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By J. Campbell

Long freezing range casting alloys are particularly susceptible to a type of porosity which is observed to form in layers parallel to the supposed position of the isotherms in the solidifying casting. Under favorable conditions (which appear to be typified by low-temperature gradients in the casting giving rise to a wide and more or less uniform pasty zone, and which arise from several factors, particularly: a) wide freezing range alloy, b) high thermal conductivity of metal, c) low thermal conductivity of mold, and d) high mold temperature3) layer porosity has been observed in many different casting alloys: copper,' aluminum, magnesium,' steels, and high-temperature alloys.3 Baker4,5 and later cibula6 argue that layer porosity occurs because of thermal contraction, in a manner analogous to hot tearing. In outline, the theory consists of the establishment of a coherent dendrite network by the impinging of dendrite tips. Subsequent shrinkage imposes tensile stresses on the network which tears perpendicularly to the stress, i.e., parallel to the isotherms. If these tears are not filled by the inflow of residual liquid then layers of porosity result. Baker7 attempted to test whether the porosity was the result of thermal contraction by casting test pieces in a mold designed to accentuate hot tearing. However, no significant increase in porosity was observed. This negative result of Baker's critical experiment appears to be substantiated by numerous observations, particularly the experiments by Lagowski and Meier8 on Mg-Zn alloys covering the range of zinc contents up to 30 pct Zn. These clearly reveal that the maxima for the incidence of hot tearing and layer porosity are well-separated, occurring at 1 and 6 pct Zn, respectively. Furthermore, the thermal contraction maximum occurred at 1 pct Zn, indicating that hot tearing is associated with contraction in the solid state, and not with porosity. These observations are further substantiated by the elementary consideration that the thermal contraction of the casting is likely to produce (if anything, since the temperature difference across casting of high thermal conductivity, such as aluminum and copper, is likely to be negligible) a compressive stress on the

Jan 1, 1969

By E. Keller

Some years ago the writer's attention was called to the fact that rolling-mill scales from auriferous copper do not have the gold content proportional to the gold contained in the copper from which they are derived.' So, later, he made a few simple experiments, which are described herewith. In order to test the gold movement on the changing surface of a copper plate under the influence of oxidation, plates 6 in. by 8 in. by 1 in. (15.2 cm. by 20.3 cm. by 2.5 cm.) of converter copper, refined, of 99.29 per cent. purity, and leaded copper with a content of 95.65 per cent, copper, were obtained. Ten cuts were made through the thickness of the plates along the longitudinal center and the silver and gold content ascertained in each of the 10 samples in both plates, as shown in the accompanying illustration. The assay results, recorded in Tables 1 and 2, show that the gold distribution is relatively uniform in both plates, while silver has greater variations, especially in the leaded plate. The plates subjected to oxidation were placed in a red-hot muffle for about 2 hr., two small scarifiers being used as supports. Arranged alongside each other, they nearly filled the width of the muffle, and so were practically under equal conditions of heat and draft. The accurate observance of the time was not possible, however, because of other work, but the time of the exposure of each plate in a pair was identical. At the end of each period, each plate was plunged into water and completely freed of scale, which was carefully collected, dried, weighed, and analyzed. Samples of the plates had also been taken of the molten metal and duly analyzed. Table 3 contains the analytical data for the two plates and their several sheets, or layers, of oxide scales. These figures show that in the oxidations of the converter copper the silver is fairly uniform, while the gold is highly irregular and especially low in the first layer. In the oxidations of the leaded copper plate, the silver and gold contents are variable; however, this irregularity is due to two different causes. The

Jan 1, 1919

By D. A. Bailey, F. L. Kadey

During recent years, expanded perlite has found extensive use in a wide variety of commercial applications. Specifications for a range of uses call for aggregates having different physical properties and requiring various types of processing. The mitre scopic examination of expanded aggregates in specially prepared thin sections has yielded important information regarding internal structure and can be a useful aid in evaluation of the product. Perlite is an acid volcanic glass containing from 2 to 5 pct combined water. When crushed and rapidly raised to a temperature of 1500° to 2100°F, the volatilization of the combined water, coincident with softening of the siliceous glass, causes the particles to expand or pop. Expansion of perlite to densities as low as 1-1/2 lb per cu ft has been achieved, although the normal range is from about 2.5 to 10 lb per cu ft. Low-density materials of this nature have found application in cryogenic insula- tions, insulating tile and board, plaster and lightweight concrete, soil conditioners, filter aids after comminution, and a host of other uses. The expansion of perlite may be controlled by a number of variables. Some of these are ore milling, furnace design, expanding temperature, use of preheating techniques, screen size distribution, and feed rate of the crude. For the specific intended uses, the art of perlite expanding has developed to the point that much is known about the effect of these variables on the end product. The requirements, however, for an aggregate to be used in plaster are different from those for an expanded perlite to be used in lightweight concrete or for cryogenics. In the study of perlite, many practical questions remain unanswered. One of the most important is, "why do some perlites make hard aggregates while others cannot resist crushing or compaction?" The usual tests and methods for evaluation of nonmetallic substances have been tried and have contributed their share to our knowledge. But chemical analyses, compaction resistance tests, screen analysis, etc., will reveal only a limited amount of information. The answers to these complex questions may well be found in an examination of the intemal structure of the expanded particle. Such questions and the ex-

Jan 1, 1962

By G. C. Gambs

The electric utility industry is the largest customer of the coal industry and consumes nearly 50% of the present coal production in the United States. The byproduct of the burning of coal in utilities is ash in several forms including fly ash, bottom ash and bottom slag. At present, very little of the coal ash produced is being used and must be disposed of as waste. The coal industry should look upon this waste material as a valuable by-product which, if it can be sold for $2 to $4 per ton, will have the net effect of reducing the cost of coal to the utility by 1¢ to 2¢ per million Btu. There are many ways to use coal ash and thus benefit both the coal industry and the electric utility industry by reducing the cost of coal as burned. The solutions to the problems are obvious and all we have to do is apply them. The electric utility industry is the largest customer of the United States coal industry, consuming nearly 50% of present coal production. By 1980, the electric utilities are expected to burn over 500 million tpy of coal or 75% of total coal production. When coal is burned in electric utility plants, ash is produced in one of several forms. These include fly ash, bottom ash and bottom slag. At the present time, approximately 20 million tons of these ashes are produced and must be disposed of by the utilities at a cost of 50¢ to $2 per ton. In 15 years, more than double this quantity will be produced. Only a small quantity of this ash is put to any practical use. Much remains to be done about expanding uses for fly ash and bottom slag. It is well known that fly ash, when used to replace a portion of the cement in a concrete mix, will produce highest quality concrete. The Corps of Engineers and the Bureau of Reclamation have constructed dams and other concrete structures for years with fly ash as a partial replacement for cement. However, many construction firms do not use it. This can become an opportunity for the coal industry to reduce the cost of coal delivered to utilities. Any fly ash, or other ash or slag, which is sold by the utilities, reduces the cost of coal burned by the utility. As much as 1¢ to 2¢ per million Btu could be taken from the fuel cost for each ton of ash sold which otherwise must be disposed of at a cost.

Jan 1, 1967

By D. McLean

For many pu@oses uniform strength is desired over a long temperature range, coupled to a band of softness at the hot end for easy shaping. Various types of material fulfill such a requirement to different degrees, depending on the regularity of their atomic structure. In long-chain polymers and vitreous glasses the irregular structure leads to a steep temperature dependence of deformation resistance and the temperature band between the hard and brittle condition and the soft condition is only about 100 C. In crystals and especially metals the atomically regular structure leads to a much smaller sensitivity over a wide temperature band, thus approaching the ideal behavim. The reason for this insensitivity is that the regular crystalline structure deforms by the movement of dislocations and the elastic interactions of dislocations in- PLASTICS, GLASSES, AND CRYSTALS The ease or otherwise of deformation varies with temperature much more in some substances than in others. This is an important matter when service over a wide temperature range is needed, especially volve energies of several hundred electron volts compared with which the energy of thermal agitation is insignificant. However, temperature affects a metal's defmmation resistance through its influence on the annealing, m coarsening, of the three-dimensional dislocation network. This coarsening is a phenomenon very similar to grain growth and ideas about grain growth can be applied to it. Taking into account also the temperature dependence of the glide resistance from alloying additions, a reasonable account can be given of the overall effect of temperature on deformation strength and of stress and grain size on deformation rake. Special structures me described. some arising from these ideas and as yet untried, which may benefit metals and polymers but not ni-treous glasses. when in addition a degree of softness suitable for shaping is required at some stage. It would be nice if one could write on this subject in as much detail about plastics, glasses, and so forth, as about metals, but there has been far more study of this matter in metals than in other substances, which is one reason why most of this paper concerns metals. However, in Fig. 1 there are shown the deformation strengths of several nonmetallic substances as a function of temperature. In many tests the attempt at deformation caused breakage and the graph lines are then drawn dashed. Long-chain plastics, a glass, and a crystalline substance are included in Fig. 1. The notable feature of all of them is the sensitivity of the

Jan 1, 1969

By M. Cohen, B. L. Averbach

Many hardened steels contain significant quantities of retained austenite even in cases where the carbon and alloy contents are low. In fact austenite has been detected in plain carbon steels containing as little as 0.50 pct carbon.1 Although the austenite may not be visible metallographically it causes definite dilatometric and magnetic effects during subsequent tempering or sub-atmospheric coo1ing.l,2,3 Therefore if the reactions which hardened steels undergo during later treatment are to be understood in quantitative fashion it is most essential to have some kind of absolute analysis for the austenite content in hardened steels. Once this analysis has been made, the austenite transformations can be followed precisely by observing such sensitive phenomena as changes in length or in magnetization but the latter techniques can only determine differences in the amount of retained austenite and usually an independent method must be found to put these differences on an absolute basis. In certain instances the microscope can be used advantageously to determine the percentage of retained austenite. The quenched sample is tempered to "darken" the martensite with minimum decomposition of the coexisting austenite, and then is polished and etched in the usual fashion. If the austenite is clearly distinguishable from the tempered martensite and other possible constituents its volume percentage can be measured quantitatively by point counting or lineal analysis.4 Such microscopic methods, however, depend on the etch being sufficiently discriminatory. In fairly coarse structures, if the austenite content is greater than 10-15 pct, there is probably little smearing of the etch, and point counting or lineal analysis seems to be quite accurate. On the other hand if the structure is difficult to resolve, as in commercially treated fine-grained . steels which contain less than 10-15 pct retained austenite, the latter may be completely obliterated by the dark etching martensite or it may appear disproportionately low as the interfaces between the two constituents become difficult to distinguish. Another disadvantage of the metallographic method is the need for "darkening" the martensite and hence the determination cannot be applied to as-hardened steels. The required tempering may spoil the structure for other tests or may even remove a small part of the austenite which is being sought. X ray methods hold more promise for covering the range under 15 pct retained austenite. Although austenite and martensite in the hardened steel may be chemically identical, their crystal structures and lattice parameters differ, and the intensity of an austenite diffraction line is some continuous function of the percentage of re-

Jan 1, 1949

By B. L. Averbach, M. Cohen

Many hardened steels contain significant quantities of retained austenite even in cases where the carbon and alloy contents are low. In fact austenite has been detected in plain carbon steels containing as little as 0.50 pct carbon.1 Although the austenite may not be visible metallographically it causes definite dilatometric and magnetic effects during subsequent tempering or sub-atmospheric coo1ing.l,2,3 Therefore if the reactions which hardened steels undergo during later treatment are to be understood in quantitative fashion it is most essential to have some kind of absolute analysis for the austenite content in hardened steels. Once this analysis has been made, the austenite transformations can be followed precisely by observing such sensitive phenomena as changes in length or in magnetization but the latter techniques can only determine differences in the amount of retained austenite and usually an independent method must be found to put these differences on an absolute basis. In certain instances the microscope can be used advantageously to determine the percentage of retained austenite. The quenched sample is tempered to "darken" the martensite with minimum decomposition of the coexisting austenite, and then is polished and etched in the usual fashion. If the austenite is clearly distinguishable from the tempered martensite and other possible constituents its volume percentage can be measured quantitatively by point counting or lineal analysis.4 Such microscopic methods, however, depend on the etch being sufficiently discriminatory. In fairly coarse structures, if the austenite content is greater than 10-15 pct, there is probably little smearing of the etch, and point counting or lineal analysis seems to be quite accurate. On the other hand if the structure is difficult to resolve, as in commercially treated fine-grained . steels which contain less than 10-15 pct retained austenite, the latter may be completely obliterated by the dark etching martensite or it may appear disproportionately low as the interfaces between the two constituents become difficult to distinguish. Another disadvantage of the metallographic method is the need for "darkening" the martensite and hence the determination cannot be applied to as-hardened steels. The required tempering may spoil the structure for other tests or may even remove a small part of the austenite which is being sought. X ray methods hold more promise for covering the range under 15 pct retained austenite. Although austenite and martensite in the hardened steel may be chemically identical, their crystal structures and lattice parameters differ, and the intensity of an austenite diffraction line is some continuous function of the percentage of re-

Jan 1, 1949

By B. L. Averbach, M. Cohen

THE PROBLEM MANY hardened steels contain significant quantities of retained austenite even in cases where the carbon and alloy contents are low. In fact austenite has been detected in plain carbon steels containing as little as 0.50 pct carbon.1 Although the austenite may not be visible metallographically it causes definite dilatometric and magnetic effects during subsequent tempering or subatmospheric cooling.1,2,3 Therefore if the reactions which hardened steels undergo during later treatment are to be understood in quantitative fashion it is most essential to have some kind of absolute analysis for the austenite content in hardened steels. Once this analysis has been made, the austenite transformations can be followed precisely by observing such sensitive phenomena as changes in length or in magnetization but the latter techniques can only determine differences in the amount of retained austenite and usually an independent method must be found to put these differences on an absolute basis. In certain instances the microscope can be used advantageously to determine the percentage of retained austenite. The quenched sample is tempered to "darken" the martensite with minimum decomposition of the coexisting austenite, and then is polished and etched in the usual fashion. If the austenite is clearly distinguishable from the tempered martensite and other possible constituents its volume percentage can be measured quantitatively by point counting or lineal analysis.4 Such microscopic methods, however, depend on the etch being sufficiently discriminatory. In fairly coarse structures, if the austenite content is greater than 10-15 pct, there is probably little smearing of the etch, and point counting or lineal analysis seems to be quite accurate. On the other hand if the structure is difficult to resolve, as in commercially treated fine-grained steels which contain less than 10-15 pct retained austenite, the latter may be completely obliterated by the dark etching martensite or it may appear disproportionately low as the interfaces between the two constituents become difficult to distinguish. Another disadvantage of the metallographic method is the need for "darkening" the martensite and hence the determination cannot be applied to as-hardened steels. The required tempering may spoil the structure for other tests or may even remove a small part of the austenite which is being sought. X ray methods hold more promise for covering the range under 15 pct retained austenite. Although austenite and martensite in the hardened steel may be chemically identical, their crystal structures and lattice parameters differ, and the intensity of an austenite diffraction line is some continuous function of the percentage of re-

Jan 1, 1948

By Torgrim Eftestoel, Leif Olsen, Ove Sandberg

IN the vertical contact Soederberg electrode for aluminum furnaces more or less serious cracks are sometimes formed in the electrode, with harmful effect on furnace operation. The problem of crack formation has been studied on a laboratory scale to obtain a better understanding of this phenomenon. The primary cause of crack formation is the shrinkage of the electrode carbon, which is opposed by the normal thermal expansion of the steel contact studs. The forces thus set up are active in the temperature interval from which the electrode obtains a rigid structure (450" to 500°C) to furnace operational temperature (950°C). A visualization of our reasoning is given in Fig. 1, which shows the different behavior of mild steel and electrode carbon during baking. Research work performed to determine relationships between crack formation and shrinkage will be described. A brief description of the method developed for measurement of shrinkage will be given, as well as a critical analysis of this method. Also, raw material quality and paste composition variables will be related to shrinkage phenomena. Laboratory Test of Crack. Formation To test the tendency toward crack formations of Soederberg electrodes from different pastes, experiments were performed to simulate conditions of actual commercial electrodes, and are described as follows. A cylindrical test electrode is prepared by tamping the electrode paste to be examined in a sheet iron casing, 350 mm diam by 700 mm height. The casing is perforated, with the holes (2 mm diam) 50 mm apart, to facilitate the escape of volatile matter during baking. A cylindrical steel stud of actual service size, 100 mm diam, is welded eccentrically to the bottom steel plate, and protrudes up through the paste. During baking, a crack may thus occur in the weaker part of the test electrode. The electrode is baked by lowering the assembly slowly into an electric furnace, the temperature of which is kept constant at 900°C. After baking of the electrode, the sheet iron casing is removed and the electrode inspected for cracks. The pictures in Fig. 2 are of three different pastes baked according to the present method. Electrode 1 has a large crack; electrode 2, a somewhat smaller one; and electrode 3, only a minor crack. As will be seen from the simplified sieve analysis diagram of Fig. 2, the compositions of the pastes in question are very different. This subject will be discussed later in greater detail. Crack Formation and Shrinkage Relationships It is well known that shrinkage occurs in coke in the higher temperature ranges of coal

Jan 1, 1958

By R. K. Waring, E. C. Truesdale

The Research Division of The New Jersey Zinc Company (of Pa.) has conducted, over a period of years, numerous tests of the reducibility of various zinc ores and the reactivity of various kinds of coal, using a number of different experimental methods. Most of these tests have involved the reduction of mixtures of ore and coal. In such cases the following simultaneous reactions are believed to be mainly responsible for the production of zinc, as was shown by Bodenstein1 some years ago: ZnO+ CO = Zn + CO2 [1] C + CO2 = 2 CO [2] Each of these reactions is dependent upon the other for the supply of CO and CO2 , respectively, and the over-all rate of formation of zinc vapor will be determined by the slower of these two reactions. An analogous pair of reactions sometimes of importance is: ZnO + H2 = Zn + H2 O [31 C + H2O = CO + Ha [4] While it is possible to obtain an indication of the relative reducibility of various ores, or of a fine versus a coarse ore, by testing them with a given coal, and while coal reactivities may be measured in a corresponding manner, a more direct determination of relative reaction rates is possible by carrying out the desired reactions, such as I and 2, separately and under reproducible conditions. It is one purpose of this paper to present some of the results that have been obtained by the latter method. C. G. Maier2 discusses the relative rates of reactions I and 2 and concludes that while at relatively low temperatures reaction I is faster than reaction 2, this difference becomes less with increasing temperatures, although at smelting temperatures reaction I is still the faster. He also says (p. 48), "At temperatures . . . between IIOO° and I3oo°C., . . . the zinc oxide reduction reaction is intrinsically more rapid than its physical limitations; that is, it is limited by gas diffusion rates." In the course of numerous reactivity tests involving the separate use of reactions and I and 2, we have obtained data that show by direct experiment, we believe for the first time, the correctness of Maier's statements concerning these reactions. We also include data on the relative rate of reaction 3, involving reduction by hydrogen. Finally, some interesting results obtained by carrying out the reduction of a zinc ore-coal briquet in streaming atmospheres of nitrogen, carbon monoxide and hydrogen, respectively, are presented. *

Jan 1, 1943

By E. C. Truesdale, R. K. Waring

The Research Division of The New Jersey Zinc Company (of Pa.) has conducted, over a period of years, numerous tests of the reducibility of various zinc ores and the reactivity of various kinds of coal, using a number of different experimental methods. Most of these tests have involved the reduction of mixtures of ore and coal. In such cases the following simultaneous reactions are believed to be mainly responsible for the production of zinc, as was shown by Bodenstein1 some years ago: ZnO+ CO = Zn + CO2 [1] C + CO2 = 2 CO [2] Each of these reactions is dependent upon the other for the supply of CO and CO2 , respectively, and the over-all rate of formation of zinc vapor will be determined by the slower of these two reactions. An analogous pair of reactions sometimes of importance is: ZnO + H2 = Zn + H2 O [31 C + H2O = CO + Ha [4] While it is possible to obtain an indication of the relative reducibility of various ores, or of a fine versus a coarse ore, by testing them with a given coal, and while coal reactivities may be measured in a corresponding manner, a more direct determination of relative reaction rates is possible by carrying out the desired reactions, such as I and 2, separately and under reproducible conditions. It is one purpose of this paper to present some of the results that have been obtained by the latter method. C. G. Maier2 discusses the relative rates of reactions I and 2 and concludes that while at relatively low temperatures reaction I is faster than reaction 2, this difference becomes less with increasing temperatures, although at smelting temperatures reaction I is still the faster. He also says (p. 48), "At temperatures . . . between IIOO° and I3oo°C., . . . the zinc oxide reduction reaction is intrinsically more rapid than its physical limitations; that is, it is limited by gas diffusion rates." In the course of numerous reactivity tests involving the separate use of reactions and I and 2, we have obtained data that show by direct experiment, we believe for the first time, the correctness of Maier's statements concerning these reactions. We also include data on the relative rate of reaction 3, involving reduction by hydrogen. Finally, some interesting results obtained by carrying out the reduction of a zinc ore-coal briquet in streaming atmospheres of nitrogen, carbon monoxide and hydrogen, respectively, are presented. *

Jan 1, 1943

By D. H. Davis

HAND picking was the earliest form of coal preparation, first practiced to improve the outward appearance of the coal being loaded and to remove any pieces that might appear objection- able to the buyer. It is still extensively practiced on the plus 1-in. sizes, and particularly on the plus 4-in. and larger sizes. The percentage of ash reduction that can be obtained by hand picking depends entirely upon the amount of free impurity occurring in the coal. In a particularly dirty seam, where a considerable quantity of rock occurs with the coal as mined, hand picking produces sizable reductions in ash. If the coal is prepared clean at the working face hand picking is a final check; in some cases, on the smaller sizes, it is practiced only to show that an effort is being made to prepare a clean product. Because of the variety and different methods of handling coal, the early plants were not always adapted for efficient hand picking. At most mines an attempt is made to remove the visual impurities at one or more of the following places in the surface plant:2 (1) in the tipple during screening; (2) on picking band, belt, or shaking conveyors;. (3) during the loading of the coal as it goes into the railroad car. Whatever the physical arrangements of the plant may be, the usual practice is to run the coal over the screen, picking table or boom at such a rate that each-piece of impurity is exposed to the view of the picker. Coal should be uniformly sized and spread out on the table so as not to exceed one particle in depth. The flow should be even in tonnage and the speed of travel should be from 30 to 60 ft. per minute and not 'exceed 80 ft. per minute. The dirtier the coal, the slower the speed required for a fixed number of pickers. Actually, picking capacity depends on the number of particles per minute that can be picked out and-rejected. The percentage of impurity removed is determined by this and the average weight of piece rejected. Handling a mixture of sizes from nut to the largest lump over the same picking table or conveyor is not conducive to efficient separation by hand picking because the lump hides the smaller impurities. Picking tables should not exceed 5 ft, in width, so that a picker on either side will be able to remove impurities from the center of

Jan 1, 1943

By P. W. Ramsey, G. L. Werley

THERE have been numerous examples in recent years of the similarity between aging behavior and diffusion behavior, where a plot of the logarithm of the aging rate versus the reciprocal of the absolute temperature yields an approximate straight line, analogous to a similar plot of the diffusion coefficient D (log D vs. 1/T). Austin and Rickettl have pointed out that this linear relationship holds empirically for the de- composition of austenite into pearlite and bainite in carbon steels, and Robertson' has shown similar trends in the aging of 24S-type aluminum alloys. Jenkins and Bucknall³ have also demonstrated the association between aging and diffusion rates for nickel-silicon-copper alloys. Jetter and Mehl,4 however, have shown that the maximum rate of dilation of a series of aluminum-silicon alloys does not show this linear relation and Mehl5 has pointed out that careful study of available knowledge indicates that "aging rates increase with temperature approximately exponentially, whereas D increases precisely exponentially." He further notes that "the rate of aging at a given temperature is the greater the lower the melting point of the alloy, which is also true for D." This paper describes the aging changes occurring in a zinc-25 pct manganese-15 pct copper-0.1 pct aluminum die casting alloy. It was found that this alloy does show this linear relationship and use was made of this relationship to estimate aging rates at low temperatures from data acquired at elevated temperatures. It should be noted that the aging reaction is being studied only indirectly, using changes in certain properties as criteria of the progress of the phenomenon. This alloy is purely an experimental one and is not available commercially. Zinc-Manganese-Copper System: The zinc-rich portion of the zinc-manganese-copper diagram which is of significance in the present work is quite uncertain. X ray examination of the alloy as die cast shows a phase similar to the epsilon phase (hexagonal close packed) of the copper-zinc system. All of the data accumulated indicate that the epsilon phase of the zinc-manganese-copper alloy is stable at high temperatures; that is, 500°C or above. Below this temperature a new phase is precipitated on annealing, and a decrease in specific volume occurs. At elevated temperatures this phase change occurs quite rapidly, while at room temperature the alloy has shown no change after several years. According to X ray data, this precipitated phase resembles the gamma phase (cubic) of the copper-zinc system, a hard and brittle structure. From examination of the microstructure and from X ray examination of the alloys annealed at

Jan 1, 1951

By F. Forscher

Pronounced porosity, decreasing with distance from the fracture surface, is found in the necked region of tensile specimens tested at room temperature or liquid nitrogen temperature. A hydrogen solution treatment followed by a quench prevents pore formation in tests at —196°C, but has little effect on tests made at room temperature. Reduction of area values at —196°C are strikingly improved by the same treatment, but show no improvement in room temperature tests. The experimental results support the hypothesis that strain-induced porosity results with hydride initially present or, in material containing less than 50 ppm H, with hydride precipitated by strain aging. ZIRCONIUM'S advent as an engineering material in nuclear reactor construction has brought forth many investigations concerned with the properties of this metal and its alloys. Some attention has been given to the ductility of the metal.1, 2 Particularly, the effect of hydrogen on the impact strength was noted," indicating a pronounced dependence of ductility on the hydrogen content and its distribution in the metal. Micro graphic:' and X-ray diffraction studies' have shown that a precipitated hydride phase causes embrittlement in zirconium,' which implies a distinctly different mechanism from that causing hydrogen embrittlement in steels."-' In the latter case, it is assumed that atomic hydrogen diffuses to rifts, where it forms molecular hydrogen under such internal pressures that it causes the rifts to enlarge, leading to fracture. Thermo-dynamic studies of the Zr-H system8, 9 also indicate that the internal pressure of molecular hydrogen would be too low to cause any damage to the zirconium at room temperature, and the formation of a zirconium hydride (d phase) is favored." It is noteworthy that this phase has a face-centered-cubic structure and nearly 18 pet larger molar volume than close-packed-hexagonal a-zlrconlum' Other features of the ductility of zirconium are the absence of a typical cup-cone failure upon tensile testing, a pronounced strain-induced porosity in the necked region of a tensile bar, Fig 1, and the associated spongy appearance of the fracture surface A tremendous improvement in ductility at liquid nitrogen temperature can be observed following a heat treatment that retains the commonly present quan- tities (10 to 50 ppm) of hydrogen in solution. Such tests show a typical cup-cone failure and the absence of strain-induced porosity, Fig. 2. The present paper reports results of an investigation into the causes of strain-induced porosity in zirconium. Room temperature tensile fractures of mild steel, aluminum, and titanium have also been examined for strain-induced porosity. In each case porosity could be detected, but the amount was orders of magnitude less than was found in zirconium. Of the three metals, titanium showed the strongest effect. Material, Specimens, and Preparation The greater part of this investigation was done on Westinghouse crystal bar zirconium, are-melted, forged, and hot-rolled. Chemical analyses of the hot-rolled plates are given in Table I, along with those of the Foote crystal bar zirconium used in this work. The specimens were machined from the hot-rolled plate (1550°F) of 1/2 in. thickness and subsequently heat-treated according to one of the treatments shown in Table IS. All specimens were machined round, the longitudinal axis in the rolling direction, with a gage

Jan 1, 1957

By R. H. Doremus, E. F. Koch

The first carbide phase that precipitates at 120°C from a iron containing about 0.02 wt pct, C was studied with the electron microscope. In both strained and unstrained material the carbide particles appeared to form on the dislocations in the iron, in agreement with the results of the kinetic study in part II. The structure of the carbide was tentatively identified as an expanded a-iron lattice (body-centered tetragonal) with about 0.7 wt pct C. This phase appeared to be metastable and apparently transformed into cementite or epsilon carbide when the iron was over-aged. WhEN a iron containing less than about 0.025 wt pct C is quenched from 700°C to room temperature the carbon is retained in solid solution and precipitates out slowly with time. The morphology and structure of the precipitating phase are still in doubt, two different carbide phases, epsilon carbide and cementite, have been identified, but there is considerable disagreement about the time and temperature at which they appear.1-4 Epsilon carbide seems to form at lower temperatures than cementite, although one group of investigators4 found only the latter phase over a wide range of aging temperatures. Usually these two phases have been identified after aging times much longer than needed to drain the carbon from supersaturated solution, at least for aging temperatures below 200oC. The precipitated carbides have been observed with the electron microscope,'-5 but again most results have come from samples aged much longer than necessary to reduce the carbon concentration in solution to a low value. In this study the carbide phases were observed in earlier stages of precipitation with the electron microscope, in order to learn more about the shape, size, and distribution of the carbide particles. Samples strained small amounts before aging, as well as unstrained samples, were studied, and the structure of the carbide phase was tentatively identified. EXPERIMENTAL "Ferrovac E" vacuum-melted iron, from which the wires for kinetic studies were also made (Refs. 6 and 7 and the following paper) was used for this work. An analysis of this material is given in Table I; it agrees well with the manufacturer's values. The number of inclusions in the iron was very small, as can be seen in the optical micrograph in the following paper. Pieces of iron about 1 mm thick and 5 to 10 mm in diam were used for all the studies except for those in which the sample was strained before aging; then the specimen was a rod 3 to 6 mm in diam and 20 cm long. The samples were held at about 700°C in wet hydrogen for at least an hour to remove residual carbon and nitrogen, after which they were heated to 950" (in the y region) and cooled to room temperature in the furnace. This treatment gave an average grain diam of more than 1 mm, so that the effect of grain boundaries on the precipitation process was negligible. The samples were carburized at 710°C for about 2 hr in hydrogen that had passed over toluene held at -30°C; then they were rapidly quenched into water. From chemical analysis this treatment gave a carbon concentration of from 0.012 to 0.016 wt pct, which is less than the solubility of carbon at this temperature. After quenching, the samples were aged at 120 "C in an oil bath for vari-

Jan 1, 1961

By W. R. Kube, W. H. Oppelt

Five low-rank coals, including two lignites, a steam-dried lignite, and two subbituminous coals, were carbonized at 940°F, in a bench-scale carbon-ize~ with a nitrogen and hydrogen atmosphere, or both, using pressures from atmospheric to 1000 psig. Coking characteristics were observed, and yields, composition, and distribution of products from thermal degradation were determined. The influence of pressure on yields from coal carbonization, as well as on modification of coke structure, has long been of interest. One of the first attempts at pressure carbonization was that of Capps and Hulett1 who in 1917 investigated the effects of pressure ranging from 1 to 20 atm on yields at 600° C for bituminous and subbituminous coals. High-pressure carbonization has not been used commercially for coke production. More recently, carbonization at relatively high pressure in the presence of catalysts and hydrogen has been proposed for the production of metallurgical-grade coke from low-rank fuels.' Another approach involves carbonization at high pressure in a hydrogen atmosphere to produce heating gas and a solid residue that is gasified with oxygen and steam to produce the hydrogen required for hydro-genation 3-4 or, alternatively, is burned to raise steam. Recently it has been proposed to carbonize coal under pressure, burn the gas in a gas turbine to produce power, and use the solid residue as fuel in a conventional steam-power plant.5 Our primary interest in pressure carbonization stems from an attempt to determine the influence of pressure on the coking characteristics of lignite to design a high-pressure slagging gasifier using oxygen and steam. At atmospheric pressure, North Dakota lignite is generally considered to be non-coking. However, lignite and subbituminous coals have been reported to show increased agglomeration properties in steam, hydrogen, or carbon-dioxide atmospheres at elevated pressures, although no strong coke was formed at pressures up to 3000 psig.6 If lignite would agglomerate seriously under gasification conditions, proper flow of charge through the gasifier could not be maintained without installing a mechanical stirring device or destroying the caking properties of the coal before gasification. Data on the caking properties of lignite or other gasification fuel, as well as on yields of products under conditions simulating the carbonization process in the pregasification zone, were required in the preliminary design stage of the gasifier. No information was available concerning the influence of pressure and type of atmosphere on North Dakota lignite. To provide this basic data, the U. S. Bureau of Mines investigated the effect of pressure and a hydrogen or nitrogen-rich atmosphere on the yield of products and on coke formation in a bench-scale pressure carbon-izer. SCOPE OF INVESTIGATION Five coals were tested at 940°F in nitrogen and hydrogen atmospheres, at pressures from atmospheric to 1000 psig. Yields and composition of solid, liquid, and gaseous products were determined as a function of the process pressure, and attention was given to the physical appearance of the solid residue. Percentage of carbon converted, sulfur retained in char, and thermal balances were calculated. In this paper, primary consideration is given to carbonization in a nitrogen atmosphere and to data concerning the solid phase. The effect of pressure in hydrogen is presented in detail for only one lignite. More complete information on the response of the other coals in a hydrogen atmosphere will be published in a USBM Report of Investigations. DESCRIPTION OF EQUIPMENT Details of the bench-scale pressure carbonizer are given in Fig. 1. The body of the carbonizer was

Jan 1, 1961

By John W. Weeton, Max Quatinetz, Robert J. Schafer

Nickel powders of 1-, 0.4-, and 0.2- average particle size were combined with 0.05- p MgO powder. Oxide was added in quantities of 4, 12, and 20 vol pct. The mixtures were vacuum hot pressed and extruded at 2100°F. In spite of a general tendency to growth of oxide particles during processing, dispersions of fineness comparable to those of Sintered Aluminum Powder, SAP, were achieved. A small amount of oxide considerably improved 1800°F stress-rupture strength, but further oxide addition resulted in a decrease of strength. RECENTLY there has been much speculation concerning the requisites for strong and stable dispersion-strengthened alloys. The nature of the dispersed phase, the stability of the alloys, and variables influencing the mechanical properties of alloys have been given consideration. Such topics have been reviewed by Bunshah and Goetzel. Of the many parameters related to the mechanical properties of dispersion alloys, mean free path between dispersed particles (a measure of the fineness of the dispersion), particle size, and vol pct of the dispersed phase have been shown to be very important. Generally, strength increases with decreasing mean free path, and there is an optimum vol pct of dispersed phase. Just how fine a dispersion ought to be is somewhat open to debate, but Irmann, Lenel, Backensto, and Rose, Gregory and Grant,4 and others have shown in the original SAP-type alloys, aluminum plus aluminum oxide alloys, that better strength is generally obtained with finer dispersions and the best strengths were obtained when the mean free path was less than . Further, Cremens, and rant' showed that in nickel plus aluminum oxide alloys, stress-rupture strength at 1500°F was definitely increasing with decreasing mean free path. In their investigation, however, the finest dispersions that were produced were about 2.0 mean free path. To determine the potential of the nickel plus oxide type of product, it would be neces- sary to obtain dispersions analogous to those of SAP alloys; namely, ones where the mean free path between oxides is less than . Unfortunately, however, it is very difficult to produce extremely fine dispersions of oxides in metals other than those which naturally form refractory oxide skins. There are several approaches to this problem including such procedures as mechanical mixing, internal oxidation, reduction of mixed oxides, and metal deposition from solution. Work at the Lewis Research Center has shown that metal powders 0.1p or finer could be produced by ball milling, when selected grinding aids were utilized.' Because these unusually fine powders were available, it was an initial objective of this study to determine if by mixing of these fine Ni powders with various amounts of MgO (0.05) a fine dispersion of MgO in Ni comparable to those in Al-Al203 might be achieved. A second objective was then to attempt to relate the parameters of structure to 1800°F stress-rupture strength of the alloys. Nickel powders of 1-, 0.4-, and 0.2-p average particle size were combined with 0.05- average particle size MgO powder. This oxide was added in quantities of 4, 12, and 20 vol pct. The mixtures were hot pressed and extruded at 2100°F.

Jan 1, 1962

By W. A. Tiller, D. H. Lane

A simple zone melting technique for investigating the effect of ultrasonic irradiation upon ingot solidification is described. The effect of i) ultrasonic power level, ii) freezing velocity, iii) constant or variable frequency, iv) direction of irradiation, and v) transducer-cozlpling bar joint upon the grain size of type 316 stainless steel have been investigated. The results of this study support the postulate that the ultrasonic vibrations increase the nucleation probability in the layer of liquid adjacent to the freezing interface. In the first paper of this series,l the possible mechanisms whereby ingot structure may be altered by irradiating a solidifying melt with ultrasonic vibrations have been discussed. A new technique for efficiently introducing the ultrasonic energy into the solid-liquid interface region was presented and applied to ingot preparation by the consumable-electrode arc-melting technique. The experimental results support the postulate that the ultrasonic vibrations may refine the ingot structure by increasing the nucleation probability in the zone of liquid adjacent to the solid-liquid interface. The present paper describes the application of the same technique to a relatively simple laboratory-scale zone-melting apparatus. This apparatus is found to be well suited to the detailed study of ultrasonic technology in this area and allows one to determine, in particular, the minimum ultrasonic power level needed to produce a certain grain size in a particular material. The results of this study support the nucleation mechanism for grain refinement, but do not provide any deeper insight into the specific nucleation mechanism responsible for the effect. EXPERIMENT The apparatus used in these experiments is shown in Fig. 1 and illustrated schematically in Fig. 2. The material to be studied, type 316 stainless steel, was in the form of a 3/4-in. sq bar 30 in. long. This bar was placed in a square open-topped mold with open ends made from high-purity graphite coated with a flame-sprayed Al2O3, skin. Surrounding the crucible was a molybdenum susceptor with 3/8-in. diam holes spaced at 1-in. intervals along its length to serve as sight ports. A tapered transducer horn was brazed to one end of the specimen. The entire assemblage was enclosed in a quartz tube, the transducer itself projecting out one end and resting in a cooling tank. A vacuum seal between the coupling bar and the end plate enclosed one end. A similar plate and seal enclosed the other end. The system is gas tight and can be operated under vacuum or an inert atmosphere. For these experiments, flowing argon at 15 in. of Hg pressure was used. The heat source for melting the stainless steel specimen was a 2-in. long 3-kc induction coil placed around the quartz tube; this source heated the susceptor, inductively melting about a 3-in. zone of the sample by radiation. To move the molten zone at a specified rate, the induction coil was moved down the tube at this rate with the aid of a simple pulling device. Thus, the sample could be irradiated at varying ultrasonic frequencies and power levels and could be solidified at varying rates. The power input to the transducer was measured using a "John Fluke Model 120 VAW-Meter." 1 The power delivered to the interface region is probably only about 50 pct of that measured on the VAW-meter. In a typical run, when the ultrasonic power was turned on, the interface of the molten zone closest

Jan 1, 1961

By C. S. Smith, L. H. Beck

KNOWLEDGE of the Cu-Zn constitution diagram was critically examined in 1944 by G. V. Ray-nor,1 who suggested the diagram reproduced in Fig. 1 as the best evaluation of available data. No pertinent work on the constitution has been published since that time, although a number of authors have discussed transformation kinetics and theory. Despite the large amount of work that has been done on the constitution of these industrially important and scientifically interesting alloys, minor uncertainties still exist. For example, it is still not possible to say definitely whether a two-phase region exists between the ordered and disordered forms of the 8 phase. A careful re-examination of the phase boundaries in this part of the diagram was therefore undertaken. Two methods were selected for the new investigation—quantitative metallography for the higher temperatures and precision lattice parameter measurement for lower temperatures. Because of the relatively narrow two-phase regions flanking the ß phase in these alloys, quantitative metallography is particularly suited for their examination, since the relative amounts of the two phases are very sensitive to their compositions. The method, however, is useless below about 350°C because of the inadequate resolution of the two constituents. Below 400°, however, the X-ray diffraction method is applicable, although it is of somewhat lower sensitivity in this system. The changes of composition that occur during quenching from above about 500°C entirely vitiate X-ray measurements at room temperature though they do not affect metallographic area measurements. The two methods overlap and supplement each other admirably. Both methods depend on the attainment of equilibrium composition of the two phases in a more or less intimate mixture and thus avoid the difficult problems of nucleation and long range diffusion involved in the conventional metallographic bracketing method. The alloys were melted from a master alloy made from re-electrolyzed cathode copper and Horsehead 99.99 pct Zn. Melting was done under a cover of either borax or charcoal and the alloys cast into a 7/8 in. sq graphite mold for the a-ß alloys or a 3/8 in. diam cylindrical graphite mold for the ß-? alloys. The a-ß alloys were rolled at 750°C to 5/8 in. sq; annealed for 24 hr at 800°C and quenched; then rolled and swaged at 200°C to 3/8 in. diam rods, annealed 24 hr at 200°C, quenched and cold rolled 2 pct reduction. This treatment was intended to obtain a small grain size and to produce many nuclei of the minor phase for growth on subsequent heat treatment. The unworkable ß-? alloys were given preliminary treatment by sealing in Vycor tubes in vacuum and annealing for 4 hr at 800°C followed by cooling in air. Samples of homogenized alloys were checked spectrographically for impurities, but the principal components were determined on samples subsequent to heat treatment. The impurities analyzed averaged approximately as follows: Ag, 0.0002 pct; Fe, 0.004; Si, 0.0008; Cd, 0.005; Mg, 0.0002; and Pb, 0.002. For metallography, samples of appropriate composition were cut into rods 5/8 in. long, sealed in pyrex tubes in vacuum and annealed for eight weeks at temperatures of 470°C and below, two weeks at 480°, 500°, and 600°C, and 4 hr at 700°C, followed by quenching in cold water. Temperatures were accurate to ±2°C. The cylinders were then machined to 8.7 mm diam and a slice weighing 1.5 g cut with a thin saw transversely from the center of each. This

Jan 1, 1953

By J. W. Marx, R. H. Langenheim

The injection of heat-bearing fluids may offer a wider application to secondary and tertiary recovery from conventional oil reservoirs than inderground combustion since the process is more easily controlled and the reservoir requirements, in general, are less critical. In all cares, conduction heat losses to overburden and un-derburden will impose an economic limit upon the size of the area which can be swept out from any one injection point for any given set of conditions. The present report describes a method for c.rtin~ating thermal invasion rates, cumulative heated area, and theoretical economic limits for sustained hot-fluid injection at a constant rate into an idealized reservoir. Full allow-ance is made for non-productive reservoir heat losses. Required solutions can be obtained directly from the numerical tables given here, as soon as all operating conditions are specified, withou extensive mathematica1 ~nanipulation on the part of the user. The injection of a heat-bearing fluid into a reservoir is frequently proposed as a means of secondary or tertiary oil production. This form of thermal recovery may offer a wider application to conventional oil reservoirs than underground combustion since the process is more easily controlled and the reservoir requirements, in general, are less critical. Because of its large gross heat capacity, steam appears to be the most efficient heat injection medium, although mixtures of steam and other gases, hot water, hot oil and hot non-condensable gases also have been employed. Whatever the nature of the injection medium, economic evaluation of such thermal recovery processes will depend upon thermal invasion rates, or rates of productive reservoir heating, at any given time after the start of heat injection. In all cases, conduction heat losses to overburden and underburden will impose an economic limit upon the size of the area which can be swept out from any one injection point, for a given set of reservoir conditions, at any given heat injection rate. The present report describes a method for estimating thermal invasion rates, cumulative heated area and theoretical economic limits for sustained heat injection at a constant rate into an idealized reservoir, making full allowance for non-productive reservoir heat losses. Required solutions can be obtained directly from the nu- merical tables given here, as soon as all operating conditions are specified, without extensive mathematical manipulation. It should be noted that ordinary water flooding may be used to move an annular-heated zone outward, even though the economic areal limit for straight heat injection has been reached. Thus well spacing need not be confined to the areal limits as determined here. However, the present calculations do not cover such supplementary heat scavenging programs. The operating element consists of a radial flow system, concentric about the point of injection, with the idealized step function temperature profile illustrated by the dashed line in Fig. 1. The solid curve shown in Fig. 1 gives a qualitative picture of the true radial temperature distribution. It will be shown later that the expressions given below, which are derived from the simplifying step idealization (dashed line in Fig. I), also can be interpreted in terms of the more realistic temperature distribution shown in Fig. 2. For this case, the thermal invasion radius is simply redefined as the distance from injection well to the mid-point of the temperature distribution.