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By George S. Rice

MECHANIZATION in coal mining is a phrase which has attracted world-wide attention, and those persons not engaged on the practical side of coal-mine operations seem to regard mechanization as a panacea for many difficulties of the industry. The term "mechanization" as now employed by experienced mining men is restricted to mean mechanical loading of coal at the face. In a broader sense mechanization in coal mining was begun nearly half a century ago with the introduction of compressed-air undercutting machines and locomotives and, later, of electrically operated locomotives, undercutting and shearing machines, and drills. The use of coal-cutting machines, which has increased until now about three- fourths of the bituminous coal produced is being mechanically cut, first displaced hand-picking except in a few long-wall mines, and later gradually displaced the dangerous and coal-smashing method of blasting-off- the-solid.

Jan 1, 1929

By P. S. Kotval, H. Hahell

PRECIPITATION of M23C6 carbides at grain boundaries in austenitic steels and nickel base superalloys has received considerable attention. Hatwell and Berghezan,1 in a study using carbon extraction replicas, observed that dendritic growth of the M23C6 carbide phase occurred at grain boundaries in austenitic steels. Merrick and Nicholson2 have observed that in thin foils of "Nimonic 75" alloy the precipitation of M23C6 carbide was discontinuous at grain boundaries. Lewis and Hattersley3 have suggested that the type of M23C6 precipitation observed in Ni-Cr austenites represented the early stages of discontinuous precipitation. In a more recent study, Singhal and Martin4 have concluded that grain boundary M23C6 precipitation involves the migration of an austenite grain boundary by a mechanism very similar to that proposed by Tu and Turnbull.5 Tu and Turnbull's suggestion essentially involves grain boundary migration under the driving force arising from the difference between the surface free energies of the opposite sides of the plate. Thus, Singhal and Martin's observation4 implies that the first stage of discontinuous precipitation has taken place and that the grain boundary has provided a diffusion short circuit for the sub-stitutional solute atoms (principally chromium) which assist the preferential growth of the M23C6 plate in contact with the grain boundary. However, no evidence of the characteristic cellular morphology typical of discontinuous precipitation was found in Singhal and Martin's studies. Presumably, this is due to the low volume fraction (i.e., low supersaturation of solute) of the precipitating carbide reported by Singhal and Martin.4 Recently, Raymond6 has studied precipitation of the M23C6 carbide in Incoloy alloy 825 and shown that the growth of this phase is perpendicular to grain boundaries at 1400°F and in the plane of the grain boundary at 1700°F. The former aging condition resulting in discontinuous or "cellular" precipitation. Raymond has suggested an explanation for this behavior based on the relative rates of chromium diffusion by volume and grain boundary diffusion at the two different aging temperatures. In the course of a recent investigation on precipitation behavior in several ' strengthened superalloys, precipitation of M23C6 carbide at grain boundaries was studied. Under conditions of a high degree of supersaturation, the M23C6 carbide precipitates in the discontinuous or cellular morphology in Waspalloy (Ni-18.51 Cr-2.0 Fe-3.53 Mo-1.16 Al-2.78 Ti-0.09 C). This note presents electron microscopy observations of this mode of precipitation and its effect on mechanical properties. Specimens of Waspalloy after "solution" heat treatment at 1950°F show essentially single phase matrix with a few residual particles of "primary" MC carbide. In normal commercial heat treatments, precipitation of Ni3(Al,Ti) ordered fcc r' phase occurs throughout the matrix and M23C6 precipitates as globular particles at the grain boundaries. In these commercial heat treatments the degree of supersaturation during precipitation is low. However, if specimens of Waspalloy are quenched from the solution heat treatment temperature of 1950°F and then aged at an aging temperature where the degree of supersaturation is high, discontinuous precipitation of M23C6 occurs. Figs. 1 and 2 show thin foil micrographs of Waspalloy, solution heat treated at 1950°F, water quenched, and aged at 1292° and 1598°F, respectively, for 500 Fig. 1—Thin foil of Waspalloy, solution heat treated at 1950°F for 1 hr, water quenched, and aged for 500 hr at 1292°F. Magnification 15,500 times. Fig. 2—Thin foil of Waspalloy, solution heat treated at 1950°F for 1 hr, water quenched, and aged for 114 hr at 1598° F. Magnification 13,000 times.

Jan 1, 1970

By Alfred G. Heggem

It is the purpose of this article to describe methods recently introduced into the oil and natural gas industry to safeguard the lives of the workmen and to protect property from destruction. Only such drilling methods are described as pertain directly to the operations necessary to maintain the well under complete control at all times. Wells Formerly Drilled Without Controlling Equipment It may seem incredible that practically all wells, until rkcently, were drilled without the provision of any means for control. To drill a hole into a boiler carrying high-pressure steam without first providing means to control the escape of steam would be unthinkable, yet in oil fields wells are drilled into a gas or oil formation with a possible pressure of 300 to 1,800 lb. per square inch and a daily flow of 20,000,000 to 80,000,000 cu. ft. of gas or 1,000 to 15,000 bbl. of oil per day. Some wells have produced in excess of 100,000 bbl. of oil per day, but these are exceptional cases. In addition to the loss of product, one must consider the great danger attendant upon the promiscuous liberation of such an amount of explosive and inflammable substance. Introduction of Metal Casing for Deep Drilling The introduction of metal casing to secure a permanent and impervious wall in a well made the drilling of deep wells possible and removed many of the original problems encountered in well drilling, but it did not insure the control of the well. To obtain the full value of the casing it was essential that a pressure-tight joint be made between the wall of the well and the lower end of the casing. Many materials in various forms were used, including cotton, hemp, stable refuse, oats, rice, cloth, leather, cork, rubber, lead, clay and cement, resulting, after a slow process of evolution, in the general adoption of two types of bottom fittings for

Jan 1, 1916

By EDWARAD A. SIVEDENBORMG

REPORTS have been made at different times on the progress of water encroachment in the Frontier sands in the Salt. Creek oil field, Natrona county, Wyoming. All previous reports have, -however, been largely based on the position of water in the sands as determined by various physical tests. Subsequent information has been secured through a preliminary investigation of the porosity, grain size and degree of saturation of the Frontier sands. Also, a closer differentiation has been made between the waters encountered incident to the production of oil by means of chemical analysis. In view of the more recent developments there has been a need of a water encroachment map of the first Wall Creek based on a field survey and additional information acquired since the water encroachment map of the sand of 1926, by J. S. Ross and E. W. Henderson, petroleum engineers of the U. S. Geological Survey. The present report is confined to a study of the first Wall Creek sand and was written in connection with the preparation of the map, showing water encroachment in this sand. The first Wall Creek sand was the discovery sand in the field, the first well having been drilled in 1908. Its thickness averages 120 ft. and, varies between 90 and 160 ft. The sand is in the Colorado group of the Upper Cretaceous series and is further considered as a part of the Frontier formation found in other parts of Wyoming.

Jan 1, 1930

By A. CHESTER BEATTY

MAGNESIUM oxide is by far the most refractory of the common oxides, since it has a melting point of 5072 deg. F. as compared with 3110 deg. F., the melting point of silica (crystobalite) ; 3722 deg. F., the melting point of alumina (corundum) ; and 4127 deg. F., the melting point of chromite (Cr2O33FeO). Its large-scale use in the lining of metallurgical furnaces dates back to the latter part of the nineteenth century, when extensive deposits of magnesium carbonate were discovered in southern Austria in the province of Styria. Before the development of Austrian magnesite, calcined dolomite, a mixture of lime and magnesia, was used in basic steel-making furnaces. The lime in the dolomite was quite objectionable, since it slaked on exposure to the atmosphere, and dolomite therefore could not be made' .into permanent furnace bottoms or into brick. The Austrian magnesite, with its very low lime content, was free from these objections and soon displaced much of the dolomite. With the extensive development of basic steel-melting, the rise of the copper industry, and other metallurgical and chemical processes which dealt with chemically basic substances, the use of magnesite grain and magnesite brick increased rapidly.

Jan 1, 1931

CARL E. SWARTZ, Chairman D. K. CRAMPTON, Past-Chairman CYRIL S. SMITH, Vice-Chairman ARTHUR PHILLIPS, Vice-Chairman FRANK T. SISCO, Secretary 29 West 39th Street, New York, N. Y. H. A. MALONEY, Treasurer Executive Committee 1943 1944 ERIC R. JETTE WILLIAM C. ELLIS LOUIS W. KEMPF ALAN MORRIS GEORGE SACHS KENT R. VAN HORN

Jan 1, 1942

R. W. Raymond, New Pork City: It seems questionable to me whether Mr. Mezger's identification of the rock-structure he describes, as the Augengneiss of previous authors, is warranted by the definitions given by them. Naumann (1854)t describes Augengneiss as a porphyry-like variety, " which has assumed, by reason of single large kernels or granular concre-

Jan 1, 1896

By D. Atkinson, C. Bodsworth, I. M. Davidson

A geometric model of interstitial solid solutions, which has been used previously as a basis for the prediction of carbon activities in Fe-C austenite, is shown to serve also for the calculation of nitrogen activities in Fe-N austenite. The model has been developed to enable predictions to be made of the activities of an interstitial element in the presence of two host atom species. The activities calculated via the model are shown to be in satisfactory agreement with the measured values in the austenite phase for carbon in Fe-C-Co, Fe-C-Cr, Fe-C-Ni, Fe-C-~n, Fe-C-Si, and Fe-C-V alloys and for nitrogen in Fe-N-Ni alloys. The effect of the second substitu-tional solute on the logarithm of the activity of the interstitial element is expressed as the product of a constant mad the atomic concentration of that solute. The constants so derived we related to the thermo-dynamic interaction coefficients which describe the effect on the activity coefficient of carbon of an added solute element. In recent years the thermodynamic activities of carbon and nitrogen in the single-phase austenite field have been determined for iron binary alloys and for several iron-base ternary alloys. In order to extend the use of these measurements, it is desirable to be able to predict with reasonable accuracy the activities of the interstitials at compositions and temperatures other than those which have been measured experimentally. In all the systems studied to date, the interstitial elements do not conform to ideal behavior. Hence, the available data cannot be extrapolated or interpolated using the simple thermodynamic concepts of solutions. Several models have, therefore, been formulated for the purpose of predicting the activity of an interstitial element in the presence of one species of host atom. These models can be divided into the geometric1"5 and energetic6-' types. The former group is based on the assumption that at low concentrations the activity of the interstitial species is determined by a composition-dependent configurational entropy term and an excess free-energy term which is temperature-dependent but independent of composition. The purpose of this paper is to show that the treatment, based on a geometric model, can be extended to enable predictions to be made of interstitial activities in the presence of two substitutional host atom species. THE CONFIGURATIONAL ENTROPY OF MIXING ICaufman5 has shown that the configurational entropy, S,, for a binary solution comprising of a host atom species, A, and an interstitial species, I, can be expressed as: where NI is the atom fraction of the interstitial species, R is the gas constant, and (2 - 1) is the number of interstitial sites excluded from occupancy by the strain field around each added interstitial atom. The number of interstitial sites per host atom, p, is unityg for the fcc austenite solutions considered here. The configurational entropy of mixing for a ternary solution comprising two substitutional atom species, A and B, and one interstitial species, I, can be derived similarly. Let the number of atoms per mole of each of these species in the solution be represented by «a, ng, and nI. From geometric considerations, it is improbable that the addition of a few atom percent of a second host atom species will change the type of sites (i.e., octahedral) in which the interstitial atom can be accommodated in the austenite lattice. At higher concentrations (determined largely by the relative atomic radii of the atomic species present and any tendency to nonrandom occupancy of the host lattice sites) other types of interstitial sites may become energetically favorable. Restricting consideration to compositions below this limit, for 1 = 1 the number of suitable interstitial sites is given by (n + nB). However, if each interstitial atom excludes from occupancy (Z - 1) additional sites, the total number of sites available for occupation is reduced to (n + ng)/Z. The number of vacant interstitial sites is given by: The total number of recognizable permutations of the atoms must include the recognizable, different configurations of the A and B atoms on the host lattice. Assuming that these arrangements are purely random, and are not affected by the presence of the interstitial species, the total number of recognizable permutations in the ternary alloy is given by: The configurational entropy is obtained by expanding, using Stirling's approximation, and collecting like items, as:

Jan 1, 1969

By N. J. Olson, G. W. Toop

A series of equations previously derived for calculating ternary thermodynamic properties using binary data has been applied to the problem of predicting ternary phase diagrams and quaternary excess free energy. The methods are considered to be rigorous for regular ternary and quaternary systerns and empirical for nonregular systems. The equations have been used to predict ternary phase boundaries in the Pb-Sn-Zn system at 926°K and the Ag-Pd-Cu system at 1000ºK. Calculated quaternary excess free-energy values are presented for the Pb-Sn-Cd-Bi system at 773°K. A method for predicting the location of ternary phase boundaries would be a useful supplement to experimental measurements in ternary systems. This has been recognized with the considerable work that has been done to find models to predict or extend thermodynamic properties and phase diagrams in binary and ternary systems1-18 for which direct experimental measurements are limited. With the access to highspeed digital computers and mechanical plotting devices, it is currently rather easy to compare mathematical models with experimental data. The regular-solution model is consistent with systems which exhibit negative heats of mixing, positive heats of mixing, and miscibility gaps, and therefore it is applicable to simple phase diagrams. The purpose of this paper is to illustrate the use of regular-solution equations to predict, empirically, phase equilibria in some types of nonregular ternary systems. Corresponding equations for regular quaternary systems are given and used to calculate empirical quaternary excess free-energy data. METHOD FOR PREDICTING THE LOCATION OF TERNARY PHASE BOUNDARIES USING BINARY DATA Meijerin1,6 has used the regular-solution model to calculate common tangent points to ternary free energy of mixing surfaces and hence to determine phase boundaries in ternary systems involving miscibility gaps. He used the following equation to calculate ternary excess free energy of mixing values: stants characteristic of the binary solutions, and Ni is the mole fraction of component i. An alternate expression which gives for regular solutions as a function of binary values of along composition paths with constant N1/N2, N2lN3, and N1/N3 may also be derived:15 ternary r xs 1 ?c-*n.Ti*.U*. This expression for is more useful for the empirical calculation of ternary excess free-energy values for nonregular systems because actual binary AFXS data may be used in the expression rather than attempting to find suitable constants for Eq. [I]. The results of this feature of Eq. [2] are illustrated in Table I where calculated excess free-energy values for the Ni-Mn-Fe system at 1232°K are compared with experimental data of Smith, Paxton, and McCabe.19 Although regular-solution equations have been shown to give calculated thermodynamic quantities which agree quite well with experiment for single-phase nonregular ternary systems,14,15 care should be exercised in the use of the equations to predict thermo-dynamic properties of multiphase ternary systems in which strong compound formation is suspected. This precaution is consistent with the simple regular-solution model which for negative values of ai_j will indicate a tendency toward compound formation but even for very large negative values of ai-jwill not give multiphase binary or ternary systems involving a distinct stable compound. Hence, calculated ternary free-energy data using Eq. [2] might be expected to vary between being rigorous and poor, in the following order, for ternary systems which are: a) regular solutions, b) nonregular single-phase liquids in which random mixing is nearly realized, c) nonregular single-phase solids, d) nonregular multiphase systems exhibiting miscibility gaps, e) nonregular multiphase systems with binary compounds but no ternary compounds, f) nonregular multiphase systems with highly stable binary and ternary compounds. The calculated data will be expected to be least accurate for the last two cases. The general method adopted in this paper involves two-dimensional plots of ternary activity curves. The principle used is that tie lines indicating two-phase equilibria join conjugate phases a and B for example, for which a1(a) = a1(B), a2(a) = a2(B), and a3(a) = a3(B). Tie lines may be determined by plotting the ternary activities of two components along an isoactivity line for the third component and the unique points where the above equalities hold may be found graphically.

Jan 1, 1970

By Samuel S. Arentz, Dorsey A. Lyon

Introduction % •................. 789 The Present Sources of Zinc ..:.......... 791 Zinc Ores.................. 791 Lead-Zinc Ores................. 793 Loss oF Zinc at the Mine.............. 793 Present Method oF Extracting Zinc From Ores....... 795 Class oF Ores Suited to Zinc Retort Smelting....... 795 Concentration Processes Used for Treating Zinc Ores .... 795 Hydro-Mechanical Processes............. 795 Electro-Mechanical Processes............. 796 Flotation Processes............... 797 Losses of Zinc in Lead and Copper Blast-Furnace Smelting .. 798 Possible Future Sources oF Zinc Supply.......... 800 The Problem oF the Metallurgist and the Present Status of New Processes................. 801 Introduction A great deal of attention has recently been given to the metallurgy of zinc, and much of that which has been said and written on this subject has been in the nature of a criticism. For instance, we are quite accustomed to hearing it said that the metallurgy of zinc has stood still, that it is antiquahed, out of date, etc. We are, however, inclined to agree with George C. Stone1 when he says that, although there have been no such spectacular and radical changes as were worked in the metallurgy of copper and iron by the introduction of converters, there has nevertheless been a decided and marked progress in the metallurgy of zinc, and especially during recent years. However, it must be admitted that, due to the fact that the chemistry of zinc is so different from that of the other metals, the retort process is the only process by which zinc is produced commercially; and, moreover, that losses which occur in the zinc industry— that is, in the mining, milling, and smelting of zinc ore—are very great, for it is stated2 that probably less than 50 per cent. of the zinc mined, even

Jan 1, 1915

By C. C. Whittier

CIVILIZATION'S PROGRESS, which has multiplied man's comforts, conveniences, a n d happiness, is based upon the extensive employment of natural minerals and sources of energy. Mineral resources are basic factors in modern economic development, machine industry, international trade and world power. A survey of mineral consumption shows that the United States leads the world in the production and consumption of energy materials, of metals, and of the large and diverse array of earth materials that fall in the nonmetallic mineral group. The use of nonrnetallic minerals exceeded both the metals and the fuels in the long period before the industrial age, but it is only in the last two decades that consumption of non- metals has kept pace with and approximated in value the output of metals. Although the data of production in the first half of the last century are meager and fragmentary, the record of the past fifty years-the period of most rapid growth-is available, and reveals an astounding growth.

Jan 1, 1933

By Walter Miller

ALTHOUGH confident of its ability to meet any demands which may be made, the petroleum refining industry is not complacent about the situation and realizes that the quantities of petroleum products to be furnished are so enormous and so far beyond what was previously estimated that the full co-operative effort of the industry must be exerted. Establishment by the President in May of the Office of Petroleum Coordinator for Defense with Secretary of the Interior Ickes at its head, plus the formation of the Petroleum Industry Council for Defense, in November, provide the channels for united endeavor within the industry and the means for gearing that endeavor within the industry and the means for gearing that endeavor in full harmony with the nation?s needs. Great strides have been made and a rapid understanding of the situation and the magnitude of the task is being attained by all concerned.

Jan 1, 1942

How Mining Engineers Will Fare in 1977 Mining Education- The State of the Discipline Coal Mining Technologists are a New Force in the Labor Pool Trained Manpower Provided by Mining Technology Programs Putting New Engineers to Work-A Management Perspective

Jan 1, 1977

P. H. ARGALL, Magdalena, N. Mex. (written discussion *).-The Chilean mill has generally been considered a fine-crushing machine and as such has had many advocates; it has also. had quite a number of denouncers; hence, the action of the Portland engineers in using the Chilean mill for the preparatory work usually accomplished in, rolls or rock breakers and adding a ball mill to do the fine grinding is novel, though of doubtful utility in the long run, even though a fair efficiency is obtained for the combination machines, as measured by Chilean mill practice. In order to follow the development of Chilean mill practice on Cripple Creek ores, I might say that two 6-ft., Chilean mills were placed in operation in Stratton's Independence mill in April, 1908, treating ore crushed by rolls to pass Y4 in. screen aperture. Screening was, however, found to be an unnecessary refinement, as was also the use of plows in the mills; both screening and plowing were abandoned before the Portland engineers finished the experiments in stamp milling upon which they were then engaged. Two additional 6-ft. Chilean mills were added in the spring of 1911, three of them giving the required 10,000 tons per month capacity, one being always in reserve. The Portland company began using Chilean mills in June, 1910, at its Victor mill, and the same company purchased the Stratton's Independence mill in June, 1915, and remodeled it; it is now known as the Independence mill. A description of Stratton's Independence milling practice, is given in the November, 191.1, issue of Mining Majazine (London). These Chilean mills were used as fine grinders and that they accomplished their purpose is shown by the screen analyses, in which 62 per cent. of the pulp passed 150-mesh screens. To make coarse crushers of these Chilean mills, the Portland engineers have increased the speed, substituted steel in various parts for cast iron, provided new and enlarged thrust bearings to take care of the centrifugal force incident to higher speed, and have, thereby, greatly increased the cost of the machines. They have also reduced the width of the tires and dies from 8 in., as used in the original mill, to 7 in., a reduction of 12 ½ per cent. in the crushing surfaces, to say nothing of the loss of abrasion or attrition incident to the larger surface. At the same time, they have apparently increased the weight of the rollers by using tires 5 7/8 in. thick as against tires varying between 3 and 4 in. on the original mills, thereby increasing

Jan 4, 1920

By Fitterer, G. R.

The impact of the work of Herty "et al" on modern liquid steel technology can only be evaluated by first setting the stage as it existed in 1926. It is important to briefly review not only the steel making process and viewpoints regarding methods of refining, but also to describe the tools which were available for research at the time. One must recall that only 15 years before the beginning of this program, the open hearth production exceeded that of the Bessemer in the United States. Many open hearths were still operating on producer gas (a very inefficient fuel), although some plants were converting to the use of natural gas and very few to oil. Continuous rolling of wide strip started this year. The Faraday Society in England held a World Conference on Physical Chemistry in Steel Making in 1925 and the contributions to this work created considerable interest throughout the world and it appeared that physical chemistry might convert the art of steel making into a science. These papers, however, attempted to solve the problems through the use of the older physical chemical concepts such as Nernst's numbers, etc. and considerable data were missing. In 1923, Lewis and Randall had published their book Thermodynanzicsl and this was later to establish and standardize the steps which are now accepted for the calculation of physico-chemical equations. At the time this research work was started, there were no small high frequency induction furnaces. Northrup had just invented his high frequency furnace and a few large units had been instilled in plants. The vacuum fusion method lor the determination of oxygen in steel was

Jan 1, 1957

By J. N. Maycock, P. W. M. Jacobs

Previous measurements of the thermoelectric power of ionic crystals are reviewed briefly. It is concluded that, while extensive measurerements are available on systems in which the electrode M has a cation in cornon with the sall MX, there is as yet little modern work on systems in which the metal electrode M' does not haue a calion in common with the salt. We haue now measured the thermoelectric power of- single cryslals of KC1 and of KC1 + SrCl2 between plati.nu?n electrodes over a much wider range of temperature than before. individual ionic heats of transport, which, while probably not very accurate, are of a reasonable order of magnitude, are obtained from this data on the basis of an assumption that charge carriers do not cross the electrode/salt interface. RELATIVELY little work has been done on thermal diffusion in ionic crystals. Reinhold and coworkers1-I measured the thermoelectric power and Soret effect in silver and cuprous salts and their mixed crystals. One electrode was kept at constant temperature and electromotive force was measured as a function of the temperature gradient. This is not a satisfactory technique if the results are to be compared with theory; rather should the electromotive force be measured for small temperature differences as a function of the mean temperature of the two electrodes. They used electrodes having the same cation as the salt. Patrick and Lawsons measured the thermoelectric power of AgBr and of AgBr containing 0.25 mole pct CdBr2 using silver electrodes and temperature gradients of 10°C in the temperature range 100° to 400°C. The results were analyzed using the Teltow9 values of the ratio of the mobility of the two types of charge carrier (cation vacancies and interstitials) found from conductance measurements and the wagnerlo estimate of the heterogeneous contribution to the thermopower, Ohet They obtained values of qi = 0.017 ev and q$ = -0.385 ev for the heats of transport of interstitial Ag ions and cation vacancies, respectively. Their data has been reanalyzed by Haga using the corrections to the Wagner formula for ehet given by Howard andLidiard; Haga found ev. Christy et a1.14 have measured the thermopower of AgBr containing 0.01 to 1.0 mole pct CdBr,. They analyzed their results in terms of the theory of Howard and Lidiard and found that excellent agreement with the theory was obtained if q5 + : + hF was set equal to 0.70 ev at 175°C and equal to 0.58 ev at 250°C. Since Teltow's value for hF, the enthalpy of formation of a Frenkel defect pair, is 1.27 ev, this means that qt + q: increases in magnitude from -0.57 ev at 175°C to -0.69 ev at 250°C. This result is in poor agreement with Patrick and Lawson's value of -0.37 ev for pure AgBr (for which the corrections to the Wagner estimate for ehet are very small). christy1' has also reported thermopower measurements for pure silver halides and for the systems he finds that qr + qt for AgBr increases in magnitude from about -0.55 ev at 150°C to about -1.1 ev at 400°C. The temperature dependence of the sum of the heats of transport in AgCl is very similar in magnitude. The sum qi + q cannot be decomposed into the individual interstitial and vacancy heats of transport without a knowledge of the entropy contribution from the change in the lattice vibrational frequencies around the interstitial and vacancy. Despite this it seems an inescapable conclusion from Christy's analysis that and -6 = Q Ag are quite strongly temperature-de pendent and that -q: is much greater in magnitude than the corresponding activation energy for vacancy migration, +0.37 ev. It remains a mystery as to why the data for pure AgBr are fitted so well by the assumption of temperature-independent heats of transport if association of impurity ions and vacancies is neglected.l The values for q$ and q: so obtained are also much more in line with those expected from a simple kinetic interpretation of the heats of transport due to wirtz.17 Christy and Hsueh have also measured the thermopower of CuCl between copper electrodes; 0 for pure CuCl is comparable with that for the silver halides but, owing to the limited solubility of divalent cation impurities it was not found possible to deduce values for the heats of transport. In contrast to these extensive measurements on cells of the type M MX 1 M, there have been relatively few attempts to measure the thermoelectric power of cells of the form M' 1 MX I M'. (We specifically exclude from discussion cells of this type in which the metal electrodes M' are in contact with gas containing a controlled partial pressure of either M or X,, since in these cells the electrochemical reactions are analogous to those of the first type.) The thermoelectric power of Pb12, PbC12, TlC1, TlBr, TlI, NaNO3, and KNO 3 between platinum electrodes was measured by Thie1e.l3 In discussing these measurements Holtan20 asserts that the thermopotential initially fluctuated wildly and even changed sign before approaching a steady value. A high degree of irreproducibility is also evident in the work of Nikitinskaya and Murin21 who first studied the thermopower of NaCl and KC1 between platinum electrodes. Much better reproduci-bility was achieved in our earlier measurements on KC1;22 these were, however, confined to a relatively narrow temperature range and one of the objects of the work reported in this paper was to extend the temperature range of the measurements of the thermoelectric power 8 of KC1. The only other published

Jan 1, 1967

By C. S. Barrett, O. R. Trautz

PREVIOUS investigations have shown that lithium is body-centered cubic from near its melting point to the temperature of liquid air1,2,3 Nevertheless there was an incentive to search again for a transformation at low temperatures: C. Zener4,5 has remarked that the low value of the elastic modulus (11 - C12)/2 of body-centered cubic metals and alloys implies a rapid increase in free energy with decreasing temperature, which would favor the occurrence of a transformation; also the shear movement to which this modulus applies is one that can transform a body-centered cubic structure into a slightly distorted face-centered cubic structure. It was confirmed that lithium does not transform spontaneously at liquid nitrogen temperature, but it was found that a transformation can be induced at this temperature by cold working the metal,6 and at slightly lower temperatures a different transformation occurs spontaneously. Transformations were also found in solid solutions of magnesium in lithium. THE NATURE OF THE TRANSFORMATIONS Before presenting a detailed treatment of the technique used and the specific data obtained, it would be well to give a brief survey of the general characteristics of the transformations. A new crystal structure begins to form spontaneously in a specimen when it is cooled below a critical temperature. In lithium the structure appears to be close-packed hexagonal; in the Li-Mg alloys most of the diffraction lines (but not all) are near those for hexagonal lithium. The transformation proceeds as the temperature is lowered and soon stops if the temperature is held constant or raised. The course of the transformation on cooling is indicated by the curve at the lower left of Fig I. This curve is drawn in stepped fashion because the transformation goes by discrete steps with audible clicks. Because of the similarity to the decomposition of austenite into martensite in steels, it seems appropriate to designate the beginning of the spontaneous transformation on cooling as the Ms point. On heating to room temperature after the low temperature treatment only the usual BCC structure is found. On heating, the low temperature modification begins to disappear at a temperature which will be designated as Ac. The transformation on heating is halted when the rise in temperature is halted. The temperature must be raised 40 to 50°C above Ac before the reversion is complete-an interval which is sensitive to the rate of heating and to the time of holding at temperatures above Ac. This behavior on heating thus has similarities also to the formation of martensite in the cooling of steels.

Jan 1, 1948

By C. S. Barrett, O. R. Trautz

Previous investigations have shown that lithium is body-centered cubic from near its melting point to the temperature of liquid air.1,2,3 Nevertheless there was an incentive to search again for a transformation at low temperatures: C. Zener4.5 has remarked that the low value of the elastic modulus (C11 — Cl2)/z of body-centered cubic metals and alloys implies a rapid increase in free energy with decreasing temperature, which would favor the occurrence of a transformation; also the shear movement to which this modulus applies is one that can transform a body-centered cubic structure into a slightly distorted face-centered cubic structure. It was confirmed that lithium does not transform spontaneously at liquid nitrogen temperature, but it was found that a transformation can be induced at this temperature by cold working the metal,6 and at slightly lower temperatures a different transformation occurs spontaneously. Transformations were also found in solid solutions of magnesium in lithium. The Nature of the Transformations Before presenting a detailed treatment of the technique used and the specific data obtained, it would be well to give a brief survey of the general characteristics of the transformations. A new crystal structure begins to form spontaneously in a specimen when it is cooled below a critical temperature. In lithium the structure appears to be close-packed hexagonal; in theLi-Mg alloys most of the diffraction lines (but not all) are near those for hexagonal lithium. The transformation proceeds as the temperature is lowered and soon stops if the temperature is held constant or raised. The course of the transformation on cooling is indicated by the curve at the lower left of Fig -I. This curve is drawn in stepped fashion because the transformation goes by discrete steps with audible clicks. Because of the similarity to the decomposition of austenite into martensite in steels, it seems appropriate to designate the beginning of the spontaneous transformation on cooling as the Ms point. On heating to room temperature after the low temperature treatment only the usual BCC structure is found. On heating, the low temperature modification begins to disappear at a temperature which will be designated as Ac. The transformation on heating is halted when the rise in temperature is halted. The temperature must be raised 40 to 50°C above Ac before the reversion is complete—an interval which is sensitive to the rate of heating and to the time of holding at temperatures above Ac. This behavior on heating thus has similarities also to the formation of martensite in the cooling of steels.

Jan 1, 1949

By Edward Saibel

The various theories that have been advanced to explain or predict the conditions under which a metal fractures may be divided into two categories: First, there are the macroscopic theories generally used in engineering practice. These are empirical in nature and limited in application. For example, the maximum normal stress criterion, which is quite satisfactory for a mild steel in simple tension at atmospheric pressure,' no longer suffices when this steel is pulled under hydrostatic pressure.2 In all of these empirical theories, the critical condition characteristic of the material and of the loading conditions must be obtained experimentally. Secondly, there are the theories based on interatomic forces,3'4 or on the energy required to form new surfaces.5,6 These have all dealt with the theoretical evaluation of the tensile stress necessary to bring about rupture in a purely brittle manner; that is, without plastic flow preceding fracture. All of these attempts have led to values of the tensile strength of crystals or of polycrystalline bodies that are 100 to 1000 times higher than observed values. On this account, it has been thought necessary by some investigators to conceive of a microcrack structure or distribution of flaws throughout the specimen such that the resulting stress concentrations provide the factor necessary to bring about agree- ment between calculation and experiment. It has been pointed out by several observers' that this point of view is highly unrealistic, in that the weakening effect of these flaws or microstructures must be very uniform from specimen to specimen, since the fracture stresses found for various specimens of the same material tested under similar conditions are so nearly constant. Furthermore, since calculations based on atomic forces or atomic energy are for purely brittle fracture, a condition probably never satisfied in tests, agreement is hardly to be expected. Thermodynamic Theory of Fürth In order to resolve this apparent discrepancy between the theoretical cohesive strengths and the observed fracture strengths, Fürth8 advanced a thermodynamic theory of the tensile strength of isotropic bodies based on work of Born relating to the melting of crystals. Assuming an isotropic material free from imperfections and flaws, behaving elastically up to the breaking point, and assuming a connection between rupture and the melting phenomenon, Fürth obtains an expression for the rupture stress a, in the form where Q is the melting energy per unit mass, p is the density, and is Poisson's ratio. Furth compares fracture stresses computed from Eq I with the fracture stresses of metals as given in the Landolt-Bernstein Tables (1927) and in the Hand-

Jan 1, 1947

By Edward Saibel

The various theories that have been advanced to explain or predict the conditions under which a metal fractures may be divided into two categories: First, there are the macroscopic theories generally used in engineering practice. These are empirical in nature and limited in application. For example, the maximum normal stress criterion, which is quite satisfactory for a mild steel in simple tension at atmospheric pressure,' no longer suffices when this steel is pulled under hydrostatic pressure.2 In all of these empirical theories, the critical condition characteristic of the material and of the loading conditions must be obtained experimentally. Secondly, there are the theories based on interatomic forces,3'4 or on the energy required to form new surfaces.5,6 These have all dealt with the theoretical evaluation of the tensile stress necessary to bring about rupture in a purely brittle manner; that is, without plastic flow preceding fracture. All of these attempts have led to values of the tensile strength of crystals or of polycrystalline bodies that are 100 to 1000 times higher than observed values. On this account, it has been thought necessary by some investigators to conceive of a microcrack structure or distribution of flaws throughout the specimen such that the resulting stress concentrations provide the factor necessary to bring about agree- ment between calculation and experiment. It has been pointed out by several observers' that this point of view is highly unrealistic, in that the weakening effect of these flaws or microstructures must be very uniform from specimen to specimen, since the fracture stresses found for various specimens of the same material tested under similar conditions are so nearly constant. Furthermore, since calculations based on atomic forces or atomic energy are for purely brittle fracture, a condition probably never satisfied in tests, agreement is hardly to be expected. Thermodynamic Theory of Fürth In order to resolve this apparent discrepancy between the theoretical cohesive strengths and the observed fracture strengths, Fürth8 advanced a thermodynamic theory of the tensile strength of isotropic bodies based on work of Born relating to the melting of crystals. Assuming an isotropic material free from imperfections and flaws, behaving elastically up to the breaking point, and assuming a connection between rupture and the melting phenomenon, Fürth obtains an expression for the rupture stress a, in the form where Q is the melting energy per unit mass, p is the density, and is Poisson's ratio. Furth compares fracture stresses computed from Eq I with the fracture stresses of metals as given in the Landolt-Bernstein Tables (1927) and in the Hand-

Jan 1, 1947