively by the industry as the rank classification. Fig. 3 shows the heat value of different ranks compared to proximate analyses. Coals may also be classified by sizes, as shown in Tables IIA and IIB, and sizes can be on both top and bottom limits. If this is done, then the coal is called double screened; otherwise, either top or bottom sizes can be specified as a limit. Bituminous coal sizing varies from field to field and depends upon the market demand. The common sizes and their main uses are outlined in Table IIA. Anthracite is usually available in many sizes at the colliery, and Table IIB summarizes standard sizes and names. Although rank, grade, and size designations help identify and describe a coal in question, there still remain other characteristics such as indicated by moisture, free swelling index, grindability tests, etc. A bituminous coal information chart Table III) suggested for use in studying the available coals in a region, lists origin and chemical and physical characteristics. Even this more comprehensive list does not completely spell out all the characteristics of a heterogenous material like coal. For example,

Jan 1, 1961

By R. T. Southin

Cast ingots of 99.99 pct purity A1 and aluminum/copper alloys containing up to 2 pct Cu have been found to contain four zones rather than the three previously accepted, i.e., chill, colummar, and equiaxed zones. The fourth zone consists of a coarse dendritic layer across the top surface of the ingot which is open to the atmosphere. It is also found that the grains in the equiaxed region have a "cornet" shape, with a head which is coarsely dendritic and a tail which grew with the same structure as the columnar grains. Experiments using mechanical barriers, and others involving the elimination of the surface dendrile layer, have indicated that nucleation of the equiaxed zone is caused by the showering of dendritic particles from this surface dendrite layer. These particles are the dendritic heads found in the comet grains. A mechanism of nucleation and growth of these comet grains is put forward. Experiments with a number of other metals and alloys suggests that these conclusions may apply generally to ingots cast without the addition of nucleating agents, and solidified under normal conditions. THE macrostructure of cast ingots may contain the following three zones: i) a peripheral zone of fine equiaxed grains, commonly called the chill zone; ii) a zone of columnar grains extending inwards from the chill zone; iii) a central zone of equiaxed grains; these are normally larger than the chill grains. All three zones are not necessarily present in any particular ingot since their existence and magnitude depend upon the casting conditions and composition of the cast material. The mode of formation of zones i and ii is fairly well understood. However, the cause of the central equiaxed zone remains a matter of conjecture. Previous theories put forward to explain the mechanism of nucleation in the equiaxed zone have been examined by Chalmers1 and Winegard.2 At the time when the present work was carried out the most re -cent hypothesis was that due to Chalmers,1 who recognized more fully than previous workers that conditions in this zone during solidification were not conducive to nucleation. In his hypothesis, he suggested that nuclei were formed near the mould wall during the very early stages of solidification, and that they can drift into the central zone by convective motion. This was supported by evidence from experiments using mechanical barriers to stop the drift of nuclei. A similar hypothesis had previously been put forward by Genders.3 More recently, Jackson et al. 4 have observed that dendrite arms in organic compounds can melt off during solidification. They have postulated that this occurs in metals and alloys, and that the dendrite arms which have been freed from the main dendrite act as nuclei for the equiaxed zone. In the present work, critical metallographic examination has shown that there is a fourth zone in the macrostructure of cast ingots which is a dendritic layer over the top surface of the ingot. It is also shown that there is a relationship between this zone and nucleation of the equiaxed zone. EXPERIMENTAL DETAILS The alloys examined were prepared from super -purity aluminum of 99.99 pct min purity (spectro-graphically detected impurities of Cu, Fe, Si, and Mg) and copper of 99.98 pct min purity (spectrographically detected impurities of Si, Zn, As, Fe, Pb, Bi, Ni, Sn, Mn, Ag, Cr, and Al). Three compositions of ingots were examined, containing 0.0, 0.1, and 2 pct Cu, respectively. The alloys were melted in an alumina-lined salamander crucible using a medium-frequency electric induction furnace; when the appropriate casting temperature was reached, the alloys were cast without degassing or fluxing treatment. The mould used was made of electrode graphite and had the following dimensions: external diameter 6 in., height 9 in., with a mould cavity 8 in. deep and a diameter tapering from 5 in. at the top to 4 in. at the bottom. Casting temperatures used were generally in the order of 70" to 90°C above the liquidus and the mould was at room temperature before casting. Inserts kere placed in the mould cavity in some experiments. These consisted of either an 18-g stainless-steel tube of 2 in. diam held axially in the mould i in. off the bottom and extending 1 in. out of the top of the mould or a "trap-door" barrier of stainless-steel gauze of 24-mesh held horizontally in the mould 31/2 in. down from the top. The construction of this insert is shown in Fig. 1. All inserts were preheated prior to casting to prevent chilling. RESULTS The macrostructures of ingots of the three compositions are described, in terms of the three generally recognized zones, in Table I, and illustrated in Figs. 2(a) to (c). The most interesting observation in this table is that relating to the shape of the equiaxed grains, which were not in fact equiaxed but of almost tear-drop shape. Closer examination of these grains showed that each consisted of a head which had a coarse dendritic structure and a tail which always grew in the opposite direction to heat flow, and which had the same structure as that of the columnar material of the ingot concerned; i.e., in the pure aluminum and 0.1 pct Cu alloy it was cellular and in the 2 pct Cu alloy it was cellular-dendritic. Identification of original cast grains was greatly hampered in the super-purity aluminum ingots, and to a lesser degree in the 0.1 pct Cu alloy,

Jan 1, 1968

Established as a Division February 16, 1948 H Rush Spedden, Chairman Neil Plummer, Associate Chairman Stephen E Erickson, First Regional Vice-Chairman D A Dahlstrom, Second Regional Vice-Chairman Win T Marston, Secretary-Treasurer Dorr-Oliver, Inc 77 Havermeyer Lane Stamford, Connecticut

Jan 1, 1960

By T. J. Fabiniak, R. A. Dodd, R. Balow

ALTHOUGH the (111) slip direction in pure bcc metals is well established, the information on operative slip planes is less unambiguously interpreted. So far, (110) {112), and (123) slip planes have been identified, but it is not certain whether glide on (112) and (123) really occurs or if it is composite slip on non-parallel (110) planes. The second of these possibilities is supported by the work of Chen and Maddin on niobium and molybdenum, and a subsequent analysis by these same workers of slip in bcc metals generally.3 The alternative possibility is exemplified by the work of Opinsky and smoluchowsky4 who concluded that slip in Fe-Si crystals can occur on any one of the systems {110}(111), {112}(111), and {123)(111), depending on which system the resolved shear stress is highest. Allen et alS5 also found that glide in ar iron could occur on any of these three systems, the operative system being determined principally by orientation. By an analysis of crystal rotation, slip lines, and X-ray asterism Harris6 concluded that niobium also deforms on these same systems, but if one of these glide planes does not coincide with the plane of maximum resolved shear stress, composite slip on nonparallel (110) planes may occur giving a macroscopic high indices slip plane. Earlier work on iron by Vogel and Brick reached the same conclusion.7 The analysis of slip in bcc metals is made more difficult by the fact that the slip lines may be quite wavy. In fact, the generality of wavy slip lines suggests that screw dislocations slip readily from one plane to another in the (111) zone ("pencil glide") although, as noted, it is not certain whether planes other than (110) really contribute to the slip. If planes of higher indices than {110} do operate, there is a possibility they may do so more readily at higher temperature Argon and Maloof9 observed {100}{211}(111) slip in tungsten single crystals plastically strained at low temperatures, but the results were interpreted in terms of an orientation-dependence rather than temperature-dependence. Therefore, at the present time corroborative evidence for the operation of higher indices slip planes at higher temperatures is lacking. The present results were obtained during the course of an investigation into the effect of cathode and anode surface crystallography on the prebreakdown currents of vacuum insulated devices. In the experiment of particular interest, the 1/8-in.-diam anode and the in.-diam cathode were tungsten crystals (total impurities -230 ppm) with (110) and (100) faces respectively. The faces were electrolytically planed and examined for initial perfection by plastic/carbon replicas and a study of Kikuchi lines in reflection electron diffraction patterns. They were aligned precisely parallel in an insulating holder incorporated into the electron microscope, the measured microscope vacuum being 2 x 10-5 torr, and the electrode spacing 0.01524 cm. The anode structure shown in Fig. 1 was obtained

Jan 1, 1970

By L. Seigle, R. Resnick

An inert-marker movement experiment indicates that the ratio of the intrinsic diffusion coefficients DC:DTa = 80:l in TaC at 2500°C. Measurements of the diffmion coefficient of carbon in nonstoichiometric TaC at temperatures from 1700° to 2700°C reveal that Dc increases with decreasing carbon content, but much less than expected from the probable change in vacancy concentration with carbon content. A diffusion process involving two simultaneously operating mechanisms is postulated, and shown to be theoretically feasible. The average value of the carbon diffusion coefficient is given by DC = 0.18 exp[(-85,000 ± 3000)/RT] sq cm per sec over the composition range 46 to 49.5 at. pct C. BECAUSE of their high melting points and hardness, the carbides of the IV, V, and VI group transition metals, along with those of uranium, have attracted considerable interest for applications at high temperatures. In these applications the reactivity of the materials is important, and, since rates of diffusion within the compounds influence reactivity, a knowledge of diffusion kinetics and mechanisms is desirable. While many investigations of the mechanical and electrical properties of these compounds have been made, only two fundamental investigations of diffusion in the carbides are known. Chubb, Getz, and Townleyl measured the diffusivity of carbon and uranium in UC, and Gel'd and Liubimov2 measured the diffusivity of carbon and niobium in NbC. This paper describes an investigation of the diffusion of carbon in tantalum monocarbide and, in particular, the influence of carbon deficiency on this process. Tantalum carbide melts at approximately 3800°C, which makes it one of the highest melting materials known. The compound exists over a rather wide range of carbon Content.3-7 At the peritectic temperature, 3240°C, the phase extends from about 36 to 50 at. pct C. Although the compound can exist with a substantial carbon deficiency, the high carbon phase boundary remains near the stoichiometric composition over the entire temperature range; i.e., no carbon excess is observed. The structure of TaC is the NaCl type wherein carbon atoms normally occupy the octahedral sites in a somewhat expanded fcc lattice of tantalum. Decrease of the lattice parameter with decreasing carbon suggests that the removal of carbon introduces octahedral vacancies into the lattice. I) EXPERIMENTAL DETAILS AND RESULTS Inert-Marker Experiments. In a compound such as TaC the interstitial element would be expected to diffuse more rapidly than the metal. This was confirmed by an inert-marker experiment, following Srnigelskas and irkeendall.8 Ideally, the markers should be placed at the interface between a slab of low-carbon TaC and graphite, and their movement during subsequent inter-diffusion measured. Unfortunately, no solid could be found which is unreactive in contact with carbon at the high temperatures employed in these experiments. In order to circumvent this problem, a specimen was designed in which the markers consisted of several small canals running just below the surface of a tantalum slab. This specimen was prepared by machining grooves on the surface of the tantalum slab and then diffusion-bonding a thin plate of tantalum to the slab over the grooves. The surface of the plate was then ground down until the distance between the canals and surface was as small as possible (about 0.01 cm). Thus, the canals would lie entirely within the TaC phase after a short period of diffusion. The diffusion anneal consisted of immersing the metal sample in high-purity graphite powder and heating for approximately 10 hr at 2500°C under vacuum. At this temperature, the vapor pressure is sufficiently high and the transfer of carbon from graphite sufficiently rapid to allow the surface of the diffusion sample to attain the stoichiometric carbon concentration very quickly. Conclusions regarding the relative diffusion rates of carbon and tantalum in the compound layers (TaC and Ta2C) can be drawn from the location of the canals after the diffusion anneals. If the growth of the layers is governed mainly by the diffusion of carbon, as expected, the canals should remain close to the sample surface. If the diffusion of tantalum contributes appreciably to formation of the compound layers, the distance from the markers (canals) to the surface should increase. Fig. 1 shows, diagrammatically, the appearance of the specimens after diffusion, and Table I presents the depth below the surface at which the

Jan 1, 1967

By Arthur Taggart

THE major portion of the work described in this paper was performed by R. W. Young,+ a graduate student in the department of Mining and Metallurgy, Sheffield Scientific School, Yale University, working under a cooperative agreement between the Hardinge Conical Mill Co., the Sheffield Scientific School, and himself. Since this cooperative scheme is at present in effect in the case of a considerable number of other students in the department and since it is the hope of the school that the privilege thus extended may be utilized even more freely in the future by mining and manufacturing companies, it may not be amiss at this point to give a summary of the general plan. Briefly it is as follows: A graduate student, whose undergraduate work in this or other universities shows promise of ability to handle research work, is chosen by conference between the company and instructor involved. The aim of the company in the agreement then entered into is to obtain the solution of one or more of the technical problems with which it may be confronted, or, at the end of 1 or 2 years, to obtain as an employee a man especially trained in its work. As. a means to accomplish one or both of these ends, the company furnishes the machine, apparatus, or material to be tested and pays the student during his graduate work a small salary, usually just sufficient to cover his living expenses, tuition and fees. The aim of the student is special training along a line in which he is particularly interested, the attainment of his advanced degree, and the chance to show to his future employer ability to handle such problems as may be presented to him. In return for the financial aid which he receives he agrees to devote at least half of his working time to the special problem submitted by his company. The other half is devoted to study of the collateral subjects required by the department for the granting of the degree which the student seeks. The student further agrees to enter the employ of the company in question at a wage not greater than that paid in like positions to recent graduates not specially trained and to remain with his employer at such wage for at least 1 year. If the student is to obtain a degree, the special work forming the basis of his investigation must be such as will involve real research and not mere routine manipulation. The subject is chosen by conference between the three parties to the agreement. The work is carried on under the direct supervision of the instructor involved. The school furnishes the general laboratory and library equipment essential to the pursuit of any extended investigation, In

Jan 4, 1917

By R. M. Brick, F. L. Vogel

THE elementary mechanism of deformation in the body-centered cubic metals has been a subject of dispute for many years. If the problem were merely that of designating the crystallographic plane or planes of slip, the solution would have appeared long ago. However, there must be greater differences in the deformation behaviors of the body-centered and face-centered types than the differences in their lattices would suggest. The lines of slip formed on the polished surface of a strained face-centered cubic metal conform to glide over a single plane of the crystal. Slip in body-centered cubic iron, however, is frequently observed as curved and forked lines which could not possibly define a single plane of atoms. This alone is sufficient reason to expect different modes of deformation to operate in the two lattice types. The literature in this field now has generally accepted the proposition that {110), {112), or (1231 planes will act as slip planes in iron. It is essential that the experimental evidence supposedly supporting this proposition be critically examined. Taylor and Elam1 in 1926, using relatively small single crystals, determined the operative slip systems by measurements of the distortion of a grid engraved on the specimens prior to deformation. Their results indicated that shearing had taken place in the close-packed direction on a plane adjacent to or coinciding with the plane of maximum shear which contained the slip direction. This led the authors to propose a theory of noncrystallographic or banal slip. The authors considered an alternate rationalization of banal glide. Slip on two (1101 planes or possibly two {112} planes containing the same <1ll> direction could produce the wavy slip lines. By employing plane segments of varying widths, the integrated plane could take any position in the <111> zone. They rejected this explanation, however, feeling that the preponderance of evidence was against it. Taylor&apos; continued the investigation of the plasticity of the body-centered cubic lattice on ß brass. He reasoned that the resistance to shearing of a given plane in the zone of the slip direction was a function of the angle between the glide plane and the closest (110),: P F=—cose sine cos(X —?) [1] where F is the resistance to shear; P, the axial load at yielding; A, the cross sectional area; e, the angle between slip direction and load axis; x, the angle between plane of maximum shear containing the slip direction and the (101) pole; and ?, the angle between observed glide plane and the (101) pole. Differentiating Eq. 1 and rearranging, dF — = tan(x-?) d? [2] F which expresses the variation of the shear resistance with the angle $. Integrating this equation between the limits 0 and ? yields In F/F0 = ?0?tan(x— ?) d? [3] Here, F, is the resistance to shear of the (110) plane and F is the resistance to shear of a plane $ degrees from the (110). Thus, the variation of shear resistance with $ can be calculated from an experimentally measured x vs $ relationship. Fahrenhorst and Schmid8 sed several methods, none of them involving direct observation, to determine the glide system in ferrite. They determined the variation of critical resolved shear stress with

Jan 1, 1954

By H. I. Aaronson, H. A. Domian, G. M. Pound

The thernodyna,nics of I the Proeutectoid ferrite re-action ha1.e been investigated on the bases of three diifevent descviptions of the statistical thernzodynamics of interstitzal solid solutions. Especially at low ternperatures, substantial dijeretzces are found in the valltes of the extrapolated y/y + a and cr/a + y equilibriurn curls, and in the To- co7nposilion metastable eqliilibriunz curl-es thus co,npited. Although neither actiztity nor phase-diagram date are able to distingrish udeqiutely among the various descviptions, the statustics of Lacher, Fouller, and Guggenheinz provide the ?nost conplete epresentation az3ailable of the single carbon-ctrbon interaction energy (w) nzodel of an intevstitiril solid solution, and the relationships deduced frojrl then2 are accordingly pre.ferred. The findings tlzut w in austenite &apos;aries significu?ztly uith tenpevntrue and that phase-diagawr data arc not accurately con?palible usith eqcrctions deduced on the basis of actility infoation indicate, hou&apos;e13er, that a wzore cornplex nlodel of the uustenite , und pvobably of the .feyrite, solirl solutions will have to forn the basis of f4tuve statistical t1.eat1nents. Some suggestions for such a ruodel arc advanced. Althoug11 w represents a vepltlsio energy in austozite, it was found to corvcsporzd in ferrite to a binding energy, in qualitatit.e accord zc,itlz the internal-friclion results of Keefer and wert. ThE transformation of austenite to proeutectoid fer-rite is becoming recognized as an exceptionally useful vehicle for quantitative studies of the kinetics of phase transformations.&apos;" Reasons for this popularity include well-characterized microstructures which develop on a convenient scale with acceptable kinetics within a considerable temperature-composition region, the absence of great sensitivity to common impurities, and, especially. the availability of a unique wealth of the ancillary information indispensable for the quantitative interpretation of kinetic measurements, including phase diagram,3 crystallographies diffusivity,5 inter-facial energy,=17 elastiit," specific vlume, &apos;&apos;&apos; and ativity&apos;-&apos; data. Development of considerable amounts of additional thermodynamic information from activity data is of particular importance with respect to kinetic studies, since much of this information is needed in temperature-composition regions not directly accessible to presently available techniques for the measurement of equilibrium properties. A generally useful approach to the thermodynamics of solid solutions, which is of especial value in this situation, is based upon the formulation of the free energy of such solutions as a function of temperature and composition. The free energy of solid solutions has been resolved into many components. Particularly in the case of interstitial solutions, with which we shall be concerned in the present study, however, only the positional entropy component has been intensively studied. The other components are conventionally taken into account by fitting equations for the activity of the interstitial species or the temperature-composition path of phase boundaries, derived principally from positional entropy considerations, to experimental information on these quantities through adjustment of one or more constants in the equations. A number of studies of the thermodynamics of interstitial solid solutions have been made primarily on this basis,&apos;"25 but only Kaufman, Radcliffe, and cohenZ2 (hereafter KRC) and ener&apos;&apos;% ave applied the results of such studies to develop relationships for the thermodynamic quantities of interest in the austenite —- proeutectoid ferrite transformation. KRC made use of a model developed by cheil&apos;&apos; (on the basis of a previous study by ohansson&apos;), and subsequently rede-rived correctly by Speiser and retnak,&apos; in which a carbon atom is considered to inhibit occupancy of a certain number of its nearest-neighboring interstitial sites. schei120 determined the number of sites in austenite thus excluded by matching calculated and experimentally measured curves for the variation of carbon activity with the mole fraction of carbon. zener17 used a different approach. He assumed that the positional entropy of carbon is ideal both in austenite and in ferrite (i.e., no excluded interstitial sites), and included all other contributions of carbon in a temperature-independent "free-energy change" accompanying the transfer of 1 mole of carbon between the two phases. This quantity was determined by "pinning" an equation derived for the boundaries of the a + y region to experimental data on the compositions of these boundaries at a single temperature. In the present investigation, three different approaches to the thermodynamics of the proeutectoid ferrite reaction are examined comparatively: I) the method of Zener; 2) the model employed by KRC and predecessors; and 3) the more detailed statistical thermodynamic treatment of the same model developed by acher and Fowler and uenheim, &apos; in which the problem of overlapping regions of influence of individual interstitial atoms is resolved. In order to make these comparisons, it is necessary to undertake an extension of one aspect of Zener&apos;s method; since the Lacher- Fowler -Guggenheim (LFG) treatment has not been previously used in the present context, the necessary thermodynamic "superstructure" for this treatment will be developed in parallel

Jan 1, 1967

By N. Brown, R. Kossowsky

Plain carbon steels with 0.48 and 0.95 pct C were quenched and tempered at 705°C to produce carbide dispersions with spacings on the order of 1 p. The morphology of the structure consisted of a carbide-dislocation network. The strengthening due to the dispersion was found to vary linearly with M-½ where M is the mean free-ferrite path determined by the entire network. No preyield microstrain preceded the upper yield point. After prestraining, the lowest stress at which dislocation movement could be detected was 104 psi; this frictional stress was independent of the dispersion and prestrains up to 6.5 pct. The Cottrell-Petch equation for grain-size strengthening was used to discuss the dispersion strengthening in this investigation. The results support an impurity mechanism for the upper yield point rather than one based on the Johns ton- Gilman theory. IT was pointed out by Gensamerl that the mean free path in the matrix is the important variable which controls the degree of dispersion strengthening. Gensamer&apos;s data on steels showed a linear relationship between the yield point and the logarithm of the mean free-ferrite path. The first theory was by Orowan,2 who suggested the mechanism of dislocations bowing between particles, with the resulting relationship that where a is the yield point, P is the distance between particles, and G is the shear modulus. The Orowan equation applies to that range of dispersion where P is large compared to the particle size and the particles are not coherent, so that the matrix is essentially free of internal stresses. As was pointed out by Orowan, there are different degrees of dispersion which, in turn, will influence the strength-controlling mechanism. However, in this investigation, we wish to confine ourselves to the region of coarse dispersion, where the Orowan mechanism should, intuitively, be applicable. It was soon evident that the data, which existed at about the time that the Orowan theory was proposed, did not agree with the Orowan equation in that the actual strengthening was always greater than the theoretical predictions. Thus, Fisher, Hart, and pry3 modified the Orowan theory by suggesting that the Orowan process took place in the microstrain region preceding macroscopic yielding and the subsequent, rapid work hardening in the form of residual dislocation loops around the particles largely determined the observed macroscopic yield point. The F-H-P theory stated that the increment of strengthening due to the work-hardening mechanism was proportional to f3/2 where f is the volume fraction of the precipitate. F-H-P used data by Shaw, Shepard, Starr, and Dorn4 on A1 3-5 pct Cu to support their theory. Roberts, Carruthers, and Averbach5 were the first to make a microstrain study of dispersion strengthening, and they found that for steel the Gensamer relationship was obeyed. Hayman and Nutting6 suggested that in the case of tempered steel 1) the ferrite grain boundary was the primary obstacle and 2) the carbide particles simply formed part of the grain boundary obstacles. They found that the strength varied as G"" where G is the ferrite grain size. Turkalo and LOW&apos; determined the structure of quenched and tempered plain carbon steel using a replica technique; they concluded that the carbide particles did not necessarily lie in the ferrite grain boundaries. When they defined the mean free-ferrite path as being determined by both particles and the ferrite path boundaries, their data obeyed the Gensamer relationship. Meiklejohn and skoda8 showed that the strengthening from iron particles in mercury was a function of the particle size and the distance between particles. Dew-Hughes9 explained the Meiklejohn and Skoda results by the following theory: 1) grown-in dislocations which surrounded the particles were produced by the thermal stresses during the time the material was cooled to the testing temperature, and 2) the observed strengthening was associated with the cutting of the grown-in dislocations by the glide dislocations. Ansell and Lenel10 proposed a theory in which the glide dislocations pile-up or surround the particle until the number of dislocations in the pile-up is sufficient to yield or fracture the particle. The resulting theory says that the yield point varies as p-1/2, where P is the distance between particles. The Ansell-Lenel theory is almost identical to the

Jan 1, 1965

By A. K. Mukherjee, John E. Dorn

The effects of strain rate and temperature on the critical resolved shear stress for (321)[111] slip were determined for the silver-rich CsCl type of intermetallic compound AgMg. The flow stress increased only slightly as the test temperature was first decreased below room temperature; a rapid increase in the flow stress was obtained with yet further decrease in temperature from about 250&apos; to 4OK. The effect of both the temperature and strain rate on the flow stress over the low-temperature range could be rationalized satisfactorily in terms of the Peiwls mechanism when the deformation was controlled by rate of nucleation of pairs of kinks. IN spite of the well-documented interest of metallurgists and engineers concerning the mechanical behavior of intermediate phases and intermetallic compounds, very little definitive information is available on this important subject. As recently summarized by westbrook,1 only limited and modest progress has been made thus far in elucidating the details of the mechanism of plastic deformation for the intermetallic compounds; the available information largely concerns phenom-enological descriptions of empirical observations and experimental facts, principally with reference to poly crystalline aggregates. The present report on the elucidation of the rate-controlling mechanism for slip in the bcc structure of AgMg is part of the comprehensive program of a systematic investigation on the mechanical behavior of intermetallic compounds. The intermetallic compound AgMg has a CsCl type of lattice structureZ and is completely ordered up to its melting point of 820c3 This material was selected for our present investigation because of its simple crystal structure, moderate and congruent melting point, ordered structure persisting up to the melting point, and some solubilities of the constituent elements, which could be expected to help in the growing of single-crystal specimens. Whereas previous investigations on the properties of AgMg include hardness,*"6 slip systems,7 tensile flow stress of polycrystalline specimens,&apos; and electrical resistivity,4 the current investigation will be directed principally at elucidating the rate-controlling dislocation mechanism responsible for slip in single crystals at low temperatures. It will be shown that the strain rate is consistent with a model involving the rate of nucleation of pairs of kinks by the Peierls mechanism for plastic deformation. EXPERIMENTAL TECHNIQUES Single-crystal specimens of the AgMg intermetallic compound were prepared and tested as follows: 1) A master alloy ingot of AgMg was produced by melting and chill casting the high-purity silver (99.995 wt pct) and high-purity magnesium (99.997 wt pct) in an induction furnace under a helium atmosphere. 2) Sections of the above-mentioned ingot were placed in a graphite mold containing a spherical cavity in which a single-crystal sphere of 1 in. diam was grown under helium by the Bridgman technique. 3) The operative slip systems were investigated at room temperature on a singlecrystal of AgMg, from measurements of the angles made by the slip traces on the two surfaces of the specimen, which were at 90 deg to each other. The investigation confirmed that the AgMg compound undergoes slip primarily in the (321) plane and in the [Ill] direction, but a small amount of secondary slip was also noticed in the (112) (111) system. No slip was observed in the (110) planes. 4) The single-crystal sphere, mentioned earlier, was oriented in a graphite mold containing a cylindrical cavity of 3/8 in. diam above the spherical receptable to give the angle xo = 45 deg between the axis of the cylindrical bar and the normal to the slip plane (321), and the angle AO = 45 deg between the slip direction [Ill] and the axis of the bar. Oriented single-crystal bar seeds were produced by melting, under a helium atmosphere, a polycrystalline bar in the cylindrical cavity above the oriented spherical seed and by growing an oriented single-crystal bar from the seed. 5) Finally, oriented single-crystal specimens were grown from these cylindrical seeds. 6) The cylindrical specimens were machined in a High-Tension Spark Cutting unit to give a 2-in. gage length. The spark-machined gage section was elec-tropolished in a bath containing 200 ml of H3PO4,

Jan 1, 1964

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members.) Members and guests who called at Institute headquarters during the period June 10, 1916 to July 10, 1916: Arthur Adams, Miami, Ariz. John M. Lovejoy, New Rochelle, N. Y. J. H. Batcheller, Mattapoisitt, Mass. J. F. Manning, Seoul, Korea. R. S. Bonsib, Low Moor, Va. E. P. Mathewson, Anaconda, Mont. E. L. Booth, New York, N. Y. Edwin W. Mills, Seoul, Korea. C. L. Bryden, Scranton, Pa. Arthur Notman, Bisbee, Ariz. F. Crabtree, Pittsburgh, Pa. L. B. Reifsneider, Daiquiri, Cuba. L. B. Eames, Pueblo, Colo. W. S. Schuyler, Berkeley, Cal. S. J. Gormly, Guayacan, Chile. 0. N. Scott, Toronto, Ont., Canada. Ernest A. Hersam, Berkeley, Cal. Arthur F. Taggart, New Haven, Conn. A. W. Hudson, Douglas, Aria. Warren D. Thompson, Boston, Mass. Chas. W. Johnston, West Norfolk, Va. Thor. Warner, IGngman, Ariz. Rodolphe L. Agassiz has been chosen president of the Calumet & Hecla Mining Co., an office which has been vacant for over a year. Percy E. Barbour, Managing Editor of the Engineering and Mining Journal, resigned his commission as 2d Lieutenant in the Main Coast.

Jan 8, 1916

At Black Lake, Quebec, Lake Asbestos of Quebec Ltd., a wholly-owned subsidiary of American Smelting and Refining Co., has opened a $36-million mining and milling operation which will produce about 100,000 tons of asbestos fiber a year and add 7 pct to the Free World&apos;s supply. The orebody once lay beneath Black Lake, and readying the ore deposit for open pit mining meant removing about 37 million cu yd of overburden- 30 million cu yd by dredging and pumping, and 7 million by power shovels and trucks. The enormous amount of material to be dredged, control of drainage during dredging, the need to cope with drainage problems in the area and to provide for flood control to replace the regulating effect of the lake, posed unusual engineering challenges and required tremendous capital investment.

Jan 1, 1959

By N. A. Stockett

SOUTHEAST Missouri is the largest and oldest lead-producing district in the United States. For the year 1941, the statistical picture of pig-lead production, stated in short tons (partly estimated by the Engineering and Mining Journal) is as follows. [Tons World production 2,000,000 United States production 460.000 Southeast Missouri production 242,000] The consumption of primary lead in the United States in 1941 was approximately 900,000 tons, or almost double the country&apos;s production. The largest previous year&apos;s consumption in the United States was 718,000 tons, in 1926. The largest quantities of lead are used for cable sheathing, storage batteries and white lead. During 1941 tetraethyl lead for auto and aviation gasoline consumed 50,000 tons of lead. The entire lead production of Southeast Missouri is now mined by the St. Joseph Lead Co., whose dominant position as the largest producer in the United States of lead directly from ores is best shown by the fact that in 1941 it produced approximately 31 per cent of the lead production of the United States from its mines in southeast Missouri, where 22,000 tons of ore, averag¬ing over 3.00 per cent lead, is mined per working day. It is known that lead was mined at Mine La Motte, Madison County, Missouri, by Renault in 1723. Other white men and Indians probably did some mining prior to that time. Since 1865, the recorded production to Jan. 1, 1942, shows that the St. Joseph Lead Co. and the various other companies that have operated in St. Francois County mined lead ore, which, after milling and smelting losses produced 5,00,000 short tons of pig lead. About 95 per cent of the present lead production of Southeast Missouri is mined in St. Francois County. The northern part of this area is 60 miles south of St. Louis. The remainder of the lead is obtained at Mine La Motte, about 25 miles southeast from the center of the producing area in St. Francois County. PROSPECTING In this district, most of the ore is discovered by surface and underground diamond drills and by prospect drilling underground with rock drills. Each 2-ft. length of the cuttings from these Jackhamer prospect holes is assayed for lead. These holes are marked and the records are entered on maps. It has been found that close drilling--100-ft. centers of holes, and sometimes less-is necessary in order to locate most of the smaller commercial ore bodies, many of which previously had been missed by drilling the areas with holes spaced 200-ft. centers or more.

Jan 1, 1943

By D. E. Hawk, R. F. Burdyn, F. D. Patchen

Earlier work on a mud separator for barite recovery is extended to the design and construct ion of a rugged field unit. Problems associated with scale-up for field use include the me of dilution water and its effect on capacity, power requirements and pressures developed. Equations for these quantities are derived and applied in maximizing the beneficial effects of dilution and minimizing the power required. Tests on the full-size rotor show that its performance can be predicted by theory. The completed unit is compact and lighter than current decanting types. Its capacity is from 10 to 22 gal/min with corresponding barite recovery efficiencies of 92 to 86 per cent. INTRODUC&apos;TION In an earlier publication a new type of centrifugal device was described for solid-liquid separations.l In that paper an operating equation was derived, and its validity demonstrated in laboratory scale experimentation. Some of the features apparent in this new device seem particularly well suited to the conservation of barite in field drilling-mud systems, hence the development was extended to the design and construction of a field unit. In the present paper the design problems associated with scale-up are considered. A full-scale, rugged self-contained field unit is described, and test results discussed which verify that the performance of the large field unit can be described by a simple operating equation. PRINCIPLE OF OPERATION OF SEPARATOR In principle, the new device is simply a perforated cylinder rotating within a body of fluid which is contained within a stationary case, as in Fig. 1. The frictional drag generated by the rotating cylinder causes part of the fluid to rotate. At the surface of the cylinder, assuming no slip occurs, the angular velocity of fluid and of the cylinder are identical. If there are suspended particles present of greater density than the fluid, the centrifugal force acting on these particles causes them to move radially away from the cylinder at some velocity vp . Where the Stokes settling equation holds, this velocity may be expressed as:2 d2 ?p rw2 If the case is provided with openings at both ends, a suspension can be pumped in at one end at a fixed rate. Part of the suspension can then be removed at a fixed rate at the other end of the case as underflow, and the remainder forced through the perforations and hollow shaft of the rotor to appear as effluent, also at a fixed rate. The radial component of the flow velocity of this stream as it reaches the rotor surface, is simply effluent flow rate divided by cylindrical surface area: Because up is a function of particle size, for some particular particle size, the velocities vp and v, will be equal in magnitude. This is defined as the critical particle size and represents the size above which all particles appear in the underflow and below which all particles appear in the effluent. For this equilibrium condition at the rotor surface, Eqs. 1 and 2 combined give

Jan 1, 1966

By D. B. Carson, D. L. Katz

Natural gases under pressure form crystalline hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methanc-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbon-rich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. Introduction Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural-gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villardl and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Dcaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on tem-peraturcs and pressures of hydrate forma. tion for pure methane, ethane, propane, n-butane, methane-ethane mixtures, meth-ane-propane mixtures, methane-butane mixtures, and some Is natural gases, all- in the Presence of excess water. However, up to the Present time no method has been available for predicting the temperature at given pressures or the pressure at given at at which natural gases will form hydrates if hydrates with water. &apos;This Paper Presents data on the methane-propane-water, methane-pentane-water and methane-hex-""e water systems in four phases, one of which is the hydrate. he application of the phase rule to the methane-~ro~ane-water data Proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid. equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1942

By D. B. Carson, D. L. Katz

Natural gases under pressure form crystalline hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methanc-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbon-rich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. Introduction Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural-gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villardl and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Dcaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on tem-peraturcs and pressures of hydrate forma. tion for pure methane, ethane, propane, n-butane, methane-ethane mixtures, meth-ane-propane mixtures, methane-butane mixtures, and some Is natural gases, all- in the Presence of excess water. However, up to the Present time no method has been available for predicting the temperature at given pressures or the pressure at given at at which natural gases will form hydrates if hydrates with water. &apos;This Paper Presents data on the methane-propane-water, methane-pentane-water and methane-hex-""e water systems in four phases, one of which is the hydrate. he application of the phase rule to the methane-~ro~ane-water data Proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid. equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1942