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By J. G. Morlet, A. R. Troiano, H. H. Johnson

Delayed failure in steel occurs by controlled initiation and growth of a crack. The incubation period for crack initiation was measured. Crack initiation and Propagation are controlled by interaction between hydrogen concentration and triaxial stress state. The incubation period results from stress-induced diffusion of hydrogen to the point of crack initiation. THIS paper describes the phenomenon of delayed failureland the kinetics of crack initiation and propagation in uniformly hydrogenated steel. The investigation was prompted by service failures of high-strength-steel components at applied stresses far below the conventional yield strength, after the part had successfully sustained equal or higher stresses for an extended time interval. This delayed failure phenomenon, often termed static fatigue, is associated1 with the presence of hydrogen. This is not surprising, since the voluminous literature on flaking and hydrogen embrit-tlement demonstrates that hydrogen may exert a potent embrittling influence. Flakes, or internal hairline cracks in alloy-steel forgings, are related to the presence of hydrogen retained from the steel-making process.2 On the other hand, embrit-tlement arises from hydrogen introduced during surface treatments such as acid pickling or electroplating. Laboratory delayed failures have been induced in notch specimens of 4340 steel by electrolytic charging of the specimen surface with hydrogen and subsequent static stressing.l,4,5 Static fatigue was observed over a wide range of applied stresses; however, failure did not occur below a critical applied stress, designated as the static fatigue limit. In this instance the extended time for failure resulted primarily from the macroscopic redistribution of hydrogen. A crack formed to the depth of the hydrogen enriched "case* upon loading; further crack growth naturally awaited diffusion of hydrogen into the material ahead of the crack. The crack-propagation rate was therefore controlled primarily by the macroscopic diffusion of hydrogen into the specimen interior during the test. Thus, in this instance static fatigue was associated with the movement of a gross concentration gradient. However, delayed failure in steel of uniform hydrogen concentration is of greater fundamental interest, as well as commercial significance. With a homogeneous hydrogen distribution a different mode of delayed failure might be expected. As the heterogeneous hydrogen distribution became more uniform,4,5 the initial crack-propagation rate decreased markedly and, in fact, what appeared to be an incubation period for crack initiation was observed. However, the macroscopic concentration gradient precluded an accurate evaluation of these observations. Although the existence of an incubation period, up to this time, has not been established definitely, it is not amiss to point out some implications of the concept. It is of interest in all hydrogen-induced embrittlement phenomena, such as flaking, delayed failure, and hydrogen embrittlement. Much discussion has centered around the possibility of an

Jan 1, 1959

The finding of gold, in enriching quantity, along the streams that issued from the western foothills of the Sierra Nevada was the prelude not only to the birth of an organized mining industry in California but to the intensive exploration of the entire Pacific slope; it presaged the feverish exploitation of the mineral resources that the ubiquitous prospector soon uncovered all over our western domain. At first when this migration began, as typified by the rush of 1849, there was no time to examine the signs of ore that were to be detected along the track of adventure, and, it must be added, not many in that motley crowd of gold-seekers were qualified to interpret the signs if they had lingered to look at them. Such intelligent curiosity as a few of them possessed was directed to the finding of gold chiefly, if not exclusively; and their good sense in this respect can not be impugned, because in a new and remote country the less valuable metals and minerals are unlikely to be worth the winning. Many of those that came to California crossed the alkaline wastes and sagebrush prairies that extend between the Great Sal? Lake and the ramparts of the snow-clad Sierra; when coming overland they found it convenient to halt on the eastern slope and to pitch their camp in the valley of the Car- son river before they began the tedious ascent of the mountains and the final entry into the land of gold. One of the trails most used by these immigrants followed the Carson river to the mountain meadows south of Lake Tahoe and then descended among the pine-woods of Placerville, where they went to work with pan and shovel in the gold-bearing streams

Jan 1, 1932

By P. D. Frost, H. A. Robinson, J. R. Doig, M. W. Mote

The mechanism of hardening in heat-treatable zirconium alloys was foUNd to be analogous to that for titanium alloys. Zirconium containing a relatively large addition of a ß -stabilizing element such as molybdenum or columbium can be hardened by the following transformation: Lean alloys, having insufficient alloy content to retain ß at room temperature are hardened by the following transformation: Application of these findings in Zr-Mo-Sn and Zr-Nb-Sn alloys produced strengths as high as 190,000 psi with reasonable ductility. PRIOR research on zirconium alloys has been concerned with development of greater strengths and creep resistance by solid-solution hardening or by dispersion hardening. Although solution and aging heat treatments had been applied earlier to zirconium alloys, quenching frequently produced low ductility. The possibility that the ß-to-w transformation, discovered earlier in titanium alloys,' might also occur in zirconium alloys and cause low ductility was considered, and, indeed, was found as predicted2 to be the case. In the earliest experiments, the heat-treatment response of titanium, too, was disappointing. However, by avoiding the formation of the embrittling w phase, it became practical to obtain room-temperature strengths higher than 180,000 psi, with elongation values of 10 pct.3 Based on the present concept of titanium heat treatment, the principal requirement for a heat-treatable zirconium alloy is that it contains a certain minimum amount of one or more ß -stabilizing elements. Only molybdenum, columbium, and tantalum, when present in sufficient amounts, are known to stabilize ß zirconium to room temperature during rapid cooling from the ß field. Tantalum was undesirable because of its high thermal-neutron cross section. Aluminum and tin are effective a stabilizers, but aluminum has been shown to seriously decrease the corrosion resistance of simple zirconium alloys in hot water. Therefore, for the present study, tin was used as the stabilizer addition. The alloys selected for this evaluation are presented in Table 1 along with their analyses and ß-transus temperatures. The analyses indicated that intended compositions were usually realized. EXPERIMENTAL PROCEDURES All of the alloys were melted from sponge zirconium and fabricated to sheet for heat treatment

Jan 1, 1960

By J. R. Long, R. S. Dean, F. S. Wartman, E. T. Hayes

The production of titanium in I5-lb. lots and with a purity sufficient to be consolidated into ductile metal, as described in a previous paper,' has provided adequate material for a study of the physical properties of titanium and a more thorough examination of its working qualities. Data on the physical properties reported in that paper were obtained on metal fabricated by a fixed procedure, standardized for the purpose of control of the reduction, and are representative only of material fabricated under those conditions. There are many possible variables in the working schedule, which will have significant effects on the properties of the finished material; and since the previous working methods were not necessarily the best, an investigation of the fabrication of titanium by other methods was undertaken. In this work the consolidation of the powder by pressing and sintering was conducted essentially as outlined in the report cited' and all efforts were centered on fabrication methods for those powders and the proper- ties produced by them. Hardness, density, microstructure, and tensile properties were determined at various stages in the working and annealing; and resistivity measurements were made on a few bars and drawn wire. Consolidation of the PowdeR The screen analysis of the available titanium powder is given in Table I. No attempt was made to alter the size distribution from that noted because this powder, although coarse by normal powder-metallurgy standards, produced acceptable compacts suitable for the present work. Because of their large specific surface, finer powders are more contaminated by oxygen and produce harder compacts, which are difficult to work. The powder as produced is soft, compresses in a normal fashion, and exhibits very little tendency to adhere to the die surfaces. Unlike aluminum and magnesium powders, it can be readily pressed without the use of die lubricants. When compacted at 50 tons per

Jan 1, 1946

By J. R. Long, E. T. Hayes, R. S. Dean, F. S. Wartman

The production of titanium in I5-lb. lots and with a purity sufficient to be consolidated into ductile metal, as described in a previous paper,' has provided adequate material for a study of the physical properties of titanium and a more thorough examination of its working qualities. Data on the physical properties reported in that paper were obtained on metal fabricated by a fixed procedure, standardized for the purpose of control of the reduction, and are representative only of material fabricated under those conditions. There are many possible variables in the working schedule, which will have significant effects on the properties of the finished material; and since the previous working methods were not necessarily the best, an investigation of the fabrication of titanium by other methods was undertaken. In this work the consolidation of the powder by pressing and sintering was conducted essentially as outlined in the report cited' and all efforts were centered on fabrication methods for those powders and the proper- ties produced by them. Hardness, density, microstructure, and tensile properties were determined at various stages in the working and annealing; and resistivity measurements were made on a few bars and drawn wire. Consolidation of the PowdeR The screen analysis of the available titanium powder is given in Table I. No attempt was made to alter the size distribution from that noted because this powder, although coarse by normal powder-metallurgy standards, produced acceptable compacts suitable for the present work. Because of their large specific surface, finer powders are more contaminated by oxygen and produce harder compacts, which are difficult to work. The powder as produced is soft, compresses in a normal fashion, and exhibits very little tendency to adhere to the die surfaces. Unlike aluminum and magnesium powders, it can be readily pressed without the use of die lubricants. When compacted at 50 tons per

Jan 1, 1946

By M. B. Ramachandra Rao

THIS paper records the results of the earth resistivity surveys made in the Godavari river in connection with the Ramapadasagar project. After describing the topographical and geological features of the area, the results of the investigation at the several sites have been mentioned. Further, a detailed account has been given of the resistivity methods adopted, the apparatus used and the interpretation of the curves. The resistivity measurements carried out over the water course have been specially outlined, and a review of the verification of the electrical indications by drilling in a number of cases, has also been presented.

Jan 1, 1947

By Cyril Wells, Robert F. Mehl

The purpose of this investigation was to prepare high-purity iron-carbon alloys, to determine as precisely as possible the A3(GOS), the Acm(SE), and the A1(PSK) transformation temperatures in the meta-stable iron-iron carbide system (up to 1.4 per cent C), and to study the influence of carefully controlled and constant rates of heating and cooling (1/8 to 2o C. per minute) upon the transformation temperature and upon the resulting microstructure. Apart from the general metallurgical importance attending the completion of such a task, it will be noted that highly precise transformation temperatures are of interest and importance in the thermodynamic study of this system1. Several determinations of the iron-iron carbide diagram have been made2. These suffer generally from the low purity of the alloys used, and from the application of methods of investigation of low sensitivity. Attempts to compare and weight the many data available in an effort to construct as accurate a diagram as possible have, in the main, been unsuccessful. In general, the wide differences in the results of different workers, the lack of complete analytical data, the omission of important details relating to the heat-treatment of the alloys, and the meager description of the methods of investigation applied, render such a process of averaging nearly meaningless. It may be seen from the summaries by Epstein2 and Körber and Oelsenl that variations as great as 30' C. exist in the reported data on the A3 temperatures in iron-carbon alloys. Fortunately, the Aa temperature in pure iron is now known to be 910" C. ± 1° C.3 The best recent work on iron-carbon alloys is that of Esser4 on hypoeutectoid steels and that of Sato5 on both hypoeutectoid and hyper-eutectoid steels. Esser made a dilatometric and magnetic study of iron and iron-carbon alloys containing 0.06 to 0.86 per cent C, for which a high purity is claimed. Presumably the electrolytic iron was reasonably pure, but the alloys contained considerable impurities, on the average totaling 0.35 per

Jan 1, 1937

By W. L. Finlay

Size effects in quenching steel are particularly prominent and well recognized because of the existence of a critical cooling rate separating nuclea-tion and growth transformations, as exemplified by the formation of pearl-ite, from the shear type of transformation characterizing the martensite reaction. The absence of a similar, sharply demarcating cooling rate is characteristic of precipitation hardening systems and size effects in these are correspondingly less prominent. This paper is concerned with a size effect in high-purity, precipitation-hardenable alloys which appears not to have been recognized previously. This effect is believed to result from the thermal fluctuations which inevitably occur in quenching a specimen of finite size into a cooling liquid rather than from the existence of a critical cooling rate. QUENCHING "ANOMALIES" The precipitation hardening literature contains many references to so-called anomalous quenching and aging results. By "anomalous", investigators usually meant that their alloys did not consistently harden on aging after quenching according to some anticipated pnttern: not infrequently virtually no age hardening occurred with compositions known to be precipitation-hardenable. Perhaps the most prominent series of anomalies was reported over a 15-year period by Gayler and coworkers on aluminum-copper.l,2,3,4 Working with silver-rich copper alloy, Cohen5 secured some very interesting Rockwell F hardness changes of from 1-5 Rockwell points between the first peak and valley. Fink and Smith borrowed one of Cohen's specimens and, following his heat treatment and quenching practice to the letter, secured6 very different results in which only one peak was obtained and in which the hardness level at the aging lime of Cohen's first peak was 20 Rockwell F points higher. Fink and Van Horn7 encountered serious deviations in age-hardening high purity aluminum-zinc alloys. They stated that "the discrepancies were larger than might be expected from possible experimental errors in the Brinell readings." Geisler, Barrett and Mehl8 likewise encountered anomalous hardening results in aluminum-silver alloys, securing quite different age-hardening curves from two identical specimens. They stated that "the treatments of these samples had been the same, so that the different behaviors could be attributed only to accidental variations in the quenching practice."

Jan 1, 1950

By G. Y. Chin, M. T. Dolan, W. L. Mammel

We have obtained by computer methods the solutions of the Taylor analysis1 for axisymmetric flow in bcc metals. Four modes of slip have been treated in detail:2-4 (111), {112}(111), {123}( 111), and a mixture of all three. In addition to obtaining anisotropy of strength data for randomly oriented or textured polycrystalline material,4 we have also obtained the lattice rotation resulting from slip on the predicted systems. The patterns of lattice rotation are essential to an improved understanding of texture development during deformation. The present note shows the results of lattice rotation for 5 pct axisymmetric compression, for fifty-two axial orientations distributed at 5-deg intervals throughout the standard stereographic triangle. The data are presented in Figs. 1 to 4 for the four modes of slip. The lattice rotation is indicated by a vector, the ends of which correspond to the positions before and after the deformation. The different vectors emanated from a given orientation represent different combinations of five slip systems that satisfy Taylor&apos;s minimum shear criterion.&apos; Fig. 1 shows the results for {110}< 111> slip. They are similar to those obtained by Bishop5 for the case of (111 )(110) slip in axisymrnetric tension, since in axisymmetric flow the sense of lattice rotation for {111)( 110) in tension is the same as that for (110) (111) in compression. The pattern of lattice rotation may be divided into three regions: region A in which the rotation is toward [100]; region B, toward [lll]; and region C, toward either [ loo] or L lll]. Although some slip combinations in region C lead to [1101, the latter is not stable as continued activity of the same combinations will eventually move the axis toward [loo] or Llll]. It may also be noted that [loo] is itself not stable. However, close inspection of the vectors in region A shows that it is impossible for an axial orientation within A to rotate outside its boundary. Hence after heavy compression, all orientations from A and some from C are expected to form a diffuse band in the [100] vicinity. By far the largest region is B. Here all orientations rotate to [lll], which is a truly stable position. Thus the [111] texture component is expected to be rather sharp. For the case of (112 }( 111) slip, Fig. 2, region C is enlarged at the expense of A, with B about the same as for {110}( 111) slip. A significant difference, however, is that [loo], as well as [Ill], is now truly stable. Fig. 3 shows the results of slip on {123}( 111) systems. Region B is substantially enlarged at the expense of C, with A being intermediate in size between the {110}(111) and {112}(111) cases. Like the case of {110)( 111) slip, [100] is itself unstable. However, the lattice rotations here are confined to less than 5 deg; hence it may be considered "stable" for practical purposes. Finally, Fig. 4 shows the results of mixed slip. Here region B is the largest, and C the smallest, of all the cases considered. Both [loo] and [ill] are stable. The behavior of the three corner positions is, in fact, identical to the case of {112)( 111) slip, Fig. 2; it turns out that in these positions for the mixed slip case, all the active slip systems (based on Taylor&apos;s criterion) belong to pure {112}( 111) .4 In summing up the results for the four modes of

Jan 1, 1968

As bizarre an example of competitive salesmanship to be imagined took place last June in Western Australia. A half dozen world renowned mining groups received a Japanese iron and steel investigatory mission. Geologists, engineers and businessmen, all specialists in iron ore, representing elements of the Japanese government and steelmakers, politely grilled each iron ore group for technical information and plans for property development. At stake were sales contracts with Japan for many millions of tons of iron ore. Since approximately two dozen visitors were involved, it was necessary to divide them into four groups for dispensing information, transportation and accommodations at the remote exploration camps. In a continent noted for its wide open spaces, the hinterland of Western Australia is spectacularly lacking in settlements. The state has better than one third of Australian land and statistically 0.8 persons per sq mile. In reality, however, over 400,000 of the 800,000 population reside in Perth. Under such circumstances, properly receiving and feting these important visitors would seem to be difficult but the competing exploration groups vied ingeniously to outdo each other in hospitality.

Jan 10, 1964

By J. T. Eash, N. B. Pilling

As a group, the alloys of iron, nickel and carbon are, in application, one of the most versatile of the ferrous alloy family, and while many investigations have been made of their properties and structure only a few attempts have been made to show the microstructural relation over a wide range of composition. It is necessary at once to be clear about the kind of structural relation with which we are concerned. The equilibrium diagram provides quantitative data regarding structural make-up and its variation with temperature, but equilibrium structures often are far different from the technologically significant ones. This is particularly true of steels and cast irons, and some of the most important components of their structure may have no place in the diagram of equilibrium. The fugitive phases that result from transformation are dealt with in a highly detailed and descriptive manner in the S-curves originated by Bain. The present effort lies in a still different field, which is to portray the relation between sweeping changes in composition and in resultant structure, under controlled but nonequilibrium conditions of thermal treatment. The Guillet1 diagram presented in 1903 was the initial attempt at such a correlation and frequent references to this diagram can be found in the literature even though later work has shown it to require considerable modification. Kase2 published in 1925 a diagram that was based upon observations of furnace-cooled melts. At low carbon contents this diagram agreed fairly well with experience in showing pearlite to exist in alloys containing up to 6 per cent nickel, and completely austenitic steels at 24 to 28 per cent nickel. At high carbon contents, however, irons were indicated as being martensitic at around 2 per cent nickel and austenitic at 12 per cent nickel; these interpretations are open to serious question. Based upon experience with steels and cast iron, Wickenden3 suggested a diagram that agreed fairly well with Kase&apos;s in the steel range but which presented a wide departure from it in the higher-carbon, high-nickel regions. In its broad picture, the Wickenden diagram is an approach to "practical" structures. [ ] Reference may be made at this point to the efforts of Marshy to construct an iron-nickel-carbon equilibrium diagram by the coordination of scattered data, which are described at length in the monograph cited. None of these preceding attempts has appeared to meet the need for an exposition of the structural sequence that is encoun-

Jan 1, 1942

Henry LOUIS, London, England (communication to the Secretary) : Prof. Richards&apos;s paper has impressed me as highly valuable. Without entering upon any discussion of it as careful and thorough as it deserves, I venture to mention one or two points which a perusal of it has recalled to my mind in connection with my own study and practice of ore-dressing. I always mentally divide jigging into two phases: 1. A particle at rest on the jig-bed is lifted and carried upwards by the rising current of water, at an increasing velocity, which tends to a maximum. When the upward current is stopped, the particle continues to rise with rapidly diminishing velocity until it comes to rest. This completes the first phase. 2. In the second phase, the particle falls from its position of rest with an increasing velocity which tends again to a maximum, and continues to fall until the rising current of water has reduced its velocity to zero. This completes the second phase. The second phase will evidently be greatly modified by the effect of suction, as Prof. Richards shows; but I do not see that his experiments very clearly imitate the action of the second phase. And the brief intervals at the end of each phase, when the mineral particle, by reason of its acquired velocity, is still moving, though in opposition to the water-current, yet remain to be investigated. I feel especially, in Prof. Richards&apos;s paper, a difficulty which I have felt with regard to all similar previous investigations, namely, that the experiments deal with particles falling a long distance, when the velocity becomes uniform. I question whether this uniform maximum velocity is attained in actual jigging-practice. If so, it is certainly for a comparatively very small proportion only of each stroke. It seems to me that an investigation like that of Prof. Richards, but confined to the first 6 or 8 inches of fall only, and carried out with suitably delicate recording-apparatus, is what we

Jan 1, 1895

By C. S. Barrett, D. B. Masson

Martensitic transformations have been found in AgCd both upon cold-working at room temperature and cooling to lower temperatures. The crystal structures of the transformation products were found to be close-packed hexagonal in the first case and or-thorhombic in the latter. The transformation characteristics also were studied. Similar treatment of AuZn alloys failed to yield any transformation. THE literature on martensitic transformations of body-centered cubic metals and alloys indicates widespread instability of this structure at low temperatures, a tendency which merits further study. The body-centered cubic ß-phase of CuZn, for example, when it contained less than 42 wt pct Zn, was found by Greninger and Mooradian&apos; and others&apos; to transform on cooling to subzero temperatures to a phase that was tentatively considered to be tetragonal. Further work by Massalski and Barrett" demonstrated that cold work at low temperatures causes a partial transformation of ß CuZn of higher Zn content. The structures of the strain-induced transformation products were found to be different from those induced by simple cooling. Another well-known martensitic transformation among body-centered cubic phases is that of ß AuCd, first studied with X-rays by Olander,&apos; then very thoroughly by Chang and Read.5,6 Here again transformation was found to occur both as a result of cooling and of strain. The alkali metals Li and Na, as well as certain Li-Mg alloys, also undergo transformation from their normal body-centered cubic structure, both on cooling and on cold-working. The phase AgCd, the subject of the present report, should be expected to behave quite similarly to CuZn for a number of reasons. It is the chemical analogue of CuZn, silver being directly below copper and cadmium directly below zinc in the periodic table. The size factors (percent difference in size) of the atoms, possibly a consideration in the stability of the ß-phases, are +3.1 in AgCd and + 4.2 in CuZn. Likewise the relative electronegativities of the two pairs of metals are about the same, CuZn possessing an electronegativity difference of 1.0 and AgCd one of 0.8. These values are from a table of electronegativities given by Darken and Gurry." The phase diagrams of the two systems around 50 atomic percent are similar, both possessing a disordered body-centered cubic phase, ß, at high temperatures and an ordered bcc phase, ß, at room temperature; however, the ß and ß&apos; phases of AgCd are separated by a hexagonal phase, [, stable in the range 220-440oC, which has no analogue in CuZn. There has been confusion in the literature as to the structures of the ß&apos; and [-phases. The phase diagram in the ASM handbook&apos;" has the structures of the two phases interchanged; however, Hansen" reports the correct relative positions and Muldawer" verified that ß&apos;, the low-temperature phase, is body-centered cubic. Work by the present authors also

Jan 1, 1959

By R. A. Wagstaff

SINCE the time of the early Egyptians, the use of copper has been a boon to the life of most of the civilized world. Its use has been varied; in many connections, the art by which it attained its greatest usefulness has been lost. In this paper an endeavor will be made to take into consideration some of the many changes that have occurred during the last 40 years of copper-smelting operations. During that period the copper blast furnace has been almost forced out of existence by new methods of ore concentration-first, gravity concentration, and then flotation. These new methods of concentration introduced many new factors into the metallurgy of copper. The product was wet, it was fine and it was high grade. To overcome all these factors many changes have been necessary throughout the smelting agenda. New equipment has been necessary for transportation, unloading, sampling, bedding and moisturing in all smelting plants, especially the custom smelter. During the early days of "flotation," little was known about filtering or the use of an alkaline circuit; often the concentrate going to the smelter contained 20 to 25 per cent moisture. It is easy to imagine the difficulty arising with a product of this nature when it had to be shoveled by hand labor. To meet these conditions, mechanical unloading and sampling devices were soon developed. In many instances such good progress was made that actual costs for handling this unfavorable product were lower than those formerly incurred on the old product. Today most sampling of copper ores and concentrates is being done by mechanical sampling, pipe or augur sampling, or shovel sampling. Where concentrates are uniform in metal content, a great many of the plants now use pipe or augur sampling. For spotty ores, the old shovel sample with cone and quartering during the final stages is still in use. Where big tonnages are handled, mechanical sampling of concentrates is being done, with satisfactory results. To curtail slow and tedious cutting and mixing procedure, mechanical mixing boxes, splitters and cutters are used to cut down labor costs. MILLING As crude ores become scarcer, the use of milling operations increases. The few crude ores that are still smelted are used as fluxing types. To use these ores finer grinding has been found advantageous. This has made for better bedding and fluxing conditions, which in turn makes for faster smelting, lower fuel consumption and better metal recovery. The degree of fineness is more or less determined by the nature of the product. Most plants have set a standard of through ¾ -in. mesh screen for roaster- reverberatory smelting and through ¾ in. mesh screen for converter fluxes. For some refractory ores; even finer grinding has been found to be advantageous for good reverberatory smelting.

Jan 1, 1944

By S. Brunauer

The hydration of portland cement is treated as a chemical reaction and the changes in matter, in energy and the rate of change of the process are discussed, Portland cement is a mixture of four major and at least as many important minor constituents. In the hydration process, the four major compounds (trical-cium silicate, dicalcium silicate, tricalcium alumi-nate and tetracalcium aluminoferrite), plus gypsum and water form five or six new compounds. In spite o the great complexity of the reaction, considerable progress has been made in its understanding, primarily with the help of such research tools as X-ray diffraction and electron microscopy. The rate of the reaction can be followed by direct and indirect methods of measurements. The effects o composition, particle size (or specific surface), temperature and water-cement ratio on the rates of hydration are discussed. The hydration of portland cement is a chemical reaction accompanied by such highly important physical phenomena as heat evolution, setting and hardening. It is a vast and complex subject, on which hundreds of papers have been published. At the time of the writing of this paper, in October 1962, a two-volume book, which alone contains dozens of papers pertaining to cement hydration appeared in print.&apos; The present paper deals with a few aspects of this vast subject, and the selection was not easy. The work reported here deals with some of the most recent investigations in the field. In any chemical reaction, the physical chemist is primarily interested in three things: changes in matter, changes in energy and the rate of change of the process or the speed of the reaction. This is true also of the chemical reaction between portland cement and water, and all three aspects of the reaction will be discussed. These three aspects are of vital interest to the engineer as well. Portland cement is not a cementing material — the hydration products, the new materials which form in the reaction, have the cementing action. The energy changes manifest themselves in a considerable evolution of heat, which may be useful or harmful. It is useful, for example, in winter concreting, but in very large concrete structures like dams, a large evolution of heat, which cannot be easily dissipated, may produce distress in the structure. Primarily for such a purpose was the Type IV or low heat portland cement developed. The speed of the chemical reaction is important because it determines the time of setting and hardening. The initial reaction must be slow enough to permit placing of the concrete before setting occurs. On the other hand, after the placing of concrete it is often highly desirable to obtain as rapid chemical reaction as possible. For this purpose the Type 111 or high early strength portland cement was developed. CHANGES IN MATTER Portland Cement: In a basic investigation, before one begins to study a reaction, one either knows the quantities and compositions of the starting materials, the reactants, or one determines them. This is obvious; the chemist expresses the changes in matter that occur in a reaction by a chemical equation, which has the quantities and compositions of the reactants on the left side of the equation and the quantities and compositions of the reaction products on the right side. The first question is then what to put on the left side of the equation in the reaction between portland cement and water? It is not very easy to answer this question. Portland cement is not a single chemical compound but a mixture of many compounds. Four of these are considered the major compounds, and at least four of the minor compounds also play important roles in the hydration reaction. In order to avoid complicating matters, the present discussion will be restricted primarily to the four major compounds, which constitute usually more than 90% of a portland cement. The relative amounts of these compounds vary from cement to cement. Actually not only the amounts but the compositions of these constituents also vary to some extent, but the variation in composition of the individual components will be neglected for simplicity.

Jan 1, 1963

By C. A. Heiland

The following summary is written for the benefit of the practical operator in the nonmetallic field who wishes to know what geophysics has done and may be expected to do in his line of work. His problem is quite different from that of the geophysicist who has operated with various or all methods and has followed the literature, and who is assumed to be familiar with the geologic possibilities and limitations of each method. This article is not written for the latter, although he may be interested in the four or five hitherto unpublished surveys described. To the operator, on the other hand, geophysics is only secondary. His problem is to determine which geophysical method is best suited to his special needs. If he wanted to know, however, which method could be used to locate a certain material of given physical properties, building stone, for instance, he would have to wade through a tremendous amount of geophysical literature, bibliographies and articles, before he could find what he wanted. Therefore, the purpose of this summary is to present the geological problems first and then to discuss the comparative merits of the geophysical methods that can be, or have been, applied. Choice of Geophysical Methods in Oil, Civil and Mining Engineering In the first two of these fields, the geological problems are not nearly so complex as in the metal and nonmetallic mining fields. The selection of the correct geophysical method in these fields is not nearly so difficult for the operator. For oil prospecting, his problems have been discussed exhaustively by E. DeGolyer.(1) † In civil engineering (foundation and ground-water work), the usefulness of electrical methods has been so well established that there is hardly any choice of other methods at present. The situation may be changed in the future with the perfection of the seismic reflection method for shallow depths. In the mining field the operator and often the geophysicist himself finds difficulty in determining which method is best suited for a given

Jan 1, 1934

By E. S. Bumps, H. D. Kessler, M. Hansen

The titanium-rich end of the Ti-AI phase diagram has been determined to the compound TiAI3 (62.7 pct Al), thus joining the aluminum-rich portion previously investigated by others and completing the diagram. Micrographic analysis and X-ray diffraction were the chief methods used to determine the phase relationships. THE Ti-Al phase diagram has been investigated as part of a program on titanium phase diagrams for the Wright Air Development Center. Included in the available information concerning the phase relationships in titanium-rich Ti-A1 alloys is a brief statement by Brown&apos; that: "aluminum raises the transformation temperature to 1000°C (183Z°F)." This observation is interesting in that it is the first example of a metallic alloying component raising the transformation temperature of titanium, and consequently widening the field of the a solid solution. Busch and Freyer&apos; presented resistivity data which indicated the formation of titanium-rich solid solutions of 1 and 3 pct A1 alloys prepared by powder metallurgy methods. Duweza found that there is only one other intermediate phase other than the known compound TiA1, (62.7 pct Al). This phase, designated as y, is of variable composition; its crystal structure is of the AuCu type and is therefore based on the composition TiAl (36.02 pct Al). Earlier work on the constitution of the aluminum-rich alloys has been reviewed by Hansen, and need not be discussed here. The tetragonal crystal lattice of TiAl,, as found by Fink, Van Horn, and Budge," was confirmed by Brauer." Recently, Schubert7 has reported that TiA1, is homogeneous within a limited composition range; however, the solubility limits were not given. The Ti-A1 phase diagram as presented in. this paper was determined by micrographic analysis of alloys containing from 1 to 62 pct Al, annealed at and quenched from temperatures between 700" and 1400°C. The phases and phase ranges investigated extend to the compound TiA1, (62.7 pct Al) to join the aluminum-rich end of the system determined by other investigators, thus completing the diagram. Methods of Investigation Preparation of Alloys: Iodide titanium, 99.9+ pct pure, obtained from the New Jersey Zinc Co., and high-purity (99.99+ pct) aluminum sheet from the Aluminum Co. of America were used to make up alloy ingots weighing 10 to 20 g. Detailed descriptions of melting techniques have been presented previously for work on the Ti-Mo and Ti-Cb> nd Ti-Si" phase diagrams. Briefly, the melting practice consisted of arc melting an accurately weighed charge in a copper block crucible insert in a non-consumable tungsten electrode furnace, under helium at atmospheric pressure. All ingots were carefully weighed after melting to detect possible losses. Comparison of weight before and after melting showed no appreciable weight changes. Also, chemical analyses were in close agreement with nominal compositions, Table I. The diagram as presented is, therefore, based on nominal compositions. Alloys were prepared having the following nominal aluminum contents: 1 ... 36 (1 pct increments), 38, 40, 41, 42.5, 44, 45, 46, 47.5, 49 . . . 64 (1 pct increments), 67, 70, 80, and 90. Ingots with up to 14 pct A1 were cold-pressed various amounts in order to increase the rate of attaining equilibrium structures on heat treatment. The amount of cold deformation that could be applied decreased with increasing aluminum content, until alloys containing 12 pct A1 or more cracked after only a few percent deformation. Annealing Treatments: Samples annealed at temperatures of 700" to 1000°C were sealed in

Jan 1, 1953

By George K. Burgess, Robert A. Hadfield

1. Introduction.—The methods of production of sound steel ingots have been described in several papers read recently before this Institute. It was thought by Director Stratton, of the U. S. Bureau of Standards, and ourselves to be of sufficient interest and importance, as a further contribution to this subject, to compare the properties of rails rolled in one mill according to American practice, from several types of ingot of substantially the same chemical composition but cast by several processes; and to compare in considerable detail the properties of an ingot manufactured by the Hadfield special-feeding process and one of the usual type for rolling into rails. We are greatly indebted to F. W. Wood, President of the Maryland Steel CO., who made this investigation possible by kindly placing his rail mill at our disposal; and he and his associates at Sparrows Point did everything possible to make the experiment a success, including the execution of several of the tests and analyses. 2. Classification and Manufacture of Ingots.—Of the ingots used in this investigation, eight were made in Sheffield and furnished by Sir Robert Hadfield, and one was made and furnished by an American steel company,l as a comparison ingot, and was supposed to represent the usual type of ingot from which rails are made. The characteristics of the ingots are given in Table I. Ingots 1, 2, 3, and 4 were cast large end up and fed by the Hadfield method in the usual manner with charcoal and blast continued until the molten steel has set on the top of the head, say varying from 20 to 40 min. To ingots 1, 2, and 4 was added 0.1 per cent. aluminum, and to the nickel-chrome ingot, No. 3, 0.125 per cent. For sake of comparison, there were also included two ingots, Nos. 8 and 9, cast with the small end up and fed by

Jan 1, 1915

By Charles T. Holland

IN connection with the problems of bumps in coal mines, much has been written concerning the manner in which roof action and methods of mining enter [ ] into the pressure effects observed but little has been written upon the relationship between the physical properties of coal and associated rocks and the cause of bumps. The question of the strength of bituminous coal, of its elasticity, and the energy it can absorb and store has been neglected to a considerable extent in connection with this problem. STRENGTH OF COAL It is generally agreed that one of the necessary conditions for bumps is a strong [ ] coal.1 Therefore, since the strength of coal is an important factor, a study of this property should be made. Several investigators have conducted laboratory experiments upon the strength of coal, using small cubical or rectangular test pieces. An attempt will not be made to go into all of these investigations, but they are briefly summarized in Table I. Experiments of the U. S. Bureau of Mines8 and of Lawall and Holland (pp. 27 and 34 of ref. 9), however, indicate that regardless of whether the coal is a soft and weak semibituminous (Pocahontas No. 3) or a hard and strong bituminous (Stockton) coal, the maximum ultimate unit stress developed in laboratory tests is higher in small cubes than in larger cubes of the same coal.

Jan 1, 1942

By J. W. Rutter, K. T. Aust

The temperature dependence of the rate of grain boundary migration was measured in bicrystals of zone-refined lead containing from 20 to less than 1 ppm by wezght of tin. The apparent activation energy in the temperature range from 320" to 200oC is markedly dependent upon the solute tin concentration and upon the orientation relationship of the grains adjacent to the grain boundavy. The quantitative experimental observat~ons are compared with the predictions of various theories of grain boundary migration. In previous work.&apos;?&apos; the mobility of individual grain boundaries was studied as a function of impurity concentration and type of boundary. Grain boundary migration occurred at the expense of dislocation arrays which were introduced into the specimen during solidification. Boundary mobility in zone-refined lead at 300°C was markedly decreased by small additions of tin. 0.004 wt pct being sufficient to decrease the rate of grain boundary migration by a factor of 1000. The mobility of grain boundaries having polar orientation relationships near 38 and 22 deg about <Ill>, and 28 deg about <100>, was much less sensitive to tin concentration in the range studied. As a result, these boundaries have relatively high mobilities. The present paper is a continuation of the above study. Data are now presented on the temperature dependence of the motion of individual grain boundaries in zone-refined lead as a function of solute tin concentration and orientation relationship of adjacent grains at the grain boundary. The experimental observations are compared with the predictions of a number of theories of grain boundary migration3-8 which, prior to the present experimental investigation, could not be critically evaluated. EXPERIMENTAL PROCEDURE The striation or lineage structure of melt-grown single crystals of zone-refined lead, containing various additions of tin, was utilized to provide a driving force for grain boundary migration, as previously described.1,2 Each grain boundary under study separated the striated single crystal from another grain which was introduced by localized plastic deformation and recrystallization of a small region of the sample. The speed of migration of grain boundaries in dilute alloys of tin in zone-refined lead was investigated as a function of 1) tin concentration from < 0.0001 to 0.002 wt pct, 2) temperature in the range of 200" to 320°C, and 3) orientation relationship of the adjacent grains at the grain boundary. The substructure driving energy available for grain boundary migration was estimated to be about 4000 ergs per cu cm, within a factor of two, from specimen to specimen.&apos; The specimen dimensions, and growth and alloying procedures for the preparation of striated single crystals of lead of known tin composition, were as described previously.&apos; Each bicrystal was carefully wrapped in aluminum foil, and annealed in a well-stirred salt bath consisting of 50 pct NaNO2 and 50 pct KNO3, for known periods of time at a series of constant temperatures (*2°C). The grain boundary positions, before and after each anneal, were determined by etching lightly in a solution of 5 pct nitric acid in methyl alcohol, in order to follow the motion of the boundary and determine its rate of migration. Thus, the rate of motion of the grain boundary in a single specimen was measured at various temperatures. The above procedure was carried out for each grain boundary in seventeen different bicrystal specimens.

Jan 1, 1960