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By W. T. Roberts, N. G. Turner

A study of the fatigue properties of several grades of commercially pure titanium has established that the strain-aging process is of minor importance in the development of a fatigue limit and a relatively high fatigue strength ratio. Metallographic observations and damping measurements at room temperature indicate that striations are able to spread from grain to grain only at stress levels above the fatigue limit. This suggests that the fatigue limit represents the stress above which large-scale dislocation unlocking takes place. Fatigue tests on annealed material at - 60" and - 196" c showed that under conditions when a thermally activated diffusion process would be suppressed the fatigue limit is not eliminated. Prestraining at room temperature did not have a detrimental effect on fatigue strength at room temperature but a decrease was recorded at — 60°C. This is further evidence that initial dislocation locking is a important strengthening mechanism. TITANIUM and titanium alloys have S-N curves with a definite fatigue limit, and a high ratio of fatigue limit to UTS can be attained. Other materials which show similar fatigue characteristics are mild steel and some Al-Mg alloys. The fatigue limit of these materials has been associated with their strain-aging capacity. It is well-known that commercial-purity titanium contains interstitial impurities which can give rise to a sharp yield point, and a small strain-aging effect following static strain has been demonstrated.7 This type of aging reaction is differentiated from the dynamic aging process when aging occurs during plastic deformation, and which is generally observed at elevated temperatures. In a titanium at room temperature, dislocation locking is associated with the interaction of interstitial oxygen, nitrogen, and carbon atoms with dislocations. Ehr-lich has shown that the distortion produced by introduction of these atoms into the hcp lattice has no shear stress component and hence there is no interaction between the stress field and the screw component of a dislocation. Thus the dislocations as a whole are only weakly locked. It is clear that strain-aging effects in hcp a titanium will be much less pronounced than those observed in bcc iron and steel. In recent years, the attribution of the fatigue limit solely to strain aging has been questioned. It has been pointed out that a definite fatigue limit is observed at temperatures as low as -196°C in some titanium alloys,' and strain aging is not expected to be effective at this temperature. The role of initial locking of dislocations in determining fatigue behavior has been examined in low-carbon steel by Oates and Wilson. They showed that under conditions in which the aging potential is low the factors which control the buildup of local stresses and hence affect dislocation unlocking, e.g., grain size, are important. There are indications that other metals can have a definite fatigue limit with no established strain-aging capacity, an example being magnesium12 which has the same crystal structure as a titanium. The spread of plasticity from grain to grain in hexagonal metals may be more difficult than in cubic metals because of the limited number of slip systems in the former, and this may account in part for their fatigue behavior. The present work was undertaken to elucidate the relative importance of crystal structure, strain aging, and initial dislocation locking in determining the properties of commercially pure titanium when subjected to cyclic stressing. 1) EXPERIMENTAL METHODS Three grades of commercial-purity titanium were used and a material of lower interstitial content was prepared by melting high-purity Japanese sponge titanium (referred to as H.P. Ti). The compositions and typical mechanical properties of the materials are shown in Table I. Fatigue tests were made in push-pull (zero mean stress) using an Amsler Vibraphore machine at a frequency of about 160 cps. Two types of fatigue specimen were used—one with a waisted gage length for determination of S-N curves and the other with a parallel gage length for metallographic studies and damping measurements. After careful machining and mechanical polishing, all specimens were electropolished prior to fatigue testing. The electrolyte consisted of 10 parts methyl alcohol, 6 parts 2-butoxyethanol, and 1 part perchloric acid (SG 1.54) and it was maintained at a temperature of -10" to -20°C during polishing. Tests at room temperature were normally carried out with the specimen immersed in a silicone oil bath which could be heated for elevated-temperature tests.

Jan 1, 1969

By W. C. Ellis, E. S. Greiner, M. E. Fine

Discontinuous changes of Young's modulus, internal friction, coefficient of expansion, electrical resistivity, and thermoelectric power are evidence for a transition in chromium near 37OC. Although the X-ray diffraction pattern gives no clue, a difference between the thermal expansivity and the temperature dependence of the lattice parameter suggests a crystal-lographic change. Young's modulus data disclosed another transition near THE thermal dependence of a number of proper- ties of chromium indicates a transition occurring over a temperature range near room temperature. Bridgman' noted this first from a minimum in the electrical resistivity near 12°C. In a sample of greater purity, Sochtig' observed the minimum at 41 °C. Erfling3 reported an inflection in the thermal expansivity curve at 36°C. These temperature-dependence curves are reversible with no hysteresis being detected. No discontinuity or inflection has been observed in the heat capacity' or the paramagnetic susceptibility.' Likewise, no one has noted a change in crystal symmetry. In the present investigation Young's modulus, internal friction, coefficient of expansion, electrical resistivity, illustrated in Fig. 1, lattice constant, Fig. 2, thermal electromotive force, Fig. 3, and paramagnetic susceptibility, Fig. 4, were measured over an extended temperature range. The samples were prepared in two ways: (1) By cold pressing a sintered electrolytic powder compact,' and (2) by electroforming from an aqueous solution. The electroformed samples were prepared by R. A. Ehrhardt and G. Bittrich by plating on copper or nickel tubes from an aqueous solution according to the method of Brenner, Burkhead, and Jennings.' The pressed powder samples (method 1) were finally annealed at 1400°C in purified helium: the electroformed samples, packed in powdered chromium, were vacuum-annealed at 1000°C. From the composition of the original powder' the purity of the pressed powder samples is estimated to be 99.8 pct Cr. Spectrochemical analysis furnished by E. K. Jaycox, revealed only slight traces of impurities in the electroformed sample (less than 0.001 pct), neither iron nor nickel being detected. Chromium deposited by this method is reported to contain approximately 0.05 pct 0.- Methods and Data Young's Modulus: For measurement of Young's modulus, an annealed, pressed powder sample, 0.114 x0.237x1.845 in., and an electroformed sample, 0.10 in. od, 0.01 in. id, and 1.86 in. long, were prepared. The resonant frequencies of the rod samples in forced longitudinal vibration were measured at a series of temperatures from —192" to 200°C by a method previously de~cribed.6,7 Because the samples were nonferromagnetic, iron- silicon or molybdenum permalloy tips (0.013 in. thick) were soldered to the ends. The softening temperature of the solder limited the temperature of measurement. Young's modulus, E,, of chromium at temperature, T, may be calculated from the resonant frequency of the composite rod, f,; the thickness of the tips, t; the length of the chromium sample at 25°C, l,.; the density of chromium at 25°C, pc (7.20 g per cc);5 and the thermal expansivity, Al/l25. Modulus differences for two temperatures, ET and E, are accurate to +0.002x10" dynes per cm2. ET = 4PAlc+2tyf Young's modulus at 25°C, Fig. la, is 28.2~10" dynes per cm' (40.8xlO" si) in wrought chromium (upper curve). The modulus of the electroformed sample is apparently lower due to cracks. From the modulus measurements two transitions were observed: one with a critical temperature at 37°C, the other at —152°C. Internal Friction: The internal friction, 1/Q, was determined from the width, Af, of the strain amplitude-frequency curve at 0.707 times the strain amplitude at resonance;' the internal friction, 1/Q, then equals Af/f. Fig. lb shows a sharp peak in internal friction at 38°C. The internal friction of the electroformed sample had a similar maximum. Thermal Expansion: The expansivity measurements, shown in Fig. 2, covering the temperature range —195" to +400°C were made by D. MacNair in an interferometric dilatometer8 sing a sample consisting of three pyramids 0.25 in. high prepared from wrought electrolytic chromium. Below —120°C the experimental points deviated up to ±2x10 from the drawn expansivity curve in Fig. 2 because of decreased precision of the quartz wedge thermometer at low temperatures. Near 38°C the thermal expansivity curve, Fig. 2, goes through an inflection corresponding to a minimum in the coefficient of expansion, Fig. ld, and a relative volume decrease on heating. Electrical Resistivity: The variation of electrical resistivity with temperature measured by the po-tentiometric method is also shown in Fig. l. The resistivity of the wrought chromium (upper curve) at 20°C is 13.6 microhm-cm; of electroformed chromium (lower curve) 12.8 microhm-cm. The lower value reflects higher purity and agrees closely with a published value." A minimum at 40°C occurs in the resistivity curves of both samples. No conclusive evidence for a transition near — 150°C was observed, but the points, Fig. 1, appear to deviate from a smooth curve between —120" and —160°C.

Jan 1, 1952

By W. G. Pfann

In zone-melting, a small molten zone or zones traverse a long charge of alloy or impure metal. Consequences of this manner of freezing are examined with impurerespect to solute distribution in the ingot, with particular reference to purification and to prevention of segregation. Results are expressed in terms of the number, size, and direction of travel of the zones, the initial intermsofsolute distribution, and the distribution coefficient. IF a charge of binary solid-solution alloy is melted and then frozen slowly from one end, as for example in the Bridgman method of making single crystals,' coring usually occurs, with a resulting end-to-end variation in concentration. Such coring, or normal segregation, is undesirable where uniformity is an object. On the other hand, for certain systems, it can be utilized to refine a material by concentrating impurities at one end of the ingot.'. ' In the present paper a different manner of freezing will be examined with respect to the distribution of solute in the ingot. A number of procedures will be indicated which have in common the traversal of a relatively long charge of solid alloy by a small molten zone. Such methods will be denoted by the general term zone-,melting, while the process described in the preceding paragraph will be called normal freezing. It will be shown that, in contrast to normal freezing, zone-melting affords wide latitude in possible distributions of solute. Segregation can either be almost entirely eliminated or it can be enhanced so as to provide a high degree of sttparation of solute and solvent. A number of simplifying assumptions will be invoked which, while not entirely realizable in practice, nevertheless provide a suitable point of departure for more refined treatments. Moreover, our own experience with zone-melting has shown that, for certain systems at least, the analysis holds quite well. The present paper will be confined to a discussion of principles and a general description of procedures. Comparison with experiment is planned for later publication. Normal Freezing Before considering zone-melting, segregation during normal freezing will be reviewed briefly. If a cylinder of molten binary alloy is made to freeze from one end as in Fig. 1, there usually will be a segregating action which will concentrate the solute in one or the other end of the ingot. If the constitutional diagram for the system is like that of Fig. 2, then the distribution coefficient k, defined as the ratio of the concentration in the solid to that in the liquid at equilibrium, will be less than one and the solute will be concentrated in the last regions to freeze. If the solute raises the freezing point, then k will be greater than one and the solute will be concentrated in the first regions to freeze. The concentration in the solid as a function of g, the fraction which has solidified, can be expressed by the relation: C = kC0 (1-g)k-1 [I] where C, is the initial solute concentration in the melt. Eq 1 is based on the following assumptions: 1—Diffusion in the solid is negligible. 2—Diffusion in the liquid is complete (i.e., concentration in the liquid is uniform). 3—k is constant. Concentration curves representing eq 1 for k's from 0.01 to 5.0 are plotted in Fig. 3. This equation, in one form or another, has been treated by Gulliver,³ Scheuer,4 Hayes and Chipman5 for alloys and by McFee2 for NaCl crystals. It is derived in Appendix I. It should be pointed out that the k which is calculated from the phase diagram will be valid only in the ideal case for which the stated assumptions are correct. In all actual cases, the effective k will be larger than this value for solutes which lower the melting point, smaller for solutes which raise the melting point, and will probably vary during the beginning of the freezing process. For simplification it will be assumed that the ideal k is valid. Zone-Leveling Processes The processes of this part are designed to produce a uniform, or level, distribution of solute in the ingot. Single Pass: Consider a rod or charge of alloy whose cross-section is constant and whose composition, C2, is constant, although permissibly varying on a microscopic scale." Such a charge might be a rapidly frozen casting or a mixture of crushed or powdered constituents. Cause a molten zone of

Jan 1, 1953

By James Douglas

In discussing the waste upon which hinges, or is supposed to hinge, so largely the preservation of our national resources, the conclusions reached would be more reliable if actual experience were consulted, and fewer deductions were drawn from general statements, which are often the product of the imagination. It cannot be questioned that the value of by-products has .not been sufficiently appreciated by us, and that our tardiness in recovering the useful ingredients of the escaping gas of our coke-ovens is one of the most glaring instances of shortcoming in that direction. And yet even for that sin there is some palliation in the immature condition of affiliated industries. I presume that it is admitted, without argument, that, except under very exceptional conditions, all the elements cannot be recovered from most of the ores or natural products which we treat. While it is a shame that the by-products from our coke-ovens should be dissipated, Edward W. Parker's report to the U. S. Geological Survey for 19061 supplies a fairly good excuse in justification of this appalling waste. He says (pp. 773 to 774.): " What has been already commented on in previous reports about the slowness of manufacturers to change from the better known but wasteful beehive practice to the by-product recovery method of coke manufacture is particularly emphasized in the statistics presented in this chapter. For it would appear from the table following that the construction of by-product ovens had about come to a standstill, especially when the records for the preceding five years are taken into consideration. At the close of 1901, when there were only 1,165 by-product ovens completed in the United States, there were 1,533 in course of construction, 498 of which were completed during the following year. At the close of 1902, 1,346 retort ovens were building, 293 of which were added to the completed plants in 1903. At the close of 1903, 1,335 new ovens were building and 954 of these

Jan 1, 1910

By George M. Fowler, F. E. Gregory, William M. Agar, Joseph P. Lyden

The fact that most of the zinc-lead ores of the Tri-State district are associated with abundant chert in the Boone formation has led us to give much consideration to the manner of occurrence of the chert throughout the formation and to its relationship to the structural and other geologic features having bearing upon the sulfide mineralization. Necessarily the question of the source and the manner of deposition of the chert has come up in the course of these studies. We do not pretend to have arrived at the answer to all the questions regarding the chert. However, we have made a very large number of field observations, which present certain facts about the chert in this district that may be worth elaboration. Whatever theories may be drawn upon to explain the presence and distribution of the chert must necessarily be capable of reconciliation to these facts. The more important theories that have been presented are briefly summarized, and some of them discussed, in this paper. This paper is in three distinct parts, each complete in itself, wherein is recorded the evidence gained from three separate methods of attack. In an earlier paper,(3)‡ we briefly described the chert and its relation-ship to the ore deposits. Chertification, as used in this paper, means the replacement of limestone by introduced silicic acid. It is a common phenomenon in many widely distributed limestones. The products of chertification may be chert, cotton rock, or tripoli, depending upon the extent to which the replacement has been carried. Chertification is used instead of silicifica-tion in order to reserve the latter for the siliceous emanations so common in connection with the sulfide ore deposits of this and many other districts. Broadly, it is meant to include all silicification in this district prior to the introduction of the jasperoid, the latter being contemporaneous with the ore-bearing solutions.

Jan 1, 1935

By William M. Agar, F. E. Gregory, Joseph P. Lyden, George M. Fowler

The fact that most of the zinc-lead ores of the Tri-State district are associated with abundant chert in the Boone formation has led us to give much consideration to the manner of occurrence of the chert throughout the formation and to its relationship to the structural and other geologic features having bearing upon the sulfide mineralization. Necessarily the question of the source and the manner of deposition of the chert has come up in the course of these studies. We do not pretend to have arrived at the answer to all the questions regarding the chert. However, we have made a very large number of field observations, which present certain facts about the chert in this district that may be worth elaboration. Whatever theories may be drawn upon to explain the presence and distribution of the chert must necessarily be capable of reconciliation to these facts. The more important theories that have been presented are briefly summarized, and some of them discussed, in this paper. This paper is in three distinct parts, each complete in itself, wherein is recorded the evidence gained from three separate methods of attack. In an earlier paper,(3)‡ we briefly described the chert and its relation-ship to the ore deposits. Chertification, as used in this paper, means the replacement of limestone by introduced silicic acid. It is a common phenomenon in many widely distributed limestones. The products of chertification may be chert, cotton rock, or tripoli, depending upon the extent to which the replacement has been carried. Chertification is used instead of silicifica-tion in order to reserve the latter for the siliceous emanations so common in connection with the sulfide ore deposits of this and many other districts. Broadly, it is meant to include all silicification in this district prior to the introduction of the jasperoid, the latter being contemporaneous with the ore-bearing solutions.

Jan 1, 1935

The fact that most of the zinc-lead ores of the Tri-State district are associated with abundant chert in the Boone formation has led us to give much consideration to the manner of occurrence of the chert throughout the formation and to its relationship to the structural and other geologic features having bearing upon the sulfide mineralization. Necessarily the question of the source and the manner of deposition of the chert has come up in the course of these studies. We do not pretend to have arrived at the answer to all the questions regarding the chert. However, we have made a very large number of field observations, which present certain facts about the chert in this district that may be worth elaboration. Whatever theories may be drawn upon to explain the presence and distribution of the chert must necessarily be capable of reconciliation to these facts. The more important theories that have been presented are briefly summarized, and some of them discussed, in this paper. This paper is in three distinct parts, each complete in itself, wherein is recorded the evidence gained from three separate methods of attack. In an earlier paper,(3)‡ we briefly described the chert and its relation-ship to the ore deposits. Chertification, as used in this paper, means the replacement of limestone by introduced silicic acid. It is a common phenomenon in many widely distributed limestones. The products of chertification may be chert, cotton rock, or tripoli, depending upon the extent to which the replacement has been carried. Chertification is used instead of silicifica-tion in order to reserve the latter for the siliceous emanations so common in connection with the sulfide ore deposits of this and many other districts. Broadly, it is meant to include all silicification in this district prior to the introduction of the jasperoid, the latter being contemporaneous with the ore-bearing solutions.

Jan 1, 1935

By F. E. Gregory, George M. Fowler, William M. Agar, Joseph P. Lyden

The fact that most of the zinc-lead ores of the Tri-State district are associated with abundant chert in the Boone formation has led us to give much consideration to the manner of occurrence of the chert throughout the formation and to its relationship to the structural and other geologic features having bearing upon the sulfide mineralization. Necessarily the question of the source and the manner of deposition of the chert has come up in the course of these studies. We do not pretend to have arrived at the answer to all the questions regarding the chert. However, we have made a very large number of field observations, which present certain facts about the chert in this district that may be worth elaboration. Whatever theories may be drawn upon to explain the presence and distribution of the chert must necessarily be capable of reconciliation to these facts. The more important theories that have been presented are briefly summarized, and some of them discussed, in this paper. This paper is in three distinct parts, each complete in itself, wherein is recorded the evidence gained from three separate methods of attack. In an earlier paper,(3)‡ we briefly described the chert and its relation-ship to the ore deposits. Chertification, as used in this paper, means the replacement of limestone by introduced silicic acid. It is a common phenomenon in many widely distributed limestones. The products of chertification may be chert, cotton rock, or tripoli, depending upon the extent to which the replacement has been carried. Chertification is used instead of silicifica-tion in order to reserve the latter for the siliceous emanations so common in connection with the sulfide ore deposits of this and many other districts. Broadly, it is meant to include all silicification in this district prior to the introduction of the jasperoid, the latter being contemporaneous with the ore-bearing solutions.

Jan 1, 1935

By Persifor Frazer

"The nebular theory is a noble speculation supported by plausible argument, and the verdict of science on the whole subject cannot be better expressed than in the words of Newcomb :—'At the present time we can only say that the nebular hypothesis is indicated by the general tendencies of the laws of nature, that it has not been proved to be inconsistent with any fact, that it is almost a necessary consequence of the only theory by which we can account for the origin and conservation of the sun's heat, but that it rests on the assumption that this conservation is to be explained by the laws of nature as we now see them in operation. Should any one be skeptical as to the sufficiency of these laws to account for the present state of things, science can furnish no evidence strong enough to overthrow his doubts until the sun shall be found growing smaller by actual measurement, or the nebulæ be actually seen to condense into stars and systems.' " Leibnitz2 is credited by Cuvier3 (who associates with him Descartcs) with " amusing their imaginations " by conceiving the world to be an extinguished sun or vitrified globe upon which the vapors, condensing in proportion as it cooled, formed the seas, and afterwards deposited the calcareous strata. Whiston4 believed the earth was crested from the atmosphere of one comet and deluged by the tail of another. The heat which remained from its origin excited the whole antediluvian population, men and animals, to sin, for which they mere all drowned in the deluge, except the fish, whose passions were apparently less violent. De Maillet5 held that the globe had been covered by water for many thousand years. The terrestrial animals were originally inhabitants of the sea, and man himself began his career as a fish. He adds it is not uncommon to meet with fishes in

Jan 1, 1905

By Sadtler, C. B.

IT is generally assumed that in most metals and alloys a given tensile stress produces a given deformation irrespective of the length of time during which the stress is applied. This assumption is justified in most of the important engineering applications of metallic materials; however, in the case of some metals and alloys used or tested at temperatures over or slightly under that at which recrystallization can occur the assumption is not warranted.1 This paper deals with the variations of deformation produced by a constant tensile stress acting for varied lengths of time in the special case of thin aluminum alloy sheet of the duralumin type, which had been subjected to different thermal and mechanical treatments. The material investigated was in the form of a sheet approximately 0.002 in. thick, which had been cold-rolled from a thickness of 0.020 in. It has been found that at a sufficiently high constant tension such material deforms continuously with the elapse of time and that the rate at which this deformation occurs is greatly influenced by the previous thermal and mechanical treatments.

Jan 1, 1927

By R. McDonald, B. C. Maine

CERRO'S power system consists of three main hydroelectric plants and one steam-electric plant. These are located on the eastern slope of the main Andes range at altitudes between 12,000 and 13,000 ft. The hydroelectric group utilizes the watershed which extends for about 150 kilometers south from Cerro de Pasco, divided into two catchment areas which lie adjacent. The northern area serve,, the medium-head plant of Mal¬paso. while the southern area provides for the high-head plants at Pachachaca and Oroya. The rainfall, as registered at the rain gauging stations of the three hydroelectric plants, averages 33 in. per year; all these stations are subject to the same hydrological conditions, and the bulk of precipitation occurs between October and March. Rainfall during the dry season, April till September, has no appreciable effect on the total annual runoff. Table 1 shows the storage capacities of the main reservoirs of the hydroelectric group. The four plants are tied together electrically by a 50-kv. transmission network, the system being 3-phase 3-wire at 60 cycles with a solidly grounded

Jan 1, 1945

By R. K. Buhr, H. Thresh, M. Bergeron, F. Weinberg

The microsegregation of nickel and chromium in directionally solidified AISI 4340 steel castings has been measured using electron probe microanalysis. Minimum concentrations were observed to occur at the center of the dendrite stalks, as reported previously. However, the position of the maximum concentrations could not be determined from the dendrite configuration. An etching technique has been developed which shows the position of maximum concentration. Measurements were made of the distribution of nickel and chromium in the dendritic structure. The ratio of maximum to minimum concentration was determined as a function of primary dendrite arm spacing for both as-cast and partially homogenized materials. The results are compared with observations reported in the literatuve. A S part of an investigation of solute segregation in directionally solidified AISI 4340 steel casting, electron probe microanalysis was used to measure the distribution of nickel and chromium in the dendritically segregated material. This complemented the observations on the segregation of radioactive phosphorus obtained by autoradiographic techniques in the same castings.' Kattamis and I?lemings2 have reported similar measurements, using electron probe microanalysis, on dendritically segregated AISI 4340 steels. They found minimum solute concentrations occurred at the center of dendrites, maximum concentrations occurred in the center of interdendritic regions, for symmetrically oriented dendrites, and a regular variation of concentration within dendrite arms. The ratio of maximum to minimum concentration was found to be essentially independent of position in the castings, except near the chill surface where it was somewhat higher. Assuming complete diffusion in the liquid and no diffusion in the solid during freezing, they considered that isoconcentration curves in the steel were homothetic. As a result, isoconcentration curves of the various elements, contour surfaces of dendrites produced by isothermal-transformation studies, and the contour of the solid-liquid interface would all be similar, and could be superimposed by a uniform expansion or contraction of the contours. Preliminary results of the present investigation suggested that isoconcentration curves were not homothetic. It was also evident that points of maximum concentration could not be predicted from the dendrite configuration. Since the ratio of maximum to minimum concentration appeared to be an important parameter in defining the overall segregation in a casting, other techniques for determining the point of maximum concentration were investigated. In addition the overall solute distribution associated with the dendritic structure was examined for both nickel and chromium, and the consistency of the distribution for neighboring dendrites was determined. METHOD Fifty-pound heats of AISI 4340 steel were cast in a manner similar to that used by Flemings et al3 with a water-cooled copper base plate and exothermic sides and top. The nominal composition of the material was C, 0.41 pct; Mn, 0.66; Si, 0.35; S, 0.012; P, 0.010; Ni, 1.88; Cr, 0.95; Mo, 0.28. The steel solidified directionally from the chill surface, with a dendritic structure which increased in dendrite arm spacing with increased distance from the chill. Results of the general investigation of the cast structure and segregation of radioactive phosphorus in these castings have been reported elsewhere.' For the present measurements, sections were cut from the casting at several distances from the chill surface. The sections were subsequently heat-treated, mounted, and then polished on a plane perpendicular to the general freezing direction of the casting. Electron probe microanalysis was carried out with the JEOL-JXA3 microprobe using a voltage of 25 kev and beam current of 0.15 µa. The take-off angle is 22 deg. Quartz crystals were used in the spectrometers and measurements made for Ka radiation from both nickel and chromium simultaneously. A thin layer of carbon was deposited on all specimen surfaces prior to examination in the microprobe. Early measurements were made on polished surfaces, with indentation marks produced by a hardness tester to indicate the area of interest. It was found desirable to use etched surfaces, as opposed to polished surfaces, to reduce sample preparation time and more readily relate the microprobe scan to the structure. To determine if this could be done, without introducing significant errors, a series of measurements were made on polished and etched surfaces of the same specimen. Both polished and etched surfaces produced similar results within normal scatter as shown in the observations. Subsequent measurements were then made on etched surfaces. Measurements with the microprobe analyzer were made by point counting, for periods of 100 sec, at 10-µ intervals. Ten-second counts were made on pure nickel and chromium standards, incorporated in the specimen mount before and after each set of measurements. The results were adjusted for background, then corrected for dead time using the expression:

Jan 1, 1969

By M. F. Burr, F. V. Lenel, G. S. Ansell

The mechanism of materials transport was studied in a model experiment in which a silver sphere was sintered to a silver plate under an applied external stress near 800° C. For this purpose the rate of growth of the neck between the sphere and the plate which is proportional to the strain rate of the creep process involved in a neck growth was determined by measuring the change in electrical resistance of the away. This rate of neck growth will depend upon the magnitude of the applied external stress. By measuring the rate just before and just after a change in the external load and therefore the applied stress, the relationship between strain rate and stress can be derived. For material transport by slip in a pure metal it is expected that the strain rate should be proportional to the 4.5th power of the stress, while for transport by diffusional flow the strain rate should be proportional to the first power of the stress. It was found that for stresses above 5 X 10' dynes per sq cm (70 psi) the exponent in the stvain rate-stress relationship was near 4.5 while for a stress of 0.7 x 108 dynes per sq cm (10 psi) an exponent of 1.8 was determined indicating that under the conditions of the experiment the transport mechanism for creep in silver shifts from diffusional flow to slip in the region of 0.7 x 106 dynes per sq cm (10 psi). The importance of these findings for an understanding of the mechanism of material transport in conventional sintering (without an external load) is pointed out. In a paper by Early et al.,' the mechanism of material transport during sintering was treated as a creep process. It was pointed out that two possible types of creep processes could operate during sintering. In one of these material transport takes place by vacancy diffusion due to a gradient in chemical potential. The vacancy sinks in this diffusion process may be either grain boundaries, as in Herring-Nabarro microcreep, or regions beneath a surface of small radius of curvature. The diffusive transport may be by volume, grain boundary, or surface diffusion. In the other mechanism, creep takes place by slip, i.e., dislocation motion with its rate generally controlled by dislocation climb. One method of distinguishing between these two modes of materials transport is to investigate the creep rate, i.e., the rate of material transport as a function of stress. For material transport by vacancy diffusion, the creep rate is proportional to the stress.' For creep by slip, controlled by dislocation climb, the creep rate is proportional to a power of the stress. For pure metals this power is 4.5;374 for dispersion-strengthened material a fourth power relationship can be derived.5 This difference in the stress dependence of the strain rate is illustrated schematically in Fig. 1, in which the logarithm of strain rate is plotted vs the logarithm of the stress for material transport in a pure metal by vacancy flux and by dislocation climb. The stress range in which the two types of material transport overlap would be expected to be relatively small. In the experiments described by Early and coworkers compacts pressed from spherical copper powder were sintered isothermally under an applied axial external load in a dilatometer. During sintering the magnitude of the applied external load was changed and the rate of axial shrinkage of the compact before and after the load change determined. In order to find the stress dependence of the strain rate the magnitude of the stress acting on the neck area between the spherical particles before and after the load change had to be calculated. This stress is the resultant of the stresses due both to the externally applied load and to surface tension. The stress due to surface tension is a function of the geometry of the powder compacts. It can be determined, at least for simple geometrical arrays,'76 but it is difficult to obtain exact values of the stresses for actual powder compacts when only average values of particle diameters and of neck diameters between particles are available. The calculation of stress and the strain rate-stress relationship is therefore only very approximate.

Jan 1, 1968

By W. A. Backofen, B. C. Wonsiewicz

The Plasticity transition in magnesium was studied by plane-strain compression of single crystals and polycrystalline material at temperatures from about 20" to 307°C. Reduction of single crystals along the c axis was accommodated by twinning on {1011) and retwinning on (10 12}, followed by basal shear in the doubly twinned volume. Deformation in that mode can result in sufficient independent shears for arbitrary shape change. Fracture in c axis compression, below about 100°C, has been related to excessive shear caused by unloading from the stress for {1011} twinning (-50 ksi at 20°C) to that for slip within the twin (-3 ksi); ductility follows from heating because the stress difference is lowered and the twin volume, in which elastic strain energy is dissipated on unloading, is increased. The stress for (1011) twinning is strongly temperature-dependent but not given by a critical resolved shear stress law. The latter is attributed to the influence of stress concentration from prior intersecting shear on nonbasal planes, the former to the temperature dependence of the preliminary slip. THE basic symmetry of hcp crystals has the effect of limiting the number of independent slip systems and making twinning an important deformation mechanism. The general result in wrought polycrystalline aggregates is a more or less sharply developed texture (or preferred orientation) which underlies a strong anisotropy in mechanical behavior. Knowing how the one influences the other is essential background for the use of such materials. Magnesium was of interest in this work because of the unexplained plasticity transition that it undergoes somewhere in the neighborhood of 200°c.''~ At lower temperatures plastic deformation before fracture in polycrystalline material is limited, while at higher temperatures extensive deformation is possible. The transition temperature commonly determines the lower limit of the range in which magnesium is worked. The limited ductility can be traced to a lack of independent crystallographic shears. A minimum of five are required for arbitrary shape change.' Around room temperature, however, slip on all known systems provides only four.' In each case, the slip direction is in the (0001) basal plane so that slip does not allow strain along the c axis. With increasing temperature, more slip occurs on the ( 1011) pyramidal plane and the ( 1010) prism plane but without change in direction.'?' Thus, that development alone cannot explain the transition temperature.

Jan 1, 1968

By F. O. Shuck, F. E. Butler

A diaphragm diffusion cell suitable for use with liquid metals was designed and tested by measuring the diffusion coefficients for a Hg-10 pct In alloy at 25°C. The binary diffusion coefficient and the coefficients for In and Hg tracers were measured at this composition. The measured coefficients for both tracers were less than the binary diffusion coefficient. When these coefficients were combined with the activity correction term of Darken, the predicted binary coefficient was somewhat higher than the experimental value. In recent years a number of investigators have been studying diffusion of liquid metals in order to gain a better understanding of the liquid state and to examine possible applications to liquid metal processing. The bulk of this work has involved either self-diffusion or diffusion of low concentrations of solute metals in an essentially pure solvent metal. The most common experimental technique employed has been the capillary-reservoir method of Anderson and saddington1 since it is well-suited to measurements involving low concentrations of solutes. As an expansion of previous studies, an investigation of the variation of diffusion coefficient over large composition ranges has been undertaken in this laboratory. Although it is possible to modify the capillary-reservoir method for such measurements, the technique loses its principal advantage of requiring only small quantities of solutes. Therefore, it was felt desirable to investigate other possible experimental techniques applicable to measurements over large composition ranges. A technique which has been used widely in measurements of other liquid systems and seemed potentially applicable to studies of liquid metals was the diaphragm cell. This method has been found to combine relative simplicity of operation with accurate and reproducible results. In use with normal liquids, the tyiical diaphragm cell utilizes a porous glass disk. However, because of the high surface tension, it is not possible to use a diaphragm of such fine pore structure with liquid metals. Furthermore. projected use at high temperatures makes the use of glass undesirable. Consequently, the first problem was the search for an appropriate cell design. EXPERLMENTAL Diaphragm Cell. A number of possible cell designs were examined. Prototypes of several were constructed and tested. The final design is shown in an exploded view in Fig. 1. The cell consists of two identical chambers, one on either side of a 0.20-in.-thick partition. The chambers are 0.15 in. deep and have a volume of 3.45 cu cm. Each chamber is provided with two small threaded holes for filling and emptying. The filling holes may be sealed with stainless-steel screws. Drilled lengthwise through the center partition is a 0.250-in.-diam hole. Inserted into this hole is a rod having seven 0.059-in.-diam holes drilled radially through it. The total "hole" volume is 0.078 cu cm. When the rod is properly aligned, the holes in it constitute the "diaphragm" through which diffusion occurs. The center section was of Teflon and the rod and face plates were of Plexiglas. Four such cells were constructed and used in this study. Subsequent to this investigation, a similar cell constructed entirely of iron was fabricated and tested at higher temperatures. Several considerations led to this final design. It is desirable to minimize the volume of the cell chambers to decrease the time required for a measurement. However, the total volume of metal in the diaphragm must be small in comparison with that in the chambers. To facilitate filling and emptying it is desirable to have a diaphragm which may be closed.

Jan 1, 1970

By F. R. Brotzen, L. D. Whitmire

Single crystals of high-purity molybdenum were de-formed at temperatures from 195°to 473°K, and the effect of deformation on the electrical resistivily was deler-mined. To separale the resislivity components of point and line defecls some cryslals were annealed at 473°K. The vale of resislivily increase wilh strain was nearly linear and was strongly dependent upon the deformation temperature. Point dejects are annealed out without any effect on the flow stress. At low temperatures the flow stress is a linear function of the square root of the resistivity increase attributable to dislocations. ELECTRICAL-resistivity measurements have been used successfully to gain information on structural changes in metallic materials. During plastic deformation the electrical resistivity rises because of electron scattering from newly created lattice defects. Such measurements lend themselves, therefore, to corroborating results from direct observation of lattice defects and, to a certain extent, to correlating defect densities and distribution with mechanical properties. Published information on research with single crystals of the bcc metals of Group VI, particularly molybdenum, is still limited. Yet, molybdenum single crystals of relatively high purity can be readily prepared by electron-beam-melting techniques. Furthermore, some valuable information on the defect structure of deformed crystals by direct observation is available. Lawley and Gaigher,1 for example, have examined dislocation configurations in deformed molybdenum crystals by means of transmission electron microscopy. Their results revealed that the dislocation density and distribution were strongly dependent upon the deformation temperature. These findings differed from those by Keh and weissmann,2 who found that the average dislocation density in polycrystalline iron deformed between 138° and 298°K depended only on the degree of strain and not on the deformation temperature. Martin3 and peiffer4 showed that point defects introduced in polycrystalline molybdenum by cold work can be eliminated by annealing at a relatively low tempera-ture. In view of their work it became apparent that resistivity measurements of suitably annealed crystals could disclose changes in their dislocation structure and contribute to the understanding of the work hardening of molybdenum crystals. EXPERIMENTAL PROCEDURE Crystals were grown by electron-beam zone melting5,6 of 0.062-in.-diam molybdenum rods (99.99 pct) supplied by General Electric Lamp and Wire Division, Dover, Ohio. The crystals, about 4 in. long, were prepared by using five zone-refining passes at a speed of about 6 mm per min in a vacuum of about 5 X l0-6 Torr. The resistivity ratio of the crystal, p(4.Z°K)/p(273°K), was generally near 10-3. These crystals were used as tensile specimens of uniform diameter in the "as-grown" condition. They were oriented for maximum shear on the (011)[111] slip system (Schmid factor >0.49). The specimens were held in spherically seated Templin-type grips so as to minimize bending. Samples were deformed on an Instron machine at a strain rate of about 5 X 10-5 sec-1 in an isopentane bath with dry ice at 195°K, in ice water at 273°K, and in a vegetable-oil thermostat at 373° and 473°K. The temperature in the latter was maintained constant within +2°K. Resistance measurements were carried out with a Kelvin double bridge. The resistance of the potential leads was kept low by using large-diameter wires outside the low-temperature bath. Many of the resistance data were checked by measurements made with an ac bridge. Current and potential leads were spot-welded to the specimens. The distance between the potential leads, about 3 in., was also considered to be the gage length for the strain measurements. Diameter and gage length of the samples were measured optically with an error of less than 2 pct. These measurements were used also to insure that the deformation had been uniform over the gage length of the specimen. Resistivity changes were then determined from the resistance measurements at 4.2°K assuming constancy of volume. In the course of a test, the crystal diameter, gage length, and resistance at 4.2°K were determined first in the initial state and subsequently for various amounts of elongation.

Jan 1, 1968

By S. A. Braley

DRAINAGE water from coal mines is probably the most serious water pollution problem today, varying in importance according to location of the mines and geological structure. Drainage may be either acid or alkaline in character. Acid discharge, the most severely detrimental to a stream, is caused by natural oxidation of the sulfuritic material (FeS2) in the strata associated with the coal seam. Since the acid is the result of a natural reaction the acid water differs because it does not cease with abandonment of the mining operations. There is no known economical method of neutralizing acid mine water or any practical method to prevent oxidation of exposed pyrite. Since production of acid from a mine does not stop when mining stops, the total quantity produced depends entirely upon the excavated areas. The increasing volume of acid water in manv mines has greatly increased operating costs. Pumping is expensive and acid mine waters are destructive of all equipment, especially metals in pumps and piping, and necessitate the use of corrosion-resistant materials. Discharge of the acid mine drainage into streams neutralizes their normal alkalinity, causes them to become acid, and produces an environment unfavorable for aquatic life and unsuited for industrial or domestic use without costly treatment. Mine drainages vary in percentage composition over wide limits, although the usual dissolved substances are ferrous and ferric iron, aluminum, calcium and magnesium sulfates, and lesser amounts of sodium, potassium and manganese sulfates and chlorides. Some alkaline discharges may contain heavy concentrations of iron as iron bicarbonate. These waters may produce iron hydroxide deposits in the receiving stream but do not cause it to become acid. In the extensive literature on acid mine water there appears to be a great deal of confusion about the importance of various components and the methods for their determination. In many instances faulty conclusions have been drawn from use of unsuitable methods of analysis. It is desirable that the factors and terms used in evaluation of analyses of mine waters should be so clearly defined that any interested person could properly appraise any analytical report. Some analysts report complete chemical analyses of mine waters and neglect to record drainage volumes. Others report only a minimum of analytical data after taking no precautions to preserve the original composition of the water during the time elapsing between collection and analysis. Some use methods of analysis intended for so-called pure waters of the potable and boiler water classes. These methods are not applicable to highly buffered waters such as mine water. Probably the most common criteria for evaluation are pH, free acidity, or acidity or alkalinity to methyl orange or methyl red, total acidity or acidity to hot phenol-phthalein, and the sulfate content. If these determinations are made on carelessly collected samples after a few days to weeks standing in warm rooms, they do not in any way represent the character of the water flowing from the mines. It is hoped that a brief discussion of the fundamental value of some of these factors may lead to a bettqr understanding of the need for more careful evaluation of mine water discharges. The term pH is one used by chemists to express relative acidity or alkalinity in terms of concentration of effective hydrogen ion in a solution. It is defined as the negative logarithm of the hydrogen ion concentration or activity in equivalents per liter. pH = logarithm A neutral solution, which is one containing the same number of hydrogen and hydroxyl ions, has a pH of 7. As the hydrogen ions increase and the solution becomes more acid, the pH decreases toward zero; and as the hydroxyl ions increase and the solution becomes more alkaline, the pH approaches 14. When dissolved in water to a dilute solution acids like sulfuric and hydrochloric, commonly known as strong acids, ionize completely, and the pH or hydrogen ion concentration varies with molar concentration of the dissolved acid. However, in high concentrations of such acids, the pH or hydrogen ion concentration is less than the acid concentration because the acid does not completely ionize. In only very dilute solutions does the pH represent the total amount of acid that can be neutralized by an alkali. All ionization reactions are equilibrium reactions. If other chemicals are added to the solution of an acid and the added chemical produces an ion that is the same as one of the ions of the acid, the degree of ionization of the acid is altered and the pH changes to some value that represents the active hydrogen ion of the new solution. Thus if iron sulfate is added to a solution of sulfuric acid the pH increases, since the common sulfate ion suppresses the degree of ionization of the sulfuric acid and decreases the effective hydrogen ion. However, the total acidity of the solution is increased. There are two salts composed of iron and sulfate— ferrous and ferric sulfate. In these salts there is no hydrogen ion that can ionize to give an acid solution, but when they are dissolved in water, the pH is less than 7 and the solution becomes acid. This is caused by a reaction known as hydrolysis and is represented by the equations FeSO4 + 2H2O ? Fe(OH)2 + 2H + SO,: or Fe,(SO,)3 + 6H2O ? 2Fe(OH)3 + 6H+ + 3504 A solution with a total acidity of 5000 ppm according to the first equation will have a pH of 4.40 but one with an acidity of 75 ppm, according to the sec-

Jan 1, 1958

By Charles Clayton

IN connection with certain coöperative work carried on between the Ordnance Department of the U. S. Army, the U. S. Bureau of Mines, and the U. S. Geological Survey during the year 1918, it was the writers' privilege to make metallographic examinations of a great many test bars and other pieces of nickel-steel gun forgings. The material studied came from many different steel plants throughout the country and consisted both of forgings that had been accepted by the Ordnance Department and those that had failed to pass the specified physical tests. In general, these tests require a minimum tensile strength of 95,000 lb. (42,091 kg.), an elastic limit of 65,000 lb. (29,483 kg.), an 18 per cent. elongation, and a 30 per cent. reduction in area. An average chemical composition of the steel studied is 0.38 per cent. carbon and 2.9 per cent. nickel. The steel was of both basic electric and basic open-hearth manufacture. The object of the metallographic work was two-fold: to assist in detecting defects in the steel and, if possible, to suggest remedies for the same; and to obtain as much information as possible in regard to the relation of the microstructure of the metal to its physical properties. The greater part of the investigation was devoted to defective metal that failed to pass the ordnance specifications. Many types and kinds of more or less serious defects thus came under observation, but most of these were due to the attempts by the manufacturer to meet the enormous demand for ordnance steel with more or less inadequate equipment, and were soon remedied. Two defects, the so-called "flakes" or "snowflakes" and a certain "fibrous" or "woody" fracture, were encountered so frequently and were so disastrous to the steel that the greater part of the study was devoted to them. As a result much information as to their nature and their effects

Jan 2, 1919

By Günter Petzow, Siegfried Steeb

DURING an investigation of the U-Co-A1, U-Ir-A1, and U-Ni-A1 ternary systems, three previously unknown phases have been identified which correspond to the phases UCoA1, UIrA1, and UNiA1, and which be- long to the C22 (Fe2P) type (P 6 2m). In the following the structure determination of the new ternary phases is reported. The alloys have been prepared in an arc furnace under purified argon from 99.97 wt pct U, 99.83 wt pct Co, 99.99 wt pct Al, 99.95 wt pct Ni, and 99.97 wt pct Ir. The pellets obtained were bright and brittle; chemical analyses agreed with the nominal compositions. To obtain equilibrium, the samples were annealed in evacuated quartz capsules at 950°C for 30 hr and then quenched in water. Guinier photographs were processed and evaluated according to a method already described previously.1,2 The hkl's, measured and calculated sin2 6 values, and in the case of UCoAl only calculated and estimated intensities, are given in Tables I to 111. Lattice parameters refined according to the least-squares method and the respective mean-square variations are presented in Table IV. Lattice parameters, especially the c/a ratio, lead to the assumption that the three phases are crystallizing in the C22-type structure. For the calculation of the intensities given in Table I, the atomic positions recently reported by wyckoff3 have been accepted for the C22 (Fe2P) type. The uranium atoms were assumed to be in phosphorus sites; furthermore the scattering amplitudes of the boron atoms have been averaged in the stoichiometric formula UB2 according to atomic percentages; i.e., for these atoms a statistical distribution on the iron sites was assumed. The two smallest distances between a uranium and

Jan 1, 1967

By C. McCulloch

OPEN-PIT mining of coal is relatively a recent innovation; men still active in the industry can trace its development. Re- viewing the growth of operations from the original horse-drawn scrapers, through the various stages of power equipment to the huge strip- ping shovels of today, one also notes changes in the methods of what the coal man calls preparation at the face. We really should not call it face preparation because, in contrast to underground mining, a face does not exist in strip mining. Further, preparation of the coal for market at the loading point has already, in but a few years, become largely of historic interest only and modern mines as well as old mines recently modernized rely almost entirely on separate and elaborate preparation plants to produce marketable coal. This practice was not voluntarily adopted by the producer but was forced upon him by the inadequacy of previous

Jan 1, 1939