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By L. F. Porter, G. J. Dienes

The effect of netltron irracliation on mart ensite transformation in the iron-nickel system was studied by means of electrical resistance and magnetic induction measuremertts. Irradiation lowers the M8 temperature of the allay, causes changes in the electrical and magnetic properties of the high-temperature phase which indicate either an accelemtion of phase separation or a clustering of nickel, and enhances strain recovery on specimens partially transformed to martensite prior to irradiation. Possible mechanisms to account for the effects; are discussed. 1 HERE is a good deal of evidence to indicate that neutron irradiation is capable of affecting phase changes in metals and alloys. While the mechanism of the effect often is not well understood, such studies hold promise of improving our understanding not only of irradiation damage but also of the phase changes involved. To date systematic and detailed investigations have been made of the influence of nuclear radiation on order-disorder transformations in the copper-gold, nickel-manganese, and copper-zinc system, and on precipitation reactions in the copper-iron, nickel-beryllium, and copper-beryllium system.' These solid-state reactions are diffusion controlled and the results can be explained largely on the basis of enhanced diffusion due to the presence of irradiation produced vacancies. Reversion of low-temperature eutectoid phases to the high-temperature phase has been observed in the fissionable uranium-molybdenum and uranium-niobium systems.2 Here it is necessary and logical to postulate a displacement spike mechanism to account for the effect. The only case of irradiation induced diffusionless transformation in metals is the allo-tropic transformation of p to a tin reported by Flee-man and Dienes. 3 They found that neutron irradiation markedly decreases the incubation time for transformation, but the mechanisnl is not well understood. Another diffusionless transformation which one might expect to be influenced by neutron irradiation is the martensite transformation. This transformation is known to be sensitive to strain, structural hardening, and the presence of imperfections.6,7 Since the transformation is diffusionless, one also

Jan 1, 1960

By J. W. Whitlow, P. K. Theobald, W. C. Overstreet

Monazite placers in a region of the Carolinas ex- in 1951-1954 by the USGS are estimated to contain at least 53,000 short tons of thorium and 4600 short tons of uranium. None of these deposits is being mined. The 5200-sq mile area investigated extends northeast along the western Piedmont from the Savannah River in South Carolina to the Catawba River in North Carolina. Much of the region is 700 to 1100 ft above sea level. Gentle hills and broad interfluves give a local relief of 100 to 200 ft. This increases to 1700 ft at the west margin of the area where the east flank of the Blue Ridge is approached in South Carolina and the South Mts. are entered in North Carolina. This report is restricted to placers in the Piedmont. Monazite deposits in the Blue Ridge and coastal plain were not covered by the investigation. Monazite Mining in the Carolina Piedmont: Discovered in 1879 by W. E. Hidden,' the monazite placers in the Carolina Piedmont were first mined in 1886. The area was a major world source for thorium and the lanthanides until 1895, when Brazilian monazite entered the trade. Total output from the Carolina Piedmont has been nearly 5500 tons of monazite,2 but the placers have been idle since 1911, except for 48 tons produced between 1915 and 1917. Monazite mining was revived in the Carolinas in 1954 when a dredge operated by the Heavy Minerals CO. opened a fluviatile placer along Horse Creek in the coastal plain near Aiken, S. C. Geology and Mineralogy: Two recent papers",' have described the geology of the monazite placer district in the Piedmont between the Savannah and Catawba rivers; the general geology of the region has been reviewed by P. B. King.' These reports show that the placers are in locally derived alluvial sediments that cover the floors of shallow, narrow valleys in an area underlain by monazite-

Jan 1, 1960

By John Drew Ridge

Tables showing world trade in metallic mineral raw materials during the years 1953 through 1957 have been prepared for the following twenty-one commodities: alumina, aluminum, bauxite, chromite, copper concentrates, partly refined and fully refined copper metal, iron ore, pig iron, iron and steel (simple shapes), lead concentrates, lead metal, manganese ore, mercury metal, nickel ore, concentrates, and matte, nickel metal, raw pyrites, sintered pyrites, tin concentrates, tin metal, zinc concentrates, and zinc metal. In each instance, the amounts given by the importing country were used except when statistics from the importing nation were lacking, incomplete, or misleading. To show the considerable divergence between importing and exporting country totals for the same years, the complete mercury table is given and, in parallel columns, shows the comparable tonnages of importers and exporters. Tables for the other twenty commodities are presented in summary form. The data of the concentrate tables are used with those of the corresponding metals as a basis for a discussion of trade in concentrates versus trade in metals. The data of all twenty-one tables provide the basis for testing the thirteen rules governing international trade in metal raw materials which I first published in Mining Engineering for July 1955. Because the 1953 through 1957 data are far more complete and considerably more extensive than those on which the 1955 rules were based, it was found possible to deduce five additional rules and to modify three of the original thirteen appreciably. The full text of the eighteen rules is given.

Jan 1, 1960

By J. B. Newkirk

ABOUT twenty-seven years ago W. bergl discovered that interesting detail could be seen in an X-ray diffraction spot made with a rock-salt crystal if the recording photographic film were held very close to the reflecting crystal. He also showed that much of this detail could be explained in terms of the deformation structure of the specimen. In the same year, 1931, Fox and parr2 reported that X-ray reflections from a quartz crystal were much more intense while the crystal was undergoing piezoelectric oscillation than when it was at rest. This observation was soon confirmed (and explained in terms of X-ray extinction) by Barrett3 in the United States and by Nishikawa et a1.,4 in Japan. During the next few years Barrett refined Berg's method for making X-ray diffraction micrographs and applied it to the study of metallic crystals. He reported this work in the 1945 annual lecture of the AIME.5 Since 1945 relatively little use has been made of the Berg-Barrett (B-B) method for making diffraction micrographs, though considerable interest in investigating subcrystal structures by other methods has developed. Some of these methods depend upon evaporation6 or chemical etching7 and, therefore, suffer from the occasional intrusion of subtle artifacts such as those recently reported by Hooker for leada and Welsh for aluminum.9 Other methods require the introduction of foreign elements which "decorate" the substructure in some way, thereby rendering it detectable by direct" or indirect1'. visual examination. Still others depend upon complex and often highly questionable analyses of X-ray diffraction line profiles. There have also been a number of related X-ray techniques, such as the Lambot,12 Schulz13 and Merlini and Guinier,14 which have proved to be quite useful for specific applications. Some of these methods give a picture of the substructure which is more or less directly related to the shape and the topography of the specimen. The Berg-Barrett method carries this desirable feature to the limit. Closely related to the B-B method are three photographic X-ray techniques recently described by Lang.15 These methods give beautiful pictures of the internal structure of crystals but are limited by the facts that the required apparatus is rather complex, exposure times are long, and the specimen crystals must be thin. An experimental appraisal which I have recently made of the original B-B method has shown that this simple technique is not only inexpensive and convenient, but can give more information than was apparently realized by its inventors. For example, first-order subgrains in iron-silicon crystals were clearly delineated and their relative orientation subject to description. Also defect structures could be seen within the subgrains and in some materials slip bands could be clearly seen with respect to the topography of the rest of the specimen. This much had already been described by Barrett. However, in the present study it was found that the actual sites of individual dislocations which emerge upon the crystal surface could be located. Furthermore, by a simple procedure, the direction (but not sign) of the dislocation Burgers' vector could be defined as well.

Jan 1, 1960

Map

Jan 1, 1960

By D. J. Mack, R. E. Reiswig

Six examples of the peritectoid transformation were selected from the literature and studied by the method of isothermal transformation. The kinetics and mechanisms of five of the examples are presented as TTT diagrams and photomicrographs. The exist-enc- of a peritectoid in the sixth case is doubtful. ALTHOUGH the peritectoid transformation per se has been known for many years, no precise published data exist concerning the kinetics or mechanisms involved in transformations of this type, except for the brief treatment by Rhines, et al. 1,10 Bearing in mind the fact that investigations of recent years are uncovering more and more peritectoids and suspected peritectoids, a thorough study of the well-established peritectoids appeared to be in order. It was for this reason that a study of the kinetics and morphological mechanisms of six binary peritectoids was undertaken. The six peritectoids selected from the literature for study were those reported at 7.02 wt pct Al-Ag, 26.0 wt pct Sb-Cu, 30.5 wt pct Sb-Cu, 32.3 wt pct Sn-Cu, 8.35 wt pct Si-Cu, and 21.2 wt pct Al-Cu. These selections were based on availability and purity of components, ease of preparation and heat-treatment, and estimated reliability of the available equilibrium diagrams in the regions of interest. EXPERIMENTAL PROCEDURE The alloys used in this investigation were induction melted in electrode-grade graphite and chill-cast in cast-iron split molds. In all cases, the alloys were so brittle that they could easily be broken into samples weighing 1 or 2 g. Chemical analyses showed that the alloys used were close to the respective peritectoid compositions reported in the literature and that the impurity levels were low in all cases. Metallographic examination showed uniform distributions of phases in all samples, indicating uniformity of composition in the samples studied. Isothermal transformation studies were carried out in fused-salt media, using the familiar inter-rupted-quench method. Uniformity of temperature in the salt baths was maintained by continuous stirring with a stainless-steel agitator. On the basis of actual observations of the temperature fluctuations, the estimated temperature control was + 10C for the Ag-Al and Cu-Sb alloys and ±30C for the Cu-Sn, Cu-Si, and Cu-Al alloys. The accuracy of all temperature measurements was estimated to be ±1°C. It was found necessary to mount metallographic specimens of the Ag-Al alloy in cold-curing methyl methacrylate, since the temperatures encountered in mounting in bakelite or lucite caused an appreciable degree of transformation to the ß phase. For the other alloys, wood-flour-filled bakelite mounts were used to avoid extraneous X-ray diffraction lines during the later examination of the metallographic specimens on a Norelco Geiger-counter d if f r ac tomete r. In the X-ray diffraction procedure, agreement between the published diffraction patterns and those obtained in this study was good. This was particularly important for phase identification, since the literature contained little in the way of micrograph description in some cases. Etching of the silver-aluminum alloy for metallographic examination was done by swabbing with either of the following reagents: 1) 10 g CrO3, 1 g (NH4), SO2, 0.5 g NH4NO3, 100 ml H2O, or 2) 10 ml NH4OH, 1 ml 20 pct KOH, 4 ml 3 pct H2O2, 5 ml H2O. The other alloys were etched with the usual bichromate etchant: 2 g K2Cr2O7, 1.5 g NaC1, 8 ml conc. H2SO4, 100 ml H20 (swabbed vigorously). EXPERIMENTAL RESULTS A) The Ag-Al peritectoid at 7.02 wt pct Al— The phase equilibrium involved in this peritectoid is shown in Fig. I.2 The phase boundaries in the vicinity of the peritectoid were most comprehensively established by Hume-Rothery, et al,3 who placed the equilibrium temperature at 448 °C and the equilibrium compositions of the a ß' and y phases at 6.11, 7.02, and 7.24 wt pct Al, respective The alloy used in this study analyzed4 6.95 wt pct A making it slightly hypoperitectoid according to the accepted equilibrium diagram. The rate of the transformation a+ y — ß' varies rapidly with degree of undercooling below the equilibrium temperature, passing through a maximum in the vicinity of 350°C. Thus the TTT dia-

Jan 1, 1960

By A. G. Buyers, J. Chilton, W. E. McKee

STUDIES in the high-temperature separations chemistry of thorium-uranium fuels are complicated by the corrosive nature of these molten metal systems at 1700°C. Separations research pointed toward the removal of fission products from irradiated alloys has included a frozen salt-bed technique which minimizes container reaction with molten metal. The procedure consists of high-frequency induction melting of the metal sample which is supported by a vertical column of unmelted salt. The molten alloy melts its immediate salt environment and as it slowly falls down through the column, many of the fission-product poisons are transferred into the fused salt environment. The molten salt-metal zone is encompassed at all times by unmelted salt, preventing container contact. EXPERIMENTAL Experimental methods were separated into three parts: salt-bed preparation, melting, and analytical evaluation. A) Bed Preparation—The procedure for casting calcium-fluoride briquettes was to compress the powdered salt at 5,000 to 10,000 psi and place this compact in a graphite crucible. This assembly was inserted into a vacuum system and surrounded by an alumina crucible as well as molybdenum, tantalum, or stainless-steel foil thermal-radiation shields. The pressure was reduced and the crucible heated under vacuum to about 800°C with the fore pump operating. Argon was then admitted to about 0.8 atm and heating continued until the CaF2 had melted 5 min at the melting point seemed satisfactory). Apparatus used included a 1-in. graphite crucible with 1/8-in. walls, 1-in. ID in a 2-in. induction coil, and a 6-kw Ajax high-frequency converter. B) Melting—Calcium-fluoride briquettes, 1 in. in diam and 1/2 to 1 in. thick, were prepared and vertically stacked to obtain the desired column length. An irradiated alloy sample (nut = 10") was placed on top of the salt column and the assembly was connected to the vacuum system. After evacuation of 5 to 10 , purified argon was admitted and the system flushed twice. The final argon pressure was about 0.8 atm. The sample was heated by induction at a power of about 6.5 kw. It then melted its way down through the salt and freely dropped into a small alumina crucible. The molten metal is followed during its downward course by the induction coil which is mounted upon a power-driven machine-threaded shaft. Experimental conditions used in the foregoing work

Jan 1, 1960

By S. C. Lindsay, D. J. I. Evans

With each year that passes hydrometallurgical processes are being more widely used to recover base metals from ores and concentrates. Generally these processes involve liquid-solid separation of metal-bearing liquors from barren residues. This may be done by countercurrent decantation, thickening and filtration, or filtration or centrifuging only. Choice of method is governed by chemical and physical characteristics of the pulps; cost of labor, power, materials, and waste disposal; and even by the amount of capital available when building plans are under way. Since all these controlling factors change with time and location and with technological advances, the separation method must be re-evaluated when new plants or expansion programs are contemplated. At the Sherritt Gordon refinery in Fort Saskatchewan, Alberta, an ammonia pressure leaching process recovers nickel, copper, and cobalt from the nickel concentrate produced at Lynn Lake, Manitoba.' Pregnant liquors are separated from the barren leach residues in a thickener-filter liquid-solids circuit. The decision to use this type of separation was based on a summation of economic factors during the pilot plant and design stages. Although countercurrent decantation was not incorporated in the refinery flowsheet, the problems solved in thickening the leach residues and the experience gained in operating the commercial plant are pertinent to countercurrent decantation, particularly where it is applied to slow-settling leach slurries or slurries having a relatively high vapor pressure of a valuable, obnoxious, or poisonous vapor.

Jan 1, 1960

By Jack D. Ramsdell

Electrorefined, magnesium-reduced, and sodium-reduced titanium samples were evaluated for recrystallization behavior, effect of cold rolling on tensile properties, and bend ductility. Curves were determined for the softening of 2.5 to 80 percent reduced cold-rolled metal that was annealed over a temperature range of 300° to 800° C. Upon annealing, coarsening of the grains was found to occur for reductions in thickness of less than 20 percent in titanium made by all three processes. The presence of metallic impurities greatly inhibits coarsening for reductions in thickness below 20 percent, but for reductions in excess of 20 percent grain size is essentially constant at each annealing temperature. The three grades of titanium did not harden excessively from cold rolling; both tensile and bend ductility were good for reduction in thickness up to 80 percent. Upon annealing, softening occurs between 400° and 600° C., and, based on microstructure and property studies, full annealing is accomplished after 30 minutes at 700° C. for the magnesium-reduced and electrorefined titanium and at 800° C. for the sodium-reduced titanium.

Jan 1, 1960

By Everett H. Dobbs

The Tripoli deposits in the southwest corner of Missouri In Newton County and the northeast corner of Oklahoma in Ottawa County, located in the vicinity of Seneca, Missouri, contains an unusual and peculiar form of silica which has not been found any other place in the world. Its outstanding characteristic is the physical structure of the individual particle, The particle structure of the Missouri-Oklahoma type Tripoli accounts for its market. It is a soft, friable, porous, double-refracting silica of the chalcedony variety, The particle is porous, has a fibrous structure, no sharp edges or comers, ad an average size of less than .01 millimeter, It varies from 90 to 98 per cent Si02 with less than 1 per cent free silica in the form of quartz, 24; has ignition loss of 1 per cent and fractional percentages of iron, alumina, lime, etc.

Jan 1, 1960

By Judson H. Whitman

To evaluate intelligently and to market a source of rare earth raw material, it is necessary that the producer understand the requirements of the processor and the manner in which these requirements effect the value and salability of his product. This paper will be an attempt to aid in such an understanding. The majority of rare earth processors are primarily chemical companies, not mining or metallurgical companies, as the complexities of the processing procedures are' much more chemical in nature than metallurgical. The rare earths and the rare earth industry are normally divided into two groups - the ?light? or cerium group and the ?heavy? or yttrium group. They are so named because cerium and yttrium are the most common elements in 'heir respective groups and are so divided on the basis of mineralogical and chemical characteristics. The dividing line of the two groups is not rigidly fixed but usually is considered as being between samarium (atomic number 62) and europium (atomic number 63). Although the two groups are quite similar, processing procedures differ significantly, hence most processors tend to specialize in one group or the other. There is, however, a growing tendency toward participation in both groups.

Jan 1, 1960

By Earl T. Hayes

THIS BIBLIOGRAPHY has been assembled to aid research by the Bureau of Mines, and others on high-purity tungsten. It appears approximately 50 years after the development of ductile tungsten-one of the first metals to be produced in a high-purity form. Requirements of the missile age are ever more demanding that engines rout hotter and space vehicles fly higher and faster. Thus, it has become necessary to reexamine all conventional materials of construction as well as to investigate new combinations. At this stage of our technology we have alloys capable of operation at 1,800° F. and several possibilities of developing some. that will be satisfactory up to 2,500° F. Strength-weight comparisons, detrimental to tungsten at, lower temperatures, disappear at this point, mid tungsten or its alloys appear to be the only metal capable of operation at truly high temperatures. The aim of this bibliography has been to include only references that concern improving the purity of tungsten-from processing the ore to treating the finished metal. In this sense it is a selected and not a critical bibliography. The period front January 1911 through February 1959 has been covered. Because repent literature has the greatest, value, most of the selected items refer to publications issued within the pest 5 years.

Jan 1, 1960

By D. J. Bauer

Liquid-liquid extraction techniques were investigated by the Federal Bureau of Mines for the fractionation of rare-earth solutions. Separatory funnel work using tri-n-butyl phosphate (TBP) for extracting ceric nitrate from solutions containing sulfate ion resulted in almost complete extraction. Similar tests using primary amines for splitting trivalent rare-earth pairs and fractions gave promising results. The ceric nitrate extraction procedure was scaled-up by use of pressure-bubbler equipment, a series of spray towers for extraction, washing, and stripping. In this case only 84 percent ceric nitrate extraction efficiency was achieved. This work was done using dilute sulfuric acid for stripping.

Jan 1, 1960

By Hargraves A. J

The paper outlines events at the Collinsville State Coal Mine, Queensland, leading to the practice of full face multiple shotfiring in bord and pillar development places. The 1954 disaster is referred to, and factors involved in simultaneous shotfiring in coal are discussed. Promising preliminary multiple shotfiring tests at the Colliery are described, as well as the resulting routine measures adopted, and the changes involved. The subsequent inducing of two outbursts under safe conditions by remote multiple shotfiring is given as justification for the changes made.INTRODUCTIONFollowing a disastrous instantaneous outburst (1.0.) of coal and gas at the Collinsville State Coal Mine in 1954, the necessity for inducer shotfiring for the control of possible further outbursts was established. However this mine, immediately classified as gassy after the 1954 outburst, is subject to the general restrictions pertaining to gassy mines which at present preclude the use of inducer shotfiring due particularly to the non-existence of a permitted exploder for more than six shots, and further, because permitted multipleexploders are not designed for remote firing through long lengths of cable. This situation was met by arresting or reducing progress in the production places, thereby reducing the danger of outbursts while means were being considered to achieve overall maximum safety.In August 1957 two full faces were successfully blasted in experimental simultaneous rounds. In June 1958 four full faces were blasted, and in October 1958 full face grunching without prior cutting, Le. inducer shotfiring, was introduced in No. 1 Tunnel as a production feature. In March 1960 it...

Jan 1, 1960

By L. J. Kane

Conventional methods for determining the size of dust suspended in a gas require that agglomerates (clusters of particles) first be broken into particles, but in evaluating industrial dust-removing equipment the size of the agglomerates as they actually exist in the gas stream is far more important. This paper presents results of an investigation by the Federal Bureau of Mines to develop methods for determining the size of dust agglomerates suspended in a gas stream. The studies are part of the Bureau's continuing research on synthetic liquid fuels. The size and size-distribution of agglomerates as they exist when the gas reaches the filter was determined by using a membrane filter in conjunction with a dust count under a microscope. A membrane filter is a cellulosic sheet about 150 microns thick containing millions of holes per square centimeter--holes of uniform diameter that run directly through the sheet without interconnection.

Jan 1, 1960

By J. E. Wilson

A bench-scale expansion tester using 71 grams of coal was developed to determine the practicability of an apparatus of this size to investigate the effect of variables such as oxidation, blending, bulk density, inerts, size consist, petrographic differences, and rate of heating on the expanding properties of coal. The value of this tester is shown by the correlation that exists between its results and those of the larger scale sole-heated oven expansion apparatus used in commercial plants. From tests on 32 coals the standard error of estimate for predicting sole-oven results from bench-scale results is ± 5.3 percentage points. A standard deviation of the difference between pairs of tests in the latter apparatus of ± 2.1 percentage points was determined for 31 samples. In the sole-heated oven test the expansion of a coal at constant pressure is directly proportional to the dry coal bulk density. Tests in the bench-scale tester show a similar relationship between expansion and bulk density. When the blending ratios of high-and low-volatile coals are varied, similar changes in expansion are observed in both the sole-heated oven and the bench-scale tester. Therefore, the effect of other variables on expansion should be similar in the latter apparatus.

Jan 1, 1960

By A. E. Dwight, P. A. Beck

A search was made for ordered phases of AB3 composition in various combinations of Ti- and V-group elements with CO-and Ni-group elements. Three new TiNi3-type phases ZrPd3, HfPd3, and HfPt3 were found. In addition, twelve new Cu3Au-type phases TiRh3, Tilr3, ZrRh3, Zrlr3, HfRh3, Hflr3, VRh3, VIr3, CbRh3, Cblr3, TaRh3, and TaIr3 were also found. The lattice contraction for all three structures considered increases with increasing relative size of the A atom, suggesting that it is mostly the A atom that cont~acts. It was noted that, for the same radius ratio the lattice contraction is larger when the A atom is Ti than if it is Cb OY Ta. It is well known that elements or disordered solid solutions, which have structures with spherical close-packing, may be described in terms of various stacking schemes of close-packed layers. Stacking of the type abab corresponds to the hexagonal close-packed structure, and stacking of the type abcabc corresponds to the face-centered-cubic structure. In binary alloys of the first, second, and third long period transition elements various AB3 phases occur with close-packed ordered structures. It was observed that these ordered structures also may be described by suitable stacking of close-packed ordered layers, Fig. 1, as first shown by Laves and Wallbaum for TiNi3.' It is clear that the units of translation in such a close-packed layer consist of four atoms, one of which (black circle) is atom A and the three others (empty circles) are atoms B. Because of the alternation of A and B atoms in every second row of each layer, the unit-cell dimension in the layer is equal to the sum of the diameters of atoms A and B: a0 = 2(rA + rB). Stacking of such layers in the sequence abab results in a hexagonal close-packed structure of the MgCd, type. The unit-cell dimension in the basal plane is approximately double of that for the disordered hexagonal close-packed structure, but in the direction of the hexagonal axis it is about the same, so that 2co/uo = 1.63 in case of spherical close-packing. Ordered hexagonal close-packed structures of this type were found to occur in MoCo3,2 WCo3,, and UPt, .4 When the ordered layers shown in Fig. 1 are stacked according to the scheme abcabc, the resulting ordered structure is of the AuCu, type (cubic). Structures of this type were found to occur in TiPt3,5 CrPt,,' CrIr,,' and URu, .4 Finally, the stacking scheme abacabac of the same ordered layers results in a hexagonal close-packed structure of the TiNi3 type.' In this case, the unit-cell dimension is doubled not only in the basal plane, but also in the direction of the hexagonal axis, so that co/ao = 1.63. Structures of this type were found to occur also in TiPd3,5 ZrPt,," and UPd,.4

Jan 1, 1960

By R. O. Williams

It is shown that Ni3Al precipitates homogeneously from nickel-rich alwminum alloys as plates on the (100) planes. Prior to actual precipitation a process occurs which is believed to be one of increasing short-range order. After precipitating the Ni3Al plates enlarge through competitive growth. Discontinuous precipitation can occur simultaneously with the above processes. Recent ideas of the origin of precipitation strengthening appear adequate to explain the hardness changes. REMARKABLY little appears to be known about the precipitation process in Ni-Al alloys in spite of their technical importance. This investigation originated to supply additional information about precipitation in general, this system in particular. Information on the structures and kinetics have been obtained through the use of hardness, X-rays, microscopy, calorimetry, and resistivity on high-purity alloys. PROCEDURES Six alloys, Table I, were prepared by melting carbonyl nickel and high-purity aluminum in alumina crucibles in vacuum and casting into 1-in. graphite molds. All rods were homogenized at least once at 1300°C for 24 hr prior to swaging and this was repeated on the first three alloys after 75 pct reduction. Alloy 4 could be reduced only 10 pct at 1000°C (probably in two-phase field) prior to fracture but 1/4-in. samples quenched from 1100°C were readily reduced cold. Alloy 5 was reduced 15 pct cold but failed on the next pass while alloy 6 of essentially the same aluminum content failed inter-granularly without apparent flow up to 1000°C. The alloys were heated in hydrogen at the elevated temperatures and formed thin, coherent aluminum oxide coatings which provided excellent oxidation resistance at lower temperatures. However, freshly prepared surfaces showed considerably less resistance at 500"to 700°C in air and apparently resulted in internal oxidation. As a consequence, low-temperature agings were carried out in evacuated tubes. RESULTS The isothermal hardening behavior of these alloys at 500"and 565C is given in Figs. 1 and 2. These results were obtained from samples cold worked 75 pct, recrystallized at 1000°C (1100°C for the 7.8 pct Al) and quenched in water. This recrystallization was used to give smaller grain sizes so as to obtain more uniform hardness values and the points represent an average of five readings. The electrical resistivity was measured on 1/16-in. wires quenched from 1000°C during aging at 495°C to give Fig. 3. The energy release and its rate are given in Fig. 4 for the 6.9 pct Al alloy during aging around 500°C. Inasmuch as this was a single run, its accuracy is not known but certainly the general shape and magnitudes are correct. The method used to obtain these results is described elsewhere.' Data for the aging at 600°, 700°, and 800°C of these alloys cold worked 50 pct are given in Fig. 5. Supplementary information from microscopy and X-ray diffraction have been included to indicate recrystallization, discontinuous precipitation and the appearance of superlattice lines from the Ni3Al. The hardness of these alloys as annealed, aged, cold worked, and cold worked and aged is given vs composition in Fig. 6. Those samples which were isothermally aged, Figs. 1 and 2, were reaged at 532°C and at successively higher temperatures for the indicated times to give the data of Fig. 7. These results as well as certain others, support the idea that the level of hardness reached for temperatures above 600°C are equilibrium values more or less independent of path. This being the case, the breaks in the curves would be the complete solution of the Ni,Al. The electrical resistivity versus temperatures for some of these alloys, both aged and unaged, is given in Fig. 8 along with those data from heating slowly (10 deg per day) to high temperatures. Interesting points include the lowering of the Curie temperature (the change in slope), the lack of any indications of a solubility limit and the large temperature coefficient for the Ni3Al. A slight break for Ni3Al around 100C shows up but this is not a Curie temperature as Ni3Al is not ferromagnetic down to -190°C. Metallographically both the nickel-rich solid solution and the Ni3Al appear very much like pure nickel. Profuse twin boundaries are present both

Jan 1, 1960

By Warren H. Weisz

A cement, in the broad sense, is any substance which will cause various materials to adhere to each other. Clay was probably the first material to be used by man as a cement or binding agent. Water occurs in or is mixed with the clay to make it plastic, so that it can be formed in place. The sun and air remove the water from the clay and on drying strength is developed. The clays unless fired are not too resistant to water, therefore, their use is best when restricted to dry areas. Gypsum used as a cementitious material is not the subject of this paper, but its use dates back thousands of years. Gypsum mortars were used by the Egyptians in building such massive masonry structures as the pyramids. The Egyptian mortar consisted of a mixture of sand with burned gypsum (of an impure type of 81.5 per cent calcium sulphate and 9.5 per cent calcium carbonate) for the cementitious material. The burning of this type of cementitious material took place at relatively low temperature. These burning reactions will be covered later when the dehydration of gypsum is discussed. The setting of the partially dehydrated gypsum is considered to be crystallization from a supersaturated solution which deposits crystals of dihydrate (gypsum). In low water-content mixes, the interlocking of the needle-like crystals helps to produce higher strengths. Slaked lime made from limestone burned at higher temperatures (1648 F is generally considered as the calcining temperature, although under certain conditions incipient calcination will take place at 1250 F) is another early-period cementitious material. During slaking with water, a colloidal or amorphous hydrated lime is formed. When it is allowed to dry, it hardens and develops low strengths. On exposure to the carbon dioxide of air in the presence of some moisture, carbon dioxide is adsorbed and part of the calcium hydroxide is converted to calcium carbonate. Structures in which a lime mortar is used continue to grow in strength as this reaction proflesses. Hydrated lime has the disadvantage of not setting under water.

Jan 1, 1960

By A. Gatti

Studies were made on the system iron plus alumina. Various methods of dispersing and various amounts of alumina were used. Powder metallurgy techniques were used to produce the final product. Microstructures and some mechanical properties are presented. Alloys containing up to 16 pct alumina by weight are ductile at all temperatures tested. The ivon-alumina materials have a higher yield stress and improved creep resistance over that of pure iron. SINCE the development of SAP' an A1- Al2O3 powder metallurgy product, great interest has been shown in the development of a SAP-like structure in metals and alloys other than aluminum. The outstanding properties of this class of materials are: 1) Good creep resistance at high temperature. 2) High yield strengths and high hardness at high temperatures. 3) High recrystallization temperature. However, the lack of ductility and formability has thus far limited the applications of SAP-like materials. The following report deals with methods of dispersing A12O3 in Fe, processing of powders into rod, structures produced after processing, and mechanical properties of the iron-alumina material produced. Methods of dispersing the alumina and also the volume fraction of alumina added were varied. MATERIAL Powder Processing— Four methods of obtaining dispersions of alumina in iron were studied. 1) Oxidation-reduction of a Fe + 8 pct Al alloy. .2) Coprecipitation of Fe(OH)3 + Al(OH)3 from aqueous solution. 3) Colloidal mixing of Fe,O3 and Al2O3. 4) Colloidal mixing of Fe powder and A1,O3. Fig. 1 is a processing flowsheet which outlines the processing steps taken to produce a final extruded bar 1/4 in. in diameter and about 30 in. long. The - 100 mesh iron-aluminum alloy was oxidized by placing a thin layer of powder on an alumina plaque. The reduction step was modified to include 1/2 hr at 1000°C since the powders tended to become pyro-phoric unless sintered slightly after low-temperature reduction. Compacting was done in a 1-1/8-in.-diam pressing die. The slugs produced averaged 1 in. in length. The billets were encased in low-carbon steel cans shown schematically in Fig. 2. The blank is included for structure and property comparison purposes. TESTING PROCEDURE All tests were made on as-extruded material.

Jan 1, 1960