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By Carroll F. Hardy

The day by day loss of industrial plants to gas and oil is chiefly by default. The coal industry is not selling its superior economy, safety, and other advantages to its customers. THE position of the coal industry has been affected by a wide variety of developments in the production and use of energy. The tempo of development and change has been increasing and the end is not in sight. Legislation is currently being proposed for commercial use of atomic power, and the employment of atomic energy in significant quantity will probably occur about the same time as the decline in production of petroleum and natural gas. But these developments are in the future and have little immediate effect on utilization and marketing of coal. While no one should try to suppress or retard the development of a new and economical source of energy, both the coal and private utility industry should be allowed to question how the nuclear power is to be used, who is to use it, and who is going to pay for it. The taxpayers have a monopoly on fissionable material and the knowledge to employ it. Any commercial use must stem from this source. It is not hard to visualize either taxpayer-subsidized private utility atomic power plants on one hand and super TVA's on the other. In view of the gains of gas and oil in the home heating field, it is interesting to compare the 1940 and 1950 census reports on the kind of fuel used for heating in occupied dwelling units. Table I shows that whereas coal provided 77 pct of the fuel for central heating (furnaces and boilers) in 1940, it was down to 45.4 pct in 1950. However, only about 1 1½ million units were lost in this 10-year period. In the non-central heating category, which principally includes stoves, the percentage declined from 39.2 to 25.6, but the units declined about 2½ million in number. The big increase was in heating units designed to burn gas and oil. Use of wood for central heating declined about one-third. Data on amount of fuels used for residential heating are not available, but information is on hand for residential and comnlercial space heating, see Table 11. Commercial space heating includes office buildings, churches, schools. and similar structures. The annual use of bituminous coal in these two categories declined about 1 million tons in the 10-year period. Other forms of solid fuel showed greater losses, except wood, which remained the same. Domestic stokers reached their high point in 1948 with about 1,200,000 in use. At the end of 1951 there were approximately 1,116,790 stokers in use. Conversions to gas and oil have been from hand-fired heating plants in the ratio of about 7 to 1 compared to stokers. In other words, for every one stoker which has been converted to gas or oil, seven hand-fired units have been converted to gas or oil. A bare recital of these data would indicate that the coal industry is holding its own reasonably well. However, 93.4 pct of the new homes built in 1951 were heated by gas or oil. Oil-burning equipment was installed in 37.8 pct and gas equipment in 55.6 pct of the new homes. This indicates that the public prefers gas when it is available, and that oil is second choice, with all forms of solid fuel apparently used when it is unavoidable. It must be pointed out, however, that during the period of rapid expansion of gas pipelines gas has been sold for house heating at prices that are in some cases actually lower than coal prices, or very nearly on a par. Gas has been sold at wells at far below the comparable price for oil produced from the same wells, and far below its actual worth. This situation is being remedied at the present time by increases in gas prices at the wells. For example, the wellhead price of gas in Texas averaged 7.494 per Mcf in 1952. In 1949 it was 4.59c per Mcf. This increase in price is being reflected in pipeline gas prices, and in most of the markets served by the pipelines the tendency is to get it out of the bargain basement type of sales. The American Gas Association estimates that at the end of 1952 there were in the United States about 11 million customers for gas house-heating, and the Association expects additional gains each year until around 18 million homes will be heated by gas in 1975. By 1975 there should be 60 million dwelling units to be heated in the United States, if dwelling units increase at the same rate as the population. If the gas industry heats 18 million dwelling units by that time, this still leaves 42 million units to be heated by some other fuel. If oil is used to heat 18 million dwelling units in that same year, 24 million would of necessity be heated by coal, coke, wood, electricity, or another fuel. The total number of dwelling units using coal listed in the 1950 Census was 18,776,000, so it would appear that coal has a chance at least to stand still in the tonnage sold for domestic use. In the first quarter of 1953, 2044 domestic stokers

Jan 1, 1955

By Luther Wagoner

Having given in a former paper1 the results of assays of sea-water, bay-mud, dredgings from San Francisco bay, etc., and believing it might be interesting to extend the work to include some deep-sea dredgings, I procured from the Smithsonian Institution six samples taken by the U. S. steamer Albatross, and marked as follows: Depth in No. station. Locality. Latitude. Longitude. Fathoms. 1. 2103. Off Delaware bay. 38' 47' 20" N., 72o 37' W., 1,091. 2. 2265 to Between Chesapeake 35° 37' N., 74O to 75O W., 49 to 70. 2297. bay and Hatteras. 3. 2420. Off Chesapeake bay. 37' 03' 20" N., 74O 31' 40" W., 104. 4. 2528. East of Georges 41° 47' N., 65o 37' 30" W., 677. bank. 5. 2572. SE. of Georges bank. 40° 29' N., 66O 041 W., 1,769. 6. 2681 South of Nantucket. 39' 43' N., 70' 29' W., 990. The above samples were assayed by the cyanide-method, described in my former paper (p. 807), about 30 g. of sample being used, and the following results were obtained: Value in Milligrams Per Metric Ton. No. Station. Gold. Silver. 1. 2103. 145 1,014 2. 2265 to 2297. 44 304 3. 2420. 15 353 4. 2628. 267 1,963 5. 2572. 125 377 6. 2681. 66 414 No. 4, Station 2528, consisting of red clay and volcanic ash, mas re-assayed ; 35 g. was roasted at a low heat for one hour and weighed 34.05 g. after roasting; the color was changed to a deep brick-red; and when assayed by the cyanide-method

Jan 1, 1908

By F. H. Callaway, W. O. Keller

The various theories as to the well spacing-recovery relationship are reviewed in considerable detail and these theories analyzed in terms of their consistency with modern reservoir engineering concepts. It is concluded that the well spacing problem must be analyzed in terms of recovery efficiency and that a positive answer to the relation between well density and recovery efficiency is not available from direct comparisons of the production histories of wells and fields. The results of an engineering analysis designed to permit approximate calculation of recovery efficiencies as a function of well spacing in a depletion type reservoir from basic reservoir data is presented. Results of this type analysis indicate that the effect of well spacing on recovery efficiency in depletion type reservoirs can be expected to be very small. Limitations of this approach are pointed out, particularly with respect to its application in lenticular reservoirs. Testing techniques are outlined which should indicate whether or not a reservoir is continuous between wells and whether or not satisfactory drainage is being obtained with present spacings. A mass of data of this type indicates continuity to exist in most fields. INTRODUCTION The purpose of this paper is to review critically the engineering aspects of the well spacing problem, both from the standpoint of certain concepts and from the standpoint of reservoir mechanics. The well spacing problem is primarily an economic problem in which the optimum well density for a particular field is that density which will yield the greatest oil recovery consistent with justifiable development costs. The well spacing answer in terms of economic conditions, however, is extremely sensitive to the variation in recovery efficiency with well density. The variation in recovery efficiency with 'References given at end of paper. Manuscript received at the office of the Petroleum Branch October 2, 1949. Paper presented at the Petroleum Branch Meeting in San Antonio. Texas, October 5-7. 1949. well density is properly an engineering problem. Different opinions as to the correct answer to this engineering problem is the basis for most of the wide difference in opinion among various members of the industry as to optimum well spacing. This paper will be confined to the engineering problem of the relation between well density and ultimate oil recovery; economic considerations necessary for the evaluation of optimum well density for any particular field will not be discussed. The paper can be logically divided into two parts. The first part deals with a critical examination of the background and logic of the Cutler Rule and of similar studies by other authors and of related well spacing concepts. It is indicated that the variations in recoveries with well density* observed by Cutler and. others can be logically attributed to regional migration. Theoretical justification of the Cutler type relation wherein observed variations in recovery with well density in the same field is attributed to variations in recovery effiiency, in terms of energy relations, is refuted. The second part consists of a review of concepts of reservoir mechanics with regard to the well density-recovery relation. It is indicated that little variation of recovery efficiency with well density can be expected in a depletion type reservoir, unless lenticular conditions prevent communication between wells. The significance of field test data with regard to the existence or non-existence of lenticular conditions is pointed out. THE CUTLER RULE The first published article concerning the engineering aspects of the well spacing problem to receive wide attention was the work of W. W. Cutler' of the U. S. Bureau of Mines, published in 1924. In a study of decline curves from a large *The expression "well density" as utilized herein refers to the number of acres attributed to each well in a uniform well pattern, and is expressed in acres per well. The term "well spacing" Is utilized to denote the average distance between adjacent wells in a uniform well pattern. †Although the Cutler rule is treated critically in this discussion the authors intend no personal criticism of W. W. Cutler or of his hark The currently accepted concepts of reservoir mechanics were no": existent at the time of Cutler's work, as were even the moat basic tools (such as the bottom hole pressure bomb) for observing reservoir behavior.

Jan 1, 1950

By R. F. Mehl, M. Gensamer

Creep investigators have made extensive studies to determine the interrelation of stress, temperature and the tensile creep rates of metals. It has been suggested that at small stresses the secondary or constant creep rates obey a simple viscous law. Building upon this suggestion, departure from pure viscosity as stress increases may be expressed mathematically as a consequence of reversibly altered viscosity or "flowability" in the same sense that temperature change reversibly alters viscosity. From the index to alteration of viscosity, a value for the energy of secondary creep may be derived having the magnitude of the free energy of vaporized metal. The suggestion is made that application of stress alters the energy of secondary creep. Strain energy is argued to be but a minor factor in the energetics of secondary creep. A deformation mechanism involving the large energy associated with secondary creep implies a sort of solid self-diffusion process. Evidence indicates that creep strain above the recrystallization temperature takes place by crystallographically directed self-diffusion at grain boundaries and points of crystal defects. A self-diffusion theory of secondary creep is proposed, embracing the principles of the Dushman-Langmuir theory of solid diffusion. An equation is suggested whereby the rate of tensile creep may be related directly to the physical and structural character of the solid metal. Basis of Investigation Much of the investigation that has been given to the creep characteristics of metals and alloys has been directed toward studying the dependence of creep rate upon stress. Great interest has centered upon the approximately uniform rate of flow that has been demonstrated for numerous metals and alloys. At temperatures above the strain-hardening ranges of materials, this uniform rate frequently is attained after a relatively short period of initial rapid flow, and the period during which it persists determines for most practical purposes the useful life of the

Jan 1, 1938

By R. F. Mehl, M. Gensamer

Creep investigators have made extensive studies to determine the interrelation of stress, temperature and the tensile creep rates of metals. It has been suggested that at small stresses the secondary or constant creep rates obey a simple viscous law. Building upon this suggestion, departure from pure viscosity as stress increases may be expressed mathematically as a consequence of reversibly altered viscosity or "flowability" in the same sense that temperature change reversibly alters viscosity. From the index to alteration of viscosity, a value for the energy of secondary creep may be derived having the magnitude of the free energy of vaporized metal. The suggestion is made that application of stress alters the energy of secondary creep. Strain energy is argued to be but a minor factor in the energetics of secondary creep. A deformation mechanism involving the large energy associated with secondary creep implies a sort of solid self-diffusion process. Evidence indicates that creep strain above the recrystallization temperature takes place by crystallographically directed self-diffusion at grain boundaries and points of crystal defects. A self-diffusion theory of secondary creep is proposed, embracing the principles of the Dushman-Langmuir theory of solid diffusion. An equation is suggested whereby the rate of tensile creep may be related directly to the physical and structural character of the solid metal. Basis of Investigation Much of the investigation that has been given to the creep characteristics of metals and alloys has been directed toward studying the dependence of creep rate upon stress. Great interest has centered upon the approximately uniform rate of flow that has been demonstrated for numerous metals and alloys. At temperatures above the strain-hardening ranges of materials, this uniform rate frequently is attained after a relatively short period of initial rapid flow, and the period during which it persists determines for most practical purposes the useful life of the

Jan 1, 1938

By C. G. Dunn, J. L. Walter

Secondary recrystallization to the (110) [001] texture in high-purity silicon iron occurs if low-oxygen material is annealed in a nonoxidizing atmosphere. Any departure from these conditions results in a growth of (100) oriented grains. The nature of the matrix and secondary recrystallization structures and textures and the nature of grain boundary interactions during growth show that the low gas-metal interfacial energy of the (110) surfaces provides the driving force for growth of these grains. A type of grain growth, characterized by a driving force which derives from energy differences of {hkl} surfaces at the gas-metal interface, has been treated in recent papers.&apos;-7 Secondary recrystallization to the cube text!:: in high-purity silicon iron provides one example. The present paper also deals with a surface energy driving force but the texture that results by secondary recrystallization is not the cube texture; it is a texture in which the (110) plane is in the plane of rolling and the [001] direction is in the direction of rolling. The phenomenon described in this paper is different from the impurity (dispersed phase)-controlled secondary recrystallization process in which the (110) [001] oriented grains grow under the action of grain boundary driving forces.8-12 It is also different from tertiary recrystallization,2 which also produces the (110) [001] texture in high-purity silicon iron, since the matrix textures and grain sizes are different. Finally, it is unlike any other form of secondary recrystallization reported in the literature. The possibility of obtaining the (110) [001] texture in high-purity silicon iron became clear in a study of the effect of impurity atoms on the energy relationships of (100) and (110) surfaces. In this study Walter and Dunn6 observed the migration of (100)/(110) boundaries, i.e., boundaries between two grains, one of which has a (100) plane and the other a (110) plane, respectively, parallel to the plane of the sheet specimen. At 1200°C the (100)/(110) boundaries advanced into (100) grains in a vacuum anneal, then reversed their direction and migrated into (110) grains in a subsequent anneal in impure argon. Finally, the direction of migration reversed once again with (110) grains growing into (100) grains in a second vacuum anneal. These results were explained in terms of a change in concentration of oxygen atoms at the gas-metal interface during the anneals. Thus, oxygen atoms were added to the surface during the anneals in impure argon to the point where ?100, the specific surface energy of the (100) oriented grains, was lower than ?110, the surface energy of (110) oriented grains. In vacuum, however, the oxygen concentration at the surface was lowered to the point where ?110 < ?100. Concerning the possibility of secondary recrystallization in high-purity silicon iron with a low initial oxygen concentration, the observed effect of adsorbed oxygen atoms has indicated6 that a good vacuum anneal would favor the rapid growth of matrix grains with the (110) plane in the plane of the sheet much more than grains in the (100) orientation. The growth of only (110) oriented grains of course would depend upon y110 being less than ?hkl, where hkl refers to any plane different from (110). The present paper is concerned with the application of the above ideas to secondary recrystallization to the (110) [001] texture in high-purity silicon iron. The matrix and secondary recrystallization textures and structures are defined and discussed. Observations of growth of nuclei for secondary recrystallization and of boundary interactions are included to provide direct information on the surface energy relationships between (110) and other (hkl) surfaces. EXPERIMENTAL PROCEDURE As before, 2,4-6 high-purity iron and silicon were melted and cast in vacuum to provide an alloy containing 3 pct Si with less than 0.005 wt pct impurities. The oxygen content of the ingot was lower than in previous ingots, being approximately 3 ppm (by weight). The carbon content of this ingot may have been slightly higher than was found for previous ingots. The same rolling and annealing schedule used previously2 was followed in this study to obtain samples 0.012 in. (0.3 mm) thick. These samples were electropolished prior to annealing. After rolling and polishing, the oxygen content of the material was approximately 6 ppm; material used in the previous studies contained about twice this amount of oxygen.

Jan 1, 1961

By Charles Trotter

AN instrument has recently been developed for determining the inclination and azimuthal direction of boreholes. This instrument is known as the Tro-Pari Instrument and is the invention of C. Trotter and G. Pajari of Sudbury, Ontario. DESCRIPTION The instrument is characterized by a unit mounted in gimbals and provided with a clockwork mechanism to clamp a compass to indicate azimuthal direction and simultaneously to clamp the unit in its plumb position to indicate inclination (Fig I). By means of a timing ring suitably calibrated in 5-min divisions, the unit may be set to lock after a lapse of time sufficient to allow the placing of the instrument at the desired point in the drill hole where readings are to be taken. The maximum time lapse obtainable with the instrument designed for use in EX or AX size holes is 1 hr 30 min which is considered to be ample time to lower to the greatest depths that may be drilled with this size of equipment. Larger sizes could be developed for larger diameter holes such as BX and NX sizes or the larger oil-well sizes and a correspondingly greater time lapse could be provided for. Up to the present time only the EX-AX size has been built. OPERATION Assuming a borehole is to be surveyed at 1000-ft depth and assuming it will take 30 min to lower the instrument to this depth, the timing ring is rotated through seven divisions which represent a time lapse of 35 min (5-min leeway) and is then returned to its zero position. This operation imparts energy to a spring which drives the clockwork mechanism. Simultaneously the compass needle is freed to swing to its magnetic north-south position and the encased mechanism is freed to hang plumb within a semicircular portion of the frame which is graduated in degrees after the fashion of a protractor. This semicircular protractor portion has a V-shaped notch at each degree division of its inner periphery. The instrument, now in its free position, is inserted in a bronze container made to suit the size of hole to be surveyed (Fig 2). Soft rubber washers are provided within the container to prevent undue shock. The container is connected to the drill rods with three 5-ft lengths of brass or aluminum alloy rods separating it from the steel rods in order to prevent distortion of the magnetic field. The assembly is then lowered to the desired point where readings are to be taken and is allowed to remain at rest until a period of time has elapsed slightly in excess of the time for which the timing ring was set. In the example cited above, when the 35 min has elapsed the compass needle is locked in its north-south position and the protractor locking pin is extruded and locks in the V notch opposite its plumb position. The device may now be removed from the borehole and it will remain in this locked position in spite of jarring or shak-

Jan 1, 1947

By Charles Trotter

An instrument has recently been developed for determining the inclination and azimuthal direction of boreholes. This instrument is known as the Tro-Pari Instrument and is the invention of C. Trotter and G. Pajari of Sudbury, Ontario. Description The instrument is characterized by a unit mounted in gimbals and provided with a clockwork mechanism to clamp a compass to indicate azimuthal direction and simultaneously to clamp the unit in its plumb position to indicate inclination (Fig I). By means of a timing ring suitably calibrated in 5-min divisions, the unit may be set to lock after a lapse of time sufficient to allow the placing of the instrument at the desired point in the drill hole where readings are to be taken. The maximum time Lapse obtainable with the instrument designed for use in EX or AX size holes is I hr 30 min which is considered to be ample time to lower to the greatest depths that may be drilled with this size of equipment. Larger sizes could be developed for larger diameter holes such as BX and NX sizes or the larger oil-well sizes and a correspondingly greater time lapse could be provided for. Up to the present time only the EX-AX size has been built. Operation Assuming a borehole is to be surveyed at 1000-ft depth and assuming it will take 30 min to lower the instrument to this depth, the timing ring is rotated through seven divisions which represent a time lapse of 35 min (5-min leeway) and is then returned to its zero position. This operation imparts energy to a spring which drives the clockwork mechanism. Simultaneously the compass needle is freed to swing to its magnetic north-south position and the encased mechanism is freed to hang plumb within a semicircular portion of the frame which is graduated in degrees after the fashion of a protractor. This semicircular protractor portion has a V-shaped notch at each degree division of its inner periphery. The instrument, now in its free position, is inserted in a bronze container made to suit the size of hole to be surveyed (Fig 2). Soft rubber washers are provided within the container to prevent undue shock. The container is connected to the drill rods with three 5-ft lengths of brass or aluminum alloy rods separating it from the steel rods in order to prevent distortion of the magnetic field. The assembly is then lowered to the desired point where readings are to be taken and is allowed to remain at rest until a period of time has elapsed slightly in excess of the time for which the timing ring was set. In the example cited above, when the 35 min has elapsed the compass needle is locked in its north-south position and the protractor locking pin is extruded and locks in the V notch opposite its plumb position. The device may now be removed from the borehole and it will remain in this locked position in spite of jarring or shak-

Jan 1, 1949

By R. D. Longyear

[Some Problems Involved in the Interpretation of Diamond-drill-hole Sampling and Surve ing (paper by J. J. Collins, Mining Tech., Jan. 1946). ............... I Geologic Interpretation of Magnetic Exploration on the Mesabi Range, Minnesota (paper by R. H. B. Jones, Mining Tech., July 1946) ................... 2] DISCUSSION R. D. LONGYEAR.*-Mr. Collins is to be commended very highly for the brief summary he has made of the currently used methods of taking diamond-drill sludge samples and the principles involved in evaluating the results. This paper should stimulate further discussion and research on this vitally important problem. It is particularly imperative that geologists and engineers know when assay results on sludge recovery can be accepted quantitatively and when they must be considered only qualitatively. In most cases where the sludge recovery is less than 95 per cent or more than 125 per cent, it is safest to consider the assays as of qualitative value only. Certain cases, however, are known where a relatively small proportion of the sludge sampling will give a reasonably accurate measure of the value of the total sample. One such case is ore in which the valuable mineral is of approximately the same specific gravity as the waste mineral, such as chalcopyrite in a massive pyrite body. The essential point is to determine the degree of accuracy of sludge sampling in any given drilling project and to weigh the results accordingly. It should be emphasized, however, that sludge sampling can be made reliable in many localities where careless practice produces unreliable results. In many instances, it is desirable to empty the core barrel in the core shack instead of at the drill, so that the engineer can examine the core as it first comes from the core barrel. It should be pointed out, however, that the drill * E. J. Longyear Co., Minneapolis, Minnesota. runner should be permitted to study the core to guide his future drilling. It is hoped that with the return of more normal conditions after the war geologists, engineers, contractors, and manufacturers will be able to carry on more research along the lines of improved core-barrel design and drilling technique with the objective of increasing core recovery so as to eliminate as far as possible the necessity of relying upon sludge samples. H. M. ROBERTS.*-Whoever in the future will have to do with the search for ore bodies and their exploration will have frequent occasion to refer to the clear and comprehensive summary on diamond-drilling methods by John Collins. His review of the experience of the last 40 years in this technique is invaluable. As Dr. L. D. Ricketts wrote in 1932, "The principles on which an art is founded are usually few and necessarily basic in nature, but he who wishes to achieve the power to select his aides and give success to important undertakings that may be intrusted to him in the future must ordinarily undergo years of drudgery in order to gain the experience that will enable him to distinguish such fundamentals through the haze of reinforcing detail that clothes and tends to disguise them."[t] Ricketts went on to say that since the beginning of the century there has been much

Jan 1, 1946

By Elmer R. Kaiser

COMBUSTION of coal and transfer of heat from flames and gases to boiler surfaces continue to be of great interest to engineers here and abroad. Numerous investigations have been in progress to improve furnace and boiler performance and economy. The importance of better understanding of the processes and opportunities for improvement is apparent when it is remembered that heat from at least 500 million tons of coal a year the world over is being transferred to boiler water at efficiencies ranging mostly between 50 and 90 pct. Even slight gains in efficiency, economy, and labor saving become very significant when multiplied by the enormous quantity of fuel consumed. Also the competitive position of the large coal, oil, and gas industries in satisfying the fuel consumers is greatly affected by the achievements made through technical progress with each fuel. This paper is part of a continuing activity of Bituminous Coal Research, Inc., to extend the knowledge of coal utilization for steam generation and to seek promising directions for future research and development in cooperation with others. Particularly in the latter regard, numerous interviews were held during the last three years to seek the experience and advice of boiler and combustion-equipment manufacturers, electric-utility executives, and fuel engineers. A wealth of published information was also reviewed, which together with the interviews pointed to the advisability of further work on ash and sulphur control. For the present purpose a number of factors important to efficient heat liberation and recovery have been grouped as follows: 1—combustion, temperatures, and rates of heat liberation; 2—radiation, convection, and furnace and boiler configuration; 3—sponge ash, slag, and hard-bonded deposits; 4— low-temperature deposits and corrosion (cooling flue gas below dew point and air-pollution control); 5—the limitations of coal cleaning and boiler size and cost as related to fuel characteristics; 6—future possibilities and conclusions. The development of combustion apparatus for power boilers is progressing at a lively pace. There has been no letup in improvements in design of pulverized-coal-fired boilers, and there is a strong trend at present toward improving dry-bottom units. Spreader stokers with overfire jets and dust collectors as standard equipment are gaining favor. Less than 10 years in commercial use, cyclone burners are going into numerous installations here&apos; and abroad.&apos; Underfeed and traveling-grate stokers have long since been developed for heavy-duty operation, yet new developments in overfire jets and humidification of air blast have improved their performance. A water-cooled vibrating-grate stoker of German origin is being introduced into the United States and Canada." The primary objectives of an ideal coal combustion device are: capacity to burn the variety and sizes of coals likely to be economically available during the life of the unit; capacity to burn the coals automatically for a wide load range and rapid load fluctuations and to burn the coals completely to CO2, H2O, and SO2, which means without smoke and cinders, or carbon in the refuse; capacity to control and discharge all the ash in final granular form without ash adhesion to walls or tubes, and without flue dust; minimum furnace volume; minimum labor and maintenance; low initial and operating cost. Regardless of the method of burning, the gaseous products of coal combustion are N2, CO2, O2, H20, and SO?. By way of illustration, the coal analyses in Table I is assumed from an installation described by E. McCarthy.&apos; When coal is burned with 20 pct excess air (theoretical air, 9.23 lb per lb of coal), the quantities of combustion gas shown in Table II are produced. In addition, the gases carry particles of fly ash, unconsumed cinders, soot particles, and small but significant amounts of vaporized oxides and sulphates of sodium, potassium, lithium, phosghorous, iron, and other metals. In recent years, germanium, one of the rare metals found in coal, has been shown to oxidize and vaporize at combustion temperatures and to be concentrated by reconden-sation at lower temperatures." Pulverized coal and cyclone flames" have peak temperatures of 3000&apos; to 3500°F. Temperatures in fuel beds of large underfeed stokers reach maxima of 3000°F, sufficient to fuse almost any ash and to volatilize some of it. These peak temperatures are above the optimum necessary for rapid combustion, but they hasten heat transfer for ignition as well as boiler heat absorption. Furnace and gas temperatures increase with combustion air preheat. Low excess air has the same effect. Fine coal pulverization and highly turbulent combustion shorten the distance for fuel burnout, increase flame temperature, and speed up heat transfer. Rates of combustion of pulverized coal exceeding 200,000 Btu per cu ft per hr have been demonstrated in atmospheric gas-turbine combusters,

Jan 1, 1955

By B. R. Hollebone

The chemical action of molten anhydrous pyridinium chloride (pyridine hydrochloride) on oxy salts and ores of some Group IV and V metals are discussed-in particular zirconium, hafnium, niobium (columbium) , and tantalum. Laboratory-scale experiments are described whose results suggest that this reaction might provide a practicable means of converting ores of these metals to the anhydrous metal chlorides. Experimental results are given which provide some insight into the nature of the reactions and some of the compounds which could be present at intermediate stages. The treatment of ores of the more refractory metals is difficult and expensive and often demands the use of gaseous chlorine, hydrogen fluoride, or other reagents which are, if nothing else, expensive and dangerous to use. This situation is, of course, due to the strong metal-oxygen affinity resulting from the high charge and the small size of the metal ion which combine to produce such high lattice energy in the metal oxide as to defeat standard reduction methods. Thus, the characteristic of these metals which leads to one of their most important properties—corrosion resistance—is the main hurdle in obtaining the metal. Many common methods&apos; for treating ores of zirconium and niobium (columbium), for example, proceed as directly as possible to the preparation of anhydrous halides. These halides are purified by now standard processes of solvent extraction, fractional distillation, and so on. This paper reports on preliminary stages in the development of a method of treating these ores—particularly of niobium—so as to prepare the anhydrous, volatile halides by the use of chemical reagents which are much more easily handled than those used at present. CHEMICAL PRINCIPLES The solvent action of aminium halides has been referred to periodically in the literature over several decades. The chemistry of pyridinium chloride has been discussed particularly by Audreith2 and Starke.3 However, since this is not familiar chemistry in its nonaqueous setting, it is perhaps well to point out some general metallurgical principles and applications. One can use, as point of departure, the fact that HC1 dissolved in pyridine is an acid very much the same as aqueous HC1. It thus gives essentially all the reactions of the HC1 with which we are familiar. However, when the ratio of HC1:pyridine reaches 1:l (a ratio far higher than is possible with H2O) the solution becomes solid C5F5NHC1, pyridinium chloride.* Inter- estingly, the acidic properties of HC1 persist in this medium, although they are manifest only in the molten state of the compound. Some typical reactions of divalent metal compounds which we have carried out in our laboratories are the following: 2PyHCl + Zn — (ZnCl2) + H2 + 2Py 2PyHCl + MnO — (MnCl2) + H2O + 2Py 2PyHCl + CuS — (CuCl2) + H2S + 2Py 2PyHCl + CaCO3 — (CaCl2) + H2O + CO2 + 2Py In these equations, the parentheses indicate a solvated compound which in water would be predominantly a hydra ted cation but which in molten PyHCl will more likely be a complex chloro-anion of the type MC14-. Some important physical properties of pyridinium chloride (PyHCl) are given in Table I. One sees from the data in Table I that at the temperature of molten pyridinium chloride both water and pyridine will boil away. Thus the system will be kept anhydrous. For this reason the reaction 2NbCl5 + 5H2O— Nb2O5 + 10HC1 has no counterpart in molten PyHCl. Instead, the chloride is made even more stable by the formation of a hexachloro complex: Nb2O5 + 12PyHC1 — 2PyHNbC16 + 5H2O + 10Py One interesting property of these complexes is their thermal instability which for the case of niobium can be illustrated as PyHNbCl6 — PyHCl + NbCl5 With a view to possible use of this chemistry in ore treatment, we have attempted to dissolve Pyrochlore (essentially FeO - Nb2O5) and recover the NbC15 from it.

Jan 1, 1968

By J. Weertman

The paper of Gifkins and Snowden considers the interesting but difficult problem of determining the stress dependence of secondary (steady-state) creep at low stresses. These authors have concluded that at stresses below 250 psi (2 x 107 dynes per sq cm) the secondary creep rate of lead is proportional to the stress (viscous creep) and is not proportional to the stress raised to about a fifth power. The experimental data considered by them were obtained on tests conducted at room temperature and at 50°C. The lowest stress employed was 50 psi (3.5 X 106 dynes per sq cm). The authors pointed out the main difficulty in determining the stress dependence of creep at low stresses. The creep tests must be run for very long lengths of time. However they made no estimates of when an experimental creep rate determination must be rejected because it does not represent a true steady-state or minimum creep rate. In order to be certain that a creep curve is within the steady-state region, the total creep strain should be of the order of 0.1 to 0.2. For a creep test of a year&apos;s duration this requirement implies that a secondary creep rate smaller than about 10-3 per hr cannot be measured reliably. The corresponding creep rate for a 10-year test is 10-6 per hr. The creep rates of the tests that were considered by the authors to prove the existence of viscous creep were of the order of or less than 10-6 per hr. One can conclude reasonably that this data does not prove unambiguously that large strain steady-state creep rate of lead is proportional to the stress in the stress range of 50 to 250 psi (3.5 x 106 to 2 X 107 dynes per sq cm). Another technique can be used to obtain the stress dependence at low stress levels. The creep rate is a very sensitive function of temperature. The creep rate can be increased by very large amounts merely by increasing the temperature. We carried out steady-state creep tests on lead single crystals25 at temperatures up to 320°C. We were able to obtain creep rate data down to stresses as low as 35 psi (2.5 x 10&apos; dynes per sq cm). Our smallest creep rate was 8 x 10-5 per hr. Thus we obtained large strain, steady-state creep rates to even lower stresses than were considered by Gifkins and Snowden. No evidence was seen for viscous creep. The creep rate was proportional to the stress raised to about a 4.5 power down to the lowest stresses. Since there is no reason to believe that changing the temperature should change the stress dependence of steady-state creep, we feel that large strain viscous creep does not occur in the stress range quoted by the authors for lead single crystals or large-grain polycrystalline samples of lead. This conclusion does not imply that viscous creep may nat occur in a lower stress range or in the same stress range for fine grain material or at creep strains very much smaller than 0.1. Support by the U.S. Office of Naval Research is acknowledged. Authors&apos; Reply R. C. Gifkins and K. U. Snowden We thank Dr. Weertman for his discussion and although, as we hope to show, we do not agree with his reservations, we do concur in stressing the importance of ensuring that creep rates are reliably obtained. Dr. Weertman appears to be content to accept n = 1 for low stresses with fine-grained material but not for single crystals. We believe our results show that the former result cannot be accepted without also accepting the latter. We will also show that the probable errors in our minimum creep rates are insufficient to alter our conclusions, that the criterion proposed by Dr. Weertman is arbitrarily restrictive and his alternative experimental approach possibly invalid. 1) A principal result of our Fig. 1(a) is that n = 1 for polycrystalline specimens at room temperature and 50°C for stresses below -250 psi. There was evidence that crystal slip and grain boundary sliding contributed approximately equaily to the overall strain in this low-stress regime. This implies that either a) grain boundary sliding controls slip within the grains or b) both grain boundary sliding and crystal slip independently occur according to mechanisms which give n = 1. Alternative a does not seem acceptable, so we were forced to consider b. This led us to reexamine work on bicrystals by Strutt and Gifkins and plot curves Fig. l(b). Previously Strutt et al. (loc. cit.), had merged these points with others using the Zener-Holloman parameter and thus, we now believe, had been led to overlook the behavior where n = 1. Curves C and D in Fig. l(b) did appear to confirm the hypotheses that n = 1 for crystal slip at these low stresses and the sliding curve F was similarly of the expected form. It was comparatively easy to find a quantitative theory to account for n = 1 for sliding and the similarity of curves C and D to curve F (all obtained from the same set of specimens) led us to feel that the single-crystal curves were valid. 2) We believe the secondary creep rates for both the polycrystalline and single-crystal specimens to be in error by factors c2. In Fig. 6 creep curves for polycrystalline specimens of lead(1) and lead(II) are reproduced as curves a and b, respectively, and curve c is for a single crystal at 100 psi. It is clear that, although the attainment of secondary creep rate takes 2 years for a and 150 days for b, thereafter the curve is linear for periods of 7 and -1 year, respectively. The single crystal has a linear portion commencing after 20 and extending to 90 days. Creep extension was measured directly using a traveling microscope reading to 0.01 mm on gage lengths marked on the specimens; the gage lengths

Jan 1, 1968

By Harold Margolin

The Ti-Al system certainly merits the investigative attention it has been receiving and this latest contribution by Blackburn is therefore to be welcomed. The titanium-rich end of the phase diagram shown here, as well as the diagram by crossley,17 Clark et a1.,18 and Tsujimoto and Adachi,29 reveal no other intermediate phase than Ti3A1, although a previous work by Ence and Margolin20 had reported an additional intermediate phase. Since then, Buerger Precession pictures of single crystals of 10.5, 11.5, and 12.5 wt pct A1 were made at New York university21 and the extinctions were found to be typical of a D6h a Ti structure. Some superlat-tice spots and/or streaks suggesting the presence of an Mg3Cd structure, i.e., Ti3Al, were also found. Since these specimens had been quenched from the y region20 and had revealed a Ti, it was concludedz1 that y does not exist and the structures interpreted as m + y could not be so considered. The absence of normal two-phase behavior in these structures had been indicated in the paper. Accordingly, the two-phase region y + 6 becomes a + Ti3Al and there is some agreement between the results of Blackburn and of Ence and Margolin20 as to both shape and existence above 900°C of an a + Ti3Al field. Crossley 17 proposed that Ti3Al is a line compound which decomposes congruently at 900°C. It is difficult to discount entirely the fact that clear two-phase structures, varying in amount with position in the two-phase field, could be detected above 900°C by Ence and Margolin.20 Precipitation during quenching could not have been so regular and the twin-phase syndrome17 does not apply. The heat treatment and quenching technique was essentially the same as was used by Crossley, whereas Blackburn, who used a rapid quenching procedure, also showed a two-phase a + Ti3A1 field above 900°C. If the two-phase field exists above 900° C, it is easy to picture a two-phase field which could account for the data of Crossley below 900°C without invoking a line compound existence of Ti3A1. All that would be necessary would be an 0 + Ti3Al/Ti3Al boundary which curved sharply to higher aluminum contents below 900° C. It is clear that the controversy must be solved by techniques which obtain data at elevated temperatures without quenching. It is conceivable that the difference in width of the a + Ti3N fields reported by Blackburn and by Ence and Margolin is due to the longer annealing times used by the latter investigators. The criterion for establishment of equilibrium in our work20 was the

Jan 1, 1969

By J. J. Kanter

A. I. Blank.*-—Mr. Kanter has spoken of failures from causes other than creep itself in metals that are subjected to creep stresses. Would it be possible for the author to enlarge on this very important matter of "cataclysmic types of failures? " J. J. Kanter.—Of course, it is always a delicate matter to discuss specific failures. I would prefer to keep the present discussion on fundamentals and principles. H. L. Burghof.*—Mr. Kanter, I should like to ask what you consider the responsibility of the designer in avoiding stress concentrations that would lead to these types of failures? J. J. Kanter.—lt was my feeling in looking over the papers of this symposium that they were significantly lacking in consideration of what happens to the metals when strained under conditions that lead to rupture. Often creep tests are run that produce only a fractional percentage of the deformation, in several thousand hours. That kind of information gives the designer no assurance whatever that cracks will not result in his structure at points where stress concentrations, and therefore deformation concentrations, exist. I think anyone in this day and age who presents a paper on creep should incorporate with those studies a thorough investigation of creep rupture if it is expected to make an impression upon the design engineer.

Jan 1, 1945

By Philip D. Wilson

IT has been my privilege to read the article prepared by R. S. Dean entitled "Production of Alumina from Low-Grade Domestic Materials" which appears on another page of this issue. Dr. Dean should be congratulated on the preparation of such an erudite and scholarly dissertation on bauxite and on the work which the Bureau of Mines has been doing in connection with the development of processes to use low-grade domestic materials.

Jan 1, 1943

By F. B. Foley

IT is with an unusual degree of personal satisfaction that I find myself in a position to pay tribute to the memory of Henry Marion Howe. One could not have spent any length of time in the presence of Dr. Howe without profiting intellectually. I do not hesitate to say that my years of association with him were the most stimulating of all my years of metallurgical study. He always impressed one with his own eager search for knowledge. Never dependent on the written word alone he sought information from anyone whose opinion he valued. His ability to piece together bits of apparently conflicting data from various sources so as to build up a logical hypothesis was unique. A small slight man with the intellect of genius he would have gone to the top in any endeavor he undertook and it was fortunate for metallurgy that its study attracted him as it did. Howe was a modest man. I like to recall an incident which left a lasting impression with me. The lab- oratory in his home, "Green Peace," was in the basement and access was by way of stairs leading down from his secretary&apos;s room. In using these stairs my attention was attracted many times to an ordinary cardboard shoe box which reposed on the shelf above the landing. It was crudely labeled on its side in black ink "Vanity Box." My curiosity was aroused to the point that I finally asked his secretary what it was. With some amusement she took the box from its shelf on the stairway, opened it and showed me its contents—numerous letters, from the foremost men of science of every civilized country throughout the world, commending his "Metallography of Steel and Cast Iron." I recall that in reply to one who thought there was not enough of Howe&apos;s own researches in his book he wrote, "Primarily I am a writer, secondarily an investigator." Howe wrote to make his readers think. No one ever strove harder than he to be right but above all, whether his viewpoint proved ultimately to be right or wrong, he was always content if by his stand, he provoked a reader to take the next step along the path to greater knowledge. I doubt that he was ever afraid to be wrong for he was always secure in the thought that his effort was guided by a sincere search for the truth. One continually searching for truth is entitled to occasional excursions up the wrong alley. A glance backward to the metallurgical confusion of some thirty to forty years ago, or need one go back so far, provides convincing proof of what a host of companions one may have in a common acceptance of ideas which the future will prove to be wholly untenable. Well over a hundred years have passed since investigators have interested themselves in the effect of increasing the temperature of iron and steel on their mechanical properties. We are told by Charles Walrandl in "Industrial Annals" for June 11, 1822, that bend tests, conducted in a Russian steel works of Prince Demidoff, on steel bars "highly heated" and bent during cooling became brittle when bent at an iris blue color. He concluded, "That when steel is heated to a temperature between 473°F and 662°F the mettle was more brittle between these limits than at a much lower or at a much higher temperature." It was a curious bit of information recognized as true to this day and still not explained satisfactorily. In 1878 Charles Houston in Annales de Mines associated this brittleness with an increase in tensile strength at 572°F. When this relatively low temperature is exceeded it is recognized that steel becomes weaker as temperature is increased up to the melting point, where no strength of practical importance remains. It is easy to believe, in fact it goes without saying, that this weakening as the temperature of a metal is increased is the result of the motion of the atoms making up the metal, a motion which itself is evidence of the temperature increase. However, if we are considering iron or steel we find that this decrease in strength is not a steady one, for, besides the increase in strength just referred to, one comes to a temperature, the critical temperature, where results of tests indicate the metal to be extremely weak and then as temperature increases to become sensibly stronger again. This apparent anomaly was made the subject of the first Howe Memorial Lecture, delivered by Albert Sauveur in 1924. It may be of interest to review these findings of Sauveur. He used two methods of investigation. One involved the twisting of bars. The bars were heated in an

Jan 1, 1951

By R. A. Vandermeer, J. C. Ogle

The preferred crystallographic orientations (texture) developed in randomly oriented, poly crystalline niobium during rolling were studied by means of X-ray diflraction techniques. The evolution of texture at both the surface and center regions of the rolled strip was carefully examined as a function of increasing defamation throughout the range 43 to 99.5 pct reduction in thickness. Certain aspects of the center texture development in niobium are in agreement with the predictions of a theory by Dillamore and Roberts, but others cannot be explained by the theory in its present form. Above 87 pct reduction by rolling, a distinctly different texture appeared in the surface layers which was unlike the center texture. The present results are compared with previous results obtained from other bcc metals and alloys. RANDOMLY oriented, poly crystalline metal aggregates when plastically deformed to a sufficiently large extent develop preferred orientations or textures. In a recent review article, Dillamore and Roberts1 pointed out that the nature of the developed texture may be influenced by a large number of variables. These include both material variables such as crystal structure and composition and treatment variables such as stress system, amount of deformation, deformation temperature, strain rate, prior thermal-mechanical history, and so forth. From a practical point of view, the control of preferred orientation may often be important for the successful fabrication of metals into usable components. During the past few decades many experiments have been devoted to the study of deformation textures. This work, however, has been confined in large part to metals and alloys that have an fcc crystal lattice. By comparison, bcc metals and alloys have received much less attention, and consequently our understanding of preferred orientations in these materials is only shallow. This state of affairs worsens when it is realized that almost all of our present howledge about this class of materials derives from studies on irons and steels.&apos; The bcc refractory metals, which are relative newcomers to the industrial world, have, on the other hand, been given at best only passing glances in the area of texture development. Our understanding of the evolution of preferred orientations in bcc metals can only remain fairly limited until systematic studies of metals and alloys other than the irons and steels have been carried out and the influence of the many variables has been determined. To that end a program was initiated to investigate in detail texture development in niobium. The present paper reports some of the results of this study. Textures were determined at both the center and surface of strips rolled variously to as much as 99.5 pct reduction in thickness at subzero temperatures. Emphasis in this paper is on texture description and on texture evolution during rolling to progressively heavier deformation. EXPERIMENTAL PROCEDURE The niobium was purchased from the Wah Chang Corp. as a 3-in.-diam electron-beam-melted billet. Chemical analysis indicated the impurities to be less than 300 ppm Ta, 40 ppm C, 10 ppm H, 170 ppm 0, and 110 ppm N. All other impurities were below the limits of detection by spectrochemical analysis. This large-grained billet was fabricated into specimen stock so that a fine-grained randomly oriented grain structure resulted. This was accomplished in three deformation steps alternated with recrystalli-zation anneals of 1 hr at 1200°C in a vacuum of low 10"6 Torr range after each deformation step. The first step was to alternately compress the billet 10 to 20 pct in each of three orthogonal directions. The second step was to compress in only two directions 90 deg apart to produce a 2-in.-sq bar. The final step was to roll this bar 50 pct to give a 1-in. by 2-in. cross section. After the final anneal, metallo-graphic examination showed the material to have an average grain size equivalent to ASTM No. 5 at 100 times (i.e., 0.065 in. diam). Specimens cut from the center and edges of this bar gave no indication of detectable preferred orientation when examined by X-ray diffraction. Samples 1.5 in. long, either 0.625 or 0.750 in. wide, and approximately 0.400 in. thick were machined from this fabricated ingot. The surfaces corresponding to the rolling planes were ground so as to be parallel. The samples were chemically polished in a solution of 60 pct nitric acid and 40 pct hydrofluoric acid (48 pct solution) prior to rolling to remove any cold work introduced in the machining operations. Rolling was accomplished with a 2-high hand-operated laboratory rolling mill that had 2.72-in.-diam rolls. Prior to operation, the rolls were polished with 600 grit paper, cleaned with acetone, and then soaked in a container of liquid nitrogen for several hours. The samples were also soaked in liquid nitrogen prior to rolling and were recooled between each pass. While some slight heating of the samples occurred during rolling, this procedure maintained the sample temperature well below 0°C at all times. The samples were rolled unidirectionally, and the rolling plane surfaces were not inverted during any phase of the operation. The draft per pass averaged between 0.010 to 0.012 in. After 96 or 97 pct reduction the draft was reduced to 0.001 to 0.002 in. per pass. Samples were rolled to various reductions in thickness between 43 and 99.5 pct.

Jan 1, 1969

BEING at the crossroads, metaphorically speaking, seldom has the advantages of the literal sense of the words. One seldom has precise knowledge of the existence of the metaphorical crossroads or forks in the road of life. A case in point is the Committee on Education of the Engineers&apos; Council for Professional Development, which for twenty years has been accrediting the engineering curricula in the educational institutions of the United States. The committee is now at odds with itself and with the National Council of State Boards of Engineering Examiners over the accrediting of courses which in the opinion of many engineers are not strictly speaking engineering curricula at all. Such courses include: fire protection engineering, crystal engineering, nuclear engineering, and geological engineering. The crossroads might be placed arbitrarily somewhere between 1936 and 1938 when the committee first started accrediting curricula and included the first course in industrial engineering. Purists might argue that the committee first wandered from the straight and narrow when it recognized subdivision of engineering into the major branches of mining, metallurgical, civil, mechanical, electrical, and chemical engineering. Accrediting is certainly an important function because it provides a standard for engineering education and it should be done on a national basis by an unbiased group like the Education Committee of ECPD. Students, educational institutions, and industry derive great benefit from proper standards. The autonomous State Boards of Engineering Examiners have long accepted ECPD accreditation as evidence of the required academic training of engineers aspiring to licensing. But the State Boards today question the wisdom of applying the name engineer to graduates of some of the so-called fringe curricula. The Education Committee, having gone so far in accrediting some of them, has numerous applications pending for accreditation of similar curricula and even new courses never before accredited. Arguments against recognizing highly specialized engineering curricula are numerous. The Salary Stabilization Board has disallowed industrial engineering from classification as engineering for its purposes. A graduate of a specialized course in geological engineering at a school in the Southwest slanted heavily for practice in the petroleum industry might not be interchangeable with a graduate of a similarly designated curricula at one of the institutions in the North Central states where the emphasis might be on metallic. mineral deposits. Industry in general should not expect the universities to supply a degree in each of the specialized engineering classifications it might set up for purposes of salary or job designation. Having gone so far, it is easy to understand the difficulty of the Education Committee. ECPD might well call a moratorium for the purpose of taking stock of its position. If the present trend is allowed to continue, it is apparent that an engineering institution could be subdivided into a multiplicity of departments teaching specialized curricula resulting in a subordination of the basic concepts of engineering. Although the parallel of the medical profession is trite, it should be pointed out that degrees in medicine are not labelled by the numerous specialities practiced by doctors. For practical purposes the ECPD would do well to accept the fact that the crossroads have been overreached "and protect the engineering profession by coming up with minimum standards for an engineering curriculum.

Jan 1, 1952

By W. G. Lidman, H. J. Hamjian

&apos; I HE fabrication of many materials from powders involves a sintering process. A mass of powder will sinter because of the excess free energy over the same mass in the densified state caused by the higher total surface area of the powder. An understanding of the kinetics and mechanism of sintering should assist in improving the properties of such materials. The present investigation conducted at the NACA Lewis laboratory deals with the sintering of chromium carbide. Dry sintering (sintering at a temperature below the melting point) was divided into two stages by Shaler:&apos; the first stage, during which the particles preserve much of their original shape and the voids are interconnected, and the second stage, during which densification occurs and the pores are isolated. The mechanism of forming interfaces between particles, or welding together of particles, has been investigated by Kuczynski2 and may be described by any one or a combination of the following mechanisms: viscous flow, evaporation and condensation, volume diffusion, or surface diffusion. The mechanism by which pores are closed or eliminated (densification) during sintering, is of interest. Grain growth observed during sintering may be attributed to the variation in the surface energies of individual grains, causing some grains to grow at the expense of others. Grain boundary migration occurs presumably by a diffusion process, therefore the rate of grain growth would be expected to increase exponentially with increasing time and temperature. Thus, for practical sintering times of less than 1 hr, a certain minimum temperature may exist at which major structural and property changes will occur. Densification and kinetics of grain growth during sintering under pressure of chromium carbide were investigated to provide additional information which will aid in describing more accurately the sintering process and the mechanisms involved. This material was selected for this study because of the current interest in high strength, oxidation resistant refractory materials, such as carbides, which are sintered to produce solid, dense materials from powders. Sintering under pressure is a process where the heat and pressure are applied to the compact simultaneously, specimens for this work were prepared by sintering under pressure at different temperatures and for various time periods. Experimental Procedure Preparation of Specimens: Chemical analysis of the commercial chromium carbide used in this investigation was as follows: Cr 86.19 pct, C 12.14 pct, and Fe 0.2 pct. X-ray diffraction powder patterns gave characteristic diffraction lines of Cr3C2 crystal structure. Powder particle size was determined microscopically and the average initial particle size was 6 microns with 85 pct between 2 and 10 microns. Specimens sintered under pressure were formed in graphite dies3 heated by induction. Sintering temperatures were measured with an optical pyrometer by sighting into a 3/8-in. hole drilled 1 in. deep at the midsection of the graphite die. A load of approximately 1 ton per sq in. was applied to the powder. The die assembly was heated in 20 min to the highest temperature (2500°F&apos;) at which no increase in grain size could be observed, and less than 2.5 min were required to heat from this temperature to the maximum temperature (3000°F). Sintering temperatures and times for the specimens of this investigation are indicated in Table I. Analysis of Specimens: Specimens polished with diamond abrasives were etched to reveal the grain boundaries with a 1:1 mixture of 20 pct potassium hydroxide and 20 pct potassium ferricyanide heated to 160°F. Representative areas of each sample were photographed at 1000 diameters. The largest diameters of all well-defined grains were measured, but only the measurements of 15 of the largest grains were averaged in order to determine an index of grain size on the assumption that they were among the first to begin growth. Densities were determined from differential weighing of the samples in air and water. The reported density values are considered correct within ±0.01 g per milliliter. Results and Discussion Metal compacts have exhibited grain growth when sintered at temperatures about two-thirds of the absolute temperature of their melting point.&apos; Grain growth also occurs during the sintering of chromium carbide and is illustrated by the micrographs shown in Fig. 1. These micrographs were prepared from specimens sintered for 90 min at temperatures ranging from 1371°C (2500°F) to 1648°C (3000°F). Average grain size and density measurements of specimens investigated are presented in Table I. The relationship between grain size and sintering tem-

Jan 1, 1954

By E. F. Poncelet

Forty years ago A. A. Griffith developed a theory explaining why brittle materials displayed such low tensile strengths.&apos; He based his views on two points. First, he found himself compelled to assume that all brittle materials are replete with flaws, cracks, and other defects that act, although quite invisible, as large stress raisers. Second, he applied the "theorem of minimum potential energy," which says that the total potential energy of a system must pass from the unbroken to the broken condition by a process involving a continuous decrease in potential energy. By this means he satisfactorily accounted for the noted low strength of such solids and also for the wide spread obtained in experimental measurement of these strengths. So successful has the theory been that it is favored by some to this day. Unfortunately this theory is of limited use beyond the explanation of these two noted phenomena and it is keenly felt that a better theoretical insight into the physics of the fracturing process is needed as the volume of experimental evidence accumulates. The author proposes in the following to build on the fundamentally sound concepts of Griffith and, with the help of increased theoretical knowledge over that available to Griffith, develop a mechanism for frac-ture which will provide far greater understanding of the experimental evidence accumulated to date than is possible from the original Griffith idea. THE GRlFFlTH THEORY Very little progress indeed can be made without accepting the first postulate of Griffith which supposes all brittle solids to be full of microcracks. It would be difficult indeed to find a better mechanism for the small strength of such brittle materials, in conjunction with the fact that the energy that must be expended for comminution is by no means small. The postulate of the existence of the microcracks permits the breakup of the various bonds a few at a time by concentrating the stress at the tip of the progressing crack, while the total energy expended is the same as if they all had been ruptured simultaneously. The only flaw in the argument is that no reasonable explanation has been proposed to account for the genesis of such cracks. Indeed their very presence is in violation of the Griffith second postulate, the potential energy theorem. This theorem is straightforward for isothermal processes, and, in spite of Griffith, there is some doubt that treating the problem isothermally is legitimate. The surface energy of bodies is a free energy, not a potential energy as stated by Griffith, and the production of new surface free energies is not necessarily an isothermal process. There is ample evidence to the contrary. Generally speaking, if heating a body increases its surface area, then, by virtue of Le Chatelier&apos;s principle, any increase of that area by other means will tend to lower its surface temperature. Lord Kelvin calculated the actual cooling that resulted in drawing out a film of liquid.2 R. A. Houston calculated the surface cooling that resulted in stretching a metal wire.3 These calculations were made by applying the Carnot cycle to the process and evaluating the thermodynamics thereof. IRREVERSIBILITY OF THE FRACTURING PROCESS While Griffith was very careful not to say so, the impression gained from studying his papers is that he considered the fracturing process as reversible, that is, a succession of quasi-equilibrium states. There is ample evidence that it is not. The indication that the new surfaces produced by the propagation of a crack are cooler than the original body points to an irreversible heat flow from the interior to the new surfaces to equalize the temperatures. If the process be reversible, any crack accidentally formed should immediately close up as, in the absence of any strain energy, the potential energy would thereby be lowered. The fact that they do not, constitutes a paradox. Such paradoxes are nothing new where certain phenomena that propagate from minuscule nuclei are assumed to be reversible. Such is, for instance, the condensation of a pure saturated vapor that is suddenly chilled by adiabatic expansion. At the beginning the tiny droplets that are formed should be only a few angstroms in size, but the vapor pressure at such droplets is so high that they should evaporate at once. A similar situation arises if a saturated pure solution becomes super-saturated upon cooling; the first tiny crystal nuclei should dissolve as fast as

Jan 1, 1964