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By J. E. Steiner, J. M. Hodge, M. A. Orehoski

Ingots of four steels (1045, 1080, Ni-Mo-V, and Ni-Cr-Mo-V) were cast at pressures varying from about 1 to 760 mm of mercury, so as to obtain a range of hydrogen contents in each steel. The susceptibility of these steels to flaking was evaluated by cooling hot-rolled blooms at a range of cooling rates, varying from water quenching to slag cooling, and studying the occurrence of flaking as a function of cooling rate. The steels exhibited differences in susceptibility to flaking, and a tlzreshold value for hydrogen content for each steel was found, below which the susceptibility was very low and above which the susceptibility increased markedly with increasing hydrogen content. Mechanical property evaluations, metallogvaplzic exantinations, and X-my diffraction determinations o,t retained austenite were made on samples from the blooms. A mechanism of flaking which is consistent with the observed behaviors, the effects of hvdrogen content, and the differences in susceptibility among the steels investigated is postulated, based on the results of mechanical property evaluations and metallographic and X-ray diffraction studies. ThE important role of hydrogen as a factor in the occurrence of "flakes" or "hair-line cracks" in steel has now been established by many investigations. These have included investigations by steel producers and forging manufacturers, to whom the prevention of flaking is a very real and serious problem, and many research studies aimed primarily at establishing the mechanism of this behavior Several investigators3 have reported that steels cast at reduced pressures (absolute pressures of about 1 mm) not only are low in hydrogen content but are essentially insensitive to the formation of flakes. These investigations have shown that a general relationship exists between hydrogen content and susceptibility to flaking. The difficulty of obtaining suitable samples of steels of a given composition with the desired range of hydrogen contents, particularly in the relatively large sections in which flaking most commonly occurs, has been the principal obstacle to quantitative evaluations of these relationships. Steels with intermediate hydrogen contents between 1 ppm, and the 4ppm or higher of air-cast steels are generally not available in commercially produced steels. Laboratory procedures, in which the hydrogen is introduced into solid steel samples by heating in a hydrogen atmosphere under pressure, generally involve a limitation in the size of the sample which can be treated, and thus are not representative of the behaviors in large sections. The availability of a facility at the South Chicago Works of U.S. Steel, in which several ingots could be cast from a single heat of steel at total air pressures ranging from 0.25 to 760 mm of Hg, has made it possible to overcome this obstacle and to obtain ingots of a given steel covering the intermediate range of hydrogen contents desired. These ingots, furthermore, are of a size suitable for the production of product with section sizes large enough to be representative of the products in which flaking most commonly occurs in commercial production. In these experiments, this facility was used to study the relationships between hydrogen content and the susceptibility to flaking of four steels, two plain carbon steels at 0.45 and 0.80 pct C and two low-carbon alloy steels representing a medium and a rather high hardenability level. These flaking studies were supplemented by evaluations of mechanical properties and by metallographic studies on samples from the blooms, in order to obtain pertinent information on the factors other than hydrogen content which influence the susceptibilities of these steels to flaking. Based on the results of these tests, a mechanism for the initiation and propagation of the flaking cracks, which is consistent with the observed behaviors, is postulated. MATERIALS AND EXPERIMENTAL WORK Steelmaking and Conversion. To provide material for the investigation, five 29- by 35-in., hot-topped, big-end-up ingots were cast from each of four 80-ton, basic electric-furnace heats of four different steels (a 1045 steel, a 1080 steel, a Ni-Mo-V steel, and a Ni-Cr-Mo-V steel). A double-slag practice was used on all steels and the two plain carbon steels were Si-A1 deoxidized with an addition of 2 lb of A1 per ton, while the Ni-Mo-V and Ni-Cr-Mo-V steels were deoxidized only with silicon and

Jan 1, 1964

By P. W. Neurath

IN recent years the domain theory of ferromag-netism has been put on a sound experimental and theoretical basis. But its application to one of the most widely used high quality magnetic materials, the cold-rolled grain-oriented 3 pct Si-Fe used in transformer cores, has been rather difficult because of the complexity of the domain structure of the poly crystalline sheet material. This paper presents some experimental data for this material, showing the relation between plastic and elastic stresses, 60-cycle watt losses, and the domain structure as observed visually. Only a very tentative qualitative explanation of the effects will be attempted. Some initial results were reported earlier.'

Jan 1, 1957

By D. F. Kaufman, E. D. Levine, L. R. Aronin

The deformation of' impure beryllium crystals by basal glide at room temperature invariably tevminates by basal cleavage after a few percent strain. It is generally accepted that .fracture of this type is caused by the splitting of low) -angle boundaries, or bend planes, by obstacles that restrict the motion of the bed planes in the deforming crystal. The details of such a process have been developed by Stroh, who showed that the high tensile stress norrnal to the basal plane in the region where the bend plane is split results in the propagation of a basal cleavage crack, provided there is no available dejorvrlatzon mode having a shear component normal to the basal plane It has been postulated that puvification of beryllium might lead to increased basal ductility by the vemoval of barviers to bend plane motion and possibly by the activation of nonbasal defor~rlation systems. Large increases in the amount of basal glide that can he sustained prior to fracture have been observed in crystals purified by zone refining. In each case, eventudal fracture was by sharp basal cleavage, suggesting that the split bend plane model still applies to tile fracture of beryllium of rensonably high purity. In the present work, calculations are made to show to what extent basal duetilits can be increased by purification while the split bend plane .fracture process remains applicable. Experimentally observed ductilities are generally somewhat lower than those predicted by calculation because of premature failure due to defects introd~cced during specimen preparation and testing. SEVERAL investigators1-4 have studied the deformation characteristics of beryllium single crystals of commercial purity, and have related the strong anisotropy of plastic deformation in single crystals to the problem of brittleness in polycrystalline beryllium. For most orientations, the principal deformation mode is basal slip, which, at temperatures between 300" and 900°K, begins at a critical resolved shear stress of approximately 1500 g per sq mm and terminates after 3 to 6 pet glide strain by cleavage on the basal plane in the neighborhood of (1120) bend planes that are formed during the deformation. This type of fracture, which is also observed in zinc at low temperatures, has been interpreted by stroh5 to be caused by the splitting of bend planes by obstacles to their motion. In the Stroh model, a (11.20) dislocation wall, or bend plane, moving along the slip direction under the action of the applied stress, encounters obstacles which cause part of the bend plane to be held up, the other part continuing to move. Stress concentrations are built up in the region where the bend plane is split, with a high tensile component normal to the basal plane, resulting in a microcrack at the end of the split wall. Because no deformation mode having a shear component at an angle to the basal plane is available to relieve the stress at the crack tip, the crack can propagate under a sufficiently high applied stress. The Stroh criterion for crack propagation is given by

Jan 1, 1964

By T. E. Leontis

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

Jan 1, 1952

By K. P. Gupta, P. A. Beck, N. S. Rajan

By determining the a phase boundaries in the following ternary systems: V-Fe-Si (at 1175oC), V-Co-Si (at 1175°C), V-Ni-Si (at 1175oC), Cr-Mn-Si (at 1000°C), Cr-Co-Si (at 1175°C), Cr-Ni-Si (at 1175°C), V-Fe-A1 (at 1175°C) and Cr-Co-A1 (at 1175°C), it was found that Si exerts a stabilizing effect on these a phases, while A1 tends to destabilize them. Si atoms in solid solution occupy sites D in the a structure, The co/ao ratio increases with increasing Si-, Mn- or Fe-content. The volume of the unit cell decreases with increasing Si-content. THE stabilization of certain metal silicides (the Nowotny phases) by the addition of relatively small

Jan 1, 1961

By R. S. French, W. R. Hibbard

FOR tensile deformation, if the stress value is defined by the ratio of the load to the actual area, and the strain value by the natural logarithm of the ratio of the immediate length to the original gauge length of the sample, the resulting data when plotted with logarithmic coordinates result in a linear relation extending from the initial plastic yielding through the maximum load and in some cases, such as for copper and brass, to fracture'.'. The normal form of the curve, therefore, is a parabola, satisfying the following equation: S = Kem [1] where S and e represent true stress and strain, K is a constant, and m is a coefficient evaluating the slope of the curve and designated therefore as the strain hardening coefficient. Hollomon² has reported that this coefficient is a function of the yield strength as effected by grain size in alpha brass, and the carbon content and heat treatment of steel. In the case of steel, the value of the proportionality constant is a function of the carbon content. It was further shown in that paper2 and also by Low and Prater -hat, if the power relation between stress and strain remains valid, the strain hardening coefficient m, is equal to the strain at the maximum or necking load. Thus, an added significant feature is that this coefficient may serve as an index of the capacity for deformation prior to localized necking and subsequent fracture, e.g. drawability. The constant K may be defined as the strength of the material at unit strain. Together the K constant and the m coefficient describe an alloy's physical properties as far as strength and ductility are concerned for a particular yield strength and, in the case of steel, a particular carbon content. The work of Lacy and Gensamer4 gives data on alloy ferrites from which very close estimates of the strength of ternary and higher iron alloys have been made. It was the purpose of this investigation to develop similar data for commercial copper base alpha solid solution alloys. Preparation of Specimens Commercial binary alloys of copper with aluminum, beryllium, cadmium, nickel, silicon, tin and zinc were investigated. In addition, laboratory castings were made of a 1 pct silicon alloy and a 2 pct aluminum alloy to complete these particular series. Two types of copper were used, oxygen free OFHC and tough pitch FC. The analyses of these alloys are shown in table I. Standard ASTM sheet tensile specimens were used to determine the usual physical properties of each alloy and to obtain stress data at strains from 0.0005 to 0.01. Small (1/4 in. x 3 in. x tk.) samples

Jan 1, 1951

By W. A. Wood, H. M. Bendler

Cylindrical fatigue specimens of OFHC* copper were subjected to alternating torsion while under axial tension. The superimposed tension strongly influenced the fatigue life of the specimens as well as causing characteristic changes in the structure of the fissures that form and develop throughout the life of the specimen. A further effect of the superimposed tension is a continuous extension of the specimen throughout its life in a manner formally similar to creep at elevated temperatures. RECENTLY, studies of the structural changes leading to fracture of metals by fatigue have been made by a technique which reveals, in section, the lattice distortion arising from slip movements inside the metal and the disturbances built up by these slip movements at the metal surface.1'2 According to this approach, fatigue develops as follows: a) fine slip movements concentrate in bands, producing little strain-hardening and thus permitting abnormal totals of plastic strain before fracture and, therefore, abnormal amounts of lattice distortion along each slip band; b) both forward and backward slip movements occur in each band which, according to their distribution across the band, may build up surface disturbances that include sharp notches; c) these notches early in the life of a specimen penetrate the distorted slip zones and transform them into deep, fine fissures; d) the fissures on continued cycling locally saturate the metal and cause local collapse in the form of a microcrack. Thus, the significant consequence of fatigue or cyclic

Jan 1, 1962

By J. C. Borland, J. H. Rogerson

Jan 1, 1963

By E. S. Greiner

STUDY of the plasticity of germanium or other semiconductor crystals affords unusual opportunities to extend our knowledge of deformation mechanisms. Crystals are available having extraordinary perfection and very high purity. They deform by slip on the systems {111} <110>,1-3 as do crystals of the simple face-centered-cubic structure. Dislocations generated in them during slip are easily revealed in the form of etch pits on either (111) or (100) surfaces.4,5 This fact alone makes possible more detailed studies of mechanisms than is usually the case with metals but, even further, the effect of deformation on their electrical conductivity is very large compared with metals. This comes about not only because the mobility of the charge carriers is reduced, as in deformed metals, but also because the number of these carriers is greatly altered. This latter effect seems closely related to the formation of both line and point imperfections during deformation and thus provides a needed tool for the study of the kinds and distributions of these imperfections. Other investigators have deformed germanium at elevated temperatures by bending,1, 6-8 compres-sion,6, 0,10 tension,2,3,6,11,12 torsion,23 and indentation." Wang and Alexander" have also reported successful indentation at room temperature. Dislocation etch pits consequent to deformation have been observed and studied.7,8,10,18,14,20 The experiments to be de- scribed here include principally the compression and the subsequent annealing of germanium with concomitant studies of etch pits, microstructures, and electrical properties. Both single crystals and heavily twinned specimens were used. Some indentation studies are included. Experimental Methods Plastic compression was effected in the apparatus shown schematically in Fig. 1. It consists of two tantalum platens contained in a helium atmosphere and so arranged that pressure can be applied by a hydraulic press. The specimen between the platens is heated by the surrounding furnace. The specimen is usually a small crystal cube about 0.30 in. on an edge. A control specimen is always inserted so, that it is subject to the same thermal cycle as the one being deformed. This serves to detect any impurity contamination that might accompany the thermal treatment. For high temperature work, where such impurity contamination often occurs, the specimens were first plated with gold whenever subsequent electrical properties were to be determined. This method" is effective in preventing significant contamination of germanium up to temperatures at least as high as 750°C, as evidenced by the constancy of the electrical conductivities of control specimens subjected to the same heat treatments. The total range of temperature used for deformation was from 375°C, the lowest at which significant flow was observed, up to 900°C. Microscopic examination was made after mechanical and chemical polishing and etching. Dislocation pits were revealed with CP-4 etchant by the tech-

Jan 1, 1958

By William D. Klopp

A study was conducted of the tensile and creep properties of are-melted and electron-beam-melted tungsten over the temperature range 2250° to 4140°F. The tensile and creep strengths vary with pain size, the finer -grained materials being stronger. The activation energy for transient creep at 2250° to 3500°F is 95,000 cal per (g)(mole), while that for steady creep at 3300o to 4000°F is 141,000 cal per (g)(mole). At 2875o to 3300°F the apparent activation energy for steady creep decreased with decreasing temperature. It is suggested that cross slip is rate controlling during transient creep, while dislocation climb is rate controlling during steady creep above 3300° F. ALTHOUGH considerable data have been generated on the high-temperature tensile properties of powder-metallurgy tungsten,1 relative few data have been published on the properties of are-melted2 or electron-beam melted tungsten.3 Furthermore, the available data show a fairly large amount of scatter at high temperatures. The effects of structure and purity have not yet been defined, aside from observations that high-purity electron-beam (EB)-melted tungsten3 and single-crystal-plasma-flame tungsten4 are weaker than less pure powder-metallurgy tungsten. The creep behavior of powder-metallurgy tungsten has been studied, but no data are available on the creep behavior of tungsten consolidated by melting. Green5 found that powder-metallurgy tungsten exhibited linear creep at 4082° to 5072°F with an activation energy of 160,000 cal per (g) (mole). The similarity of this activation energy to that of 153,000 cal per (g)(mole) for volume self-diffusion6 suggests that recovery of strain hardening by dislocation climb is rate controlling in this temperature range. In studies at 4800°F, Sutherland and Klopp7 concluded that grain size significantly affected the creep behavior of commercial powder-metallurgy materials. This grain-size effect was suggested by sherby,8 although the opposite relation had been reported for aluminum.&apos; The purpose of the present study was twofold: first, to provide baseline data on high-temperature tensile and creep properties of are-melted and EB-melted tungsten for concurrent tungsten alloy studies, and, second, to determine the phenomenolo-gical effects of structural and purity variables on the high - temperature mechanical properties of tungsten. EXPERIMENTAL The are-melted tungsten materials were prepared by melting sintered 1-1/4-in.-diam electrodes into 2-1/2-in.-diam by 5-in.-long ingots. The are-melting facility has been described previously.&apos; Eight ingots were melted, machined, and hot-extruded at

Jan 1, 1965

By G. W. P. Rengstorff, L. E. Olds

High purity molybdenum ingots containing controlled amounts of a single impurity element (oxygen, nitrogen, or carbon) were prepared. These ingots were tested for ductility by bending test specimens at various temperatures. The relationship between the plastic behavior of the ingots and their chemical composition has been determined. MANY proposed applications for molybdenum require ductility at or near room temperature. At the present time, it is possible to obtain wrought molybdenum with considerable ductility only if special fabrication techniques are used to control the grain structure. Starting with are-cast or powder metallurgy ingots, the usual methods for obtaining ductility rely on fabrication procedures that result in fibered microstructures in the finished product. Recently, it has been found that the ductility of either powder metallurgy or are-cast molybdenum can be improved by uniform recrystallization of the metal to a very fine equiaxed grain structure.&apos; The need for a fibered or a fine grained structure may limit the practical usefulness of molybdenum. For example, welding. which may be used in fabricating the metal, generally produces coarse grained structures that lead to brittleness. This applies, certainly, to currently available commercial molybdenum. Although commercial molybdenum is brittle when the grains are coarse, it has been shown experimentally that fine grained structures are not always essential for ductility. For instance, as-cast molybdenum with a coarse columnar grain structure is ductile if it is sufficiently pure.&apos; Because high purity cast molybdenum has good ductility even when coarse grained, it is probable that the brittleness in coarse grained commercial molybdenum is caused by the impurity content of the metal. Although the general effects of impurities on the cold ductility of molybdenum have been known in a qualitative manner for some time, no quantitative evaluation of these effects has been available. The present investigation was made in order to determine more accurately the effects of oxygen, nitrogen, and carbon on the cold ductility of cast molybdenum. Oxygen has long been known to be detrimental to ductility, although the minimum amount which will embrittle molybdenum has been open to speculation. Parke and Ham" showed that ingots with oxygen contents above 0.003 pct could not be forged. Maringer and Schwope have described the embrittle-ment of molybdenum wire by oxygen. A discussion on the effects of heat treatment on the distribution of oxygen in molybdenum has been given by Perry, Spacil, and Wulff." Although nitrogen would also be expected to have harmful effects on ductility, no extensive work has been done previously to determine whether this is so. However, Tury and Krausz" found that wires presumably with less than 0.007 pct N were brittle. Carbon is added to commercial cast molybdenum for deoxidation. Parke and Ham" have shown that molybdenum containing as much as 0.06 pct C could be forged if the oxygen was kept below 0.003 pct. Also, Bruckart and others&apos; found that the room temperature ductility of sintered molybdenum improved with carbon contents up to 0.84 pct. However, Rengstorff and Fischer&apos; found that residual carbide particles in cast molybdenum apparently had an unfavorable effect on room temperature ductility.

Jan 1, 1957

By J. A. Snyder, W. L. Finlay

SEVERAL notable studies of the effects of sub- stitutional solutes have been reported. Outstanding among these for its elucidation of general principles, is the summarized work of Hume-Rothery and coworkers.1 For a systematic study of the effects of substitutional solutes on the mechanical properties of the solvent lattice, the work of Brick, Martin, and Angier² on copper; of Frye and coworkers³,4,5 on copper and silver; and of Lacy and Gensamer6 and of Austin7 on iron may be mentioned. Titanium is one of the few elements offering the possibility of a similar study of interstitial solutes since, unlike most metallic elements, it exhibits extended solid solubility for most of the interstitial solutes—hydrogen, boron, nitrogen, oxygen, and carbon. This paper reports a survey of the effects of dilute solutions of nitrogen, oxygen, and carbon on the mechanical properties of high-purity alpha titanium. Previous Work: Van Arkel and De Boer showed" that high purity titanium was quite ductile and De Boer, Burgers and Fast established".&apos; that not only were oxygen and nitrogen very soluble in solid titanium but that, long before the limit of solid solubility of either had been reached, these interstitial solutes rendered the metal brittle. Their electrical resistance data as a function of

Jan 1, 1951

By H. A. Domian, H. Biloni, G. F. Bolling

Jan 1, 1965

By W. H. Class

The embrittling effects of oxygen, ozone, nitrogen, air, and surface residues, on NaCl has been investigated. The embrittlement by ozone and oxygen was found to be associated with the formation of a NaClO3 surface compound. In these cases the initial crack that was responsible for fracture (in a bend test) always nucleated at the corners between the tension and side faces. The behavior of air was very erratic and on certain days did not produce enzbrittlement. During these periods, crystals that had become embrittled by the ozone treatment completely recovered their ductility after a short exposure to the ambient atmosphere, It was established many years ago1 that considerable ductility could be obtained in NaCl single-crystal specimens if the crystal surfaces were dissolved in water either during or immediately prior to the test. The original interpretation of this effect by Joffe attributed the enhanced ductility to the removal of surface microcracks by dissolution. Later investigations2&apos;3 have suggested that the exclusion of air from the specimen surface is the criterion for extensive plastic flow prior to fracture. The air em-brittlement in this later work was attributed to the diffusion of gaseous atoms into the surface layers of the crystal, thereby impeding the movement of dislocations. This model satisfactorily accounts for the reembrittlement observed after further air exposure subsequent to the water dissolution treatment. However, the situation has recently become more complex by the observations in several laboratories4-t that under certain conditions air exposure does not impair the ductility of NaC1. It has also been recognized5 that improper drying operations after water dissolution can leave surface precipitates that lead to embrittlement. Cleavage defects on as-cleaved crystals can often be another source of embrittlement. In the present work the effect of the gaseous atmospheres nitrogen, argon, air, oxygen, and ozone, on the ductility of rock salt was studied extensively. The embrittlement resulting from oxygen and ozone exposures was found to be associated with the formation of a NaC1O3 surface film. It is suggested that certain atmospheres, one of which often can be ambient air, which inhibit the formation or favor the decomposition of this compound, can promote ductility. Thus one aspect of the Joffe effect is certainly related to the removal of surface compounds or complexes by water dissolution. The effect of surface precipitates that remain after drying operations and of cleavage defects were also studied. In neither of the latter cases was the embrittlement as severe as that found with a NaClO3 surface layer. PROCEDURE AND SPECIMEN PREPARATION The nature of the embrittlement produced by the agents mentioned above was studied by means of microscopy, mechanical testing, and X-ray diffraction. Specimens were cleaved from large crystals of optical quality sodium chloride obtained from the Harshaw Chemical Co., and, except for those tested in the as-cleaved condition, were given a 15- to 20-sec immersion in distilled water followed by a rinse in absolute methyl alcohol. The specimens were then blotted on a soft, absorbent paper, and dried by a few seconds exposure to a stream of warm, dry air. Such a procedure was found to give a control surface which was microscopically free of residues. (A few crystals were intentionally painted with a concentrated NaCl solution in order to investigate the effect of surface residues). All specimens were of 0.140 sq in. cross-section. Crystals prepared in the above manner were immediately placed in a gas train where they could be exposed to the desired gases for preselected periods of time. For the oxygen and nitrogen exposures, pure reagent-grade gases were employed. The ozone was provided in the form of an ozone-oxygen mixture (approximately 10 pct ozone) prepared by passing commercial grade oxygen over a strong ultraviolet light source. All gases were dried prior to their introduction into the train. Since argon was found to be completely inert in its behavior (i.e., residue-free specimens that were exposed to argon were not embrittled), it was periodically utilized to check the control specimen surfaces as well as the condition of the gas train used for aging the specimens. After exposure to the gaseous media in question, the crystals to be used for the measurement of the strain to fracture were transferred from the gas train to a protective oil bath (without further exposure to the atmosphere) where the tests were conducted in three-point bending. The apparatus was so adjusted that the load could be applied at a constant, continuous rate. Other Snecimens from the gas train were deformed

Jan 1, 1962

By R. G. Hudson, L. Yang

In electrochemical separation of metals, it is necessary to control the potential applied between the electrodes so that only the desired electrode reactions can occur. A knowledge of the minimum potential needed for a given electrode reaction to take place continuously is therefore pertinent to the success of the process. In molten chloride systems at high temperatures, activation polarization is believed to be small,1,2 so the minimum potential needed for the electrolytic decomposition of a molten metal chloride MC1n (n = valence of the metal ion) is therefore essentially the equilibrium electrode potential E of the metal-chlorine galvanic cell in the solution. If the decomposition products are pure M and chlorine at a pressure of p atm, E*Eo-rt/nf in [i] Since EO (the standard electrode potential of MCln) is a constant at a given temperature and R (the gas constant), and F (the Faraday&apos;s constant) are all constants, the variation of E with the electrolytic bath conditions is largely determined by the effect of the latter on the activity of the metal chloride amcln (standard state = pure MC1,). Measurement of E and study of how amCin varies with temperature and concentration, the nature of the solvent, and that of the coexisting solutes are therefore pertinent in the selection of optimum operating conditions for the electrochemical separation of metals. Because of its low melting point, high decomposition potentials of its components, and the low solubility of heavier metals in it, the LiC1-KC1 eutectic melt is a useful solvent and has been used in the electrodeposition of Mo,3Ce,4 and u5 metals. Senderoff and Brenner3 measured the potentials of Zn/Zn++, Fe/Fe++, Cu/Cu+, Mo/Mo+++, and Ag/Ag+ against an Ag/AgCl (pure) reference electrode at 600°C and a concentration of 4.1 mole pct of each chloride and came to the conclusion that complex ion formation occurred in some of the melts. Laitinen and LiUe gave an electromotive force series at 450°C for a number of {Metal/Metal ions (unit activity)) electrodes in LiC1-KC1 eutectic melt, the {pt/pt++ (unit activity)) electrode being chosen as the reference. Walker and Danly7 studied the ther-modynamic properties of NiC12 in LiC1-KC1 eutectic melt over a wide range of temperatures and concentrations by measuring the electrode potential between a nickel electrode and a chlorine electrode in the melt. Since potential measurements made by using the chlorine reference electrode are of more direct significance both in the study of electrochemical separation and in the evaluation of the thermodynamic properties of the melt, it is therefore decided to measure the electrode potentials of cells of the type {M/MCin (mole fraction = N) in LiC1-KC1 eutectic melt/Cl2 over a range of N values and temperature for a number of metal chlorides. The results should indicate the order by which the various metals plate out on the cathode and how this order is affected by temperature and the concentration of the metal chloride in the solu-

Jan 1, 1960

By John J. Gilman

F many years it has been suspected that a correlation existed between pits produced by etching and the density of dislocations in crystals. In 1953, the interest in this correlation was greatly stimulated when Vogel et al&apos; demonstrated a 1:l correlation between etch pits and dislocations in low angle grain boundaries of germanium. About two years ago, the author began attempts to produce etch pits at dislocation sites in zinc mono-crystals. These attempts met with success a year or so ago,&apos; and since that time a survey has been made of the etch pit patterns that are associated with various modes of deformation in zinc monocrystals. Unfortunately, the etching technique that will be described is too delicate for use as an accurate quantitative tool. Nevertheless, it has been of considerable assistance in clarifying the structure of plastically deformed crystals. Technique Many attempts were made to produce etch pits in high purity zinc crystals. It was found that several techniques would produce surface grooves at grain boundaries that had misorientation angles greater than about l°, but no technique was successful for boundaries with smaller angles. Among the things that were tried were: electrolytic CrO, (both etching and polishing concentrations), HNO, in various water and alcohol solutions, dilute HC1, many 0-0,-Na,SO, solutions, Cr0,-HC1 solutions, picral, electrolytic Na,S,O,, and electrolytic NaOH and KOH. A few attempts to use cathodic sputtering and thermal etching were also made.

Jan 1, 1957

By W. H. Herrnstein, J. B. Clark, E. C. Utley, A. J. McEvily

The ratio of the endurance limit (10&apos; cycles) to tensile strength of age-hardened aluminum alloys is approximately 0.3, whereas the ratio for annealed alloys is about 0.5. The lower value for the age-hardened alloys has been associated with the instability of coherent precipitate during cyclic loading, but it has not been definitely established whether this instability is due to overaging or reversion during cyclic loading. The results of the present investigatzon support the reversion viewpoint. In this work specimem of 2024-T4 aluminum alloy were aged for 16 hr at 150°C after cycling for 10 pct of the life at 25.000 psi. These specimens were then tested to failure and exhibzted a marked increase in fatigue life. It is proposed that during the early stages of fatigue in this alloy dislocations cut through the coherent precipitate and bring about the reversion of the precipitate. Subsequent aging at 150ºC induces reprecipitation in the precipitate-free zones so that the weakened regions are strengthened and the fatigue life is extended. It Is recognized that the fatigue strengths of precipitation hardened aluminum alloys are unusually low relative to their tensile strength.&apos;-= This feature is illustrated in Fig. 1 where it can be seen that age-hardened alloys have lower fatigue ratios (the ratio of the fatigue strength to the tensile strength) than those in the annealed or cold worked state. Further, as shown in Fig. 2, the more an alloy is dependent upon precipitation hardening for its total strength, the lower is the ratio of the fatigue strength to the tensile strength. This state of affairs has been associated with an instability of the metastable metallurgical structure of precipitation hardened aluminum alloys during cyclic loading. Evidence2 in support of this view is that the fatigue ratio increases in these alloys as the test temperature is lowered, thereby indicating that thermo-mechanical instability, rather than some other factor such as a non-uniform distribution of precipitate, is the factor responsible for the low fatigue ratio at room temperature. Two mutually exclusive proposals have been ad- vanced to account for this instability. Hanstock has proposed that overaging takes place during cyclic loading, and in support of this view, Broom et a1.2 have indicated that an overaging process might be promoted by the large numbers of vacancies which are created during cyclic loading. The creation of vacancies by radiation4 has been shown to lead to rapid overaging. Hanstockl obtained visual evidence of overaging in an aluminum alloy after cyclic loading, but in this instance it has been pointed ou? that because of the high frequency used (60,000 cpm) the observed effect may have been due to normal high temperature precipitation around energy dissipating cracks. Efforts to discern visual evidence of overaging in this alloy at lower test frequencies were not successful.3 The alternative postulate3 is that reversion takes place during cyclic loading and leads to localized soft spots at which fatigue cracks are readily initiated. Evidence for this process has recently been provided by Polmear and Bainbridge5 who demonstrated metallographically that regions depleted of precipitate were created during cyclic loading of an aluminum alloy. Inasmuch as precipitate particles bordering the depleted region had not grown in size, it was concluded that the solute atoms which had constituted the missing particles had gone back into solution. No mechanism for the reversion process was presented. The present study was undertaken to investigate further the conditions leading to instability during cyclic loading, and to determine whether reversion or overaging had taken place as a result of cyclic loading. BACKGROUND AND TEST PROCEDURE In order to differentiate between the processes of reversion and overaging, rest periods at an elevated temperature, which ordinarily would insure additional precipitation, were used in this investigation. It was expected that after a period of cyclic loading an elevated temperature rest period would result in a decrease in the remaining life of the specimen if overaging were occurring during cyclic loading, whereas in the case of reversion, reprecipitation would occur and the fatigue life would be extended. Such an expectation is based on the assumption that the crack-nucleation phase is a significant portion of the total fatigue life, and that such a treatment is of influence in the crack-nucleation stage and is relatively unimportant thereafter.

Jan 1, 1963

By M. J. Spendlove, H. W. St. Clair

An automatic surface-follower mechanism was used to measure the surface temperature and the rate of evaporation of molten zinc while undergoing distillation at low pressure. At pressures of 50 to 100 microns Hg, the rate of evaporation may be 60 to 80 pct of the theoretical maximum corresponding to the measured temperature. The rate decreases rapidly at pressures above 100 microns Hg, to only 7 pct of the theoretical maximum at 2000 microns Hg. Measured temperature gradients at the surface are in agreement with theoretical gradients calculated from the heat of vaporization, rate of evaporation, and thermal conductivity of molten zinc. THIS paper covers a series of careful measurements of the rate of evaporation of molten zinc at low pressures, undertaken as a part of a general investigation on the separation of metals by distillation.&apos; Preliminary results on the rate of evaporation of zinc were described in a previous publication.&apos; The results of the preliminary study are as follows: 1—The observed rates of evaporation of zinc were as high as 0.60 g per sq cm per min, corresponding to 75 pct of the maximum rate as determined by the temperature of the metal. 2—The evaporation rate was decreased from 0.30 g per sq cm per min at a pressure of 25 microns to only 0.09 g per sq cm per min when the pressure was increased to 5 mm. 3—The temperature of the surface during rapid evaporation may be 35" to 100°C less than the main mass of metal. Observed temperature gradients at the surface are consistent with those calculated from the heat of vaporization and the thermal conductivity of liquid zinc. In the preliminary experiments, the rate of evaporation was determined from the loss in weight of the metal in the crucible during the test. This was compared with the weight of the condensate. Obviously, this method was subject to error because of some uncertainty as to the period of evaporation that should correspond to the loss in weight. Furthermore, this method did not permit taking into account probable variations in the rate of evaporation during the test. A more serious shortcoming was that the temperature at the evaporating surface was not known, so the maximum theoretical rate of evaporation could not be calculated accurately. To improve the precision of rate measurements and to allow accurate measurements of the surface temperature, a refined experimental technique was developed whereby the temperature and position of the surface could be measured accurately. This was done by an automatic surface-follower mechanism that gave a continuous record of the surface temperature and the amount of zinc evaporated. These data permitted an instantaneous determination of the actual rate of evaporation and the surface temperature throughout the test. Pure zinc (99.99 pct Zn) was used in all experiments. Description of Distillation Furnace The details of construction of the distillation furnace are shown in Fig. l. The furnace is enclosed in a large quartz tube open at one end. The open end of the quartz tube is sealed by means of a water-cooled head. The entire enclosure is vacuum tight. The connection between the water-cooled head and the quartz tube is sealed by means of a rubber gasket which fits tightly against the smooth end of the tube. The metal is heated by induced current set up in the molten zinc and the walls of the graphite crucible by means of a water-cooled induction coil outside the quartz tube. High frequency current is passed through the induction coil from a 6 kw mer-

Jan 1, 1952

By B. A. Wilcox

ThERE are several reports in the literature which indicate that both solid-solution hydrogen and hydride precipitates can promote low-temperature em-brittlement of tantalum.1-3 For example, Imgram et al.2 showed that hydrogen additions in the range of 140 to 580 ppm promoted a ductile-to-brittle transition at slightly above room temperature in both wrought and recrystallized tantalum. This contrasts with the observation that tantalum of norma1 purity is very ductile, even at liquid-nitrogen temperature. Imgram et al. also found that hydrogen additions caused a deterioration of notch tensile properties of tantalum. The purpose of this communication is to present some limited evidence that hydrogen can also cause fatigue embrittlement of tantalum. The material used in this investigation was wrought, stress-relieved (1000°C, 1 hr), are-melted tantalum rod (5/8-in. diameter) containing the following impurities in weight percent: 0.005 C, 0.007 02, 0.0005 H2, 0.003 N2, 0.08 Cb, 0.01 W, and 0.01 Fe. Hydrogen charging was done in an atmosphere of flowing dry hydrogen for 3 hr at 600°C, followed by an homogenizing anneal in purified argon for 15 min at 600°C, and cooling in an argon atmosphere. Typical micro-structures of the hydrogen-free and the hydrogen-charged materials are shown in Fig. 1(a) and Fig. 1(b), respectively. Fig. 1(b) shows the appearance of hydride precipitates which, in many cases, formed preferentially parallel to the rod axis. The hydride dispersion was uniform across the diameter of the specimen. The fact that the precipitate was a tantalum hydride was tentatively confirmed by X-ray diffraction on a metallographically prepared surface. After hydrogen charging, chemical analyses by vacuum fusion revealed the hydrogen content to be 0.0295 wt pct. In addition, the oxygen and nitrogen contents were slightly raised to 0.0095 O2 and 0.005 N2.

Jan 1, 1964

By H. Conrad, E. Stofel

The fracture behavior of 60-deg-oriented sapphire crystals was investigated for both tension and compression. Plastic flow on the basal plane was found to be a factor in reducing the tensile stress required to produce fracture in the temperature RECENT experiments1-&apos; have shown that single crystals of a alumina (sapphire) can deform plastically, particularly at temperatures greater than 1000°C. The effect of this plastic flow on the fracture behavior of sapphire was not established, but range 1100º to 1500ºC. Mechanical twins, both (0001) and (0111) types, were produced by compression in the temperature range 1100" to 1300°C. Cracks propagated more readily along the twin boundaries than in the nontwinned crystal. experiments with other ceramic crystals4&apos;5 have shown that plastic flow can initiate cracks that lead to catastrophic failure. This suggests by analogy that plastic flow might also be an important factor in the fracture of sapphire crystals. A recent experimental investigationS undertaken to determine the mechanism of plastic flow in sapphire provided an opportunity to study the type of fracture produced after various amounts of plastic shear strain. The results of this study of fracture are reported in the present paper. During the course of

Jan 1, 1963